EPA 560/6-76-015
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task IB - Hexachlorobutadiene
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Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
June, 1976
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EPA-560/6-76-015
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task IB - Hexachlorobutadiene
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
June 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 trade names or commercial
products is for purpos.es of clarity only and does not constitute endorse-
ment or recommendation for use.
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CONTENTS
Summary • 1
Section
I Introduction ...... .... 3
II Experimental Procedures 5
Sampling Procedures • 5
Analysis Procedures 5
III Selection of Sampling Sites 8
Selection Criteria ...... ... 8
Recommended Sampling Sites •• 10
IV Presampling Surveys and Field Sampling 14
Presampling Surveys .... ...... 14
Field Sampling 14
V Discussion of Results and Conclusions .... 19
Vulcan Materials Company, Wichita, Kansas 19
Linden Chlorine Plant, Linden, New Jersey . 28
Stauffer Chemical Company, Louisville, Kentucky ... 30
Dow Chemical Company, Pittsburg, California 37
E. I. du Pont.de Nemours and Company, Inc.,
Corpus Christi, Texas 41
Diamond Shamrock Corporation, Deer Park, Texas ... 44
Ciba-Geigy Corporation, St. Gabriel, Louisiana ... 49
Olin Corporation, Mclntosh, Alabama ... 51
PPG Industries, Inc., Lake Charles, Louisiana .... 53
11
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CONTENTS (concluded)
Section Page
VI Summary and Conclusions for Program Task IB ...... 60
Summary 60
Conclusions 63
References . ............ 64
Appendix A - Presampling Survey and Field Sampling ........ 65
Appendix B - Analytical Data 118
Appendix C - Method Development for Sampling and Analysis .... 131
111
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FIGURES
No.
1 Air Sampling Train 6
2 Geographic Location of Recommended Sampling Sites. ..... 12
3 Presampling Survey and Field Sampling Schedule ....... 15
4 Average Concentrations of HGBD in Air Per 20-Hr Period at
18 Sampling Stations at Vulcan Materials Company, Wichita,
Kansas 21
5 HCBD Concentration Per 20-Hr Period at Sampling Stations
Within the Plant Perimeter (Vulcan) 22
6 HCBD Concentration Per 20-Hr Period, Downwind Stations
(Vulcan) 23
7 HCBD Concentration Per 20-Hr Period, Upwind Stations
(Vulcan) 24
8 Average Concentrations of HCBD in Air at Nine Sampling
Stations at Stauffer Chemical Company, Louisville,
Kentucky .................. . 33
9 HCBD Concentration Per 24-Hr Period at Sampling Stations
Around the Plant (Stauffer) 34
10 Average Concentrations of HCBD in Air at Eight Sampling
Stations at Dow Chemical Company, Pittsburg, California. . 38
11 Average Concentrations of HCBD in Air at Five Sampling
Stations at E. I. du Pont de Nemours Company, Corpus
Christi, Texas 42
12 Average Concentrations of HCBD in Air at Eight Sampling
Stations at Diamond Shamrock Corporation, Deer Park,
Texas* * 47
iv
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FIGURES (concluded)
No. . Page
13 Average Concentrations of HCBD in Air at Eight Sampling
Stations at Ciba-Geigy Corporation, St. Gabriel,
Louisiana 50
14 Average Concentrations of HCBD in Air at Eight Sampling
Stations 52
15 Average Concentrations of HCBD in Air at 10 Sampling
Stations at PPG Industries, Lake Charles, Louisiana ... 55
16 Summary of HCBD Concentrations in Air 62
A-l Presampling Survey and Field Sampling Schedule. ...... 67
A-2 Sampling Locations at Vulcan Materials Company - Wichita
Plant 69
A-3 Vulcan Materials Company - Wichita Plant, and Surrounding
Areas 72
A-4 Sampling Locations at Stauffer Chemical Company - Louisville,
Kentucky 78
A-5 Sample Locations at Dow Chemical Company, Pittsburg,
California 85
A-6 Sample Locations at E. I. du Pont de Nemours and Company,
Inc., Corpus Christi, Texas 90
A-7 Sampling Locations at Diamond Shamrock Corporation,
Deer Park, Texas 97
A-8 Sample Locations at Ciba-Geigy Corporation, St. Gabriel,
Louisiana ... q... ....... 101
A-9 Sampling Locations at Olin Corporation, Mclntosh, Alabama . 107
A-10 Sampling Locations at PPG Industries, Lake Charles,
Louisiana ....... 114
C-l Apparatus for Recovery of HCBD From Water by Vaporization
at Reduced Pressure ........... 135
v
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0
-
TABLES
Estimated Quantities of HGBD Present in Industrial Wastes,
By-Products, And Products in 1972
2. Production Capacity, Process Technology and Waste Disposal
at Recommended Sites* ........... . ...... 13
3 Field Sampling Summary ........... ........ 17
4 Summary of Air Sampling Parameters. ..... ...... . 18
5 Comparison of HCBD Levels at 4 and 11 ft for Five Time
Periods .......... . ........... ... 25
6 HCBD Concentrations in Soil and Sediment From Vulcan
Materials Company, Wichita, Kansas ............ 27
7 HCBD Concentrations in Water From Vulcan Materials Company,
Wichita, Kansas .................. ... 29
8 HCBD Concentrations in Water and Solids From Linden
Chlorine Company, Linden, New Jersey ........... 31
9 HCBD Concentrations in Soil and Sediment From Stauffer
Chemical Company, Louisville, Kentucky ..... ..... 36
10 HCBD Concentration in Water From Stauffer Chemical Company,
Louisville, Kentucky ....... . ......... .. 36
11 HCBD Concentrations in Soil From Dow Chemical Company,
Pittsburg, California ............ . ..... 40
12 HCBD Concentrations in Soil and Sediment From E. I. du
Pont de Nemours and Company, Corpus Christi, Texas. ... 43
13 HCBD Concentrations in Water From E. I. du Pont de Nemours
and Company, Corpus Christi, Texas. ..... ...... 45
vi
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TABLES (continued)
No. . Page
14 HCBD Concentrations in Soil From Diamond Shamrock
Corporation, Deer Park, Texas ....... 48
15 HCBD Concentrations in Water From Diamond Shamrock
Corporation, Deer Park, Texas 48
16 HCBD Concentrations in Soil and Sediment, Olin Corporation,
MeIntosh, Alabama ............... 54
17 HCBD Concentrations in Soil and Sediment From PPG Indus-
tries, Lake Charles, Louisiana* ............. 57
18 HCBD Concentrations in Water From PPG Industries, Lake
Charles, Louisiana. 58
19 Data Summary for Program Task No. 1 • • • • 61
A-l Mr Sampling Data at Vulcan Materials Company, Wichita,
Kansas. . 70
A-2 Plant Activities During Sampling at Vulcan Materials
Company, Wichita, Kansas 73
A-3 Weather Conditions During Sampling at Vulcan Materials
Company, Wichita, Kansas. ................ 74
A-4 Air Sampling Data at Stauffer Chemical Company, Louisville,
Kentucky. 79
A-5 Plant Activities During Sampling at Stauffer Chemical
Company, Louisville, Kentucky 81
A-6 Weather Conditions During Sampling at Stauffer Chemical
Company, Louisville, Kentucky 82
A-7 Air Sampling Data at Dow Chemical Company, Pittsburg,
California 86
A-8 Weather Conditions and Plant Activities During Sampling
at Dow Chemical Company, Pittsburg, California 87
VI1
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TABLES (continued)
No. Page
A-9 Air Sampling Data at E. I. du Pont de Nemours and
Company, Inc., Corpus Christi, Texas . . . . . 91
A-10 Plant Activities During Sampling at E. I. du Pont de
Nemours and Company, Inc., Corpus Christi, Texas .... 93
A-ll Weather Conditions During Sampling at E. I. du Pont de
Nemours and Company, Inc., Corpus Christi, Texas .... 94
A-12 Air Sampling Data at Diamond Shamrock Corporation,
Deer Park, Texas 98
A-13 Weather Conditions During Sampling at Diamond Shamrock
Corporation, Deer Park, Texas. 99
A-14 Air Sampling at Ciba-Geigy Corporation, St. Gabriel,
Louisiana. .......... 102
A-15 Weather Conditions During Sampling at Ciba-Geigy,
St. Gabriel, Louisiana 104
A-16 Air Sampling Data at Olin Corporation, Mclntosh, Alabama . 108
A-17 Weather Conditions During Sampling at Olin Corporation,
Mclntosh, Alabama 110
A-18 Air Sampling Data at PPG Industries, Lake Charles,
Louisiana. 115
A-19 Weather Conditions During Sampling at PPG Industries,
Lake Charles, Louisiana. ...... ... 117
B-l HCBD Concentrations in Air Samples From Vulcan Materials
Company, Wichita, Kansas 119
B-2 HCBD Concentrations in Air Samples From Stauffer Chemical
Company, Louisville, Kentucky 124
B-3 HCBD Concentrations in Air Samples From Dow Chemical
Company, Pittsburg, California .. 126
B-4 HCBD Concentrations in Air Samples From E. I. du Pont de
Nemours and Company, Corpus Christi, Texas 127
viii
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TABLES (concluded)
No. Page
B-5 HGBD Concentrations in Air Samples From Diamond Shamrock
Corporation, Deer Park, Texas 128
B-6 HCBD Concentrations in Air Samples From Ciba-Geigy
Corporation, St. Gabriel, Louisiana 129
B-7 HCBD Concentrations in Air Samples From PPG Industries,
Lake Charles, Louisiana ................. 130
C-l Recovery Studies of HCBD by n_-Hexane Extraction 133
C-2 Recovery of HCBD From Water by Concentration on XAD-4 ... 133
C-3 Loss of HCBD Due to Vaporization 134
C-4 Recovery of HCBD From Water-Saturated Air 136
C-5 Recovery of HCBD From Sediments 137
IX
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SUMMARY
The purpose of this program is to provide sampling and analysis ca-
pabilities to EPA's Office of Toxic Substances, so that the levels of
suspected toxic substances in air, water, soil, and sediment at desig-
nated locations throughout the United States may be determined. Four
tasks have been assigned on this program. The first task was the sam-
pling and analysis for hexachlorobutadiene (HCBD).
Methods for sampling and analyzing HCBD in air, water, soil, and
sediments were evaluated. A protocol was developed and approved.
Nine industrial plants were selected for sampling. The plants rep-
resent six major industries: perchloroethylene, trichloroethylene, car-
bon tetrachloride, chlorine, triazine herbicides, and pentachloronitro-
benzene.
In general, of the six industries sampled, higher concentrations
of HCBD were associated with the production of perchloroethylene, tri-
chloroethylene, and carbon tetrachloride. In the one plant that pro-
duced only carbon tetrachloride, however, the HCBD levels were quite
low. No HCBD was detected in samples from the pentachloronitrobenzene
production plant. The levels of HCBD associated with plants producing
chlorine and triazine herbicides were very low.
Several different waste-disposal methods were used at the perchloro-
and trichloroethylene plants that were sampled. The highest level of HCBD
was detected in air and soil at the plant using on-site landfill and open
pit storage. High HCBD levels were detected in- loading and transfer areas
at plants using off-site disposal methods. Lower levels of HCBD were found
at plants using on-site incineration but downwind air concentrations were
still elevated above background at both plants. The production of perchloro-
and trichloroethylene by low temperature oxychlorination and the incinera-
tion of liquid bottom wastes resulted in a low HCBD level in the air but
high levels in the effluent water. Levels of 10 |j,g/liter HCBD were found
in treated process water more than 3,000 ft from the plant effluent.
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The highest level of HCBD found in the air on plant property was 463
M-g/m . Levels of HCBD in open wastewater treatment streams were as high
as 244 and 75 Hg/liter at two plants. Soil levels of HCBD reached 980 and
29 |J,g/g at two plants.
The maximum air concentration of HCBD off plant property was 22 [J.g/m-'.
O
A level of 10 p^g/itr was detected at the boundary of another plant. The high-
est levels in water off plant property were 23 and 10 ^g/liter. A level of
0.11 Hg/g HCBD in soil was found off plant property and levels of 0.15 and
0.34 |J.g/g were found at the boundary of two other plants.
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SECTION I
INTRODUCTION
Environmental contamination of HCBD has been reported in the United
States. HCBD has been found in fish samples taken from the lower
Mississippi River.— In addition, HCBD has been detected in waste streams
and solid waste disposal sites near chemical manufacturing sites^i'
On July 5, 1973, Midwest Research Institute (MRI) initiated a study to
estimate the quantities and identify sources of HCBD in the environment.
The origin of HCBD in the environment in the United States was identified
as the waste materials or by-products from the production of perchloro-
ethylene, trichloroethylene, carbon tetrachloride, chlorine, pentachloro-
/s\
nitrobenzene and the herbicide Dacthal . Specific industrial plants from
the above industries were recommended to EPA as potential sampling sites.
On June 27, 1974, the current MRI project (3953-C) entitled "Sampling
and Analysis of Selected Toxic Substances" was initiated. The objective of
this program is to provide the EPA with sampling and analysis capabilities
to determine the levels of toxic substances in air, water, soil and sedi-
ment from designated sources and ambient locations throughout the United
States. The first task of this program was the sampling and analysis for
HCB and HCBD. Tasks II, III, and IV of this program are the sampling and
analysis for ethylene dibromide, evaluation of vinyl chloride levels in
outdoor and indoor air due to the presence of PVC products and additional
sampling and analysis for ethylene dibromide, respectively. The Task II
ethylene dibromide study has been completed and reported to the Office of
Toxic Substances in September 1975 under the title of: "Sampling and Anal-
ysis of Selected Toxic Substances: Task II - Ethylene Dibromide," EPA Re-
port No. 560/6-75-001. The Task III study has been completed and reported
to the Office of Toxic Substances in April 1975 under the title "Sampling
and Analysis of Selected Toxic Substances: Task III - Vinyl Chloride,
Secondary Sources," EPA Report No. 560/6-76-002.
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This report describes Task IA of the program, i.e., the sampling
and analysis for HGBD as follows: experimental procedures; screening
and selection of sampling sites; presampling surveys and field sam-
pling; and discussion of results and conclusions. Site surveys and field
sampling data for individual sites, analytical data, and methods develop-
ment efforts are appended to the report.
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SECTION II
EXPERIMENTAL PROCEDURES
SAMPLING PROCEDURES
Water was sampled by two different methods—grab sampling and porous
polymer extraction. The grab water samples were composited and stored in
glass 1-gal. bottles that had been used for pesticide grade solvents. In
the second technique, water was mechanically pumped through a 30 x 5.2
cm i.d. glass tube packed with 250 g Amberlite XAD-4. The Amberlite resin
removed HCBD quantitatively from the water stream flowing at 0.6 to 1.4
liters/min. The composited water samples and the Amberlite resin tubes
were capped and stored in ice chests until ready for analysis.
Air was sampled through a 37 mm diameter, 0.8 pm pore size, milli-
pore filter, followed by a 15 cm, 1.2 cm i.d., glass sampling tube* packed
with 1 g Tenax -GC. Air was drawn through the filter and Tenax®-GC tube
with the aid of a mechanical pump. The flow rate was regulated with either
an 18 gauge needle (~ 3.5 liters/min) or a 26 gauge needle (~ 0.4 liters/
min). A schematic of the air sampling train is shown in Figure 1.
Soil and sediment samples from the top 2 to 5 cm were collected at
designated sites. From 0.5 to 1 kg of sample was composited and stored
/¥J\
in wide-mouth glass bottles with Teflon -lined caps and kept in an ice
chest until ready for analysis.
ANALYSIS PROCEDURES
Sample Preparation
fS\
The millipore filter and the Tenax -GC resin for each air sample
was sequentially extracted with 20, 20, and 10 ml of pesticide grade
hexane using an ultrasonic water bath. During the extraction, ice was
added to the ultrasonic bath to minimize evaporative loss of HCBD. The
hexane extracts were combined and diluted to 50.0 ml.
* In sampling some industrial plants, two Tenax®-GC tubes were used
in tandem.
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Critical
Orifice
K
Millipore
Filter
\
Tenax-GC
Tubes
Mechanical
Pump
Figure 1. Air sampling train
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The soil samples were first sifted on a U.S. Standard No. 18 sieve to
remove stones and other foreign material. A 1.00 g sample was then extracted
with 100 ml of j}-hexane in a soxhlet apparatus overnight. The hexane ex-
tracts were transferred to 100 ml volume flasks and diluted to volume. A
similar sample preparation procedure was used on the sediment samples ex-
cept that the sifting step was omitted.
A 500 to 1,000 ml portion of each grab water sample was extracted
sequentially with 20, 20, and 10 ml of hexane. The extracts were collected
in a 50 ml volumetric flask and diluted to volume. The Amberlite XAD-4
resin was extracted with 250 ml hexane using a soxhlet apparatus. The
extract was collected in a 250 ml volumetric flask and diluted to volume.
All of the extracted samples were kept in a walk-in cold room main-
tained at 4 C. Prior to analysis, the samples were brought to room tem-
perature and diluted or concentrated as necessary for analysis.
Instrumentation and Conditions
A Microtek-2000R gas chromatograph equipped with an electron cap-
ture (tritium) detector was used. The output of the gas chromatograph
was connected to a Hewlett-Packard 3380A integrator-recorder, which
provides a printout of the chromatogram with integrated areas of in-
dividual peaks and respective retention times. A 4 ft x 1/4 in. glass
column packed with 1.5% OV-17/1.95% QF-1 coated on 100/120 mesh Supel-
/S\
coport was used for analysis. The chromatographic operating conditions
were: injector temperature, 200 C; column temperature, 100 C; detector
temperature, 180 C; carrier flow rate, 50 ml/min nitrogen; purge flow
rate, 90 ml/min nitrogen; and detector voltage, 10 V DC.
The instrumental limit of detection for HCBD at the above mentioned
conditions was 1 pg (10~12 g). Therefore, as an example, for any amount
of air sampled, the quantity of HCBD in the sample required for detec-
tion was greater than 5 ng (based on 10 p.1 injections of a 50 ml solution).
Calibration
A 10 ng/ml composite standard solution of HCBD was used to obtain
the calibration curves. The standard solution was prepared by dilution
of a stock solution made up from EPA reference standards obtained from
Pesticides and Toxic Substances Effects Laboratory, National Environ-
mental Research Center, Research Triangle Park, North Carolina. Concen-
tration ranges chosen for the calibration curve were from 10 to 60 pg,
and linearity was observed.
A new calibration curve was obtained daily for the sample analysis.
During the day, a known amount of the standard was injected periodically
into the GC to check for changes in retention time and peak intensity.
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SECTION III
SELECTION OF SAMPLING SITES
The objective of this task was to determine environmental Levels
of HCBD by the sampling and analysis of samples from selected indus-
trial plants. Therefore, it was important that the selected sampling
locations be representative of the total industrial locations that are
sources of HCBD.
SELECTION CRITERIA
Selection criteria were chosen to achieve representative sampling
of sites that are most likely to have detectable quantities of HCBD
present.
The criteria used for the selection of industrial plants for sam-
pling of HCBD are: .
* Estimated quantity of HCBD in industrial wastes, products, and
by-products.
* Methods of production.
* Methods of waste disposal.
* Geographic location of the industrial plants.
Estimated Quantity of HCBD in Industrial Wastes, Products, and By-Products
In 1974, there was no manufacturer of HCBD in this country. However,
industry sources report that HCBD contained in the "heavy ends" waste
materials (residues) in the production of many chlorinated organic com-
pounds, as well as in the electrolytic processes (either diaphragm or
mercury cells) for chlorine gas when graphite anodes are used. An esti-
mation of the amount HCBD produced in industrial wastes, by-products,
and products is given in Table 1. As indicated in Table 1, over 99% of
the HCBD contamination in the environment was estimated to be from the
2 /
perchloroethylene, trichloroethylenc, and carbon tetrachloride industries.—
8
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Table 1. ESTIMATED QUANTITIES OF HCBD PRESENT IN INDUSTRIAL
WASTES, BY-PRODUCTS, AND PRODUCTS IN 1972^'
Product
Perchloroethylene
Trichloroethylene
Carbon tetrachloride
Chlorine
Daethai®
Vinyl chloride
Atrazine, propazine, simazine
Pentachloronitrobenzene
Mirex
U.S.
Production
in 1972
(tons)
367,400
213,500
498,500
9,538,000
1,000
2,545,000
56,000
1,500
500
HCBD (tons)
3,251
1,132
1,047
26
0
0
0
0
0
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Therefore, industrial plants that produce these chemicals were
given high priority in the selection of sampling sites.
Method of Production
The production method affects the quantity of HCBD formed as a by-
product. Therefore, the potential environmental contamination is depen-
dent upon the production method. For example, carbon tetrachloride, per-
chloroethylene and trichloroethylene are produced in several ways. If
chlorine and the respective aliphatic hydrocarbons are fed into a high-
temperature reactor and the products are collected by distillation, HCBD
is discharged as a by-product in the "heavy ends" wastes. However, if
the production of carbon tetrachloride involves the reaction of chlorine
with carbon disulfide, coproducts or by-products other than reusable
sulfur are greatly reduced.
Methods of Waste Disposal
Disposal methods for "heavy ends" wastes played a role in the selec-
tion of plants for sampling. The selected plants used a variety of dis-
posal methods including landfill, deep well, sealed lagoons, on-site in-
cineration, and shipment of wastes to other disposal firms.
Geographic Location of the Industrial Plant
Industrial plants were selected from across the country to determine
whether the potential for environmental contamination was a national
problem.
RECOMMENDED SAMPLING SITES
Using these general criteria as a guide, 10 industrial plants were
selected for inclusion in this study. These industrial plants are listed
below.
Perchloroethylene
Stauffer Chemical Company Louisville, Kentucky
Vulcan Materials Company Wichita, Kansas
Trichloroethylene
PPG Industry, Inc. Lake Charles, Louisiana
Diamond Shamrock Corporation Deer Park, Texas
10
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Carbon tetrachloride
E. I. du Pont de Nemours and Company, Inc. Corpus Christi, Texas
Dow Chemical Company Pittsburg, California
Chlorine
Linden Chlorine Linden, New Jersey
Kaiser Aluminum and Chemical Corporation Gramercy, Louisiana
Triazine herbicides (atrazine, propazine, simazine)
Ciba-Geigy Corporation St. Gabriel, Louisiana
Pentachloronitrobenzene
Olin Corporation Mclntosh, Alabama
The geographic location and EPA region of these plants are shown in
Figure 2.
During the process of selecting the sampling sites, efforts were
made to select industrial plants that produce a unique product rather
than a combination of several products. The efforts were successful for
the two chlorine plants selected. However, plants producing low molecu-
lar weight chlorinated hydrocarbons do not generally produce a single
product. All five plants that produce trichloroethylene also produce
perchloroethylene. Fortunately, not all the perchloroethylene produc-
tion plants produce trichloroethylene. However, these plants also pro-
duce carbon tetrachloride. The annual production capacity (1972), pro-
cess technology, and latest waste disposal methods for each of the
sampling sites are presented in Table 2.
(R)
The Dacthal production facility (Diamond Shamrock Corporation) in
Greens Bayou, Texas, was not selected for sampling because the waste
handling and product contamination were substantially changed from pre-
1972 procedures.
Vinyl chloride and mirex production facilities were omitted from
this survey.
11
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\\
I IDAHO!
NORTH D«KOTA
SOUTH DAKOTA
COLORADO
• Perch loroethylene
O Trichloroethylene
A Carbon Tetrachloride
^ Chlorine
• Pentachloronitrobenzene
D Afrazine
o a.
Figure 2. Geographic location of recommended sampling sites
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Table 2. PRODUCTION CAPACITY, PROCESS TECHNOLOGY AND WASTE DISPOSAL AT RECOMMENDED SITES
EPA
Producers Production sites region
Perch loroethvlene
Stauffer Chemical Corapany Louisville, Kentucky IV
Vulcan Materials Conpany Wichita, Kansas VTI
Trich loroethvlene
PPG Industry Company Lake Charles, Louisiana VI
Diamond Shamrock Corporation Deer Park, Texas VI
Carbon tetrachloride
E. I. du Pont de N'emours and Corpus Christi, Texas VI
Company, Inc.
Dow Chemical Company Pittsburg, California IX
Chlorine
Linden Chlorine Company Linden, New Jersey II
Kaiser Aluminum and Chemical Gramercy, Louisiana VT
Corporation
Triazine herbicides
Ciba-Geigy Corporation St. Gabriel, Louisiana VI
Pentachloronitrobenzene
Olin Corporation Mclntosh, Alabama IV
Annual
production
capacity
(105 tons)
35
25
140
60
250
23
66
58
> 75
1.5
Waste disposal
HCB recovered for sale,
remainder recycled to
chlorinator
Earth-covered groundfill
Incineration, landfill
Ship to Rollins Inter-
national for incineration
Landfill, ship to outside
firm for disposal
Incineration
Discharge to holding pond
Landfill
Still bottoms incinerated
by an outside processor to
extinction
Stored in "blocks" covered
with plastic sheet
/
Process technology"
Chlorination with low molecular
weight hydrocarbons, e.g., eth-
ane, propane
Ethylene and chlorine as raw ma-
terials, under catalytic reaction
at 250 to 300°C
Chlorination with methane at
elevated temperature
Mercury cell; graphite electrode
Diaphragm cell; graphite electrode
Reaction of cyanuric chloride
with appropriate amino hydrocar-
bons at elevated temperature
Nitration of pentachlorobenzene
or Chlorination of various chloro-
nitrobenzenes in the presence of
catalyst
^/ Kirk-Othmer, Encyclopedia of Chemical Technology 2nd ed., Interscience Publishers, New York, New York (1972).
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SECTION IV
PRESAMPLING SURVEYS AND FIELD SAMPLING
To plan the strategy for successful field sampling at the selected
industrial plants, a presampling survey was conducted at each plant gen-
erally from 2 to 4 weeks prior to sampling. Each presampling survey was
arranged through telephone contact with the appropriate plant officials
whose names were provided by the EPA project officer. Figure 3 shows the
complete schedule for presampling surveys and field sampling.
PRESAMPLING SURVEYS
During the presampling site survey, a plant map was obtained. Infor-
mation regarding the possible sources of HCBD contamination, the produc-
tion technology, and waste disposal techniques were obtained. In addition,
the production and waste disposal sites, as well as the transportation
routes were delineated. Accessible electrical outlets inside the plant
were also located for possible use in air sampling. Meterological condi-
tions, such as wind direction and rainfall were investigated. Tentative
sampling dates were agreed upon, subject to final confirmation by plant
officials prior to the departure of the sampling crew from MRI.
FIELD SAMPLING
Upon the completion of a presampling site survey, the sampling
strategy was planned. In general, air sampling stations were positioned
upwind and at several distances downwind from the suspected source(s)
of contamination. The air samplers were usually positioned 4 ft above
ground. When the wind direction was uncertain, stations were positioned
around the entire plant area.
Water sampling was conducted at suspected sources of contamination
such as upstream and downstream of waste effluent. Storm runoff was col-
lected whenever possible. Water samples from equilization ponds or solar
ponds were collected to determine if the ponds were sources of air con-
tamination through liquid vapor equilibrium HCBD.
14
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May
June
July
August September
Vulcan Materials
Wichita, Ks.
Linden Chlorine
Linden, N.J.
Stauffer Chemical
Louisville, Ky.
Dow Chemical
Pittsburg, Calif.
du Pont
Corpus Christ! , Tex.
Diamond Shamrock
Deer Park, Tex.
Ciba-Geigy Corp.
St. Gabriel , La.
Olin Corp.
Mclntosh, Ala.
Kaiser Aluminum
Gramercy, La.
PPG Industries
Lake Charles, La.
A wmm
A
A
—
A
A
A
A
A
-
-
-
-
-
A
A
-
A Presampling Visit
^m Field Sampling
Figure 3. Presampling survey and field sampling schedule
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Soil sampling was generally conducted along the plant boundaries,
transportation routes, and around waste disposal and storage areas. Sed-
iment samples were collected from streams, equilization ponds and natural
solar ponds. Solids and liquid were also sampled from open disposal pits.
The preparation for sampling usually was conducted 3 to 5 days prior to
the sampling date. Sampling equipment was sent to the plant scheduled
for sampling. Major sampling equipment included vacuum pumps, poles, rub-
ber hoses, electrical prongs and adapters, and sampling bottles. To avoid
possible breakage and contamination, the air sampling train componentSj
i.e., the filter and the Tenax®-GC tubes, as well as the Amberlite XAD-4
sampling tubes were all hand carried to the site by the sampling crew.
Generators were rented at local dealers when electrical outlets were not
available in the plant.
Because of the extensive sampling involved in the first two sites,
i.e., Vulcan Materials Company and Stauffer Chemical Company, a four-man
crew was required. The rest of the sampling trips were conducted by two-
or three-man crews. Generally, 3 days were spent on each sampling site.
The total number of samples analyzed for each sampling site is presented
in Table 3. A summary of air sampling parameters for each site is given
in Table 4. The sites at which HCBD breakthrough occurred are indicated.
Breakthrough of HCBD was observed at 4,000 liters total volume of air
sampled at a rate 3.5 liters/min. Breakthrough was not observed if the
total volume was 2,000 liters or less. Detailed descriptions of the field
sampling and presampling surveys conducted at each plant are presented in
Appendix A.
16
-------
Table 3. FIELD SAMPLING SUMMARY
Site
Vulcan
Linden
Stauffer
Dow
Du Pont
Diamond Shamrock
Ciba-Geigy
Olin
PPG
Air samples^'
(stations x train components x
sampling period)
18 x 2 x 5
No air samples
9x2x6
8x2x1
8x2x1
8x3x1
8x2x1
8x3x1
10 x 3 x 1
Total samples
(number/type)
180 air
10 soil
4 water
6 water
3 solid
1 soil
108 air
5 soil
6 water
3 sediment
16 air
3 soil
1 water
10 air
3 soil
7 water
3 sediment
24 air
3 soil
2 water
16 air
4 soil
2 water
24 air
11 soil
10 water
1 sediment
30 air
4 soil
7 water
3 sediment
_a/ The total number of air samples consist of the number of air sampling
stations times the components of the train, i.e., filter and Tenax^-GC
resin times the number of sampling periods.
17
-------
Table 4. SUMMARY OF AIR SAMPLING PARAMETERS
Plant
Vulcarr"
b/
Stauffer-
Dow
Du Pont
c/
Ciba-Geigy-
Diamond
Shamrock
c/
Oliil^
PPG
Average
sampling
vol. (4)
(1) .150-200
(2) 800-1,000
(3) 4,000
450
4,100
4,200
1,200-2,100
550
1,500-2,000
1,200
Average
sampling
time
(hr)
(1) 1
(2) 4
2
20
21
6-8
24
9
24
Rate
(Vmin)
0.5
0.5
3.5
3.5
3.5
3.5
0.4
3.5
0.4
HCBD
break-
through
No
No
No
Yes
Yes
No
No
No
No
_a/ Five 4-hr periods.
b/ Six 4-hr periods (2 hr on, 2 hr off).
_c/ Three 8-hr periods (each 2 to 3 hr sampling).
18
-------
SECTION V
DISCUSSION OF RESULTS AND CONCLUSIONS
Air, soil, water, and sediment samples were collected from nine rec-
ommended industrial plants whose products included perchloroethylene, tri-
chloroethylene, carbon tetrachloride, triazine herbicides, pentachloroni-
trobenzene and chlorine. In general, HCBD concentrations varied from a
maximum, near the production and waste disposal areas, to a minimum, in
the samples taken upwind. HCBD was detected as a vapor in every case. The
results from each sampling site are discussed below.
VULCAN MATERIALS COMPANY, WICHITA, KANSAS
Field sampling at Vulcan Materials Company's perchloroethylene plant
at Wichita, Kansas, was conducted on May 20, 1975. Other compounds of
interest produced at this plant include carbon tetrachloride and chlorine.
The samples collected were: 180 air (90 filters and 90 Tenax®-GC columns),
10 solid, and 4 water.
Air Samples
The 180 air samples were collected from 13 samplers positioned upwind
of the facility, nine samplers positioned immediately downwind of the gen-
eral production and waste storage areas, and six additional samplers set
further downwind beyond the northern plant boundary. The six samplers
beyond the northern boundary were positioned at three locations with two
samplers per location at 4 and 11 ft above ground, respectively. The up-
wind and farthest downwind samplers were operated continuously for a 4-hr
period while those closer to the general production and waste storage area
were operated only for the first hour of each 4-hr period. After each 4-hr
/n\
period, the filter and the Tenaxw-GC column in each sampler were replaced
by fresh components. The sampling strategy was designed so that results of
the analysis would elucidate: (a) the major sources and level of HCBD
emission, (b) the diurnal and operation-related effects of HCBD emission,
(c) the physical form, i.e., particulate or vapor of HCBD in the plant
air, and (d) the variation of HCBD concentrations with respect to sampler
distance above ground.
19
-------
Sources and Levels of HCBD Emissions - The analytical data for the 180 air
samples are tabulated in Table B-l of Appendix B. Figure 4 shows the av-
erage concentrations of HCBD during the 20-hr sampling period at the 18
sampling stations. It is obvious that major sources of HCBD in the air
are the production and waste storage ("Hex Pit") areas.
HCBD levels were highest, ranging up to 460 M.g/m , in samples taken
near the "Hex Pit;" the average HCBD concentration in that area was ap-
proximately 65 |J.g/m . The average HCBD concentration in all samples taken
from the seven stations north of the plant boundary, downwind of the pro-
duction and waste holding ("Hex Pit") areas, was approximately 8 IJ/g/m .
Only trace levels of HCBD were detected in upwind samples.
Variation of HCBD Emission with Time - The variation of HCBD levels over
the 20-hr sampling period is shown in Figures 5 . through 7. Figure 5 shows
the levels of HCBD in the air samples immediately downwind of the produc-
tion and waste storage areas. The air levels appear to reflect the plant
activities, i.e., dumping of "hex residue." This is especially so at Sta-
tions 4 through 6 which are nearest the "Hex Pit."
The variation of HCBD levels in samples beyond the plant's northern
boundary is shown in Figure 6. Each point is the average of two samplers
positioned at different heights (4 and 11 ft). Again the figure indicates
that the HCBD level increased at Stations 12 and 13 during hex dumping.
The low and rather constant HCBD levels detected in upwind samples
during the entire sampling period as shown in Figure 7 indicate that the
major source of HCBD is vapor from the "Hex Pit" and production plant
and not from the buried wastes or plant area soil.
HCBD Concentrations Versus Sampler Heights - Samples were collected at
two heights, 4 and 11 ft, simultaneously, at three locations for five
successive time periods. Those results summarized in Table 5 demonstrate
that there was no effect of sampler height.
20
-------
12 (H.2)
13 (10.2)
(5.65) 3.
(13.98)2.
(8.90) 1.
LEGEND
Numbera 1 to 18 Air Sampling Sites
Numbers in Parentheses Represent
Average Concentration of HCBD
Per 20 Hour Period
in.
= Perc Plant
10 (4.72)
11 (4.62)
Scale 1/2"= 150'
(0.01) 17
(0.08)16.
11...
South Ridge Rood I !
3
Figure 4. Average concentrations (p.g/m ) of HCBD in air per 20-hr period at 18 sampling
stations at Vulcan Materials Company, Wichita, Kansas
-------
60
50
40
CO
i
Perc Plant
Dumped Hex
t-o
ISJ
30
Perc Plant
and Hex Pit
Dumped Hex
1
2
O Station
A Station
D Station 3
• Station 4
O Station 5
x Station 6
9 StaHon 7
A Station 8
O Station 9
Figure 5. HCBD concentration per 20-hr period at sampling stations
within the plant perimeter (Vulcan)
-------
UJ
Perc Plant
Dumped Hex
Hex Pit
Dumped Hex
Perc Plant
and Hex Pit
Dumped Hex
• Stations 10&11
A Stations 12&13
D Stations 14&15
1113
1433
Figure 6. HCBD concentration per 20-hr period, downwind stations (Vulcan)
-------
Perc Plant
Dumped Hex
0.2
i
Hex Pit
Dumped Hex
Perc Plant
and Hex Pit
Dumped Hex
• Station 16
A Station 17
a Station 18
2005
0010
0025
0345
0355
0744
0752
1152
1200
1430
Figure 7. HCBD concentration per 20-hr period, upwind stations (Vulcan)
-------
Table 5. COMPARISON OF HCBD LEVELS AT
4 AND 11 FT FOR FIVE TIME PERIODS
HCBD.
Station pairs 4 ft 11 ft
10 and 11 12.2 12.1
6.5 6.5
2.6 2.4
1.6 1.4
0.7 , 0.7
12 and 13 20 19
22 22
6 4
5 4
3 2
14 and 15 0.004 0.02
0.2 0.2
0.03 0.1
0.1 0.2
4.2 3.8
25
-------
Precision of Sampling and Analysis - The agreement between each of the
sample sets listed in Table 5 is excellent. If it is assumed that the HCBD
levels were the same at the two sampler heights (4 and 11 ft), the re-
sults from each paired station, i.e., 10 and 11, 12 and 13, and 14 and
15, at each of the five sampling periods can be considered as dupli-
cates and a pooled relative standard deviation (PRSD)* determined. The
PRSD calculated from these data indicates the overall precision of the
air sampling and analysis methods including sample collection, storage,
recovery, and analysis. The PRSD was 14%. The PRSD is based on 13 dupli-
cates for HCBD. Two duplicate measurements near the detection limit
(< 0.1 (ig/m^) were not included in the calculations.
Soil Samples
The nine soil samples and one "Hex Pit" solid sample were collected
at the following locations: along the plant boundaries, transportation
routes, landfill, the "Hex Pit" area and the production area (see Figure
A-2). These sites were selected to determine HCBD soil levels associated
with production waste disposal and transportation of wastes for disposal.
Samples were also taken upwind and in adjacent agricultural fields to de-
termine background concentrations in areas in the vicinity of the plant.
The results of the analysis of the nine soil and one solid samples,
tabulated in Table 6, indicate that HCBD soil concentrations were gen-
erally in the high parts per billion range with the exception of the
"Hex Pit" soil and the "Hex Pit" solids. HCBD is 0.17,, in the "Hex Pit"
soil and 10% in the "Hex Pit" solids.
Specifically,, of the four plant boundaries, the highest level of
HCBD, 0.106 ppm, was observed in soil from the southern boundary (S-8).
On the other three boundaries, levels of the two substances ranged from
0.005 to 0.030 ppm for HCBD. . •=
The observation of relatively high concentrations of HCBD in the
southern boundary soil sample (S-8) could very well be the source of
HCBD in the air samples collected at Air Sampling Stations 16 through
18. The high concentrations in upwind soil samples (S-8) could be due
to the nearby landfill. This rationale is supported by the presence of
0.36 ppm of HCBD found in the S-5 sample, which indicates the landfill
is a source of surface contamination in the immediate area.
* The PRSD was calculated as follows:
S = V £ (X-X)2/0.889
RSD = S/X x 100
PRSD = V 2 RSDi2/n 26
-------
Table 6. HCBD CONCENTRATIONS IN SOIL AND SEDIMENT
FROM VULCAN MATERIALS COMPANY, WICHITA, KANSAS
a/
Samples—
S-2
S-3
S-4
S-5
S-6
S-7
S-8
S-9
S-10
"Hex Pit"
solids
Control
Sample
weight (g)
42.8
2.5
48.4
38.7
40.5
29.6
35.6
43.5
34.2
0»95
Concentration (ug/g)
HCBD
2.28
980
0.22
0.36
0.049
0.030
0.106
0.018
0.005
10%
ND
a/ S-2 - Route from 'Terc Plant" to "Hex Pit."
S-3 - "Hex Pit."
S-4 - Route from "Hex Pit" to landfill.
S-5 - Landfill (60 yards north of 63rd Street and 0.4 miles east of
Ridge Road.
S-6 - Landfill (180 yards north of 63rd Street and 0.4 miles east of
Ridge Road.
S-7 - Landfill (Ridge Road to telephone pole).
S-8 - Upwind.
S-9 - Downwind.
S-10 - Western boundary (cornfield).
Control - Soxhlet apparatus.
27
-------
From 0.22 to 2.2 ppm of HCBD were observed in the soil on the route
to the "Hex Pit" (S-2) and in the soil from the "Hex Pit" to the landfill
(S-4). The high concentrations of HCBD found in the "Hex Pit" solids were
expected since the "hex residues" consist mainly of HCB and HCBD.— Re-
sults of the analyses of air samples collected at Air Sampling Stations
4, 5, and 6 showed consistently high concentrations of HCBD (see Figur6
5). Furthermore, the HCBD levels found in the water layer covering the
"Hex Pit" were also relatively high. The results of the water analysis
are presented below.
Water Samples
Two samples were taken from Cowskin Creek (Figure A-3) which receives
water from the sanitary sewer system and plant heat exchangers. Samples
were taken from the "Hex Pit" and "Solar Pond" to determine their contri-
bution to HCBD levels in air and into the deep well which receives water
from the "Solar Pond."
The results of the analyses are shown in Table 7. No HCBD was de-
tected in Cowskin Creek. The presence of a high level of HCBD (231 ppb)
in the "Hex Pit" water is expected since this water was used to cover
the "hex residues" dumped in the pit. This water should be saturated
with HCBD. The level of HCBD in the "Solar Pond" is two orders of mag-
nitude lower than that in the "Hex Pit" water. The source of HCBD in
the "Solar Pond" water could be from leaching of the soil or from vapor
or airborne particulate from the neighboring "Hex Pit."
Plant Summary
The results of the analysis of all air, soil, and water samples
indicate that the "Hex Pit" is the source of the highest levels of HCBD.
All of the HCBD found in the air was as the vapor; no particulate HCBD
was observed. Variations in the air levels at the downwind stations were
related to the dumping of solid "hex residues." HCBD concentrations in
soil (excluding the "Hex Pit" area) ranged from 0.005 ppm to over 2 ppm.
The water samples taken from the "Hex Pit" and "Solar Pond" contained
231 and 2.2 ppm HCBD, respectively. No HCBD was detected in Cowskin
Creek.
LINDEN CHLORINE PLANT, LINDEN, NEW JERSEY
The survey of Linden Chlorine Plant was conducted on May 29, 1975.
During the intended presampling survey, it was apparent that an extended
air sampling plan was not warranted. Therefore, sediment, water, and soil.
samples were taken during the survey.
28
-------
Table 7. HCBD CONCENTRATIONS IN WATER FROM VULCAN
MATERIALS COMPANY, WICHITA, KANSAS
Samples
"Hex Pit" water
Solar Pond
Volume sampled
(liter)
0.315
0.335
Concentration (]ig/4)
HCBD
231
2.2
Upstream
(Cowskin Creek) 323 ND
Downstream
(Cowskin Creek) 365 ND
ND - None detected.
29
-------
The Linden Plant was selected as a tentative sampling site because
graphite electrodes were used in the production of chlorine and the plant
produced a single product. During our visit we learned that graphite elec-
trodes had been phased out at the end of March 1975.
Seven water and four solid samples were analyzed for HCBD. The re-
sults are listed in Table 8. The results indicate that parts per trillion
levels of HCBD were present in the holding pond (inlet and outlet), spent
brine, and the upstream and downstream water of the plant. No HCBD was
found in the tap and process water.
Three of the four solid samples contained HCBD at a level of 0.04
to 0.18 Mg/g. The highest level of HCBD, 0.18 Hg/g, was observed in the
waste stream sludge downstream of the plant.
Due to the complexity, i.e., large number of peaks, of these chro-
matograms, selected samples were fortified with standards to confirm the
presence of HCBD. In addition, the samples were prepared and analyzed
in duplicate and/or in triplicate.
Plant Summary
Air samples were not taken at the Linden Chlorine Plant because
graphite electrodes had been phased out prior to our sampling. Water
samples contained low levels of HCBD (0.02 to 0.05 lag/liter). The high-
est concentration of HCBD (0.18 p-g/g) was found in the sludge taken from
the waste downstream of the plant. The level of HCBD detected in the wa-
ter and solid samples indicate this plant is not a current source of sig-
nificant quantities of this material.
STAUFFER CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Field sampling at Stauffer Chemical Company's perchloroethylene
plant at Louisville, Kentucky, was conducted on June 12, 1975. A total
of 108 air, (54 filters and 54 Tenax®-GC columns) 5 soil, 3 sediment,
and 6 water samples was collected. The results of the analysis of these
samples for HCBD are discussed below.
Air Samples
The 108 air samples were collected from nine samplers positioned
at nine locations surrounding the plant. Because the entire western and
part of the northern boundaries of the plant are surrounded by a flood
wall along the Ohio River, the positioning of downwind samplers was
limited.
30
-------
Table 8. HGBD CONCENTRATIONS IN WATER AND SOLIDS FROM
LINDEN CHLORINE COMPANY, LINDEN, NEW JERSEY
Concentration (ugAO
Sample HCBD
Water
Holding pond, inlet 0.04
Holding pond, outlet 0.04
GAF weir, upstream of C^ plant 0.05
Waste stream, downstream of Cl2 plant 0.02
Process water ND
Tap water ND
Spent brine water 0.08
Solid Concentration (ug/g)
Holding pond, settled and suspended 0.04
Dredged solids adjacent to holding pond 0.09
Waste stream, downstream of C^ plant 0.18
Soil, around one of the cell buildings ND
31
-------
Sampling at these nine locations was divided into six 4-hr periods
and all samplers were operated 2 hr of each 4-hr period. After each 4-hr
(R)
period, the filters and the Tenax -GC columns in the samplers were re-
placed. The sampling was conducted so that the analytical results would
indicate (a) the sources and levels of HCBD, (b) the diurnal and plant
operational effects,'if any, and (c) the physical form of the substance
in the air.
Sources and Levels of HCBD - The results of the analyses are listed in
Table B-2 of Appendix B. The filters collected at the same sampling sta-
tion at various sampling times were combined to form one sample. The com-
bined filter analysis remains indicative of the specific form of HCBD
present in the plant air while reducing the number of filters to be an-
alyzed from 54 to nine. The average HCBD concentration per 24-hr period
at each sampling station is shown in Figure 8.
The average HCBD concentrations at upwind Stations 1 and 2 were 0.03
M-g/m-^, while at the downwind stations (3 through 9), HCBD concentrations
were from 0.06 to 5.8 Hg/m . Of the downwind stations, the highest levels
of HCBD were observed at Stations 4 and 5 which were located downwind
from the perchloroethylene-carbon tetrachloride plant. The level of HCBD
was somewhat lower at Station 6, which was further downwind from the
perchloroethylene-carbon tetrachloride plant. All HCBD was found in the
vapor form.
Variation of HCBD Emissions with Time - HCBD levels detected during the
24-hr sampling period for each of the nine sampling stations are plotted
versus sampling time in Figure 9.
The diurnal effect on HCBD levels was indistinct. Only slightly lower
levels were observed for the downwind stations during the early morning
hours.
The removal of the solid waste drums from the plant area occurred
during the latter part of the first sampling period and early part of
the second (1400 to 1500 hr). Levels of HCBD peaked during the third
sampling period at downwind Stations 5 and 6. The exact time when the.
drums were removed from the drum loading area and transported off-site
was not known.
Soil and Sediment Samples
Five soil samples were collected from the soil along the plant
boundaries near the hex storage facilities and along the waste trans-
portation route. Two sediment samples were taken from the Ohio River
32
-------
U)
0
150 200
Scale in Feet
Immediate Plant
Boundary
(0.45)
Production Area
Numbers in Parentheses Represent
Average Concentration (/J-g/m )
of HCBD per.24 hr Period
(0.03)
©(0.3)
Figure 8. Average concentrations of HCBD in air at nine sampling stations
at Stauffer Chemical Company, Louisville, Kentucky
-------
HCBD
U)
-P-
Stations
• 1
X 2
O 3
A 4
D 5
e 6
A 7
O 8
• 9
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
Figure 9. HCBD concentration per 24-hr period at sampling
stations around the plant (Stauffer)
-------
and one was taken from the holding pond. The results, shown in Table 9,
indicate that the soil and sediment levels were from 1 to 30 ppb except
for the soil at the drum loading area (28.5 ppb), and the sediment from
the holding pond (26 ppb). The soil concentrations follow the same gen-
eral pattern as the air concentrations, i.e., the upwind sample had the
least amount of HCBD, 0.001 M-g/g, while the downwind sample (northern
plant boundary) contained 0.03 [Ag/g HCBD. The soil samples from the main
road and the settling pond area had HCBD levels between the downwind and
upwind levels. The soil in the drum loading area which contained 28.5
|ig/g HCBD was obviously contaminated during waste handling operations.
Of the three sediment samples analyzed, the settling pond sample
contained the highest levels of HCBD, 26 l^g/g. Sediments collected at
the Ohio River, both up and downstream, were in the parts per billion
range.
The higher level of HCBD in the upstream sample compared to the
downstream sample is probably due to contamination from sampling or
sample preparation. Both HCBD sediment values however are near the de-
tection limit where the relative error in analysis is high.
Water Samples
The six water samples were collected from the plant well and the
settling pond.
The results, listed in Table 10, indicate that HCBD was present in
the plant well water at 0.1 |J,g/liter. Analysis of the grab inlet and
outlet water samples from the settling pond shows that the settling
pond treatment has a negligible effect on HCBD concentration. The XAD-4
results agree quite closely with the results obtained for the outlet
grab sample. The comparison served as a check on the trapping effi-
ciency and recovery for the XAD-4 system in a real waste stream. How-
ever, data from the 24-hr composite sample (collected by Stauffer) in-
dicate no HCBD was present in both inlet and outlet samples.
The differences in results observed in "grab" versus 24-hr compos-
ite samples imply that sampling time as well as sampling technique is
important for HCBD. Generally, the 24-hr composite sample is more repre-
sentative. However, in the samples analyzed here, it is very likely that
HCBD was lost during sampling for the 24-hr composite because of the rela-
tively high volatility of HCBD. Furthermore, the agreement between results
obtained for the Amberlite XAD-4 resin and the grab sample substantiate
their validity.
35
-------
Table 9. HCBD CONCENTRATIONS IN SOIL AND SEDIMENT FROM
• STAUFFER CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Concentration (ug/g)
Samples HCBD
Soil
S-l - Upwind (southern plant boundary) 0.001
S-2 - Plant road 0.006
S-3 - Drum loading area 28.5
S-4 - Downwind (northern plant boundary) 0.03
S-5 - Settling pond area 0.005
Sediment
R-l - Settling pond 26
R-2 - Ohio River (upstream) 0.017
R-3 - Ohio River (downstream) 0.002
Table 10. HCBD CONCENTRATION IN WATER FROM STAUFFER
CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Concentration (ug/l)
Samples HCBD
Plant well water 0.1
Settling pond inlet (grab) 25
Settling pond outlet (grab) 23
Settling pond inlet (24-hr composite) ND
Settling pound outlet (24-hr composite) ND
Settling pond outlet (Amberlite XAD-4) 21
36
-------
Plant Summary
The results of the analyses of all air samples indicate that the
carbon tetrachloride-perchloroethylene plant is the major source of HCBD
in the general plant area. No significant diurnal variation was observed.
All of the detected HCBD was present in the vapor form.
The highest concentration of HCBD in soil (28.5 |J-g/g) was near the
"drum loading area." This level indicates a localized contamination from
solid waste handling. Otherwise, HCBD levels ranged from 0.001 to 0.03
in other soil samples around the plant.
A sediment sample from the settling pond showed a high level of
HCBD, 26 Hg/g, but levels observed in samples taken from the Ohio River
were insignificant.
Results for grab samples collected at the settling pond outlet show
excellent agreement with samples collected through Amberlite XAD-4 resin,
and 23 versus 21 u.g/ liter of HCBD.
DOW CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
Field sampling at Dow Chemical Company's carbon tetrachloride-
perchloroethylene plant at Pittsburg, California, was conducted on
August 7, 1975. A total of 24 air, including 8 filters and 16 Tenax®-GC
columns, 3 soil, and 1 water samples was collected.
Air Samples
The 24 air samples were collected from 8 samplers, 2 of which were
placed upwind at the western plant boundary, 3 at the midplant area, im-
mediately downwind from the production and incinerator areas, and 3 far-
ther downwind at the eastern plant boundary. Because no significant di-
urnal effects were observed at the Vulcan and Stauffer plants where air
sampling was conducted in discrete 4-hr periods, the sampling at Dow was
conducted for an integrated 24-hr period. Each sampling train was set up
with two Tenax -GC columns in tandem to check for breakthrough of HCBD.
The samplers were positioned so that results of the analysis would in-
dicate (a) the source and level of HCBD emission, (b) the physical form
of HCBD, and (c) the efficiency of HCBD collection.
Sources and Levels of HCBD - The results are presented in Table B-3 of
Appendix B. Average HCBD concentrations are shown in Figure 10. HCBD
37
-------
00
Numbers in Parentheses Represent
Concentration (/ig/m^) of
HCBD per 24 hr Period
(0.04)
(0.03)
N
0
500
i
1000
Scale in Feet
(0.06)
Immediate Plant
Boundary
Figure 10. Average concentrations of HCBD in air at eight sampling stations
at Dow Chemical Company, Pittsburg, California
-------
concentrations in the upwind samples were from nondetectable to less than
0.01 l-ig/nH, while the downwind samples showed concentrations from 0.04 to
2.0 M/g/nr*. The maximum concentration of HCBD (2.0 Hg/m^) was detected at
Station 4 which was located east of the plant area. The recorded wind di-
rection during the sampling was primarily from the west. Station 1 directly
upwind of the plant area contained 0.01 M-g/m^ HCBD.
The high concentrations at Stations 3 through 5 indicate that the
source of emission is localized and centered in the production area which
includes the thermal oxidizer. The remaining results show that there was
no widespread contamination of the plant. All HCBD was found in the vapor
form.
fS)
HCBD Collection Efficiency - The detection of HCBD in the back-up Tenax^-GC
tube indicates that HCBD, at 24-hr continuous sampling time with 4,000
liters sampled, passed through the first tube. It is believed that HCBD
first loaded the front tube and was gradually displaced and transported
into the back-up tube. This speculation is based upon the data observed
at Station 7 where the sample was collected at a slower rate resulting
in a lower volume of air sampled (962 liters). At this station, 0.3 M-g/m
HCBD was found in the first tube and none in the back-up tube. Based on
these results, air sample volumes were reduced for 24-hr integrated air
samples taken subsequent to these analyses.
Soil Samples
Three soil samples were collected along the eastern, western, and
southern plant boundaries.
The results shown in Table 11 indicate that HCBD was not detected
in the western and eastern plant boundary soil, while the southern bound-
ary contained a very low concentration of 0.005 M-g/g.
Water Sample
One water sample was collected from the New York slough at the north-
west corner of the plant. However, the sample was lost when the bottle
containing the water was broken during shipping.
Plant Summary
The results of the analysis of air samples from the Dow plant in-
dicate that the chlorinated hydrocarbon plant area which includes the
carbon tetrachloride, tri- and perchloroethylene plants is a source of
HCBD. HCBD levels are lower at the upwind western boundary (< 0.01 jig/tip)
than at downwind locations (0.02 to 0.3 M-g/nP) indicating that the source
of HCBD is vapor from the plant area.
39
-------
Table 11. HCBD CONCENTRATIONS IN SOIL FROM DOW
CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
Concentration (^g/g)
Samples HCBD
Western plant boundary ND
Eastern plant boundary ND
Southern plant boundary 0.005
40
-------
The absence of HCBD in the millipore filter indicates that HCBD is
in the form of vapor rather than particulates in the plant air.
HCBD was found only in the soil collected along the southern plant
boundary.
E. I. DU PONT DE NEMOURS AND COMPANY, INC., CORPUS CHRISTI, TEXAS
Field sampling of Du Font's carbon tetrachloride plant at Corpus
Christi, Texas, was conducted on August 3, 1975. Because of generator
failure, only five air sampling stations were in operation, which re-
sulted in the collection of a total of 15 air samples. The generator
failure limited the location as well as the number of samples taken.
In addition to the air samples, 6 soil and sediment, and 7 water sam-
ples were collected.
Air Samples
The 15 air samples were collected from five samplers of which two
were positioned upwind, and three were positioned downwind from the gen-
eral production area. The samplers were operated continuously for a pe-
/fes
riod of 24 hr, with two Tenax -GC columns in tandem.
Sources and Levels of HCBD - The results of the analysis are listed in
Table B-4 of Appendix B and shown in Figure 11. The average concentra-
tions of HCBD at upwind Stations 1 and 2 ranged from 0.003 to 0.22 fig/m3,
while downwind Stations 3 through 5 showed concentrations from 0.027 to
0.034 p.g/m . The HCBD was present entirely as a vapor which agreed with
previous sampling results.
HCBD Breakthrough - The detection of HCBD in the back-up Tenax®-GC tube
indicates that HCBD, sampled under conditions similar to those used at
Dow's Pittsburg, California, plant (24-hr sampling period and 4,000 liters
sampled), passed through the first tube. As a result, lower air flow rates
were used for subsequent air sampling.
Soil and Sediment Samples
The three soil samples were collected along the southern and north-
ern plant boundaries, and near the landfill site. The sediment samples
were collected at the storm runoff outfall, settling pond inlet and outlet^
Results of analysis are listed in Table 12.
41
-------
Landfill Soil
Composite
(0.003)
Equalization Pond
Production
Area
(0.034)
Numbers in Parentheses Represent
Concentration (fj.g/m^) of
HCBD HCBD per 24 hr Period
(0.022) (7)|
Scale in Feet
Immediate Plant
Boundary
Figure 11. Average concentrations of HCBD in air at five sampling stations at
E. I. du Pont de Nemours Company, Corpus Christi, Texas
-------
Table 12. HCBD CONCENTRATIONS IN SOIL AND SEDIMENT FROM E. I. DU
PONT DE NEMOURS AND COMPANY, CORPUS CHRISTI, TEXAS
Concentration (ug/g)
Soil samples HCBD
Upwind (southern boundary) ND
Downwind (northern boundary) ND
Landfill area 0.004
Sediment
Settling pond inlet ND
Settling pond outlet ? ND
Storm runoff outfall 0.061
43
-------
HCBD was not detected in either the upwind or downwind soil samples.
HCBD concentration in the landfill sample was 0.004 (J-g/g.
In the sediment, HCBD was detected only in the storm runoff outfall
sample at 0.061 M-g/g. No HCBD was detected in either the inlet or outlet
settling pond sediments.
Water Samples
The seven water samples were collected from plant facilities where
water was used either during the production process or for cleanup fol-
lowing production. Two types of sampling were conducted at the settling
pond, grab sampling and sampling through an Amberlite XAD-4 column.
The results of the analysis of the seven samples are listed in Table
13. HCBD was detected only in the water standing in the landfill at 0.319
|J.g/liter HCBD.
Plant Summary
The slightly elevated levels of HCBD in the downwind air samples
indicate that the production area is a source of HCBD emission.
The concentration of HCBD was highest in the soil collected around
the landfill area. Of the water samples, HCBD was detected only in the
landfill standing water.
In general, the levels of HCBD in this plant were very low. The
plant began operations as recently as 1973 and appears to be successful
in minimizing HCBD emissions.
DIAMOND SHAMEOCK CORPORATION, DEER PARK, TEXAS
Field sampling at Diamond Shamrock Corporation's trichloroethylene
plant at Deer Park, Texas, was conducted on August 20, 1975. A total of
24 air, including 8 filters and 16 Tenajc^-GC columns, 3 soil, and 2 wa-
ter samples was collected.
Air Samples
The 24 air samples were collected from eight sampling stations,
five of which were positioned in a circle around the production area;
two. were located along the north boundary and one was at the south
boundary of the plant area. Changing wind directions (Table A-13) dur-
ing sampling prevented the samplers from being positioned in upwind
and downwind locations. The sampling was conducted over three 8-hr sam-
pling periods covering 3 days. Rain interrupted the second sampling
44
-------
Table 13. HCBD CONCENTRATIONS IN WATER FROM E. I. DU PONT
DE NEMOURS AND COMPANY, CORPUS CHRISTI, TEXAS
Concentration (ug/l)
Samples HCBD
W-l Raw plant water before use ND
W-2 Settling pond inlet (amberlite) ND
W-3 Settling pond inlet (grab) ND
W-4 Settling pond outlet (amberlite) ND
W-5 Settling pond outlet (grab) ND
W-6 Storm runoff outfall (grab) ND
W-7 Water standing in landfill 0.32
45
-------
period and prevented sampling during 1200 to 1700 hr on any of the 3
days. The samplers were operated at 0.4 liters/min, resulting in 600
(R)
liters or less of air sampled. Two Tenax^-GC columns were used in tandem.
Source and Levels of HCBD - The results of the analysis are listed in
Table B-5 in Appendix B. A simplified plant map with the sampling lo-
cations and the 24-hr average concentrations is shown in Figure 12.
HCBD was detected in concentrations ranging from 0.09 to 2.4 Hg/
nr. The highest concentration of HCBD was detected at the southern
plant boundary. The next highest concentration of HCBD, 1.80 p,g/m ,
was detected at Station 5 which is located immediately north of the
general production area. The remaining samples were of similar con-
centration and in the 0.1 to 0.2 p.g/m range. All HCBD was detected
as a vapor. There was no pattern of upwind-downwind concentrations
because of variable wind direction during the sampling.
Collection Efficiency - The HCBD was trapped entirely by the front
Tenax -GC column. The breakthrough observed in previous sampling at
Dow and Du Pont was eliminated by using a smaller critical orifice
(26 gauge needle) that resulted in an air flow of 0.4 liters/min.
Soil Samples
Three soil samples were collected from along the northern plant
boundary, along the southern plant boundary, and the production area.
The results of the analysis of the three soil samples are shown
in Table 14. The data indicate that the highest concentrations of HCBD
(19 P-g/g) was detected in the production area. A higher level of HCBD
was detected in the soil sample collected near Stations 7 and 8. These
levels coincide with the fact that the HCBD concentration at Air Sam-
pling Station 1 was higher than those observed at Stations 7 and 8.
The source of the relatively higher levels of HCBD in air and soil at
the southern boundary is not known.
Water Samples
Two water samples collected from the raw plant water and plant ef-
fluent for the analysis of HCBD. The results shown in Table 15 indicate
that no HCBD was detected in the raw water. However, 2.0 p.g/liter of
HCBD was detected in the plant effluent. This plant effluent is dis-
charged into nearby Patrick Bayou.
46
-------
0 300 600
Scale in Feet
Immediate Plant
Boundary
Numbers in Parentheses Represent
Concentration (/j.g/m-j) of
HCBD per 24 hr Period
Figure 12. Average concentrations of HCBD in air
at eight sampling stations at Diamond Shamrock
Corporation, Deer Park, Texas
47
-------
Table 14. HCBD CONCENTRATIONS IN SOIL FROM DIAMOND SHAMROCK
CORPORATION, DEER PARK, TEXAS
Concentration (ug/g)
Soil samples HCBD
Upwind (southern boundary) 0.15
Downwind (northern boundary) 0.057
Production area 19
Table 15. HCBD CONCENTRATIONS IN WATER FROM DIAMOND
SHAMROCK CORPORATION, DEER PARK, TEXAS
Concentration
Samples HCBD
W-l Raw unused plant water ND
W-2 Plant effluent 2.0
48
-------
Plant Summary
The level of HCBD in the air ranged from 0.09 to 2.4 M
-------
(0.03)
(O.I)
Numbers in Parentheses Represent
Average Concentration (/j.g/m3)
of HCBD per 24 hr Period
(ND)Cf
2)(0.03)
Production
Area
(0.02)
Effluent Pond
£> (0.02)
N
0 400 800
1 | (
Scale in Feet
Immediate Plant
Boundary
Figure 13. Average concentrations of HCBD in air at eight sampling stations
at Ciba-Geigy Corporation, St. Gabriel, Louisiana
-------
Soil Samples
Four soil samples were collected from the general areas of Air Sam-
pling Stations 1, 3, 5, and 7, respectively. HCBD was not detected in
any of the samples.
Water Samples
Two grab samples were collected, raw plant water and process ef-
fluent. HCBD was not detected in either sample.
Plant Summary
Concentrations of HCBD in the plant air were very low--from nonde-
tectable to 0.096 |J.g/m3. No HCBD was detected in the soil. Since HCBD
was not detected in the process effluent, the water discharged into the
Mississippi River contains less than 5 parts per trillion of HCBD.
OLIN CORPORATION, MCINTOSH, ALABAMA
Field sampling at Olin Corporation's pentachloronitrobenzene (PCNB)
plant at Mclntosh, Alabama, was conducted on August 18, 1975. This plant
was sampled predominately for HCB. The samples were, however, analyzed
for HCBD and the results are included in this report.
A total of 24 air, including 8 filters and 16 Tenax -GC columns,
12 soil and sediment, and 10 water samples was collected. In addition
to the PCNB plant, this facility included a chlorine production plant
which used graphite electrodes in the production process.
Air Samples
The 24 air samples were collected from eight samplers. Two were po-
sitioned at the southern boundary, 3 were in the mid-plant area, north
of the PCNB production plant, and 3 were at the northern boundary. Each
sampling train consisted of a millipore filter and two Tenax -GC columns.
The samplers were operated 3 hr of each. 8-hr period for three 8-hr pe-
riods. The wind direction during the sampling was varied so that no
upwind-downwind stations could be designated.
Sources and Levels of HCBD - No HCBD was detected in any of the filters
or Tenax -GC traps from the sites shown in Figure 14.
Soil and Sediment Samples
The 12 soil and sediment samples were collected from plant bound-
aries, transportation routes, landfill and storage areas.
51
-------
(ND)
2
••—
(ND)
0
(ND)
Chlorine
Production
Area
(ND)
Weak
Brine
Pond
Production
Area
Numbers in Parentheses Represent
Average Concentration
of HCBD per 24 hr Period
(ND)(if
Hex
Storage
Area
(ND)
0
I
160
i
320
i
Scale in Feet
Immediate Plant
Boundary
Figure 1.4. Average concentrations of HCBD in air at
eight sampling stations at Olin Corporation,
Mclntosh, Alabama
52
-------
The results of the analysis of these samples are shown in Table 16.
HCBD was found in only three samples in a range of 0.006 to 0.009 lAg/g.
The "old landfill site" was previously used for disposal of "hex" wastes.
Water Samples
Ten water samples were collected from ditches, the nearby creek,
the settling pond, the solar pond, and the two brine ponds (strong and
weak). No HCBD was detected in any of the samples.
Plant Summary
From the analysis of the air samples, it was determined that this
production facility is not a source of HCBD. Only three soil or sedi-
ment samples had detectable levels of HCBD while none of the water sam-
ples contained HCBD.
PPG INDUSTRIES, INC., LAKE CHARLES, LOUISIANA
Field sampling at PPG Industries' trichloroethylene and perchloro-
ethylene plant at Lake Charles, Louisiana, was conducted on September 4,
1975. A total of 30 air, including 10 filter, 20 Tenax®-GC columns, 7
soil and sediment, and 7 water samples was collected.
Air Samples
The 30 air samples were collected from 10 samplers which circled
the plant. The samplers were not positioned in an upwind-downwind ar-
ray because varied wind direction was expected from information obtained
during the presampling site visit. However, the wind was predominately
from the east and east-southeast during sampling. Samplers were also
positioned to take advantage of existing electrical outlets. The sam-
pling was conducted for an integrated 24-hr period; two Tenax -GC col-
umns in tandem were used.
Source and Levels of HCBD - The results of the analysis are shown in
Table B-7 in Appendix B. A simplified plant map with the sampling lo-
cations and the 24-hr average concentrations (Tenax -GC plus filter)
of HCBD is shown in Figure 15. HCBD concentrations were from nonde-
tectable at Stations 7 and 8 to 0.55 Hg/nP at Station 10.
The pattern of HCBD distribution indicates that the primary source
of HCBD is not the plant or incinerator. Station 10 which showed the
highest HCBD concentration was located near the barges which are some-
times used for temporary storage of the "liquid bottoms" resulting from
the production process when repair or modification of the incinerators
A /
is required.— Detectable levels of HCBD at the stations downwind of the
old landfill site and downwind of the incinerator suggests that they are
also sources. All HCBD was detected in the vapor form only.
53
-------
Table 16. HCBD CONCENTRATIONS IN SOIL AND SEDIMENT
OLIN CORPORATION, MCINTOSH, ALABAMA
Concentration (ug/g)
Samples HCBD
Soil
S-l Northern boundary road 0.006
S-2 Old landfill (northeastern boundary) 0.008
S-3 Brine pond area ND
S-4 Center road (running north/south) 0.009
S-5 High-lift route (organic plant to storage
area) ND
S-6 Southeast landfill ND
S-7 "Hex" storage area ND
S-8S/ Old "Hex" dump area
S-9 East road ND
S-10 West road ND
S-ll South road ND
Sediments
Strong brine pond sediment ND
a/ This sample is mostly tar which is used to cover the general old "Hex"
area; the extracted solution was so dirty that analysis was not pos-
sible even after cleanup.
54
-------
Numbers in Parentheses Represent
Concentration (yLtg/rrr) of
HCBD per 24 hr Period
(0.20) (4
Immediate Plant
Boundary
Figure 15. Average concentrations of HCBD in air at 10 sampling stations
at PPG Industries, Lake Charles, Louisiana
-------
Soil Samples
The four soil samples were collected at the plant boundaries, plant
roads, and the landfill. The results of the analysis are shown in Table
17. The levels of HCBD in the soil ranged from 0.008 |J,g/g around Air Sam-
pling Stations 8 through 10 to 6.4 M-g/g at the landfill area.
Analysis of the soils from the Mobil South Road (0.34 [ig/g HCBD)
and the northern plant boundary along Air Sampling Stations 4, 5, and
7 (0.29 M-g/g HCBD) gave similar results.
The elevated levels of HCBD at Stations 4, 5, and 7 are consistent
with a prevailing east and east-southeast wind resulting in particulate
fallout and vapor condensation from the incinerator and production plant.
The concentration detected in the Mobil South Road composite sample in-
dicates the PPG canal is a possible source of HCBD. The results of sedi-
ment and water analyses discussed below verify this possibility.
Sediment Samples
The three sediment samples were taken from the PPG canal (near Air
Sampling Station 1), the ship channel, and the main effluent from the
organic plant. HCBD was detected in all three sediment samples; the low-
est level (0.04 P-g/g HCBD) was in the ship channel and the highest level
(33.1 |ig/g HCBD) was at the organic plant effluent. The presence of HCBD
in the ship channel sediment may be associated with waste loading into
the barges.
The presence of a significant amount of HCBD (0.93 l^g/g) in the down-
stream PPG canal sediment indicates accumulation of deposits from the or-
ganic plant effluent. This sediment was collected 1,000 ft beyond Air Sam-
pling Station 1, i.e., at least 4,000 ft from the organic plant effluent.
Water Samples
The seven water samples were collected from the lake (incinerator
feed), incinerator scrubber, treatment canal, landfill (standing water),
PPG canal, and ship channel.
The results of the analysis of the seven water samples are shown in
Table 18. The highest concentrations of HCBD (240 y-g/liter) were found
in the treatment canal inlet sample. The treatment canal outlet contained
HCBD levels at 75 M>g/liter, indicating that the treatment removed about
60% of the HCBD. The sample collected downstream of the PPG canal near
Air Sampling Station 1 contained HCBD levels at 11 M>g/liter. The obser-
vation of such a relatively high concentration of HCBD in the canal wa-
ter at more than 3,000 ft downstream from the effluent point is consis-
tent with the level detect.ed in sediments collected 1,000 ft further
downstream.
56
-------
Table 17. HCBD CONCENTRATIONS IN SOIL AND SEDIMENT
FROM PPG INDUSTRIES, LAKE CHARLES, LOUISIANA
Concentration (ug/g)
Samples HCBD
Air Stations 4, 5, 7 soil composite 0.29
Air Stations 8, 9, 10 soil composite 0.008
Mobil south road 0.34
Landfill 6.4
PPG sediments
Sediment 1 (downstream PPG canal) 0.93
Sediment 2 (main organic plant effluent) 33
Ship channel sediment 0.04
57
-------
Table 18. HCBD CONCENTRATIONS IN WATER FROM PPG
INDUSTRIES, LAKE CHARLES, LOUISIANA
Concentration (ug/4)
Sample HCBD
Incinerator feed water (lake water) 0.08
Scrubber water 0.04
Inlet (treatment canal) 244
Outlet (treatment canal) 75
Surface water (landfill) 125
Downstream PPG cnaal (Mobil Bridge No. 1) n
Ship channel (next to Air Station No. 10) 0.52
Note: ND » none detected.
58
-------
The lake water (incinerator feed water) contained 0.08 ^g/liter HCBD.
The scrubber water from the incinerator contained a lower level of HCBD
(0.04 (J.g/liter) than the feed water and the treatment canal inlet. There-
fore, the contribution of the incinerator scrubber water to levels of HCBD
in the PPG canal appears to be negligible.
Plant Summary
The primary source of HCBD in air appears to be the "liquid bottom"
storage in the ship channel while the incinerator, plant effluent water,
and the old landfill are secondary sources. HCBD was detected only as a
vapor. The inlet and outlet water to the treatment canal contained 244
and 75 tig/liter of HCBD, respectively. The canal, 3,000 ft downstream
from the organic plant effluent, still contained 11 |ig/liter HCBD. Sedi-
ment samples at the organic plant effluent and 4,000 ft down the canal
contained 33 and 0.9 M-g/g HCBD, respectively.. The PPG canal flows into
Lake Charles.
59
-------
SECTION VI
SUMMARY AND CONCLUSIONS FOR PROGRAM TASK IB
SUMMARY
A summary of results is listed in Table 19. The high and low con-
centrations of HCBD are listed for each type of sample, along with the
products and waste-disposal methods for each site.
Figure 16 shows the highest levels of HCBD in air and the levels
detected in the samples taken the greatest distance downwind from the
suspected source(s) at each plant. Sampling distances from each source
are shown in parentheses.
In general, of the six industries sampled, higher concentrations
of HCBD were associated with the production of perchloroethylene and
trichloroethylene. Because most of the chlorinated hydrocarbon plants
produced a combination (perchloroethylene, trichloroethylene, carbon
tetrachloride, etc.) of products, it is difficult to extrapolate the
results obtained at a particular plant to a single product. In the one
plant that produced only carbon tetrachloride, the HCBD levels were
quite low. No. HCBD was detected in samples from the pentachloronitro-
benzene production plant. The levels of HCBD associated with plants
producing chlorine and triazine herbicides were very low.
Several different waste-disposal methods were used at the per-
chloro- and trichloroethylene plants that were sampled. They included
off-site and on-site landfill combined with open pit or pond storage;
and off-site and on-site incineration. The highest level of HCBD was
detected in air and soil at the plant using on-site landfill and open
pit storage. High HCBD levels were detected in loading and transfer
areas at plants using off-site disposal methods. Lower levels of HCBD
were found at plants using on-site incineration but downwind air con-
centrations were still elevated above background at both plants. The
lowest levels of HCBD for perchloro- and trichloroethylene production
plants were detected at the plant using production by low temperature
oxychlorination and the on-site incineration of liquid bottom wastes.
60
-------
Table 19. DATA SUMMARY FOR PROGRAM TASK NO. 1
Company
Vulcan Materials Company
Wichtta, Kansas
Stauffer Chemical Company
. Louisville, Kentucky
Dow Chemical Company
Pittsburg, California
E. I. du Pont de Nemours
Corpus Christi, Texas
Diamond Shamrock
Deer Park, Texas
Olin Corporation
Mclntosh, Alabama
Ciba-Geigy Corporation
St. Gabriel, Louisiana
PPG Industries
Lake Charles, Louisiana
Linden Chlorine
Linden, New Jersey
Air (HK/m3) Water (Hg/O
Products Substance High Low High Low
Perch loroethy lane
Carbon tetrachloride HCBD 460 0.05 230 ND
Chlorine
Perchloroethylene
Carbon tetrachloride HCBD 35 -0.17 25 0.1
Methylen chloride
Chloroform, chlorine
Perchloroethylene ..
Carbon tetrachloride HCBD 2.0 ND sample
Chlorine
Carbon tetrachloride
HCBD 0.03 0.003 0.32 ND
Trichloroethylene
Perchloroethylene HCBD 2.4 0.09 2.0 ND
Chlorine
Pentachloronitrobenzene
Chlorine ^. HCBD ND ND ND ND
Atrazine
Propazine HCBD 0.1 ND ND ND
Simazine
Trichloroethylene
Perchloroethylene HCBD 0.55 ND 240 0.04
Vinyl chloride
Vinylidene chloride
Chlorine, etc.
Chlorine No
HCBD sample 0.08 ND
Soil (ng/z) Sediment (ng/g)
High Low High Low Waste disposal
., On-site landfill,
NO
980 0.005 sample and deep uel1
Off-site landfill
29 0.001
N Incineration
°-°°5 ND sample
On-site landfill
0.004 ND 0.06 ND and off-site
disposal
No Off- site
19 0.06 sample incineration
Only Solid wastes (in
0.009 ND ND one blocks) stored in
sample open field covered
with plastic
No Off-site
ND ND sample incineration
Incineration, land-
6.4 0.008 33 0.04 fill, and treatment
cana 1'
Only Holding pond
ND one 0.18 0.04
sample
-------
3 -
2 -
E
\
o>
1 -
(900
460
(3000
35
LEGEND
-3
-2
-
-
^
26
3)
V
(7
P50
0
(30000
1
^
IN AIR AT 8 INDUS
HCBD CONCENTR/
AT DOWNWIND SI
(]
(10000
5TRIAL PLANTS
iJIONS IN AIR
FATIONS
3000
-
(18000 ' ($
(3000(16000 i:ix( 23000
N.D. N.D. :;;;;! ~|
- 1
VULCAN STAUFFER
DOW DUPONT CIBY-GE1GY DIAMOND OLIN
SHAMROCK
PRODUCTION PLANT
PPG
Figure 16. Summary of HCBD concentrations in air
-------
The production of perchloro- and trichloroethylene by low temper-
ature oxychlorination and the incineration of liquid bottom wastes
resulted in a unique HCBD ratio in the air and water samples. Generally,
high levels of HCBD in the air are associated with high levels in water.
Conversely, low levels in the air are accompanied by low levels in water.
The low temperature process resulted in low HCBD levels in the air but
very high levels in the water. Levels of 10 |J,g/liter HCBD were found in
treated process water more than 3,000 ft from the plant effluent.
The overall relative standard deviation of the air sampling and
analysis procedure, i.e., sample collection, storage, extraction, and
analysis, was calculated to be less than 2070, based on determinations
of HCBD levels from sample pairs positioned at the same distances, but
at different heights from the emission source. HCBD was collected ef-
ficiently on a single Tenax -GC plug for air sample volumes up to 2,000
liters; HCBD breakthrough was observed at 4,000 liters. Good agreement
was obtained from the analysis of water samples collected by "grab" sam-
pling and by concentration of HCBD on XAD-4 resin.
CONCLUSIONS
Industrial Sources of HCBD
Considering the estimated production volumes of each of the six in-
dustries and concentrations detected in this study, perchloroethylene
and trichloroethylene production was easily the most significant source
of HCBD for the industries sampled. Although the total volume of chlorine
produced was estimated to be 20 times that of perchloroethylene and tri-
chloroethylene combined, the production of chlorine did not appear to be
a significant source of HCBD. Carbon tetrachloride production alone did
not appear to be a significant source of HCBD but this conclusion could
be biased by the fact that the single-product carbon tetrachloride plant
was the newest facility that was sampled (on-line in 1973). The production
of PCNB did not result in the release of detectable levels of HCBD. Esti-
mated triazine herbicide production volumes and the associated HCBD lev-
els determined in this study were very low; therefore, the production of
these compounds is not a significant source of HCBD.
Effects of Waste Disposal Methods
In general, methods that involve open storage (pits, lagoons, etc.)
resulted in elevated levels of HCBD in air and surrounding soil. Waste
holding areas were often the most significant emission source within the
plant area. Contaminated soil appeared to be a secondary source of HCBD
at two sites. On-site incineration resulted in elevated air—HCBD levels
for 750 and 2,300 ft, respectively, at two sites. Elevated HCBD levels at
the latter site (~ 0.2 M.g/m3) extended at least 3,000 ft downwind of the
incinerator. The HCBD levels in water were reduced from 0 to 70% at three
plants that passed liquid wastes through holding ponds or treatment canals.
63
-------
REFERENCES
1. Food and Drug Administration, Compliance Program Guidance Manual.
Program 7320.30, Project Code 05, Problem Code FH-18, "HCBD in
Foods Survey."
2. Mumma, C. E., and E. W. Lawless, "Survey of Industrial Processing
Data: Task I - Hexachlorobenzene and Hexachlorobutadiene Pollu-
tion from Chlorocarbon Processes," Final Report by Midwest Re-
search Institute on Contract No. 68-01-2105 for the Environmental
Protection Agency, June 1975.
3. "Sampling and Analysis of Selected Toxic Substances: Task IA -
Hexachlorobenzene," Final Report by Midwest Research Institute
on Contract No. 68-01-2646 for the Environmental Protection
Agency, June 1976.
4. Personal communication with Mr. C. A. Burns, Environmental Control
Specialist, PPG Industries, Lake Charles, Louisiana, November
1975.
64
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APPENDIX A
PRESAMPLING SURVEY AND FIELD SAMPLING
65
-------
Presampling surveys and field sampling were conducted on the recom-
mended industrial plants according to the schedule shown in Figure A-l.
Essentially, during the presampling survey, information such as the sur-
rounding terrain, meteorological conditions, production technology, and
waste disposal technique was gathered. Following each site visit, a de-
tailed field sampling strategy was devised and carried out approximately
2 to 4 weeks after the presampling survey date. Presented below are de-
tailed descriptions of the presampling survey and field sampling conducted
at each plant.
VULCAN MATERIAL COMPANY, WICHITA, KANSAS
PRESAMPLING SITE SURVEY
The presampling site survey at Vulcan Materials Company's Wichita,
Kansas, plant was conducted on May 6, 1975. The following personnel were
present:
Mr. J. I. Jordan, Jr. Manager, Research and Development,
Vulcan Materials Company
Mr. R. A. Bondurant, Jr. Director, Environmental Control
Safety, Vulcan Materials Company
Mr. Dave Harrison Acting Technical Manager, Wichita
Plant, Vulcan Materials Company
Mr. P. Constant Midwest Research Institute
Mr. P. Kuykendall Midwest Research Institute
Dr. J. Spigarelli Midwest Research Institute
Vulcan Materials Company is located approximately 7 miles southwest
of downtown Wichita and approximately 4 miles from any major residential
area. The surrounding terrain is level with only one nearby water source,
Cowskin Creek. The prevailing wind in May is generally from the south,
southeast or southwest.
Perchloroethylene is produced by the reaction of hydrocarbons and
chlorine. The hydrocarbons are generally of a widely variable composition
and are obtained from many sources. The chlorine is produced by Vulcan
and piped directly from their liquification station to the perchloroethylene
reaction pot. Their chlorine production utilizes diaphragm cells and ap-
proximately 25% o£ their anodes are graphite, the remainder being dimensionally
stabilized /modes.
66
-------
May
June
July
August September
Vulcan Materials
Wichita, Ks.
Linden Chlorine
Linden, N.J.
Sfauffer Chemical
Louisville, Ky.
Dow Chemical
Pittsburg, Calif.
du Pont
Corpus Christi, Tex.
Diamond Shamrock
Deer Park, Tex.
Ciba-Geigy Corp.
St. Gabriel , La.
Olin Corp.
Mclntosh, Ala.
Kaiser Aluminum
Gramercy, La.
PPG Industries
Lake Charles, La.
A _
A
A
—
A
A
A
A
A
-
-
-
-
-
A
A
-
A Presampling Visit
^m Field Sampling
Figure A-l. Presampling survey and field sampling schedule
-------
Vulcan uses two types of waste disposal, deep wells and landfills.
The deep wells are used for the disposal of storm runoff, while the land-
fills are used for the disposal of "heavy ends" waste from perchloro-
ethylene production. The residues are collected in a sealed vessel, trans-
ferred to another sealed vessel mounted on a trailer, and transported to
an open pit where they are stored under water. When the residue level in
the pit reaches a certain level, it is transferred by means of a backhoe
to a dump truck and transported to the landfill, which is located south-
east of the plant. There it is dumped^ covered with polyethylene sheeting,
then covered with dirt.
At the conclusion of the presampling survey, it was agreed upon that
field sampling would be tentatively scheduled in the week of May 19, 1975.
FIELD SAMPLING
Field sampling at the Vulcan plant was conducted on May 20, 1975.
Air, soil, and water samples were collected as planned. Detailed descrip-
tion of the sampling, plant activities, and weather conditions, are dis-
cussed below.
Air Sampling
Five general areas were chosen for air sampling: (a) perchloroethylene
plant; (b) "Hex Pit;" (c) solar pond - landfill; (d) downwind of these loca-
tions; and (e) upwind of these locations. The total sampling time was
divided into 4-hr periods. The upwind and downwind samplers were operated
continuously during each 4-hr period, whereas all other samplers were
operated only for the 1st hr of each 4-hr period. Each sampling location
is shown in Figure A-2. Exact location was measured with respect to the
suspected emission source and was reported along with other sampling data
in Table A-.l.
Soil Sampling
Soil sampling covered eight general areas:
S.-l Around the perchloroethylene plant
S-2 Route from perchloroethylene plant to "Hex Pit"
S-3 Around the "Hex Pit"
S-4 Route Erom "Hex Pit" to landfill
S-5 Between old and current landfill sites
68
-------
vO
7 . \ Meteorological
*~ \ Station
I
o
o
12
'13
10
11
s.
x
I
J,'
3 .
2 •
1 •
o >ei
1 C=> S-'
LEGEND:
Numbers 1 to 18 Air Sampling Sites
S-l Perc Pjgnt
S-2 Route from Perc Plant to Hex Pit
S-3 Hex Pit
S-4 Route from Hex Pit to Landfill
S-5,S-6,S-7 Landfill
S-8 Upwind
S-9 Downwind
S-10 Western Boundary (Cornfield)
Scale 1/2" =150'
18
-c
1
17
16
°P
I
I
South Ridge Road
West Soil Composite S-10
Figure A-2. Sampling locations at Vulcan Materials Company - Wichita plant
-------
Table A-l. AIR SAMPLING DATA AT VULCAN MATERIALS COMPANY, WICHITA, KANSAS
General Sample
area no.
1
"Perc Plant''
2
3
4
"Hex Pit"
5
6
7
Solar pond-
landfill 8
9
10 and 11
Downwind 12 and 13
14 and 15
16
17
18
Exact location
250 ft north of "Perc Plant"- 1st
250 ft west of Sample No.
2
250 ft north of "Perc Plant" 1st
250 ft north of "Perc Plant"- 1st
50 ft east of Sample No.
2
150 ft north of "Hex Pit" 1st
75 ft west of Sample No.
2
150 ft north of "Hex Pit" 1st
150 ft north of "Hex pit"- 1st
75 ft east of Sample No.
2
1,500 ft north of landfill- 1st
225 ft northwest of solar
pond
Sampling
period
hr of 4 hr
hr of 4 hr
hr of 4 hr
hr of 4 hr
hr of 4 hr
hr of 4 hr
hr of 4 hr
1,500 ft north of landfill- 1st hr of 4 hr
225 ft north of solar pond
1,500 ft north of landfill- 1st
440 ft northeast of solar
pond
525 ft north of plant boundary-
340 ft east of Ridge Road
525 ft north of plant boundary-
850 ft east of Ridge Road
525 ft north of plant boundary-
2,100 ft north of Ridge Road
On southern plant boundary-
225 ft east of Ridge Road
On southern plant boundary-
300 ft east of Ridge Road
On southern plant boundary-
hr of 4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
Total
sampling
time (hr)
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
19.5
Sampling rate
( i/rnin)
0.5
0.5
0.5
0.5
0.5
0.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
Total
sample
vol. (£>
178
149
207
156
232
195
813
1,123
1,198
3,646
3,862
3,930
4,172
4,291
4,272
3,744
3,176
3,353
Sampler
height (ft)
11
11
11
4
4
4
4
4
4
10-4
11-11
12-4
13-11
14-4
15-11
4
4
4
700 ft east of Ridge Road
-------
S-6 North of current landfill site
S-7 Along the eastern plant boundary
S-8 Along the southern plant boundary, passed 63rd Street
S-9 Beyond the northern plant boundary, along Racon Road
S-10 Along the western plant boundary, along the cornfield
All the samples were composites except the landfill samples. In addition,
a sample of the "Hex Pit" solids was also collected.
Water Sampling
Water samples were taken from four general areas:
1. Upstream from waste inflow - Cowskin Creek
2. Downstream from waste inflow - Cowskin creek
3. Solar pond water
4. "Hex Pit" water
The location of the solar pond and "hex" pit is shown in Figure A-2; the
sampling locations in Cowskin Creek are shown in Figure A-3.
Samples from Cowskin Creek were collected on Amberlite XAD-4 resin
via a battery-operated pump. Grab samples were taken from the solar
pond and "Hex Pit."
Plant Activities and Weather Conditions
Plant activities were observed during the sampling period and are
tabulated in Table A-2.
The weather conditions during the sampling period are summarized in
Table A-3. Fortunately, the wind was from the south or southeast during
the entire sampling period except for the last 4-hr interval. The change
in wind direction coincided with a thunderstorm which forced a termination
of sampling during the final 4-hr period.
71
-------
Downwind Air Samples
Upwind Air Samples 1
'
Figure A-3. Vulcan Materials Company - Wichita plant, and
surrounding areas (2.6 in. = 1 mile)
72
-------
Table A-2. PLANT ACTIVITIES DURING SAMPLING AT VULCAN MATERIALS COMPANY,
WICHITA, KANSAS
Time
May 21
1900
2000
2100
2200
2300
2400
May 22
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
"Perc plant"
Normal
Normal
Normal
Normal
Normal
Dumped "Hex"
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Dumped "Hex"
Normal
Rain
"Hex pit"
Fuller than usual
Fuller than usual
Fuller than usual
Fuller than usual
Fuller than usual
Fuller than usual
Dumped "Hex"
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Dumped "Hex"
Rain
Solar pond
landfill
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Rain
Downwind
Normal
Normal
Normal
Normal
Normal
Dumped "Hex"
Dumped "Hex"
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Dumped "Hex"
Dumped "Hex"
Rain
Upwind
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Norraa 1
Normal
Normal
Normal
Normal
Normal
Rain
73
-------
Table A-3. WEATHER CONDITIONS DURING SAMPLING AT VULCAN MATERIALS COMPANY, WICHITA, KANSAS
Time
May 21
1900
2000
2100
2200
2300
2400
May 22
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
Temperature
(°C)
27
27
24
23
23
23
23
23
23
23
21
21
23
25
25
26
26
27
29
29
29
Barometric
pressure
(mm Hg)
722
722
723
724
724
724
724
724
724
724
723
723
723
725
725
725
725
725
725
725
725
Precipitation
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
Rain
Speed
15
12
11
12
13
12
11
12
13
10
9
9
9
9
11
10
12
15
15
12
10
Wind
Direction
South southeast
South southeast
Southeast
Southeast
South southeast
South
South southeast
Southeast
South southeast
South southeast
South
South southeast
South southeast
South southeast
South southeast
South
South
South
South
South
Northwest
-------
LINDEN CHLORINE COMPANY, LINDEN, NEW JERSEY
Presampling site survey at Linden Chlorine Company was conducted on
May 29, 1975. The following personnel were present:
Mr. Ronald Burkett
Mr. Bill Heineman
Mr. Edward J. Finfer
Linden Chlorine Plant
Linden Chlorine Plant
Environmental Protection Agency,
Region II
Mr. Martin L. Sanvito DEP, BAPC
Mr. William J. O'Sullivan DEP, Springfield office
Mr. William A. McGough
Mr. Richard Hills
Dr. George Scheil
Dr. J. Spigarelli
Central Jersey Regional Air Pollution
Control Agency
Central Jersey Regional Air Pollution
Control Agency
Midwest Research Institute
Midwest Research Institute
Linden Chlorine Company is located in the middle of a heavy industrial
area. The closest residential areas are greater than 1 mile away, and
nearby water source is the Arther Kill River.
During the visit, it was learned that graphite electrodes are no longer
used in production of chlorine, instead platinum-coated titanium electrodes
(dimensionally stabilized anodes) have been used since the end of March 1975.
Because the potential for producing HCB and HCBD is much less for this type
of electrode, it was decided that air sampling was not necessary. However,
the holding pond that contains brine sludge and eroded graphite from previ-
ously used electrodes may contain significant quantities of chlorinated
organics. In addition to carbon from eroded electrodes, the pond also con-
tains spent carbon filters that were used to remove organics from process
and surface water which flows through an open ditch to the Arthur Kill River.
By far the largest portion of this water is made up of wastes from the nearby
Gaf dye plant. The Gaf flume appeared to have a high organic content before
the wastes from the chlorine plant enter the stream. Because of possible
past HCB and HCBD contamination in the holding pond, samples were taken from
the pond and wastewater stream. The samples are described below:
75
-------
Sample type Sample location
Water Holding pond, inlet
Water Holding pond, outlet
Water Gaf weir, upstream of Cl2 plant
Water Waste stream, downstream of Cl£ plant
Water Tap water (control)
Solids From holding pond, settled and suspended
Solids Dredged solids adjacent to holding pond
Sludge Waste stream, downstream of Clo plant
The following samples were sent to Midwest Research Institute, on a
later date by the Linden Chlorine Plant: process water, circulating brine,
and uncontaminated soil.
STAUFFER CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
PRESAMPLING SITE SURVEY
The presampling site survey at Stauffer Chemical Company's Louisville,
Kentucky, plant was conducted on May 30, 1975. The following personnel were
present:
Mr. Arthur Wood Manufacturing Manager, Stauffer Chemical
Company
Mr. Harry Kutz Plant Manager, Louisville plant
Mr. Kenneth G. Hebel EPA/OSHA Testing Coordinator, Eastern
Research Center, Dobbs Ferry, New
York
Mr. Arthur E. Dungan Assistant Plant Manager, Louisville plant
Mr. John R. Blunk Process Superintendent, Louisville plant
Dr. George Scheil Midwest Research Institute
Dr. J. Spigarelli Midwest Research Institute
Stauffer Chemical Company is located on the east bank of the Ohio
River approximately 6 miles southwest of downtown Louisville, Residential
areas surround the plant, the closest being about 1 mile northeast of the
plant. The wind direction, according to the weather bureau records (10-
year average) at the Louisville airport indicated that during the month
of June there is a 5070 probability of a south wind (from one of the four
southern quadrants) and a much lower probability from any other direction.
76
-------
The "hex" solids from the perchloroethylene production plant are
gravity fed into drums (batch-wise). After several drums (unsealed, pos-
sibly covered with a pleastic sheet) accumulate, they are removed from
the plant area. Company officials said that the drums are usually re-
moved once a day at 8:00 a.m. The plant operated 24 hr a day, 7 days a
week.
The drums are transported to an area just west of the surplus storage
building where they are loaded onto trucks and taken to an approved land-
fill site approximately 15 miles from the plant. Cooling water and sur-
face runoff from the plant area are fed to a sump where the pH is adjusted
to 6 to 9, the liquid is pumped to a concrete settling pond, and gravity
fed through a pipe into the Ohio River.
Based on the plant operation described above, three possible sources
of HCB and HCBD contamination were considered, namely: (a) the production
area, especially at the location of the open barrels, (b) the settling
pond and (c) the "hex" loading area and the transportation route to the
landfill.
FIELD SAMPLING
Field sampling at the Stauffer plant was conducted .on June 12, 1975.
Air, water, soil, and sediment samples in and around the plant were col-
lected. Detailed descriptions of the sampling and plant activities during
sampling are discussed below.
Air Sampling
Eight sampling stations encircling the immediate plant area, and one
downwind station were set up. The total sampling period was divided into
six 4-hr periods and samplers were operated 2 hr of each 4-hr period. Each
sampling location is shown in Figure A-4. Exact locations with respect to
the perchloroethylene plant area, are listed along with other sampling data
in Table A-4.
Soil Sampling
Soil sampling was conducted in five general areas:
S-l Upwind (along the southern plant boundary)
S-2 Plant road (along the main road)
S-3 Drum loading area
77
-------
00
t"-
I (7
2 Sediment Sample
(700 Meters Upstream)
ifr.. „ Surplus
Holding); r
AreaT Storage
Settling
Pond
Outflow ~
R-3
Sediment
Sample
S-1 Soil Composite
Figure A-4. Sampling locations at Stauffer Chemical Company - Louisville, Kentucky
-------
Table A-4. AIR SAMPLING DATA AT STAUFFER CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
VD
Sample
General area
Upwind-
Upwind
East of "Perc Plant"
Northeast of "Perc
Plant"
Downwind
Downwind
Northwest of "Perc
No.
1
2
3
4
5
6
7
Exact location
450 ft south southwest of T'Perc
Plant" area
500 ft south southeast of "Perc
Plant" area
340 ft east of "Perc Plant" area
250 ft northeast of "Perc Plant"
area
300 ft north of "Perc Plant" area
400 ft north of "Perc Plant" area
330 ft northwest of "Perc Plant"
Sampling
period
1st
1st
1st
1st
1st
1st
1st
2
2
2
2
2
2
2
hr
hr
hr
hr
hr
hr
hr
of
of
of
of
of
of
of
4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
4 hr
Total
sampling
time (hr)
12.3
11.8
10.6
12.5
12.9
13.1
13.2
Sampling
rate
U/min)
3.5
3.5
3.5
3.5
3.5
3.5
3.5
Total
Sample
vol.
(-£)
2,588
2,626
2,221
2,768
2,787
2,662
2,850
Sampler
height
(ft)
4
4
4
4
4
4
4
Plant"
West of "Perc Plant"
north of settling
pond
Southwest of "Perc
Plant," northwest
of settling pond
area
8 420 ft west of "Perc Plant" area 1st 2 hr of 4 hr 13.3
9 540 ft southwest of "Perc Plant" 1st 2 hr of 4 hr 13.5
area
3.5 2,872
3.5
2.926
-------
S-4 Downwind (along the northern plant boundary)
S-5 Settling pond area
All samples were composites.
Water Sampling
Water sampling was limited to the plant well water and the settling
pond.
W-l Plant well water
W-2 Settling pond inlet (24 hr composite)
W-3 Settling pond inlet (grab sample)
W-4 Settling pond outlet (24 hr composite)
W-5 Settling pond outlet (grab sample)
W-6 Settling pond outlet (through Amberlite XAD-4)
Sediment Sampling
Sediment sampling was conducted at three locations:
R-l Settling pond sediment
R-2 Ohio River, 700 m upstream of Stauffer outflow
R-3 Ohio River, 250 m downstream of Stauffer outflow
Plant Activities and Weather Conditions
Plant activities were observed during the sampling period and are shown
in Table A-5.
The weather conditions during the sampling period are summarized in
Table A-6.
80
-------
Table A-5. PLANT ACTIVITIES DURING SAMPLING AT STAUFFER CHEMICAL COMPANY,
LOUISVILLE, KENTUCKY
Time
12 June
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
13 June
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
"Perc plant"^/
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Drum loading area
Normal
Normal
Normal
Normal
"Hex" drums removed
"Hex" drums removed
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Settling pond
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
Normal flow
a/ Normal operation utilizing HCBD recovery.
81
-------
Table A-6. WEATHER CONDITIONS DURING SAMPLING AT STAUFFER CHEMICAL
COMPANY, LOUISVILLE, KENTUCKY
Time
12 June
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
13 June
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
Temperature
(°C)
26
28
29
29
29
29
29
27
25
24
25
23
21
20
20
19
18
17
16
16
17
17
19
22
25
Barometric
pressure
(mm Hg)
757
757
757
757
757
757
758
758
758
758
759
759
759
759
759
760
760
760
760
760
760
760
760
760
760
Wind
Precipi-
tation
None
None
None
None
None
None
None
None
None
None
None
None
None
10 min rain
None
None
None
None
None
None
None
None
None
None
None
Speed
4
4
4
6
8
7
6
7
6
6
5
2
5
5
4
4
2
2
0
0
0
0
0
0
0
Direc-
tion
S
S
S
S
S
S
S
S
S
S
S
S
S
E
S
S
S
S
S
S
S
S
S
S
S
82
-------
DOW CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
PRESAMPL1NG SITE SURVEY
Presampling site survey at Dow Chemical Company's Pittsubrg, California,
plant was conducted on June 30, 1975. The following personnel were present:
Mr. Ed Elkins Manager, Environmental and operational
Services, Dow Chemical Company
Mr. David Baur Dow Chemical Company
Mr. Mike Thomas Dow Chemical Company
Mr. Paul Constant Midwest Research Institute
Mr. Jim Spigarelli Midwest Research Institute
Dow Chemical Company is located approximately 2 miles northeast of
Pittsburg, California, and 4 miles west of Antiocb, California, and is
situated on the southern bank of the New York slough of the San Joaquin
River. The immediate vicinity is flat, but mountains lie approximately
5 miles south of the plant. Approximately 70% of the time during July
the wind is from west or west-northwest. Residential areas are in
Pittsburg and Antioch.
Chemicals produced at this Dow facility include chlorine, carbon tetra-
chloride, and perchloroethylene. According to Mr. Elkins, all wastes from
the chlorinated hydrocarbon production flow to a thermal oxidizer, are con-
verted to hydrochloric acid and are recycled. In most instances, surface
runoff from the plant areas flow into a solar pond. However, inspection
on the plant and the solar pond area were not allowed. Only the plant
perimeter and beyond were surveyed.
Air sampling locations were planned based on the thermal oxidizer
parameters such as stack gas temperature, gas flow rate, aid stack height
and diameter.
FIELD SAMPLING
Field sampling at the Dow plant was conducted on August 7, 1975, after
several postponements. Air, soil, and water samples were collected. De-
tailed descriptions of the sampling, plant activities, and weather condi-
tions are discussed below.
83
-------
Air Sampling
Eight sampling stations were located so that two upwind, three near
downwind, and three far downwind samples were obtained. Air was sampled over
a 24-hr period with the exception of Stations 2 (upwind) and 7 (far down-
wind) . Two air sampling tubes were operated in series at each station.
Each sampling location is shown in Figure A-5. The exact location was mea-
sured with respect to the production plant area and is listed along with
other sampling data in Table A-7.
Soil Sampling
Soil sampling was conducted in three general areas:
S-l Upwind (western plant boundary)
S-2 Southern property boundary
S-3 Downwind (eastern plant boundary)
All samples were composites.
Water Sampling
One grab water sample of the New York Slough was obtained at the north-
east corner of Dow's property. Water sampling at the solar pond was not
permitted by the Dow officials.
Plant Activities and Weather Conditions
Plant activities and weather conditions during sampling are shown in
Table A-8.
84
-------
CD
Ln
^ Plant Boundary °ch Polnt .
, .
1°52'30"
Mapped, edited, and published by the Geological Survey
Control by USGS, USC&GS, and USCE
Culture and drainage in part by USC&GS from aerial photographs taken
Figure A-5. Sample locations at Dow Chemical Company, Pittsburg, California
-------
Table A-7. AIR SAMPLING DATA AT DOW CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
00
Total
Sample sampling
General area No. Exact location Sampling period time (hr)
Upwind 1
Upwind 2
Near downwind 3
Near downwind 4
Near downwind 5
Far downwind 6
Far downwind 7
2,630 ft west-northwest of 24 hr continuous 20.7
"Perc Plant"
2,780 ft west of "Perc Plant" 24 hr continuous 2.0^
900 ft east-northeast of 24 hr continuous 19.8
"Perc Plant"
830 ft southeast of "Perc 24 hr continuous 18.4
Plant"
1,280 ft south- southeast of 24 hr continuous 17.7
"Perc Plant"
2,550 ft east of "Perc Plant" 24 hr continuous 20.5
3,600 ft southeast of "Perc 24 hr continuous 4.6-
Sampling Sample Sampler
rate vol. height
U/min) U) (ft)
3.5 4,336 4
3.5 427 4
3.5 4,166 4
3.5 3,870 4
3.5 3,713 4
3.5 4,314 4
3.5 962 4
Plant"
Far downwind 8
5,100 ft south-southeast of
"Perc Plant"
24 hr continuous 18.9
3.5
3.963
a/ Generator failure.
-------
Table A-8. WEATHER CONDITIONS AND PLANT ACTIVITIES DURING
SAMPLING AT DOW CHEMICAL COMPANY, PITTS BURG,' CALIFORNIA*/
Time
August 7
1700
1800
1900
2000
2100
2200
2300
2400
August 8
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
Temper-
ature
(°F)
97
96
92
87
84
82
79
80
74
74
74
73
71
69
67
73
83
87
91
96
98
101
101
103
102
99
Barometric
pressure Wind
(mm Hg) Speed
760 8
12
10
10
760 8
8
6
2
760 0
6
8
6
760 4
0
0
0
760 0
2
6
2
760 4
4
10
12
759 12
13
Direction
West
West
West
West
West
West
West
West
.
West
West
West
West
-
-
-
-
West
West
Northwest
Northwest
West
West
West
West
West
Plant
activities
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Incinerator feed
rate reduced
Normal
Normal
Normal
Normal
Possible event
Normal
Normal
Normal
a/ No precipitation during sampling period.
87
-------
E. I. du PONT de NEMOURS AND COMPANY, INC., CORPUS CHRISTI, TEXAS
PRESAMPLING SITE SURVEY
The presampling site survey at du Font's Corpus Christi, Texas, plant
was conducted on July 11, 1975. The following personnel were present:
Mr. Charles Evans Plant Manager, du Pont
Mr. Dave Brooks Assistant Plant Manager, du Pont
Mr. Phil Kuykendall Midwest Research Institute
This du Pont plant is located on Corpus Christi Bay approximately 3
miles northeast of downtown Corpus Christi. The immediate area surrounding
the plant contains several industries, but the small town of Ingleside is
about 1 mile east of the plant. Wind direction in the summer is generally
from the south, south southeast, and south southwest.
Carbon tetrachloride is produced by chlorination of methane or ethylene
at elevated temperatures. All by-products are continuously recycled to in-
sure total chlorination. Chlorine is obtained from an outside source. Solid
wastes from the process are minimal and are not frequently removed from the
reaction vessel.
Solid wastes are generally drummed and shipped to an outside firm for
disposal although some wastes are dumped into du Font's two landfills. One
landfill is dedicated to the disposal of a mixture of cement, lime, and
catalyst from Freon production. The other landfill normally receives such
wastes as contaminated containers, spills, or "heavy ends" waste from the
carbon tetrachloride production.
Wastewater is handled separately as process waste and storm runoff.
Process wastes are channeled via open concrete ditches, to an equalization
pond where the residence time is 3 to 6 days. Underground pipes discharge
the wastewater into Lacita Channel at a flow rate of approximately 2,000
gal/min.
Storm runoff is discharged, via open dirt ditches, directly into
Lacita Channel
FIELD SAMPLING
Field sampling at the du Pont plant was conducted on August 3, 1975.
Air, soil, water, and sediment samples were collected. Detailed descrip-
tions of the sampling, plant activities, and weather conditions, are dis-
cussed below.
88
-------
Air Sampling
Due to equipment failure,only five air sampling stations were operated.
Two were upwind and three were downwind. All samples were operated for 24
hr utilizing one filter and two Tenax tubes in tandem. Sampling locations
are shown in Figure A-6. Exact distance of each station to the production
area was determined and reported along with other sampling data in Table
A-9.
Soil Sampling
Soil sampling was conducted in three general areas:
S-l Upwind (at Stations 1 and 2 on southern boundary)
S-2 Downwind (at Stations 3, 4, and 5 on northern boundary)
S-3 Landfill area (20 ft from edge of miscellaneous landfill)
All soil samples were composites.
Water Sampling
Water sampling was conducted at seven locations:
W-l Raw plant water before use
W-2 Settling pond inlet (amberlite)
W-3 Settling pond inlet (grab)
W-4 Settling pond outlet (amberlite)
W-5 Settling pond outlet (grab)
W-6 Storm runoff outfall (grab)
W-7 Water standing in landfill
Sediment Sampling
Sediment sampling was conducted at four locations:
R-l Settling pond inlet
R-2 Settling pond outlet
R-3 Storm runoff outfall
89
-------
STORM SEWER
••PROCESS SEWER
1" • 150'
Figure A-6. Sample Locations at E. I. du Pont de Nemours and Company, Inc., Corpus Christi, Texas
-------
table A-9. AIR SAMPLING DATA AT E. I. DU PONT DE NEMOURS AND COMPANY, INC., CORPUS CHRISTI, TEXAS
General area
Upwind
Upwind
Downwind
Downwind
Downwind
Sample
No.
1
2
3
4
5
Exact location Sampling period
675 ft south of production area 24 hr continuous
700 ft south southeast of produc- 24 hr continuous
tion area
640 ft north northwest of produc- 24 hr continuous
tion area
64- ft north northwest of produc- 24 hr continuous
tion area
640 ft north northwest of produc- 24 hr continuous
tion area
Total Sampling
sampling rate
time (hr) (,2/min)
22.8 3.5
19.5 3.5
21.2 3.5
21.2 3.5
21.3 3.5
Sample Sampler
vol. height
U) (ft)
4,371 4
3,621 4
4,070 4
4,007 4
3,965 4
-------
Plant Activities
Plant activities during sampling are shown in Tables A-10 and A-11,
respectively.
92
-------
Table A-10. P1ANT ACTIVITIES DURING SAMPLING AT E..1. DU
PONT DE NEMOURS AND COMPANY, INC., CORPUS CHRISTI, TEXAS
Time
August 3
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
Chlorocarbon
unit
Normal production
Normal production
Normal production
Down
Down
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Normal production
Landfill
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
No activity
Settling pond
flow
(gal/min)
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
2,300
93
-------
Table A-ll. WEATHER CONDITIONS DURING SAMPLING AT E. I. DU PONT DE
NEMOURS AND COMPANY, INC., CORPUS CHRISTI, TEXAS
Temperature
Time
August 3
0700
0800
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
August 4
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
(°C)
28
28
28
29
29
29
29
30
29
29
27
28
28
28
28
27
27
27
27
26
28
27
28
29
29
29
30
30
30
Barometric
pressure
(mm Hg)
762
762
762
762
761
761
761
761
761
760
760
760
760
760
760
762
762
762
762
762
761
761
761
761
761
760
760
760
760
Precipitation Speed
none
none
none
none
none
none
none
none
none
rain
rain
none
none
none
none
none
none
none
none
none
none
none
none
none
none
none
none
none
rain
19
17
15
11
11
11
10
10
12
22
9
10
10
9
9
7
10
10
10
18
16
17
17
15
15
18
15
13
12
Wind
Direction
South
South
South
South
South southeast
South southeast
South southeast
South southeast
South southeast
North northwest
East
East southeast
Southeast
Southeast
Southeast
Southeast
Southeast
South southeast
South southwest
South
South
South
South
South
South southwest
South southwest
South southwest
South southwest
Southwest
94
-------
DIAMOND SHAMROCK CORPORATION, DEERK PARK, TEXAS
PRESAMPLING SITE SURVEY
The presampling site survey at Diamond Shamrock's, Deer Park, Texas,
plant was conducted on July 10, 1975. The following personnel were present:
Mr. Lavern R. Heble Environment Control Manager, Gulf Coast
Area, Diamond Shamrock Corporation
Mr. William C. Hutton Senior Environmental Control Engineer,
Diamond Shamrock Corporation
Mr. Bob Baxter Perchloroethylene Unit Manager,
Diamond Shamrock Corporation
Ms. Sandra Quinlivan TRW, Rodondo Beach, California
Mr. Phil Kuykendall Midwest Research Institute
This Diamond Shamrock plant is located in the heart of a huge industrial
area along the Honston ship channel. The nearest residential area is Deer
Park, located approximately 5 miles south of the plant. Wind direction in
the summer months is mostly from the south.
Perchloroethylene and trichloroethylene are produced in this plant by
the reaction of chlorine and hydrocarbons. The chlorine used is produced at
a nearby Diamond Shamrock plant and is piped to the production area. "Hex"
solids resulting from the process are stored in large tanks awaiting disposal.
The major possible sources of HCB and HCBD are (a) the production area
and (b) the "Hex" solids storage area.
Diamond Shamrock uses two types of waste disposal; contracted solid
waste disposal and channeling of wastewater into Patrick Bayou. The solid
wastes are transferred from the holding tank to a tank truck which trans-
ports the waste to an outside firm for incineration or landfill disposal.
Solid waste removal does not occur daily. A solvent flush of the lines into
the tank truck follows each dumping of "Hex" solids. Wastewater is steam-
stripped in the production area then piped to a waste treatment plant prior
to discharge into Patrick Bayou.
95
-------
FIELD SAMPLING
Field sampling at the Diamond Shamrock plant was conducted on August
20, 1975 after several postponements due to plant down time. Air, soil,
and water samples were collected. Detailed description of the sampling,
plant activities, and weather conditions, are discussed below.
Air Sampling
Eight air sampling stations were used—three upwind and five downwind.
To avoid possible breakthrough of the Tenax®-GC5 smaller critical orifices
were used. All samples were operated for three 8-hr periods, resulting in a
24-hr sampling time. Sampling locations are shown in Figure A-7. The exact
distance of each station to the production area was determined and reported
along with other sampling data in Table A-12.
Soil Sampling
Soil sampling was conducted at three areas:
S-l Upwind (along southern boundary)
S-2 Downwind (along northern boundary)
S-3 Production area
All soil samples were composites.
Water Sampling
Water sampling was conducted at two points:
W-l Incoming channel water
W-2 Process water outfall
All samples were grab samples.
No sediment sampling was conducted because of no existing sampling
site.
Plant Activities and Weather Conditions
The weather conditions during sampling are shown in Table A-13.
Plant activities were normal during the entire sampling period.
96
-------
N
PRODUCTION
AREA
Figure A-7. Sampling locations at Diamond Shamrock Corporation,
Deer Park, Texas
97
-------
Table A-12. AIR SAMPLING DATA AT DIAMOND SHAMROCK CORPORATION, DEER PARK, TEXAS
Sample
Genera: area No.
Far upwind 1
Near upvind' 2
Near uswinc 3
vD
00
Near downwind 4
Near downwind 5
Near downwind 6
Far downwind 7
Far dpwnvind 8
Exact location Sampling period
1,300 ft south of "Perc Plant" area 24 hr continuous
510 ft southwest of "Perc Plant" 24 hr continuous
area
420 ft southeast of "Perc Plant" 24 hr continuous
area
1,200 ft northeast of "Perc 24 hr continuous
Plant" area
1,300 ft northwest of "Perc 24 hr continuous
Plant" area
1,860 ft north northeast of 24 hr continuous
"Perc Plant" area
2,850 ft north northwest of 24 hr continuous
"Perc Plant" area
2,900 ft north of "Perc Plant" 24 hr continuous
Total
sampling
time (hr)
24.2
24.9
20.2
22.5
22.6
25.3
23.3
23.1
Sampling
rate
(2/tnin)
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
Sample
vol.
580
598
485
540
542
608
559
555
Sampler
height
(ft)
4
4
4
4
4
4
4
4
area
-------
Table A-13. WEATHER CONDITIONS DURING SAMPLING AT
DIAMOND SHAMROCK CORPORATION, DEER PARK, TEXAS
Time
August 20
1600
1700
1800
1900
2000
2100
2200
2300
2400
August 21
0100
0200
0300
0400
0500
0600
0700
0800
2100
2200
2300
2400
August 22
0100
0200
0300
0400
0500
0600
0700
0800
0900
Tempera-
ature
(°C)
34
34
33
33
31
31
29
29
27
26
26
28
28
30
30
30
30
28
28
27
25
25
28
29
29
31
31
31
30
31
Barometric Precipi-
pressure tation Speed
766 None 4
766
766
766
767
767
767
767
767
766
766
766
766
765
765
5
4
3
2
1
1
1
1
1
1
1
1
' 2
6
765 ^ 5
765 Rain 3
765 Rain 1
765 None 1
765
765
765
765
766
766
766
766
766
766
1
1
1
1
1
1
1
1
1
1
766 V 2
Wind
Direction
Southeast
South southeast
South
South southeast
South southeast
South
South
South
South
South
South
North northwest
North
North northwest
Southeast
South
North northwest
East northeast
East
North northeast
North
North northeast
North
West northwest
East
East
East
North northeast
East northeast
North northeast
99
-------
CIBA-GEIGY CORPORATION, ST. GABRIEL, LOUISIANA
PRESAMPLING SITE SURVEY
The presampling site survey at Ciba-Geigy Corporation, St. Gabriel,
Louisiana, plant was conducted on July 15, 1975. The following personnel
were present:
Mr. William F. Snyder Staff Engineer, Environmental
Engineering, Ciba-Geigy
Mr. Phil Kuykendall Midwest Research Institute
Ciba-Geigy Corporation is located in a large industrial area which is
approximately 20 miles south of Baton Rouge. The plant is on the east bank
of the Mississippi River in a predominantly swampy area with minimal residences.
Wind direction during the summer months are generally from the south and
west.
Triazine herbicides are produced by the amination of cyanuric chloride.
The production processes result in the accumulation of "still bottoms" with
an approximate concentration of 2,000 Ug/g.
Solid wastes are drummed and shipped to an outside firm for incinera-
tion. A vent scrubber is used for vapor emissions. Wastewater is dis-
charged via open ditches to a holding pond, then discharged into the
Mississippi River at an average flow rate of 2,000 gal/min. An emergency
wastewater outfall into Bayou Braud is occasionally used.
FIELD SAMPLING
Field sampling at the Ciba-Geigy plant was conducted on August 13,
1975. Air, soil, and water samples were collected. Detailed description
of the sampling, plant activities, and weather conditions, are discussed
below.
Air Sampling
Eight air sampling stations were positioned around the plant because
of the erratic wind direction. Only one Tenax®-GC tube was used. To avoid
possible breakthrough of the Tenax®-GC, sampling was operated 2 hr out of
every 8-hr period. The sampling locations are shown in Figure A-8. Exact
distance of each station to the production areas was determined and reported
along with other sampling data in Table A-14.
100
-------
I i | i; j 1ill | I
600 j 100 p
'• " J
OO ! i I 9*0° M1 i 95OO I {I
i • h r
1 ',' I 1 I I 1
Process Water Outflow into Mississippi River
Figure A-8. Sample locations at Ciba-Geigy Corporation, St. Gabriel, Louisiana
-------
Table A-14.. AIR SAMPLING AT CIBA-GSIGY CORPORATION, ST. GABRIEL, LOUISIANA
Sample No.
1
2
3
4
5
6
7
Exact location
2,200 ft northwest of produc-
tion area
920 ft north of production area
1,600 ft northeast of produc-
tion area
800 ft east southeast of produc-
tion area
2,200 ft southeast of production
area
950 ft south of production area
1,600 ft southwest of production
Sampling period
1st 2 hr of 8 hr
1st
1st
1st
1st
1st
1st
2 hr of
2 hr of
2 hr of
2 hr of
2 hr of
2 hr of
8 hr
8 hr
8 hr
8 hr
8 hr
3 hr
Total
time
7.
8.
6.
. 6.
6.
sampling
(hr)
6
8
8
3
4
Lost
6.
1
Sampling
rate (i/min)
3
3
3
3
3
3
3
.5
.5
.5
.5
.5
.5
.5
Sample
vol. U)
1,772
2,164
1,630
1,442
1,561
Lost
1,277
Sampler
height (ft)
4
4
4
4
4
4
4
1,000 ft west of production area 1st 2 hr of 8 hr 5.6 3.5 1,298
-------
Soil Sampling
Soil sampling was conducted at four locations:
S-l Northwest of plant at Air Sampling Site No. 1
S-2 Northeast of plant at Air Sampling Site No. 3
S-3 Southeast of plant at Air Sampling Site No. 5
S-4 Southwest of plant at Air Sampling Site No. 7
All soil samples were composites.
Water Sampling
Water sampling was conducted at two locations:
W-l Raw plant water before use
W-2 Process outflow
All water samples were grab samples.
Sediment Sampling
No sediment samples were taken. The process outflow ditch has a
gravel bottom. The effluent pond was not available for sampling, per Ciba-
Geigy's request.
Plant Activities and Weather Conditions
The weather conditions during sampling are shown in Table A-15.
Plant activities were normal.
103
-------
Table A-15. WEATHER CONDITIONS DURING SAMPLING AT
CIBA-GEIGY, ST. GABRIEL, LOUISIANA
Temper-
ature Precipi- Wind
Time
August 13
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
August 14
0100
0200
0300
0400
0500
0600
0700
0800
0900
1000
1100
1200
1300
(°C) tation Speed
39 none 3
37
37
36
36
36
34
32
32
29
27
27
27
29
29
30
32
32
33
35
35
36
7
5
5
4
7
5
5
3
5
5
6
8
7
7
5
4
6
5
6
4
4
36 V 2
Direction
North northwest
Northwest
Northwest
North northwest
Southwest
South
South
South
Southwest
Southwest
West southwest
Southwest
Souwthwest
West
West
West
West northwest
Northwest
Northwest
North northwest
North northwest
North northwest
North northwest
104
-------
OLIN CORPORATION, MCINTOSH, ALABAMA
PRESAMPLING SITE SURVEY
The presampling site survey at Olin Corporation's Mclntosh, Alabama,
plant was conducted on July 23, 1975. The following personnel were present:
Mr. J. Oertling Works Manager, Olin
Mr. F. Champion Production Manager, Organic
Section, Olin
Mr. C. Hovater Q. C. Manager, Olin
Mr. R. Reams Technical Manager, Olin
Mr. N. Barone Specialist - Environmental Affairs,
Olin
Mr. D. Sauter Midwest Research Institute
Olin Corporation is located approximately 30 miles north of Mobile,
Alabama. The area in the immediate vicinity of the plant is flat and
marshy. Residential areas around the plant are minimal. Winds are gen-
erally from the south during the summer.
The production of pentachloronitfobenzene is by chlorination and
nitration of isomeric chlorobenzenes. The production process results in
the accumulation of "still bottoms" which are cast into 27-ft^ blocks
containing 80 to 90% HCB. The rated capacity of the plant for PCNB is ap-
proximately 7 million pounds per year. Approximately 2.8 to 3.0 million
pounds per year of HCB is generated in this process.
Chlorine is also produced by mercury cells using carbon electrodes at
a rate of 130,000 tons/year.
Solid wastes (HCB blocks) are stored in an open field in the southeast
corner of the plant. The HCB block pile is covered with plastic. This pile
represents HCB wastes from the last 2-1/2 years of PCNB production. Ultimately,
Olin hopes to reclaim the HCB.
Wastewater is discharged into two open ditches with an average combined
flow of 5 million gallons per day. The south ditch, which is adjacent to
the PCNB plant and receives runoff from the waste disposal settling pond,
contributes mostly to this flow. Both ditches combine outside the plant
boundary, and flow into a basin, and ultimately into the Tombigbee River.
105
-------
At least two landfills were observed. The first landfill is located
directly outside the northeast corner of the plant boundary. This land-
fill was used for HCB disposal before 1971. The second landfill is the
southeastern section of the plant is primarily a garbage dump. No land-
fills are currently in use for chemical disposal.
At the conclusion of the presampling survey, it was agreed upon that
field sampling would be tentatively scheduled in the week of August 18,
1975.
FIELD SAMPLING
Field sampling at the Olin plant was conducted on August 18, 1975.
Air, soil, water, and sediment samples were collected. Detailed descrip-
tion of the sampling, plant activities, and weather conditions, are dis-
cussed below.
Air Sampling
Eight sampling stations were positioned to give two upwind, three mid-
plant, and three downwind sites. Two Tenax®-GC sampling tubes were operated
in tandem at each site for three, 3-hr periods. Sampling locations are
shown in Figure A-9. The exact distance of each station to the production
area was determined and reported along with other sampling data in Table
A-16.
Soil Sampling
Composite grab samples were taken outside and inside the plant boundary:
S-l Downwind (north boundary)
S-2 Old landfill (northeast boundary)
S-3 Brine pond area
S-4 Center road (running north/south)
S-5 High lift route (organic plant to storage area)
S-6 Southeast landfill
S-7 "Hex" storage area
S-8 Old "Hex" dump area
S-9 East road
106
-------
' ' ' '
Figure A-'J . Saiqsling locations at Olin Corporation, Mclntosh, Alabama
107
-------
Table A-16. AIR SAMPLING DATA AT OLIN CORPORATION, MCINTOSH, ALABAMA
Sample
General area No. Exact location
Far downwind 1 2,100 ft north northeast of
production area
Far downwind 2 2,100 ft north of production
area
Far downwind 3 2,200 ft north northwest of
j_, production area
o
00
Near downwind 4 720 ft north northeast of
production area
Near downwind 5 700 ft north of production
area
Near downwind 6 800 ft north northwest of
production area
Upwind 7 640 ft south of production
area
Upwind 8 640 ft south of production
area
Total
sampling
Sampling period time (hr)
1st 3 hr of 12 hr 10.0
1st 3 hr of 12 hr 5.2
1st 3 hr of 12 hr 5.7
1st 3 hr of 12 hr 6.9
1st 3 hr of 12 hr 7,0
1st 3 hr of 12 hr 7.0
1st 3 hr of 12 hr 7.8
1st 3 hr of 12 hr 7.3
Sampling
rate
(,2/min)
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
Sample
vol.
2, 103
1,100
1,204
1,445
1,473
1,472
1,630
1,525
Sampler
height
(ft)
4
4
4
20^
20^
20^
4
4
a/ Samplers were positioned on Brine Pond dike.
-------
S-10 West road
S-ll Upwind south road
Water Sampling
The following grab samples were obtained:
W-l Weak brine pond
W-2 Strong brine pond
W-3 Settling pond
W-4 North/south running ditch
W-5 Southern ditch area (upper drop)
W-6 Combined creek (200 yard before basin)
W-7 Basin (at mouth of creek)
W-8 24-Hr composite of plant effluent (combined creek)
W-9 Solar pond, west
W-10 Solar pond, east
Sediment Sampling
One sediment sample was collected at the strong brine pond.
Plant Activities and Weather Conditions
The weather conditions during sampling are shown in Table A-17,
Plant activities were normal.
109
-------
Table A-17. WEATHER CONDITIONS DURING SAMPLING AT
OLIN CORPORATION, MC1NTOSH, ALABAMA
Time
August 18
1500-7
1600-/
17002/
1800
1900
2000
2100
2200
2300
2400^
August 19
01002/
02002/
0300i/
0400
0500
0600
0700
OSOO^/
09002/
lOOO^/
IIOO^./
12001/
Tempera-
ture
(°C)
37
37
36
26
23
23
23
25
27
29
32
35
Barometric
pressure
(ram Hg)
738
738
738
756
741
740
740
740
740
739
739
738
Speed
2-4
2-4
4-10
6-13
4-6
2-6
2-4
2-4
2-4
2-4
-
-
-
-
2-4
-
2-6
Wind :
Direction
South
Southeast
North northeast
North
Southeast
East
Northwest
West
No wind
South
Southwest
No wind
No wind
No wind
No wind
No wind
North northeast
No wind
No wind
No wind
No wind
North
Precipi-
tation
None
None
None
Rain
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
a/ Indicates air sampling.
110
-------
KAISER ALUMINUM AND CHEMICAL CORPORATION, GRAMERCY, LOUISIANA
The presampling site survey at Kaiser Aluminum was conducted on
August 14, 1975. The following personnel were present:
Dr. Robert M. Hansen Research and Development, Kaiser
Mr. Phil Fourmet Environmental Manager, Kaiser
Mr. Bob Curtis Environmental Control Specialist,
Kaiser
Mr. Phil Kuykendall Midwest Research Institute
Upon discussion with the plant officials, it was learned that chlorine
production utilizing graphite anodes had been terminated in 1973, and was
replaced by dimensionally stabilized anodes. For waste disposal, prior to
1973, solid wastes were dispoded by landfill. These residues have since
been covered by aluminum production wastes. Water effluent is channeled
into the Mississippi river following on-line pH adjustment.
As a result of the change in production technology and the solid wastes
disposed since 1973, it was decided that sampling at this plant would yield
no usable data. Furthermore, samples collected from the Linden Chlorine
Company, at Linden, New Jersey, and the other chlorohydrocarbon plants,
which also produce chlorine, would serve the purpose of monitoring the chlorine
production plant for the HCB and HCBD emission.
PPG INDUSTRIES, LAKE CHARLES, LOUISIANA
PRESAMPLING SITE SURVEY
The presampling site survey at PPG Industries' Lake Charles, Louisiana,
plant was conducted on August 22, 1975. The following personnel were present:
Mr. T. G. Taylor Technical Plant Manager, PPG
Mr. Thomas C. Jeffery Chief Process Engineer, PPG
Dr. Earl Gorton Senior Research Supervisor, Organics,
PPG
Mr. C. A. Burns Environmental Control Specialist, PPG
Mr. Mark Wood Environmental Analysis Coordinator, PPG
Dr. Raymond Li Midwest Research Institute
111
-------
PPG Industries is located more than 2 miles west of downtown Lake
Charles, Louisiana. The surrounding terrain is flat and marshy. The PPG
canal runs through the plant and into the Calcasieu River which flows to
Lake Charles. The closest residential area is about 1 mile northwest of
the plant. The wind, in the summer months, is very variable but most likely
from south southeast and least likely from the west.
Chemicals produced in this plant include trichloroethylene, perchloro-
ethylene, ethylene dichloride, ethyl chloride, vinylidene chloride, methyl
chloroform, vinyl chloride, chlorine, hydrochloric acid, caustic soda, and
silica pigments. The current production capacities of trichloro- and per-
chloroethylene are 350 tons/day. However, the production of 725 tons/day
could be achieved and was produced in the past. The plant operates 24 hr
a day, 7 days a week.
Trichloro- and perchloroethylene are produced by a catalytic oxy-
chlorination process rather than the thermal process of chlorine and
hydrocarbons, thus resulting at a lower reaction temperature. The chlorine
is produced in the plant (DSA has been used since 1969). The production
wastes are piped into the incinerator and burnt at a residence time from
1/4 to 1/3 sec at 2500°F. The water effluent is channeled into the PPG
canal which flows into the Calcasieu River. The PPG canal also received
runoffs from the organochlorine production as well as effluents from the
power plant.
Prior to the operation of the incinerator, landfill was used for waste
disposal. The old landfill site was covered with water. It is still being
used for wastes than cannot be burnt in the incinerator or when incinerator
breakdown occurs.
At the conclusion of the presampling survey, it was agreed upon that
field sampling would be tentatively scheduled in the week of September 2,
1975.
FIELD SAMPLING
Field sampling at the PPG plant was conducted on September 4, 1975.
Air, soili water, and sediment samples were collected. Detailed descrip-
tion of the sampling, plant activities, and weather conditions, are dis-
cussed below.
Air Sampling
Ten sampling stations were positioned to encircle the plant's in-
cinerator and organochlorine production area. Two Tenax-GC®sampling tubes
were operated in tandem with 24-hr continuous sampling time. Sampling
112
-------
locations are shown in Figure A-10. The exact distance of each station to
the incinerator/production area is listed along with other sampling data in
Table A-18.
Soil Sampling
Composite grab samples were taken outside and inside the plant area.
S-l Landfill composite
S-2 Composite at Air Stations 7, 5, and 4
S-3 Composite at Air Stations 8, 9, and 10
S-4 Composite near Air Station 1 on Columbia Southern Road
Water Sampling
Grab samples were obtained at the following locations:
W-l Incinerator feed water, lake water
W-2 Scrubber water
W-3 Inlet treatment canal organic effluent before scimmer
\
W-4 Outlet treatment canal organic effluent after scimmer.
W-5 Surface water, landfill
W-6 Downstream PPG canal, at Mobile Bridge No. 1, 1 gal. taken
W-7 Ship channel, adjacent to Air Station No. 10
Sediment Sampling
Sediment samples were collected at three general areas.
R-l Downstream PPG canal near Air Sampling Station No. 1
R-2 Main organic plant effluent, near Air Sampling Station No. 2
R-3 PPG ship channel, near Air Sampling Station No. 10
113
-------
^
INDUSTRIAL
CHEMICAL^ DIVISION
Figure A-10. Sampling locations at PPG Industries, Lake Charles, Louisiana
-------
Table A-18. AIR SAMPLING DATA AT PPG INDUSTRIES, LAKE CHARLES, LOUISIANA
Sample
No.a/
1
2
3
4
5
6
7
8
Location Sampling period
4,700 ft south of production 24 hr continuous
area
2,500 ft south southeast of 24 hr continuous
production area
1,550 ft south of production 24 hr continuous
area
2,300 ft west northwest of 24 hr continuous
production area
2,000 ft northwest of produc- 24 hr continuous
tion area
3,500 ft north northwest of 24 hr continuous
production area
1,250 ft north of production 24 hr continuous
area
1,250 ft northeast of production 24 hr continuous
Total
sampling time (hr)
21.6
21.4
21.3
21.0
19. O^7
22.0
20.7
21.8
Sampling
rate (l/tnin) .
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
Sample
vol. U)
1,180
1,170
1,210
1,170
950^
1,250
1,180
-
1,190
Sampler
height (ft)
4
4
4
4
4
4
4
4
area
10
2,250 ft east of production 24 hr continuous
area
2,700 ft east southeast of
production area
24 hr continuous
21.9
21.9
0.9
0.9
1,250
1,130
a/ Stations were positioned surrounding the production area.
b/ Approximate value due to pump failure, indicates minimum volume.
-------
Plant Activities and Weather Conditions
The weather conditions during sampling are shown in Table A-19. Plant
activities were normal.
116
-------
Table A-19. WEATHER CONDITIONS DURING SAMPLING AT PPG INDUSTRIES,
LAKE CHARLES, LOUISIANA
Temperature
Time (°F)
Spetember 4
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
September 5
0100
0200
0300
0400
0500
0600
0700
0800
0900
85
86
88
85
85
85
82
80
78
77
76
75
76
75
75
75
75
75
75
75
74
73
72
Barometeric
pressure
(mm Hg)
763
762
762
762
762
762
762
762
763
763
763
763
762
762
762
762
762
762
762
763
763
763
763
Speed
(mph)
7
7
7
7
7
7
8
7
5
4
3
2
• -
-
3
6
5
3
2
3
2
3
3
Wind
Direction
East
East
East
East
East
East southeast
East southeast
East
East
East
East
West
-
'
East
East
East
East
East
East
East
East ,
a/
East-'
a/ Rain.
117
-------
APPENDIX B
ANALYTICAL DATA
118
-------
Table B-l. HCBD CONCENTRATIONS IN AIR SAMPLES FROM VULCAN
MATERIALS COMPANY, WICHITA KANSAS
Sampling
station
1
2
3
4
Sampling
. time
1935-2035
0120-0227
0430-0523
0841-0941
1320-1424
1935-2035
0120-0227
0430-0523
0841-0941
1320-1424
1935-
0120-0227
0430-0523
0841-0941
1320-1424
1945-2045
01 1(1-0220
0450-0555
0902-1010
1307-1425
Volume sampled
(liter)
26
42 .
33
37
40
17
36
29
32
35
Lost
57
45
51
54
27
32
JO
31
36
Type of
sample
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
•Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
KHtor
Tonax
Filter
Tenax
Filter
Tenax
Filter
Tenax
HCBD
< 1 16.4
425
< 1 13.3
560
< 1 6.4
210
< 1 5.0
' 185
<1 3.4
135
< 1 11.9
200
< 1 12.6
455
< 1 28.4
825
< 1 6.4
205
< 1 10.6
370 ' .
< 1 5.4
310
< 1 4.1
185
< 1 3.0
150
< 1 10.1
545
< 1 57
1,55(1
< 1 h!>
2.083
< 1 65
1,938
< 1 52
1,600
< 1 49
1,750
119
-------
Table B-l. (continued)
Sampling
atatlon
5
6
7
8
Sampling
time
1945-2045
0110-0220
0450-0555
0902-1010
1307-1425
1945-2045
0110-0220
0450-0555
0902-1010
1307-1425
1950-2050
0051-0158
0456-0555
0904-1010
1308-1425
1950-2050
0103-0202
0458-0600
0908-1010
1308-1420
Volume sampled
(liter)
41
48
44
46
53
34
40
37
39
45
148
166
146
163
190
212
209
220
227
255
Type of
sample
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
HCBD
Total ng
< 1
700
ND
850
< 1
2,250
< 1
1.650
< 1
< 1
< 1
695
< 1
345
< 1
928
< 1
1,712
< 1
20,867
< 1
475
< 1
590
< 1
417
< 1
1,862
< 1
3,250
< 1
510
< 1
146
< 1
1,850
< 1
4,375
< 1
3,625
tig/in-*
17
18
si
36
< 0.02
20
9
25
44
463
3.2
3.6
2.8
11.4
17
2.4
0.7
8.4
19.2
14.2
120
-------
Table B-l. (continued)
Sampling
station
9
10
11
12
Sampling Volume sampled
time (liter)
1950-2050 227
0103-0202 . 223
0458-0600 234
0908-1010 242
1308-1420 272
1910-2310 809
0005-0330 691
0340-0728 768
0737-1117 741
1124-1433 637
1910-2310 856
0005-0330 732
0340-0728 814
0737-1117 785
1124-1433 675
1919-2315 863
2350-0315 738
0325-0712 817
07:'l-ll(H ivi
1113-1433 720
Type of
sample
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
I'llcor
Tenax
Filter
Tenax
HCBD
Total ng
< 1
63
< 1
83
< 1
490
< 1.
3,860
< 1
4,631
< 1
9,850
< 1
4,500
< 1
2,000
•< 1
1,200
< 1
438
< 1
10,350
< 1
4,750
< 1
1,950
< 1
1,090
Sample lost
408
< 1
17,500
< 1
16,333
< 1
4,500
-. 1
4,000
< 1
1,833
ug/m3
0.3
0.4
2.1
16
17
12.2
6.5
2.6
1.6
0.7
12.1
6.5
2.4
1.4
0.7
20
22
6
,t
3
121
-------
Table B-l. (continued)
Sampling
station
13
14
15
Id
Sampling
time
1915-2315
2350-0315
0325-0712
0721-1101
1113-1433
1920-2259
2335-0258
0310-0640
0650-1046
1057-1435
1920-2259
2335-0258
0310-0640
0650-1046
1057-1435
.'OOV-lHMO
0025-0345
0355-0744
0752-1154
1200-1430
Volume sampled
(liter)
917
784
867
840
764
806
816
844
949
876
837
805
832
935
863
;!(>.'
702
804
849
527
Type of
sample
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Miter
1'enax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Total B
< 1
17,000
< 1
17,000
< 1
3,500
< 1
3,000
. < 1
1,400
< 1
3.5
< 1
150
< 1
25
< 1
130
< 1
3,642
< 1
13.5
< 1
160
< 1
46
< 1
164
< 1
3,300
< t
133
< 1
30
< 1
48
KD
ND
ND
29
HCBD
!£ U8/m3
19
22
4
4
2
0.004
0.2
0.03
0.1
4.2
0.02
0.2
0.1
0.2
3.8
o.:
0.04
0.1
ND
0.1
122
-------
Table B-l. (concluded)
Sampling
station
17
18
TenajPGC
blank
Millipore
filter
blank
Sampling
time
2005-0010
0025-0345
0355-0744
0752-1154
1200-1430
2010-
0022-0355
0400-0755
0759-1121
1215-1430
Volume sampled
(liter)
730
596
682
721
447
548
711
785
858
451
Type of
sample
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
HCBD
Total ng
ND
2
ND
5 .'
ND
5
ND
9
ND
9
< 1
130
< 1
54
< 1
61
< 1
123
< 1
39
ug/m3
0.003
0.008
0.007
0.01
0.02
0.2
0.1
0.1
0.1
0.1
ND
ND
a/ Concentration based on the sum of ng found on the filter and Tenax.
b/ ND - None detected.
123
-------
Table B-2. HCBD CONCENTRATIONS IN AIR SAMPLES FROM STAUFFER
CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Sampling
station
1
2
3
4
5
Type of Volume sampled
Sampling time
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
sample
Tena*®-GC
Tena*®-GC
Tena}®-GC
Tenaj^-GC
TenaxSX-GC
Tenax®-GC
Filters
Tenax^-GC
Tenax®-GC
Tenax®-GC
Tena^SX-GC
Tena*S§>-GC
Tenax@-GC
Filters
Tenax@-GC
Tenax®-GC
Tenax@-GC
Tenax®-GC
TenaxfSLcc
Tenax@-GC
Filters
Tenax®-GC
TenaxSX-GC
Tenax®-GC
Tenax®-GC
Tenak®-GC
Tenax@-GC
Filters
Tenax@-GC
Tenax@-GC
Tenax®-GC
Tenax@-GC
Tenax®-GC
Tenaxf®-GC
Filters
(liter)
415
414
540
390
380
449
455
408
514
463
336
450
384
438
490
448
Lost
461
432
456
454
519
437
470
420
470
540
496
426
435
Concentration
fag/m3)
HCBD
0.01
0.01
0.06
0.06
0.03
0.02
ND
0.04
0.06
0.02
0.03
0.01
0.01
ND
0.14
0.11
0.06
1.84
—
0.11
ND
6.42
5.13
5.75
9.32
5.57
1.24
ND
10.71
6.65
8.22
4.36
2.60
2.33
ND
124
-------
Table B-2. (concluded)
Concentration
Sampling
station
6
7
8
9
Sampling time
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
Type of
sample
Tenax@-GC
Tenax®-GC
Tenax^-GC
Tenax®-GC
Tenax®-GC
Tenax®-GC
Filters
Tenax®-GC
Tenax@-GC
Tenax®-GC
Tenax^GC
TenaxR-GC
Tenax^-GC
Filters
Tenax^-GC
Tenax®-GC
Tenax®-GC
Tenax@-GC
Tenax@-GC
Tenax®-GC
Filters
Tenax^GC
Tenax@-GC
Tenax®-GC
Tenax®-GC
Tenax®-GC
Tenax®-GC
Filters
Volume sampled
(liter)
408
455
464
442
425
468
450
472
563
469
426
470
450
488
554
476
436
468
455
492
562
483
466
468
(ug/mj)
HCBD
5.82
1.83
10.56
3.92
2.65
1.09
ND
0.24
0,17
0.21
0.46
0.46
1.27
ND
0.15
0.18
0.06
0.19
0.10
0.15
ND
0.04
0.02
0.02
0.14
0.05
0.11
ND
125
-------
Table B-3. HCBD CONCENTRATIONS IN AIR SAMPLES FROM DOW
CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
Sampling
station
1
2
3
4
5
6
7
8
Type of
samp le
Tenax®GC (front)
Tenax^GC (back)
Filter
Tenax^bc (front)
Tenax@GC (back)
Filter
Tenax%C (front)
Tenax®GC (back)
Filter
Tenax^C (front)
Tenax%C (back)
Filter
Tenax®GC (front)
Tenax^GC (back)
Filter
Tenax®GC (front)
Tenax^bc (back)
Tenax®GC (front)
Tenax®GC (back)
Filter
(R)
Tenax GC (front)
Tenax%C (back)
Filter
Vo lume
sampled
(liter)
4,336
427
4,166
3,870
3,713
4,314
962
3,963
Concentration
(ug/m3)
HCBD
< 0.01
< 0.01
ND
ND
ND
ND
0.1
0.1
ND
0.96
1.03
ND
0.4
0.3
ND
0.02
0.02
ND
0.3
ND
ND
0.03
0.03
ND
Note: ND = none detected.
126
-------
Table B-4. HCBD CONCENTRATIONS IN AIR SAMPLES FROM E. I. DU PONT
DE NEMOURS AND COMPANY, CORPUS CHRISTI, TEXAS
Sampling
station
1
2
3
4
5
Type of
Tena^-GC
Tena^GC
Filter
Tenax®-GC
Tenax@-GC
Filter
Tena^-GC
Tena^-GC
Filter
Tenaa®-GC
Tena^SX-GC
Filter
Tenax^-GC
Tenax@-GC
Filter
sample
, front
, back
, front
, back
, front
, back
, front
, back
, front
, back
Volume sampled
U)
4,371
4,371
4,371
3,621 .
3,621
3,621
4,070
4,070
4,070
4,007
4,007
4,007
3,965
3,965
3,965
Concentration (ug/nr)
HCBD
0.013
0.009
ND
0.002
0.001
ND
0.015
0.012
ND
0.017
0.012
ND
0.018
0.016
ND
127
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Table B-5. HCBD CONCENTRATIONS IN AIR SAMPLES FROM DIAMOND
SHAMROCK CORPORATION, DEER PARK. TEXAS
Sampling
station
1
2
3
4
5
6
7
8
Volume sampled
Type of sample
Tenax®.GC,
Tenax®-GC,
Filter
Tena*®-GC,
Tenaj^SX-GC,
Filter
Tenax®-GC,
Tenax@-GC,
Filter
Tenax@-GC,
Tenax@-GC,
Filter
Tenax^-GC,
Tenax®-GC,
Filter
Tenaj^-GC,
Tenaj@-GC,
Filter
Tena^-GC,
Tenax@-GC,
Filter
Tenax®-GC,
Tenax®-GC,
Filter
front
back
front
back
front
back
front
back
front
back
front
back
front
back
front
back
U)
580
580
580
598
598
598
485
485
485
540
540
540
542
542
542
608
608
608
559
559
559
555
555
555
Concentration (pg/m^)
HCBD
2.44
ND
ND
0.09
ND
ND
0.15
ND
ND
0.12
ND
ND
1.80
ND
ND
0.19
ND
ND
0.20
ND
ND
0.14
ND
ND
128
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Table B-6. HCBD CONCENTRATIONS IN AIR SAMPLES FROM
CIBA-GEIGY CORPORATION, ST.' GABRIEL, LOUISIANA
Sampling
station
1
2
3
4
5
6
7
8
Type of sample
Tenax@-GC
Filter
Tena^-GC
Filter
Tena^-GC
Filter
Tena:£)-GC
Filter
Tenax@-GC
Filter
Lost
Tenas®-GC
Filter
Tenax®-GC
Filter
Volume sampled
(A)
1,772
1,772
2,164
2,164
1,630
1,630
1,442
1,442
1,561
1,561
Lost
1,277
1,277
1,298
1,298
o
Concentration (HK/nr)
HCBD
0.025
ND
0.028
. ND
ND
ND
0.017
ND
0.019
ND
Lost
ND
ND
0.096
ND
129
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Table B-7. HCBD CONCENTRATIONS IN AIR,SAMPLES FROM PPG
INDUSTRIES, LAKE CHARLES, LOUISIANA
Sampling
station
1
2
3
4
5
6
7
8
9
10
Volume sample'd
Type of sample
Tena^-GC, front
Tenax3)-GC, back
Filter
Tena^Si-GC, front
Tena3®-GC, back
Filter
Tenax®-GC, front
Tena^-GC, back
Filter
Tenax®-GC, front
Tenax®-GC, back
Filter
Tena:x@-GC, front
Tenax®-GC, back
Filter
Tena3@-GC, front
Tenaj£B>-GC, back
Filter
Tena^-GC, front
Tenaj®-GC, back
Filter
Tenaj@-GC, front
Tena^-GC, back
Filter
Tena^®-GC, front
Tena3@-GC, back
Filter
Tenaj^-GC, front
Tenaj@-GC, back
Filter
U)
1,180
1,180
1,180
1,170
1,170
1,170
1,210
1, 210
1,210
1,170
1,170
1,170
950
950
950
1,250
1,250
1,250
1,180
1,180
1,180
1,190
1,190
1,190
1,250
1,250
1,250
1,130
1,130
1,130
Concentration (pg/m3)
HCBD
0.03
ND
ND
0.09
ND
ND
0.04
ND
ND
0.18
0.02
ND
ND
ND
ND
0.17
ND
ND
ND
ND
ND
ND
ND
ND
0.16
ND
ND
0.48
0.07
ND
130
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APPENDIX C
METHOD DEVELOPMENT FOR SAMPLING AND ANALYSIS
131
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LITERATURE SEARCH
A search of the literature to 1967 revealed that there was no specific
method for sampling HCBD in water. The method used most often for sampling
pollutants in water was the "grab technique." Detailed procedures of the
grab technique can be found in many of the standard method texts.iz!/ HCBD
in water samples is concentrated by extraction with appropriate organic sol-
vents. Ether and ri-hexane extraction of HCBD in water has been reported by
Lebedeva et al._' and Timofeeva and Shvartsman,—' respectively. In some cases,
HCBD is concentrated by passing the water sample through a column filled
with an appropriate trapping medium. The compound was then extracted by treat-
ing with acetone and hexane. This kind of concentration technique, with other
trapping media such as activated charcoal, and polystyrene copolymer, Amberlite
XAD-2 and XAD-4, has been successfully applied in trapping other chlorinated
p es t ic ides .Jilli/
Sampling of HCBD in air is generally carried out by trapping the com-
pounds either in an appropriate organic solvent or in an appropriate organic
resin. The sampling of HCBD by bubbling air through two impingers filled
with organic solvents such as benzene, ethanol, petroleum ether, cyclohexane,
and hexane has been reported-12-147 Columns of wood-charcoal cigarette-
filter in series as well as silica gel have been used to trap HCBD in
air.4-,13,14/ The HCBD is recovered by appropriate solvent extraction.
Organic resins such as Chromosorb A and Chromosorb 101 have been used to
trap HCBD and other chlorinated pesticides.15,16/ A nylon-chiffon cloth
(0.25 or 0.5 m^) impregnated with ethanediol and held vertically in a
wooden frame and exposed to the atmosphere for 5 days has been reported to
trap organochlorine as well as organophosphorus compoundS..IZ' Another organic
resin, Tenax®-GC, has been reported to be an efficient trapping medium for
aromatic hydrocarbon and organochlorine.—'
WATER SAMPLING AND RECOVERY STUDIES
As a result of the literature search, it was decided that for water
sampling, the "grab" method would be employed as the primary method. If the
concentration of HCBD was suspected to be low, an Amberlite XAD-4 column
would be used to concentrate the substance. Both sampling techniques were
evaluated prior to actual field sampling.
Hexane Extraction
Table C-l show the results of recovery studies for ri-hexane extrac-
tion of HCBD from water samples fortified with 1 to 30 Vig/liter. Each of
the water samples (1 liter) was extracted with three 10-ral aliquots n-
hexane, made up to the mark of a 100-ml volumetric flask, and analyzed
for HCBD by gas chromatography. The average recovery was over 80% for HCBD.
132
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Table C-l. RECOVERY STUDIES OF HCBD BY n-HEXANE EXTRACTION
Amount in water
Sample (u.g)
1 1
2 2
3 3
4 5
5 10
6 20
7 30
Blank None
Amount found in ri-hexane
(yig) % recovery
0.8 80
1.5 75
2.3 77
4.5 90
8.6 86
17.2 86
23 77
None
Elution from Amberlite XAD-4
Water samples fortified with 1 to 30 u.g/liter of HCBD were passed
through Amberlite XAD-4 columns containing 7 g of the trapping material.
Recovery of the two substances was accomplished by eluting, first with a
small amount of acetone, followed by a larger volume of ri-hexane. Table
C-2 shows that the average recovery of HCBD is close to 60% (first five
runs).* The relatively lower recovery observed for HCBD, i.e., close to
60%, indicated that a significant amount of HCBD was lost, probably due
to volatilization. Volatilization losses were eliminated when a closed sys-
tem was used. The recovery of HCBD from the solvent eluent of the Amberlite
XAD-4 improved to 93% (Run 6) with the closed system.
Table C-2. RECOVERY OF HCBD FROM WATER BY CONCENTRATION ON XAD-4
Run (u.g/4)
1 (30)
2 (30)
3 (1 )
4 (5 )
5 (30)
6 (30)^
a/ Closed
Flow rate
(ml/min)
2
2
2
2
8
10
elution system.
Recovery from
ri-hexane
elution (%)
57
56
60
45
67
93
Recovery from
Soxhlet
extraction
0
0
Trace
Trace
0
Trace
Recovery from
water
extraction
Trace
0
Trace
0
Trace
0
When actual environmental samples were analyzed, the amount of Amberlite
XAD-4 used in sampling (250 g) was so high that recovery by elution was
very time-consuming. Elution was replaced by overnight Soxhlet extraction.
133
-------
Evidence of significant volatilization loss of HCBD was further demon-
strated by the results of the following experiment. Five 250 ml water sam-
ples fortified with 5 u.g/liter HCBD were placed in five 250 ml separatory
funnels. Three of the funnels were left uncapped overnight while the re-
maining two funnels were capped. Each water sample was then extracted and
analyzed for HCBD. The results, shown in Table C-3, indicate that appreci-
able amounts of HCBD were lost due to volatilization from the open system.
Table C-3. LOSS OF HCBD DUE TO VAPORIZATION
Run Separatory funnel HCBD recovery (%)
1 Capped 72
2 Capped 74
3 Uncapped 10
4 Uncapped 11
5 Uncapped 17
AIR SAMPLING AND RECOVERY STUDIES
Chromosorb 101 and Tenax®-GC were tested for their trapping effi-
ciency utilizing a device shown in Figure C-l. This device was initially
designed to check the recovery of HCBD from water by vaporization at re-
duced pressure. The results also indicate efficiency for collecting HCBD
from water-saturated air.
One liter of water, fortified with 1 to 30 u.g/liter of HCBD, was placed
in a one-neck 24/40 flask with a thermometer pit so that the water tempera-
ture was monitored. The vapor was drawn through a Tenax®-GC or Chromosorb
101 (approximately 1 g) column with a vacuum pump or water aspirator. The
vapor flow rate through the trapping column was monitored with a calibrated
flowmeter and was maintained at 3 liters/min. After passing a known volume
of vapor through the column, the trapping material was first extracted with
_n-hexane in an ultrasonic bath, then by overnight Soxhlet extraction. The
remaining water was also extracted with ri-hexane. All the extracts were
analyzed for HCBD by electron capture gas chromatography.
Table C-4 shows the results of a set of seven experiments. Runs 1 and 2
were designed to compare the efficiency of Chromosorb 101 and Tenax®-GC,
while Runs 3 through 7 were repeated experiments to evaluate the efficiency
of Tenax®-GC at various HCBD concentrations. In general, under these experi-
mental conditions, the trapping and recovery of HCBD with Tenax®-GC is more
effective than with Chromosorb 101.
134
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To Meleod Gauge
U)
Ul
6 in.
Trapping Column
18/7
Ball Joint
Thermometer
Pit
Heating
Mantle
To Water Aspirator
or Mechanical Pump
Figure C-l. Apparatus for recovery of HCBD from water by vaporization at reduced pressure.
-------
Table C-4. RECOVERY OF HCBD FROM WATER-SATURATED AIR
Run
2
3
4
5
6
7
Column
Chromosorb
Tenax®-GC
Tenax®-GC
Tenax®-GC
Tenax®-GC
Tenax®-GC
Tenax®-GC
Amount of
HCBD in
sample
30
30
1
1
5
30
30
7° Recovery
from
ultrasonic
extraction
50
70
88
78
79
85
7» Recovery
from
Soxhlet
extraction
None de-
tected
Trace
0
Trace
Trace
1
1
7° Recovery
from
extraction
of water
12
4
Trace
Trace
1
2
1
SEDIMENT SAMPLING AND RECOVERY STUDIES
Sediment was taken from two Kansas City area creeks. The samples were
collected from the top 1 to 2 in. of sediment. The samples were fortified
with HCBD and recoveries were determined using standard procedures (for
sediments) described in the Manual of Analytical Methods prepared by the
Pesticides and Toxic Substances Effects Laboratory of the National Environ-
mental Research Center, USEPA. A Florisil™ column was used for sample
cleanup and 67,, ethyl ether in petroleum ether was used for the elution of
HCBD.
Two different procedures were used to prepare fortified sediment sam-
ples. In the first method, HCBD was added to known amounts of sediment prior
to evaporation of moisture from the sediment; in the second method HCBD
was added after the moisture in the sediment had evaporated almost to dryness.
Results of the recovery studies of these sediment samples (Runs 1 through
4) are shown in Table C-5.
Because of the low recovery of HCBD in Runs 1 through 4, direct Soxhlet
extraction (1:1 acetone/hexane) of the fortified sediment samples was tested.
Runs 6 and 7 in Table C-5 show the results of Soxhlet extraction. The re-
covery of HCBD improved significantly. Therefore, direct Soxhlet extraction
of the sediment was chosen as the standard method. However, if interferences
from other impurities were present, Florisil™ cleanup would be used. The
amount of HCBD determined in the sample analysis was reported on dry weight
basis.
136
-------
Table C-5. RECOVERY OF HCBD FROM SEDIMENTS
Run Sample weight (g) Amount HCBD added (y.g) % Recovery (HCBD)
50 5 22
2l/ 50 5 24
50 5 40
50 5 35
5 50 Control ND
6£/ 50 5 83
?£/ 50 5 79
a/ HCBD added before moisture in sample was almost evaporated to dryness.
t>/ HCBD added after moisture in sample was almost evaporated to dryness.
£/ Direct Soxhlet extract of sample.
137
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REFERENCES FOR APPENDIX C
1. Standard Methods; Water and Wastewater, 13th Edition, APHA (1971).
2. ASTM Standards. "Water—Atmospheric Analysis," Part 23 (1972).
3. Cox, G. V., Amer. Lab.. 6O):36 (1974).
4. Lebedeva, T. A., et al., Metody Anal, Pestits, pp. 57-59 (1970) in
Russian.
5. Timofeeva, 0. A., and G. A. Shvartsman, Novye Metody Tekhnol. Konstr,
Vinodel. Proizvod, pp. 117-119 (1972) in Russian.
6. Hyndshaw, A. Y.» J.A.W.W.A., 64j309 (1972).
7. Buelow, R. W., J. K. Carswell, and J. M. Symons, J.A.W.W.A,, 65:57
(1973). ~~
8. Ibid., 65:195 (1973).
9. Burnham, A. K., G. V. Calder, J. S. Fritz, G. A. Junk, H. J. Svec,
and R. Willis, Anal. Chem., 44:139 (1972).
10. Kennedy, D. C., Environ. Sci. Technol., 7(2):138 (1973).
11. Burnham, A, K., G. V. Calder, J. S. Fritz, G. A. Junk, H. J. Svec, and
R. Vick, J.A.W.W.A., 65j722 (1973).
12. Asriev, E. A., Metody Anal. Pestits, pp. 8-11 (1970) in Russian.
13, Dranovskaya, L. M., and A. G. Gul'ko, Ostsillogr. Peremen. Polyarografiya,
pp. 163-167 (1971).
14. Gul'ko, A. G., L. M. Dranovskaya, and V. F. Chernokan, Aktual. Vop.
Gig. Epidemiol., pp. 71-73 (1972).
15. Mann, J. B., H. F. Enos, J. Gonzalez., and J. F. Thompson, Environ. Sci.
Technol., 8(6):584 (1974).
16. Aue, W. A., and P. M. Teli, J. Chromatogr., 62(l):15-27 (1971).
17. Tessari, J, D., and D. L. Spencer, J. Assoc. Offie. Anal. Chem.,
54(6):1376-1382 (1971).
18. Enagonio, D. P., W. E. May, and S. P. Cram, Paper presented in the
25th Pittsburgh Conference on Analytical Chemistry and Applied
Spectroscopy (1974),
138
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 560/6-76-015
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Sampling and Analysis of Selected Toxic Substances
Task IB - Hexachlorobutadiene
5. REPORT DATE
June 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R. T. Li, J. E. Going, and J. L. Spigarelli
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. July 1974-September 197
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A sampling and analysis program was conducted to determine the extent of environ-
mental contamination by hexachlorobutadiene around nine chemical manufacturers. The
plants selected represented six major industries: perchloroethylene, trichloroethylem ,
carbon tetrachloride, chlorine, triazine herbicides, and pentachloronitrobenzene. Air
water, soil, and sediment samples were collected on and around the plants.
In general, higher levels of HCBD in air were associated with production of per-
chloroethylene and trichloroethylene while the level in the vicinity of chlorine and
triazine herbicide plants was very low. No HCBD was found in the air at the pent a- .
chloronitrobenzene plant. The highest level of HCBD in air and soil was at a plant
using on-site landfill and open pit storage waste-disposal methods. High levels were
detected in loading and transfer areas at plants using off-site disposal methods.
The highest level of HCBD found in the air on plant property was 463
Levels of HCBD in open wastewciter treatment streams were as high as 244 and 75 p,g/
liter at two plants. Soil levels of HCBD reached 980 and 29 n,g/g at two plants.
_ (continued) _
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Monitoring - Air, Water, Soil, Sediment
Hexachlorobutadiene
Organic. Chemistrj
3. DISTRIBUTION STATEMENT
Releast Unlimited
19. SECURITY CLASS {This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
139
-------
o
The maximum air concentration of HCBD off plant property was 22 |o,g/m
A level of 10 (ig/rn^ was detected at the boundary of another plant. The high-
est levels in water off plant property were 23 and 10 |j,g/liter. A level of
0.11 |ig/g HCBD in soil was found off plant property and levels of 0.15 and
0.34 |-ig/g were found at the boundary of two other plants.
140
------- |