EPA-560/6-76-001
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task IA - Hexachlorobenzene
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
June 1976
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EPA-560/6-76-001
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
Task IA - Hexachlorobenzene
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 purposes of clarity only and does not constitute endorse-
ment or recommendation for use.
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CONTENTS
Page
Summary ............................. 1
Section
I Introduction 3
II Experimental Procedures ........ 5
Sampling Procedures . . . . 5
Analysis Procedures • 5
III Selection of Sampling Sites 9
Selection Criteria .. 9
Recommended Sampling Sites • . . . . 11
IV Presampling Surveys and Field Sampling ........ 15
Presampling Surveys ••• 15
Field Sampling 15
V Discussion of Results 20
Vulcan Materials Company, Wichita, Kansas 20
Linden Chlorine Plant, Linden, New Jersey 33
Stauffer Chemical Company, Louisville, Kentucky ... 36
Dow Chemical Company, Pittsburg, California ..... 43
E. I. du Pont de Nemours and Company, Inc.,
Corpus Christi, Texas 45
Diamond Shamrock Corporation, Deer Park, Texas ... 50
Ciba-Geigy Corporation, St. Gabriel, Louisiana ... 53
Olin Corporation, Mclntosh, Alabama . 57
PPG Industries, Inc., Lake Charles, Louisiana .... 61
11
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CONTENTS (concluded)
Section Page
VI Sewage Treatment Facilities 69
Sampling 69
Experimental Procedures ... 69
Results 70
VII Summary and Conclusions for Program Task IA 71
Summary 71
Conclusions ........ 74
References 76
Appendix A - Presampling Survey and Field Sampling ....... 77
Appendix B - Analytical Data 130
Appendix C - Method Development for Sampling and Analysis .... 144
111
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FIGURES
No.
1 Air Sampling Train ••• 6
2 Geographic Location of Recommended Sampling Sites ... 13
3 Presampling Survey and Field Sampling Schedule .... 16
4 Average Concentrations of HCB in Air Per 20-hr Period
at 18 Sampling Stations at Vulcan Materials Company,
Wichita, Kansas 22
5 HCB Concentration Per 20-hr Period at Sampling Stations
Within the Plant Perimeter (Vulcan) 23
6 HCB Concentration Per 20-hr Period, Downwind Stations
(Vulcan) 24
7 HCB Concentration Per 20-hr Period, Upwind Stations
(Vulcan) 25
8 Average Vapor and Particulate Concentrations of HCB in
Air Per 20-hr Period at 18 Sampling Stations .... 26
9 Variation in Vapor and Particulate HCB Levels at
Station 4 (Vulcan) 28
10 Variation in Vapor and Particulate HCB Levels at
Station 18 (Vulcan) 29
11 Average Concentrations of HCB in Air at Nine Sampling
Stations at Stauffer Chemical Company, Louisville,
Kentucky 37
12 Average Concentration of HCB in Vapor and Particulate
at Nine Sampling Stations (Stauffer) 39
IV
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FIGURES (continued)
No. Page
13 HCB Concentration Per 24-hr Period at Sampling
Stations Around the Plant (Stauffer) 40
14 Average Concentrations of HCB in Air at Eight Sampling
Stations at Dow Chemical Company, Pittsburg,
California 44
15 Sampling Stations at E. I. du Pont de Nemours and
Company, Corpus Christi, Texas 48
16 Stations at Diamond Shamrock Corporation, Deer Park,
Texas 51
17 Average Concentrations of HCB in Air at Eight Sampling
Stations at Ciba-Geigy Corporation, St. Gabriel,
Louisiana • •• 55
18 Average Concentrations of HCB in Air at Eight Sampling
Stations at Olin Corporation, Mclntosh, Alabama ... 58
19 Average Concentrations of HCB in Air at 10 Sampling
Stations at PPG Industries, Lake Charles, Louisiana . 64
20 Average Concentrations of HCB in Vapor and Particulate
at 10 Sampling Stations Around the Plant (PPG
Industries) 65
21 Summary of HCB Concentrations in Air 73
A-l Presampling Survey and Field Sampling Schedule .... 79
A-2 Sampling Locations at Vulcan Materials Company -
Wichita Plant 81
A-3 Vulcan Materials Company - Wichita Plant, and Surround-
ing Areas 84
A-4 Sampling Locations at Stauffer Chemical Company -
Louisville, Kentucky 90
A-5 Sample Locations at Dow Chemical Company, Pittsburg,
California 97
v
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FIGURES (concluded)
No. Page
A-6 Sample Locations at E. I. du Pont de Nemours and
Company, Inc., Corpus Christi, Texas . 102
A-7 Sampling Locations at Diamond Shamrock Corporation,
Deer Park, Texas 109
A-8 Sample Locations at Ciba-Geigy Corporation, St. Gabriel,
Louisiana .......... 113
A-9 Sampling Locations at Olin Corporation, Mclntosh,
Alabama 119
A-10 Sampling Locations at PPG Industries, Lake Charles,
Louisiana 126
C-l Apparatus for Recovery of HCB from Water by Vaporiza-
tion at Reduced Pressure ...... 148
VI
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TABLES
No.
1 Estimated Quantities of RGB Present in Industrial
Wastes, By-Products, and Products in 1972 10
2 Production Capacity, Process Technology and Waste Dis-
posal at Recommended Sites ............. 14
3 Field Sampling Summary • • 18
4 Summary of Air Sampling Parameters 19
5 Comparison of HCB Levels at 4 and 11 ft for Five Time
Periods 30
6 HCB Concentrations in Soil and Sediment from Vulcan
Materials Company, Wichita, Kansas 32
7 HCB Concentrations in Water from Vulcan Materials
Company, Wichita, . Kansas 34
8 HCB Concentrations in Water and Solids from Linden
Chlorine Company, Linden, New Jersey 35
9 HCB Concentrations in Soil and Sediment from Stauffer
Chemical Company, Louisville, Kentucky 42
10 HCB Concentration in Water from Stauffer Chemical
Company, Louisville, Kentucky 42
11 HCB Concentrations in Soil from Dow Chemical Company,
Pittsburg, California 46
12 HCB Concentrations in Soil and Sediment from E. I. du
Pont de Nemours and Company, Corpus Christi, Texas . 49
VI1
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TABLES (continued)
No.
13 HCB Concentrations in Water from E. I. du Pont de
Nemours and Company, Corpus Christi, Texas ..... 49
14 HCB Concentrations in Soil from Diamond Shamrock
Corporation, Deer Park, Texas 52
15 HCB Concentrations in Water from Diamond Shamrock
Corporation, Deer Park, Texas 54
16 HCB Concentrations in Soil from Ciba-Geigy Corporation,
St. Gabriel, Louisiana 56
17 HCB Concentrations in Soil and Sediment, Olin Corpora-
tion, Mclntosh, Alabama ..... 60
18 HCB Concentration in Water from Olin Corporation,
Mclntosh, Alabama ......... 62
19 HCB Concentrations in Soil and Sediment from PPG
Industries, Lake Charles, Louisiana .... 66
20 HCB Concentrations.in Water from PPG Industries,
Lake Charles, Louisiana 68
21 Data Summary for Program Task No. 1 . . 72
A-l Air Sampling Data at Vulcan Materials Company, Wichita,
Kansas ......... • 82
A-2 Plant Activities During Sampling at Vulcan Materials
Company, Wichita, Kansas .............. 85
A-3 Weather Conditions During Sampling at Vulcan Materials
Company, Wichita, Kansas • 86
A-4 Air Sampling Data at Stauffer Chemical Company,
Louisville, Kentucky 91
A-5 Plant Activities During Sampling at Stauffer Chemical
Company, Louisville, Kentucky 93
A-6 Weather Conditions During Sampling at Stauffer Chemical
Company, Louisville, Kentucky 94
viii
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TABLES (continued)
No.
A-7 Air Sampling Data at Dow Chemical Company, Pittsburg,
California 98
A-8 Weather Conditions and Plant Activities During Sampling
at Dow Chemical Company, Pittsburg, California . • . 99
A-9 Air Sampling Data at E. I. du Pont de Nemours and
Company, Inc., Corpus Christi, Texas ... 103
A-10 Plant Activities During Sampling at E. I. du Pont de
Nemours and Company, Inc., Corpus Christi, Texas . . 105
A-ll Weather Conditions During Sampling at E. I. du Pont de
Nemours and Company, Inc., Corpus Christi, Texas . . 106
A-12 Air Sampling Data at Diamond Shamrock Corporation,
Deer Park, Texas 110
A-13 Weather Conditions During Sampling at Diamond Shamrock
Corporation, Deer Park, Texas Ill
A-14 Air Sampling at Ciba-Geigy Corporation, St. Gabriel,
Louisiana 114
A-15 Weather Conditions During Sampling at Ciba-Geigy,
St. Gabriel, Louisiana 116
A-16 Air Sampling Data at Olin Corporation, Mclntosh,
Alabama 120
A-17 Weather Conditions During Sampling at Olin Corporation,
Mclntosh, Alabama 122
A-18 Air Sampling Data at PPG Industries, Lake Charles,
Louisiana 127
A-19 Weather Conditions During Sampling at PPG Industries,
Lake Charles, Louisiana 129
B-l HCB Concentrations in Air Samples from Vulcan Materials
Company, Wichita, Kansas .... 131
B-2 HCB Concentrations in Air Samples from Stauffer
Chemical Company, Louisville, Kentucky 136
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TABLES (concluded)
No.
B-3 HCB Concentrations at Air Samples from Dow Chemical
Company, Pittsburg, California ... 138
B-4 HCB Concentrations in Air Samples from E. I. du Pont
de Nemours and Company, Corpus Christi, Texas .... 139
B-5 HCB Concentrations in Air Samples from Diamond Shamrock
Corporation, Deer Park, Texas • 140
B-6 HCB Concentrations in Air Samples from Ciba-Geigy
Corporation, St. Gabriel, Louisiana ... 141
B-7 HCB Concentrations in Air Samples from Olin Corpora-
tion, Mclntosh, Alabama 142
B-8 HCB Concentrations in Air Samples from PPG Industries,
Lake Charles, Louisiana 143
C-l Recovery Studies of HCB by ri-Hexane Extraction .... 146
C-2 Recovery of HCB from Water by Concentration on XAD-4 . 146
C-3 Loss of HCB Due to Vaporization 147
C-4 Recovery of HCB from Water-Saturated Air 149
C-5 Recovery of HCB from Sediments . 150
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SUMMARY
The purpose of this program is to provide sampling and analysis
capabilities to EPA's Office of Toxic Substances, so that the levels
of suspected toxic substances in air, water, soil, and sediment at des-
ignated locations throughout the United States may be determined. Four
tasks have been assigned on this program. The first task included the
sampling and analysis for hexachlorobenzene (HCB).
Methods for sampling and analyzing HCB 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.
Of the six industries sampled, higher concentrations of HCB were
associated with the production of perchloroethylene, trichloroethylene,
and carbon tetrachloride. In the one plant that produced only carbon
tetrachloride, HCB levels were quite low. HCB concentrations detected
in samples from the pentachloronitrobenzene plant were relatively high,
i.e., low micrograms per cubic meter range in air and generally over
100 )j,g/g along in-plant roads. The levels of HCB 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 HCB
was detected in air and soil at the plant using on-site landfill and open
pit storage. High HCB levels were detected in loading and transfer areas
at plants using off-site disposal methods. Lower levels of HCB were found
at plants using on-site incineration but downwind air concentrations were
elevated above background at these plants. The production of perchloro-
and trichloroethylene by low temperature oxychlorination and the incinera-
tion of liquid bottom wastes resulted in a high HCB level (jig/m ) in the
air but relatively low levels in the effluent water.
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The highest level of HCB found in the air on plant property was 24
The HGB level in an open waste treatment pond was 306 |J/g/liter.
The level of HCB in soil within the plant area was over 1,000 |jbg/g at
three plants.
The maximum concentration of HCB in air sampled off plant property
was 0.36 (ig/nP. A level of 3 ng/m^ was detected at the boundary of another
plant. Soil taken from a cornfield adjacent to one plant contained 1.1
M-g/g, and over 3,000 |J.g/g were detected along a boundary road of another.
HCB levels in water sampled beyond the plant property exceeded 1 ng/liter
at two plants.
Samples were collected from two sewage treatment plants; negligible
quantities of HCB were detected.
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SECTION I
INTRODUCTION
Environmental contamination of hexachlorobenzene (HCB) has been
reported internationally and nationally. Detection of HCB in human adi-
pose tissue has been reported in Australia, Germany, and Japan.——' In
the United States, HCB has been detected in cattle raised in Louisiana,
and sheep raised in New Mexico, Colorado, and California.— In addition,
concentrations of HCB at 16 |j,g/m have been detected in air samples col-
lected by the Louisiana State Air Control Commission.—
On July 5, 1973, Midwest Research Institute (MRl) initiated a study
to estimate the quantities and identify sources of HCB in the environ-
ment. The origin of HCB in the environment in the United States was iden-
tified as the waste materials or by-products from the production of per-
chloroethylene, trichloroethylene, carbon tetrachloride, chlorine, penta-
chloronitrobenzene and the herbicide Dacthal®. Specific industrial plants
from the above industries were recommended to EPA as potential sampling
sites.
On June 27, 1974, MRI project (3953-C) entitled "Sampling and Anal-
ysis of Selected Toxic Substances" was initiated. The objective of this
program was 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 (Task IA) and HCBD (Task IB). Tasks II and III of this program are
the sampling and analysis for ethylene dibromide, and evaluation of vinyl
chloride levels in outdoor and indoor air due to the presence of PVC prod-
ucts, respectively. The ethylene dibromide study has been completed and
reported to the Office of Toxic Substances in September 1975 under the
title of: "Sampling and Analysis of Selected Toxic Substances: Task II -
Ethylene Dibromide," EPA Report No. 560/6-75-001.
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This report describes the Task IA of the program, i.e., the sam-
pling and analysis for HCB as follows: experimental procedures; screen-
ing and selection of sampling sites; presampling surveys and field sam-
pling; discussion of results, sewage treatment facilities; and summary and
conclusions. Site surveys and field sampling data for individual sites,
analytical data, and methods development 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 HCB 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 |j,m 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
in wide-mouth glass bottles with Teflon®-lined caps and kept in an ice
chest until ready for analysis.
ANALYSIS PROCEDURES
Sample Preparation
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 bath. During the extraction, ice was added
to the ultrasonic water bath to minimize evaporative loss of HCB. 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
\
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 100-g sample was then ex-
tracted with 100 ml of n-hexane in a soxhlet apparatus overnight. The
hexane extracts were transferred to 100-ml volume flasks and diluted to
volume. A similar sample preparation procedure was used on the sediment
samples except 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 col-
lected 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-
coport® was used as the primary column for analysis. A 6 ft x 1/4 in.
glass column packed with 37o XE-60 on 80/100 mesh chromosorb WHP was
used to verify and differentiate HCB from a-BHC. The chromatographic
operating conditions were: injector temperature, 200°C; column tem-
perature, 150°C; detector temperature, 180°C; carrier flow rate, 100
ml/min nitrogen; purge flow rate, 90 ml/min nitrogen; and detector
voltage, 10 V DC.
The instrumental limit of detection for HCB at the above men-
tioned conditions was 2 pg (10 ^ g). Therefore, as an example, for
any amount of air sampled, the quantity of HCB in the sample required
for detection was greater than 10 ng (based on 10 |j,l injections of a
50-ml solution).
Calibration
A 10 ng/ml composite standard solution of HCB 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. Con-
centration ranges chosen for the calibration curve were from 10 to 60
pg, and linearity was observed.
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A new calibration curve was obtained daily for the sample analy-
sis. During the day, a known amount of the standard was injected peri-
odically 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 HCB by the sampling and analysis of samples from selected industrial
plants. Therefore, it was important that the selected sampling locations
be representative of the total industrial locations that are sources of
HCB.
SELECTION CRITERIA
Selection criteria were chosen to achieve representative sampling
of sites that are most likely to have detectable quantities of HCB
present.
The criteria used for the selection of industrial plants for sam-
pling are:
* Estimated quantity of HCB in industrial wastes, products, and
by-products.
* Methods of production.
* Methods of waste disposal.
* Geographic location of the industrial plants.
Estimated Quantity of HCB in Industrial Wastes, Products, and By-Products
In 1974, the only active domestic producer of HCB for sale was
Stauffer Chemical Company. However, industry sources report that HCB
is contained in the "heavy ends" waste materials (residues) in the
production of many chlorinated organic compounds, as well as in the
electrolytic processes (either diaphragm or mercury cells) for chlo-
rine gas when graphite anodes are used. An estimation of the amount
of HCB produced in industrial wastes, by-products, and products is
given in Table 1. As indicated in Table 1, about 90% of the HCB con-
tamination in the environment was estimated to be from the perchloro-
ethylene, trichloroethylene, and carbon tetrachloride industries.—
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Table 1. ESTIMATED QUANTITIES OF RGB PRESENT IN INDUSTRIAL
WASTES, BY-PRODUCTS, AND PRODUCTS IN 1972I/
U.S.
Production
in 1972
Product (tons) HCB (tons)
Perchloroethylene 367,400 1,313
Trichloroethylene 213,500 171
Carbon tetrachloride 498,500 150
Chlorine 9,538,000 143
Dacthal® . 1,000 45
Vinyl chloride 2,545,000 13
Atrazine, propazine, simazine 56,000 3.5
Pentachloronitrobenzene 1,500 2.3
Mirex 500 0.8
10
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Method of Production
The production method affects the quantity of HCB formed as a by-
product. Therefore, the potential environmental contamination is depen-
dent upon the production method. For example, carbon tetrachloride,
perchloroethylene, 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 distilla-
tion, HCB is discharged as a by-product in the "heavy ends" wastes.
However, if the production of carbon tetrachloride involves the reac-
tion 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 se-
lection of plants for sampling. The selected plants used a variety of
disposal methods including landfill, deep well, sealed lagoons, on-site
incineration, and shipment of wastes to other disposal firms.
Geographic Location of the Industrial Plant
Industrial plants were selected from across the country to deter-
mine whether the potential for environmental contamination posed a na-
tional 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
Tr i chloroethy1ene
PPG Industry, Inc. Lake Charles, Louisiana
Diamond Shamrock Corporation Deer Park, Texas
11
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Carbon tetrachloride
E. I. du Pont de Nemours and Company, Inc. Corpus Christ!, 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 Fig-
ure 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 mo-
lecular weight chlorinated hydrocarbons do not generally produce a single
product. All five plants that produce trichloroethylene also produce per-
chloroethylene. Fortunately, not all the perchloroethylene production
plants produce trichloroethylene. However, these plants also produce car-
bon tetrachloride. The annual production capacity (1972), process tech-
nology, and latest waste disposal methods for each of the sampling sites
are presented in Table 2.
The Dacthal® production facility (Diamond Shamrock Corporation) in
Greens Bayou, Texas, was not selected for sampling because the waste hand-.
ling and product contamination were substantially changed from pre-1972
procedures.
Vinyl chloride and mirex production facilities were omitted from
this survey.
12
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SOUTH DAKOTA
• Perch loroethylene
O Trichloroethylene
A Carbon Tetrachloride
^ Chlorine
• Pentachloronitrobenzene
D Atrazine
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
Producers
Perchloroethvlene
Stauffer Chemical Company
Vulcan Materials Company
Trichloroethylene
PPG Industry Company
EPA
Production sites region
Louisville, Kentucky IV
Wichita, Kansas VII
Lake Charles, Louisiana VI
Annual
production
capacity
QO-3 tons)
35
25
140
Waste disposal
HCB recovered for sale,
remainder recycled to
chlorinator
Earth-covered groundfill
Incineration, landfill
a/
Process technoloev~
Chlorination with low molecular
weight hydrocarbons, e.g
ane, propane
Ethylene and chlorine as
. , eth-
raw tna-
Diamond Shamrock Corporation Deer Park, Texas
VI
terials, under catalytic reaction
at 250 to 300°C
60 Ship to Rollins .Inter-
national for incineration
Carbon tetrachloride
E. I. du Pont de Nemours and
Company, Inc.
Dow Chemical Company
Chlorine
Linden Chlorine Company
Kaiser Aluminum and Chemical
Corporation
Triazine herbicides
Ciba-Geigy Corporation
Corpus Christi, Texas VI
Pittsburg, California IX
Linden, New Jersey II
Gramercy, Louisiana VI
St. Gabriel, Louisiana VI
250
23
66
58
> 75
Landfill, ship to outside
firm for disposal
Incineration
Discharge to holding pond
Landfill
Chlorination with methane at
elevated temperature
Mercury cell; graphite electrode
Diaphragm cell; graphite electrode
Still bottoms incinerated Reaction of cyanuric chloride
by an outside processor to with appropriate amino hydrocar-
extinction bons at elevated temperature
Pentach1oroni trobenzene
Olin Corporation
Mclntosh, Alabama
IV
1.5 Stored in "blocks" covered Nitration of pentachlorobenzene
with plastic sheet or chlorination of various chloro-
nitrobenzenes in the presence of
catalyst
j/ 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.
Each presampling survey was arranged through telephone contact with the
appropriate plant officials whose names were provided by the EPA proj-
ect officer. Figure 3 shows the complete schedule for presampling sur-
veys and field sampling.
PRESAMPLING SURVEYS
During the presampling site survey, a plant map was obtained. In-
formation regarding the possible sources of HCB contamination, produc-
tion technology and waste disposal techniques were obtained. In addi-
tion, the production and waste disposal sites, as well as the trans-
portation routes were delineated. Accessible electrical outlets inside
the plant were also located for possible use in air sampling. Meteoro-
logical conditions, such as wind direction and rainfall were investi-
gated. Tentative sampling dates were agreed upon, subject to final con-
firmation 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 upstream and downstream of waste ef-
fluent. Storm runoff was collected when appropriate. Water samples from
equilization ponds or solar ponds were collected to determine if the
ponds were sources of air contamination through liquid vapor equilibrium
of HCB.
15
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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 —
A
A
—
A
A
A
A '
A
-
-
-
-
-
A
A
-
A Presampling Visit
•• Field Sampling
Figure 3. Presampling survey and field sampling schedule
-------
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 natu-
ral 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, rubber hoses, electrical prongs and adapters, and sampling bot-
tles. To avoid possible breakage and contamination, the air sampling
train components, 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 elec-
trical 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 HCB particulate was detected are indicated.
Detailed descriptions of the field sampling and presampling surveys con-
ducted at each plant are presented in Appendix A.
17
-------
Table 3. FIELD SAMPLING SUMMARY
Site
Air samples^'
(stations x train components x
sampling period)
Total samples
(number/type)
Vulcan
Linden
Stauffer
Dow
Du Pont
Diamond Shamrock
Ciba-Geigy
01 in
PPG
18 x 2 x 5
No air samples
9x2x6
8x2x1
8x2x1
8x3x1
8x2x1
8x3x1
10 x 3 x 1
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.
18
-------
Table 4. SUMMARY OF AIR SAMPLING PARAMETERS
Plant
Vulcan^
Stauffer^
Dow
Du Pont
Ciba-Geigy-/
Diamond
Shamrock
OlinS/
PPG
Average
sampling
vol. (j£)
(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
(jg/min)
0.5
0.5
3.5
3.5
3.5
3.5
0.4
3.5
0.4
Particulate
(HCB)
Yes
Yes
Limited
No
No
No
No
No
Yes
a] Five 4-hr periods.
b_/ Six 4-hr periods (2 hr on, 2 hr off).
£/ Three 8-hr periods (each 2 to 3 hr sampling),
19
-------
SECTION V
DISCUSSION OF RESULTS
Air, soil, water, and sediment samples were collected from nine
recommended industrial plants whose products included perchloroethyl-
ene, trichloroethylene, carbon tetrachloride, triazine herbicides,
pentachloronitrobenzene and chlorine. In general, HCB concentrations
varied from a maximum, near the production and waste disposal areas,
to a minimum, in the samples taken upwind of a recognizable source.
However, in a few instances, HCB contamination was observed over the
general plant area and a specific emission source was difficult to
determine. HCB was detected as both a vapor and a particulate; the
predominate form was dependent upon the production and waste dispo-
sal methods of each plant. 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 com-
pounds of interest produced at this plant include carbon tetrachlo-
ride 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 three samplers which were
positioned upwind, nine samplers immediately downwind of the general
production and waste storage areas, and six sampling devices positioned
further downwind beyond the northern plant boundary. The samplers be-
yond the northern plant boundary were positioned at three locations
with two samplers per location at 4 and 11 ft above ground, respec-
tively. The upwind and farthest downwind samplers were operated con-
tinuously for a 4-hr period while those closer to the general produc-
tion and waste storage area were operated only for the first hour of
each 4-hr period. After each 4-hr period, the filter and the Tenax®-GC
column in each sampler were replaced by fresh components. The sampling
20
-------
strategy was designed so that results of the analysis would elucidate:
(a) the major sources and level of HCB emission, (b) the diurnal and
operation-related effects of HCB emission, (c) the physical form, i.e.,
particulate or vapor of HCB in the plant air, and (d) the variation of
HCB concentrations with respect to sampler distance above ground.
Sources and Levels of HCB Emission - 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 HCB during the 20-hr sampling period at the 18
sampling stations. It is obvious that major sources of HCB in the air
are the production and waste storage ("Hex Pit") areas. In addition,
other sources of HCB are indicated by the upwind air concentrations.
The HCB levels in samples immediately downwind of the production
and storage areas ranged from 0.1 to 24 |J,g/m3. The levels of HCB in the
upwind samples and samples taken downwind beyond the northern plant bound-
ary were similar and in the range of 0,1 to 2.1
Variation of HCB Emission with Time - The variation of HCB levels over
the '20-hr sampling period is shown in Figures 5 through 7.
Figure 5 shows that the HCB levels in air samples immediately
downwind of the production and waste storage area did not increase
following the dumping of the "hex residue" at the "Perc Plant" or the
"Hex Pit." The increase in HCB at Stations 4 and 6 occurred either
prior to or significantly after dumping.
The variation of HCB levels in samples beyond the northern boundary
of the plant is shown in Figure 6. Each point is the average of two sam-
plers positioned at different heights (4 and 11 ft).
Figure 7 shows that during the entire sampling period, HCB lev-
els were relatively high in upwind Stations 16 through 18; in fact,
the 20-hr average values were greater than some of the downwind sta-
tions. Among the three stations, higher concentrations were detected
at Stations 17 and 18 which were closer to the landfill than Station 16.
Physical Form of HCB - The average vapor and particulate concentrations
of HCB over the 20-hr sampling period at each station are shown in Fig-
ure 8. The physical state of the HCB detected was dependent upon the sam-
pling location. Particulate HCB was not detected in samples taken near
the solar pond (Stations 1 through 9) and at the northeast corner (Sta-
tions 14 and 15), northwest corner (Stations 10 and 11) and southwest
corner (Station 16) of the sampling area. At all other sampling stations,
particulate HCB was approximately equal to or much greater than (Sta-
tions 4 through 6) the HCB detected as a vapor.
21
-------
14 (O.U)
' 15 (0.10)
(0.36)8'
(I.I8>'7.
(5.72)6-
(1.56)5.
(5.52)4.
Meteorologica
rl v. Station
\
I \
T
QHex Pit I
NORTH
12 (0.88)
'13 (1.16)
(0.55) 3.
(2.96)2.
(0.34) 1«
§ Perc Plant
10 (0.20)
' 11 (0.44)
LEGEND
Numbers 1 to 18 Air Sampling Sites
Numbers in Parentheses Represent
Average Concentration of HCB
Per 20 Hour Period
Scale 1/2" = 150'
(0.82) 18«
(1.08) 17«
(0.38)16.
South Ridge Road
Figure 4. Average concentrations (|Jig/m ) of HCB in air per 20-hr period at 18
stations at Vulcan Materials Company, Wichita, Kansas
sampling
-------
to
u>
Perc Plant
Dumped Hex
Perc Plant
and Hex Pit
Dumped Hex
O Station
A Station
D Station
• Station
© Station
Station 6
A Station
A Station
O Station
Figure 5. HCB concentration per 20-hr period at sampling stations within
the plant perimeter (Vulcan)
-------
1.5
1.4
1.3
1.2
1.1
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
Figure 6. HCB concentration per 20-hr period, downwind stations (Vulcan)
-------
N)
Ul
2.0
1.5
try
i
1.0
2005
0010
Perc Plant
Dumped Hex
Hex Pit
Dumped Hex
0025
0345
0355
0744
I
0752
1154
Perc Plant
and Hex Pit
Dumped Hex
• Station 16
A Station 17
O Station 18
1200
1430
Figure 7. HCB concentration per 20-hr period, upwind stations (Vulcan)
-------
CO
Tenax
Filter
J I I. I
1 2 3
56 7 8 9 10
STATIONS
11 12 13 14 15 16 17 18
Figure 8. Average vapor and particulate concentrations of HCB in air
per 20-hr period at 18 sampling stations (Vulcan)
-------
The variation of HCB levels over the 20-hr period in samples taken
near the "Hex Pit" was due almost entirely to variation in particulate
levels. Figure 9 shows the HCB vapor concentration at Station 4 was rel-
atively constant, near the 1 |j,g/m level, whereas the particulate level
fluctuated from 0 to 10 |j,g/m . Particulate HCB was not observed during
the 0110 to 0220 and 0450 to 0550 sampling periods when vehicular ac-
tivity was probably low; particulate levels were 5 )j,g/m^ or higher dur-
ing the periods of 1945 to 2045, 0902 to 1010, and 1307 to 1425. Figure
10 shows a similar, but less pronounced pattern for upwind Station 18;
the HCB vapor concentration ranged from approximately 0.3 to 0.7 (ig/irP
while the particulate HCB varied from 0 to 1.2 (j,g/m .
All samples showed a relatively constant HCB vapor concentration
during the entire sampling and fluctuating HCB particulate concentra-
tion (when detected) that probably reflects the activity in the immedi-
ate area of the sampling stations. A slight increase in HCB vapor con-
centration during the'warmer sampling periods was observed at some
sampling stations (Figure 10). This increase was not apparent until
the particulate and vapor concentrations were considered separately.
HCB Concentration Versus Sampler Height - A comparison of HCB concen-
trations at 4 and 11 ft for five time periods is shown in Table 5. The
results indicate that the differences in levels at the two heights were
not significant.
Precision of Sampling and Analysis - If it is assumed that the HCB lev-
els were the same at the two sampler heights (4 and 11 ft), the results
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 duplicates and a
pooled relative standard deviation (PRSD)* determined. The PRSD calcu-
lated from these data indicates the overall precision of the air sam-
pling and analysis methods including sample collection, storage, recov-
ery, and analysis. The PRSD is 17%. The PRSD is based on 13 duplicates.
Two duplicate measurements were not included in the calculations: one
pair was near the detection limit (< 0.1 pog/m^) and the other station
had a high particulate level and was considered an outlier. The quanti-
ties of vaporous HCB detected in this station pair (Stations 12 and 13)
were approximately equal.
* The PRSD was calculated as follows:
S = V 2 (X-!02/0.889
RSD = S/X x 100
PRSD = V S RSDi2/n
27
-------
to
c»
10
9
8
7
6
D);
4
3
2
0
HCB Station 4 (Downwind Hex Pit)
Filter
Tenax-GC
I
1945-2045
0110-0220 0450-0550
SAMPLING TIME
0902-1010
1307-1425
Figure 9. Variation in vapor and particulate HCB levels at Station 4 (Vulcan)
-------
1.2
1.0
i
=L
0.5
O1 u
HCB Station 18
-------
Table 5. COMPARISON OF HCB
LEVELS AT 4 AND 11 FT FOR
FIVE TIME PERIODS
HCB,
Station pairs 4 ft 11 ft
10 and 11 0.3 0.3
0.2 0.2
0.2 0.2
0.1 0.1
0.2 0.2
12 and 13 1.0 1.0
0.4 0.5
1.2 1.3
1.4 1.3
0.4 1.7
14 and 15 0.1 0.03
0.1 0.1
0.1 0.1
0.1 0.1
0.3 0.2
30
-------
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. These sites
were selected to determine HCB soil levels associated with production,
waste disposal and transportation of wastes for disposal. Samples were
also taken upwind and in adjacent agricultural fields to determine back-
ground concentrations in areas in the vicinity of the plant.
The results of the analysis of the nine soil and one solid samples,
listed in Table 6, indicate that HCB soil concentrations were in the 1
to 1,500 ppm range, with the exception of the "Hex Pit" soil and the "Hex
Pit" solids. HCB was 5% in the "Hex Pit" soil* and 21% in the "Hex Pit"
solids.
Of the four plant boundaries, the highest level of HCB, 126 ppm,
was observed in soil from the southern boundary (S-8). HCB levels ranged
from 1.1 to 1.3 ppm in samples taken along the other boundaries.
The observation of relatively high concentrations of HCB in the
southern boundary soil sample (S-8) could very well be the source of
high concentrations of HCB in the air samples collected at Air Sampling
Stations 16 through 18. The high concentration in the soil samples up-
wind of the production area could be due to the nearby landfill. This
rationale is supported by the presence of over 1,000 ppm HCB in the S-5
sample, which indicates the landfill is a source of surface contamina-
tion in the immediate area.
The soil on the route to the "Hex Pit" (S-2) and the soil from the
"Hex Pit" to the landfill (S-4) contained over 100 ppm HCB. HCB concen-
trations found in the water layer covering the "Hex Pit" were also rela-
tively high. The results of the water analysis are presented below.
Water Samples
Two samples were taken from Cowskin Creek (Figure A-3) which re-
ceives water from the sanitary sewer system and plant heat exchangers.
Samples were taken from the "Hex Pit" and solar pond to determine
their contribution to HCB levels in air and into the deep well which
receives water from the solar pond.
Taken from a 10-ft radius of the "Hex Pit."
31
-------
Table 6. HCB CONCENTRATIONS IN SOIL AND SEDIMENT
FROM VULCAN MATERIALS COMPANY, WICHITA, KANSAS
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.
40.
29.
35.
43.
,7
.5
,6
,6
.5
34.2
0.95
Concentration
HCB
109
57,
157
1,453
5.6
1.3
126
1.2
1.1
21%
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.
32
-------
The results of the water analyses are shown in Table 7. The HCB lev-
els were relatively low—parts per trillion in the Cowskin Creek water.
A high concentration (306 ppb) in the "Hex Pit" water was expected
since this water covers the "hex residues" dumped in the pit. This water
is likely to be saturated with HCB. The concentration in the solar pond
was over two orders of magnitude lower than that in the "Hex Pit" water.
The source of HCB in the solar pond water could be from leaching of the
soil in the plant area 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 in-
dicate that the "Hex Pit" is the source of the highest levels of HCB. HCB
is present in particulate and vapor form in air samples taken from within
the plant area. The HCB detected in the downwind air samples beyond the
plant perimeter was present mainly as a vapor. There appears to be a rel-
atively constant air concentration of HCB vapor of approximately 0.1 to
1.0 ng/nr even in the upwind air samples. This background level of HCB
in air may be due to the HCB present in the general plant area soil and
landfill. The variation in HCB levels over the sampling period was due
primarily to variations in HCB detected in particulates. HCB concentra-
tions in soil (excluding the "Hex Pit" area) ranged from 1 to 1,500 ppm.
The water samples taken beyond the plant area from Cowskin Creek contained
very low levels of HCB (parts per trillion range). Downstream levels of
HCB were twice as high as upstream levels.
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.
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 HCB. The results
are listed in Table 8. HCB was detected in the spent brine at 0.34 |j,g/liter.
Based on the instrumental detection limit for HCB, 2 pg (2 x 10 g)j the
volume of water extracted, 1 liter; and the final extract volume, 50 ml;
the minimum detectable concentration of HCB in water was 10 parts per
trillion.
33
-------
Table 7. HCB CONCENTRATIONS IN WATER FROM VULCAN
MATERIALS COMPANY, WICHITA, KANSAS
Volume sampled Concentration
Samples (liter)
ND - None detected.
"Hex Pit" water 0.315 306
Solar Pond 0.335 0.7
Upstream
(Cowskin Creek) 323 0.009
Downstream
(Cowskin Creek) 365 0.018
34
-------
Table.8. HCB CONCENTRATIONS IN WATER AND SOLIDS FROM
LINDEN CHLORINE COMPANY, LINDEN, NEW JERSEY
Concentration (us/I)
Sample HCB
Water
Holding pond, inlet ND
Holding pond, outlet ND
GAF weir, upstream of Cl£ plant ND
Waste stream, downstream of Cl£ plant • ND
Process water ND
Tap water ND
Spent brine water 0.34
Solid Concentration (ug/g)
Holding pond, settled and suspended 0.1
Dredged solids adjacent to holding pond 0.6
Waste stream, downstream of Clo plant 7.6
Soil, around one of the cell buildings 1.7
35
-------
All four solid samples contained HCB (from 0.1 to 7.6 |j,g/g)« The
highest level was observed in the waste stream sludge, downstream of
the plant. The HCB level in soil outside a cell building was 1.7 |j,g/g.
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 RGB. In addition, the samples were prepared and analyzed in
duplicate 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. HCB was
detected in spent brine. The highest concentration of HCB (7.6 |-ig/g)
was found in the sludge taken from the waste downstream of the plant.
The levels detected in the water and solid samples indicate this plant
is not a current source of significant quantities of HCB.
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 are discussed below.
Air Samples
The 108 air samples were collected from nine samplers which were
positioned at nine locations surrounding the plant. The positioning of
downwind samplers was limited by a flood wall along the Ohio River.
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
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 HCB, (b) the diurnal and plant
operational effects, if any, and (c) the physical form of HCB in the air.
Sources and Levels of HCB Emission - The results of the analyses are
listed in Table B-2 of Appendix B. The filters collected at the same
sampling station at various sampling times were combined to form one
sample to reduce the analysis time. The combined filter analysis is
still indicative of the specific form of the two substances present
in the plant air. The average HCB concentration per 24-hr period at
each sampling station is shown in Figure 11.
36
-------
u>
150 200
Immediate Plant
Boundary
Numbers in Parentheses Represent
Average Concentration
of HCB per 24 hr Period
Figure 11. Average concentrations of HCB in air at nine sampling stations
at Stauffer Chemical Company, Louisville, Kentucky
-------
The 24-hr average concentrations on the filter and in Tenax®-GC
resin at each sampling station are shown in Figure 12. The average HCB
concentration in upwind samples (Stations 1 and 2) were 0.07 and 0.05
fig/m , respectively, while downwind samples ranged from 0.04 to 1.2
|j,g/m . Of the downwind stations, the highest level of HCB was observed
at Station 4 which was located downwind from the perchloroethylene-
carbon tetrachloride plant. The level of HCB was somewhat lower at Sta-
tion 6, which was further downwind from the perchloroethylene-carbon
tetrachloride plant. Stations 3 and 7 also show significant levels of
HCB.
Variation of HCB Emission with Time - HCB levels detected during the
24-hr sampling period are plotted versus sampling time for each of the
nine sampling stations in Figure 13.
Higher levels of HCB were observed during the first two sampling
periods (1000 to 1800 hr) which may be indicative of a diurnal effect.
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). HCB levels were uniformly high during
this period. The exact time when the drums were removed from the drum
loading area and transported off-site was not known.
Physical Form of HCB - There is some contribution to the total HCB lev-
els from particulates collected on the filters at Stations 3 through 6,
Surprisingly, HCB was not detected on the filters at Station 7, which
was near the drum loading area. Although particulate HCB was not de-
tected, settled particulates could contribute to the HCB level through
the solid-vapor equilibrium of HCB-contaminated particulates. HCB has
a boiling point of 230°C, but it co-distills with water vapor at low
temperature and readily sublimes. It is apparent from Figure 12 that
the major portion of HCB in the air was in the vapor state, since all
the stations showed higher levels in the Tenax®-GC resin than on the
filters.
Soil and Sediment Samples
Two soil samples were collected along the plant boundaries, one
along the waste transportation route, and two from near waste handling
areas; three sediment samples were taken, two from the Ohio River and
one from the holding pond.
38
-------
CO
E
\
O)
HCB
—— Tenax
Filter
Figure 12. Average concentration of HCB in vapor and particulate
at nine sampling stations (Stauffer)
-------
3.0-1
KCB
2.0-
-P-
o
^
o>
i.o-
0.5-
Stations
• 1
x 2
O 3
A 4
a 5
e 6
A 7
0 8
• 9
1000-1400
1400-1800
1800-2200
2200-0200
0200-0600
0600-1000
Figure 13. HCB concentration per 24-hr period at sampling
stations around the plant (Stauffer)
-------
The results, shown in Table 9, indicate that HCB soil concentrations
were generally in the low parts per million range with the exception of
the soil sample around the drum loading area (S-3), which contained 5,700
ppm HCB.
The soil concentrations followed the same general pattern as the air
concentrations, i.e., the upwind sample had the least amount of HCB, 0.25
|j,g/g; the downwind sample (northern plant boundary) contained 4.75 |j,g/g.
Other soil samples—the settling pond, main road, and northern plant
boundary—show HCB levels from 5 to 20 times greater than levels found in
the upwind samples.
Of the three sediment samples analyzed, the settling pond sample con-
tained the highest level of HCB, 284 ^g/g. The downstream HCB .concentra-
tion was higher (0.05 |j,g/g) than the upstream concentration (0.008 |J,g/g).
However, both concentrations are near the detection limit where the rela-
tive error in analysis is high.
Water Samples
Six water samples were collected—one from the plant well and five
from the settling pond. The results are listed in Table 10. HCB was pres-
ent in the plant well water below the parts per billion level, i.e., 0.2
jj,g/liter. The HCB concentration in the settling pond (grab) after treat-
ment, i.e., the sample collected at the outlet, was half the HCB concen-
tration in the sample taken from the inlet (grab). However, data from
the 24-hr composite sample (collected by Stauffer) indicate that almost
all HCB was eliminated after treatment. The XAD-4 results agree quite
closely with the results obtained for the outlet grab sample.
Generally, the 24-hr composite sample is more representative. How-
ever, in the samples analyzed here, it is very likely that some HCB was
lost during sampling for the 24-hr composite. The agreement between re-
sults obtained for the Amberlite XAD-4 resin and the grab sample substan-
tiate their validity.
Plant Summary
The results of the analyses of all air samples indicate that the
carbon tetrachloride-perchloroethylene plant is the major source of HCB
in the general plant area. Slightly elevated levels of HCB were also ob-
served on the eastern and western boundaries of the plant. The source of
this contamination is very likely from vapor-solid equilibrium of the
particulate "fall out" accumulated on the soil. The background level of
41
-------
Table 9. HCB CONCENTRATIONS IN SOIL AND SEDIMENT FROM
STAUFFER CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Concentration (ug/g)
Samples HCB
Soil
S-l - Upwind (southern plant boundary) 0.25
S-2 - Plant road 2.25
S-3 - Drum loading area 5,700
S-4 - Downwind (northern plant boundary) 4.75
S-5 - Settling pond area 1.3
Sediment
R-l - Settling pond 284
R-2 - Ohio River (upstream) 0.008
R-3 - Ohio River (downstream) 0.055
Table 10. HCB CONCENTRATION IN WATER FROM STAUFFER
CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Concentration (ug/l)
Samples HCB
Plant well water 0.2
Settling pond inlet (grab) 15
Settling pond outlet (grab) 7
Settling pond inlet (24-hr composite) 35
Settling pound outlet (24-hr composite) 0.7
Settling pond outlet (Amberlite XAD-4) 7
42
-------
o
HCB in the air was 0.06 |j,g/m . Average concentrations of HCB on the mil-
lipore filter versus the Tenax®-GC resin indicate that the major portion
of HCB in air was in the form of vapor rather than particulate. The HCB
concentration was highest in soil near the "drum loading area"--5,700
|ig/g« This level indicates a localized contamination from solid waste
handling. Otherwise, HCB concentrations from 0.25 to < 5 (ig/g were ob-
served in other soil samples around the plant. A slight buildup of HCB
levels was observed in samples taken along the waste transportation
route. Sediment samples from the settling pond showed high levels of
HCB, 284 M^g/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; 7 p,g/liter of HCB for both.
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 sample 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 tanden to check for possible breakthrough
of HCB. The samplers were positioned so that results of the analysis
would indicate (a) the sources and levels of HCB emission, (b) the phys-
ical form of HCB, and (c) the efficiency of HCB collection.
Sources and Levels of HCB Emission - The results are presented in Table
B-3 of Appendix B. The average HCB concentration at each station is shown
in Figure 14. The upwind (Stations 1 and 2) concentration was 0.02 |j,g/m ,
while downwind concentrations ranged from 0.02 to 0.08 [j,g/m . The recorded
wind direction during the sampling was primarily from the west.
The increase in HCB concentration observed for Stations 3 and 4 in-
dicates the production area which includes the thermal oxidizer (inciner-
ator) is a source of HCB emission. Elevated HCB levels did not extend be-
yond the plant boundary. HCB levels for the upwind Stations 1 and 2 are
about the same as those at downwind Stations 6 through 8. The results in-
dicate there is no widespread contamination of the plant area.
43
-------
Numbers in Parentheses Represent
Concentration (fj.g/m^) of
HCB per 24 hr Period
6) (0.02)
7) (0.02)
N
t
0 500 1000
I | |
Scale in Feet
©(0.02)
Immediate Plant
Boundary
Figure 14. Average concentrations of HCB in air at eight sampling stations
at Dow Chemical Company, Pittsburg, California
-------
Physical Form of HCB - HCB was not detected on any of'the filter samples.
Since the instrumental limit of detection was 2 pg (2 x 10 g) for HCB,
for an average of 4,000 liters of air sampled, the quantity of RGB col-
lected in the form of particulates on each millipore filter was less than
10 ng. Therefore, HCB was present in the vapor form only.
HCB was not found in the back-up Tenax®-GC tube, indicating that it
does not migrate through the Tenax®-GC resin.
Soil Samples
Three soil samples were collected along the eastern, western, and
southern plant boundaries. The highest level (2.6 ^.g/g) was observed in
soil from the southern boundary (Table 11). Without additional informa-
tion on plant activities that might involve transportation of chlorinated
hydrocarbons, we cannot explain the distribution of HCB in the soil sam-
ples. The relative concentrations do not coincide with wind direction.
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
HCB. Relatively low levels of HCB, 0.02 |j,g/m^, were detected in air at
the eastern and western boundaries of the plant. Midplant HCB levels
were slightly elevated over background. The absence of HCB on the mil-
lipore filter indicates that HCB was in the form of vapor rather than
particulate in the plant air. The concentration of HCB was highest in
the soil collected along the southern plant boundary. HCB concentrations
of 0.22 |ig/g or less were observed in the soils collected from the west-
ern and eastern plant boundaries.
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.
45
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Table 11. HCB CONCENTRATIONS IN SOIL FROM DOW
CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
Concentration (p»g/g)
Samples HCB
Western plant boundary 0.22
Eastern plant boundary 0.014
Southern plant boundary 2.6
46
-------
Air Samples
The 15 air samples were collected from five samplers which were
positioned at two upwind, and three downwind locations from the gen-
eral production area. The samplers were operated continuously for a
period of 24 hr, with two Tenax®-GC columns in tandem.
Levels of RGB - The results of the analysis are listed in Table B-4
of Appendix B. HCB was not detected in either the upwind or the down-
wind samples. Sampling locations are shown in Figure 15. Based on the
instrumental limit of detection for HCB, 2 pg (2 x 10 g), and a 50-
ml solution with a 10-^,1 injection for gas chromatographic analysis,
the amount of HCB collected in a 4,000-liter sample was less than 10
ng.
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 out-
let. The HCB level observed in the landfill sample, 0.39 fig/m^, was higher
than the level in the upwind or downwind soil samples (Table 12).
In the sediment, the highest level of HCB was detected in the storm
runoff outfall sample, 0.11 p,g/g. HCB (0.01 |o,g/g) was detected in the set-
tling pond outlet.
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. HCB was not detected in the raw plant water. The highest con-
centration was detected in the water standing in the landfill, 2.8 p,g/
liter. HCB was detected in the settling pond water, 0.037 |j,g/liter in
the inlet and 0.015 p,g/liter in the outlet. However, HCB was not de-
tected in the grab samples taken at the inlet and outlet of the set-
tling pond because only 1 liter of water was sampled versus 125 liters
sampled through the Amberlite XAD-4 column.
47
-------
00
Landfill Soil
Composite
Equalization Pond
O Production
Area
3)(ND)
ND
Scale in Feet
Immediate Plant
Boundary
Figure 15. Sampling stations at E. I. du Pont de Nemours and Company, Corpus Christi, Texas
-------
Table 12. RGB CONCENTRATIONS IN SOIL AND SEDIMENT FROM E. I. DU
PONT DE NEMOURS AND COMPANY, CORPUS CHRISTI, TEXAS
Concentration (ug/g)
Soil samples RGB
Upwind (southern boundary) 0.16
Downwind (northern boundary) (h015
Landfill area 0.39
Sediment
Settling pond inlet ND
Settling pond outlet 0.01
Storm runoff outfall 0.11
Table 13. RGB CONCENTRATIONS IN WATER FROM E. I. DU PONT
DE NEMOURS AND COMPANY, CORPUS CHRISTI, TEXAS
Concentration
Samples HCB
W-l Raw plant water before use ND
W-2 Settling pond inlet (amberlite) 0.037
W-3 Settling pond inlet (grab) ND
W-4 Settling pond outlet (amberlite) 0.015
W-5 Settling pond outlet (grab) ND
W-6 Storm runoff outfall (grab) ND
W-7 Water standing in landfill 2.8
49
-------
Plant Summary
HCB was not detected in any of the air samples. The concentration
of RGB was highest in the soil collected around the landfill area. Of
the water samples, the highest concentration of HCB was detected in the
landfill standing water. The landfill area is a source of elevated soil
and groundwater HCB levels. In general, the levels of HCB in this plant
were very low. The plant began operations as recently as 1973 and ap-
pears to be successful in minimizing HCB emissions.
DIAMOND SHAMROCK 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 Tenax®-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 locations were along the north boundary and one at the south bound-
ary of the plant area. Changing wind directions (TAble A-13) during sam-
pling prevented the samplers from being positioned in upwind and downwind
locations. The sampling was conducted over three 8-hr sampling periods
covering 3 days. Rain interrupted the second sampling period and pre-
vented sampling during 1200-1700 hr on any of the 3 days. The samplers
were operated at 0.4 liters/min, resulting 600 liters or less of air
sampled. Two Tena:x®-GC columns were used in tandem.
Sources and Levels of HCB Emission - A simplified plant map with the
sampling locations is shown in Figure 16. HCB was not detected in any
of the samples.
Soil Samples
Three soil samples were collected from (a) along the northern .
plant boundary, (b) along the southern plant boundary, and (c) the
production area.
The results of the analysis of the three soil samples are shown
in Table 14. The highest concentration of HCB was detected in the pro-
duction area, i.e., 24 |ig/g. A higher level of HCB was detected in the
soil sample collected near air sampling Station 1 (0.68 (j,g/g) than in
.the samples collected near Stations 7 and 8 (O.OlT~|j,g/g).
50
-------
N
0 - • 300 600
Scale in Feet
Immediate Plant
Boundary
Figure 16. Stations at Diamond Shamrock Corporation, Deer Park, Texas
51
-------
Table 14. HCB CONCENTRATIONS IN SOIL FROM DIAMOND SHAMROCK
CORPORATION, DEER PARK, TEXAS
Concentration (ug/g)
Soil samples HCB
Upwind (southern boundary) 0.68
Downwind (northern boundary) 0.08
Production area 24.0
52
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Water Samples
The two water samples collected for the analysis of HCB were the
raw plant water and plant effluent. The results shown in Table 15 in-
dicate that HCB was not detected in the raw water. However, 0.1 (o,g/
liter of HCB was detected in the plant effluent. This effluent is dis-
charged into nearby Pattrick Bayou.
Plant Summary
HCB was not detected in the air samples from any of the sampling
stations. HCB was detected in soil samples collected along the northern
and southern plant boundaries at parts per billion levels. The concen-
tration of HCB in production area soil was 24 |J,g/g« The inlet plant wa-
ter did not contain detectable quantities of HCB while the process plant
effluent showed an HCB level of 0.1 |j,g/liter.
CIBA-GEIGY CORPORATION, ST. GABRIEL, LOUISIANA
Field sampling at Ciba-Geigy Corporation's triazine herbicide plant
in St. Gabriel, Louisiana, was conducted on August 13, 1975. A total of
16 air, 4 soil, and 2 water samples was collected.
Air Samples
The 16 air samples were collected from eight samplers which sur-
rounded the entire production area. Stations 2, 4, 6, and 8 were posi-
tioned about 400 ft, and Stations 1, 3, 5, and 7 were approximately
1,000 ft from the production area. One Tenax®-GC column was used in
the sampling train. The sampling was conducted 2 hr of every 8-hr pe-
riod, over a 24-hr period.
Sources and Levels of HCB Emission - The results of the analyses are
listed in Table B-16 of Appendix B. The average concentrations of HCB
are shown for each sampling station in Figure 17. HCB concentrations
were from nondetectable to 0.02 fig/m . The wind directions were quite
erratic during sampling, and upwind-downwind patterns were not observed.
HCB in the plant air was in the form of vapor rather than particulate.
Soil Samples
Four soil samples were collected from the general areas of Air
Sampling Stations 1, 3, 5, and 7, respectively. The results of the
analysis are listed in Table 16. HCB was found in only two samples—
around Air Sampling Stations 3 and 5, at 0.003 and 0.011 |j,g/g, respec-
tively. The analysis of the soil samples collected near Station 7 was
negative.
53
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Table 15. HCB CONCENTRATIONS IN WATER FROM DIAMOND
SHAMROCK CORPORATION, DEER PARK, TEXAS
Concentration
Samples HCB
W-l Raw unused plant water ND
W-2 Plant effluent 0.1
54
-------
Numbers in Parentheses Represent
Average Concentration
of HCB per 24 hr Period
(0.02) (3
2)(O.OI)
(ND) (8
Production
Area
(0.01)
Effluent Pond
0
I
400
I
800
I
Scale in Feet
Immediate Plant
Boundary
Figure 17. Average concentrations of HCB in air at eight sampling stations
at Ciba-Geigy Corporation, St. Gabriel, Louisiana
-------
Table 16. HCB CONCENTRATIONS IN SOIL FROM CIBA-GEIGY CORPORATION,
ST. GABRIEL, LOUISIANA
Concentration (ug/g)
Soil samples HCB
S-l Northwest of plant at Air Sampling ND
Site No. 1
S-2 Northeast of plant at Air Sampling 0.003
Site No. 3
S-3 Southeast of plant at Air Sampling 0.011
Site No. 5
S-4 Southwest of plant at Air Sampling ND
Site No. 7 . ,
56
-------
Water Samples
Two grab samples were collected, raw plant water and process efflu-
ent. HCB was not detected in either sample.
Plant Summary
The concentrations of HCB in the plant air were very low--from 0.01
to 0.02 |j,g/m . In the soil, HCB was detected in the low parts per billion
range. Since HCB was not detected in the process effluent, the water dis-
charged into the Mississippi River contains less than 10 ng/liter of HCB.
OLIN CORPORATION, MCINTOSH, ALABAMA
Field sampling at Olin Corporation's pentachloronitrobenzene (PCNB)
plant at Mclntosh, Alabama, was conducted on August 18, 1975. A total of
24 air, including 8 filters and 16 Tenax®-GC columns, 12 soil and sedi-
ment, 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 two samplers positioned at
the southern boundary, three at the mid-plant area, three north of the
PCNB production plant, and three at the northern boundary. Each sampling
train consisted of a millipore filter and two Tenax®-GC columns. Essen-
tially no breakthrough of HCB through the first column was observed. The
samplers were operated 3 hr of each 8-hr period for three 8-hr periods.
The wind direction during the sampling varied. Therefore, upwind-downwind
stations could not be designated.
Sources and Levels of HCB Emission - The results of the air sample anal-
ysis are listed in Table B-7 of Appendix B. The sampling locations and
average 24-hr HCB concentrations are shown in Figure 18; HCB concentra-
tions ranged from 0.04 to 2.2 |j,g/m . From the map of the plant area shown
in Figure 18, three possible sources of HCB are apparent: the PCNB pro-
duction area, the "hex" storage area, and the chlorine production area.
The highest concentrations of HCB were observed in the samples collected
along the southern boundary. These samples were south-southwest of the
"hex" storage area, which, is in the southeast corner of the plant. The
wind was recorded from almost all directions during the sampling, but
the highest wind speed was observed when the direction was from the
north-northeast and the north. Neglecting direction and notwithstanding
Station 1, the closer the sampler was to the "hex" storage area, the
greater the HCB concentration. These results indicate that the "hex"
storage area is the primary source of HCB. Because of the varied wind
57
-------
(0.04)
2
V_x
(0.06)
(0.26)
Chlorine
Production
Area
(0.03) (0.24) (0.48)
Strong
Brine
Pond
Weak
Brine
Pond
O
Production
Area
Numbers in Parentheses Represent
Average Concentration
of HCB per 24 hr Period
(i.ID®
Hex
Storage
Area
(2.22)
N
1
0 160 320
I i i
Scale in Feet
Immediate Plant
Boundary
Figure 18. Average concentrations of HCB in air at
eight sampling stations at Olin Corporation,
Mclntosh, Alabama
58
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conditions, it is difficult to quantitatively determine the contribu-
tion of the PCNB production plant to HCB emissions but it appears to
be much less than the "hex" storage area. The HCB emission from the
chlorine production plant is negligible since the air concentrations
at stations closest to the chlorine production area were from 0.03 to
0.06 |j,g/m3.
Physical Form of HCB
HCB was not detected in any of the filters indicating that it was
present as a vapor rather than in particulate form. The absence of par-
ticulate HCB is somewhat surprising since the heavy wastes from PCNB pro-
duction are stored in solid blocks in the storage area. The blocks are
covered with plastic sheets which appear to be effective in eliminating
particulate HCB in the air but not HCB vapor. Sporadic rain and low wind
speed during the sampling also may have reduced the particulate HCB.
Soil and Sediment Samples
The 12 soil and sediment samples were collected from plant bound-
aries, transportation routes, landfill and storage areas.
The results of the analysis of these samples are shown in Table 17.
The concentration levels were from a low of 0.98 fj,g/g (soil from the
brine pond area) to a high of 13% (soil from the "hex" storage area).
The blocks of "hex" wastes stored in this area contain up to 80 to 90%
HCB. The soil sampled along the transportation route of the "hex" blocks
showed an HCB concentration of 4,100 pg/g. HCB concentrations over 100
ppm were detected in samples collected along the road to the old land-
fill, and from within the old landfill. It was learned that prior to
the practice of casting the "hex" wastes into blocks, the old landfill
was used for the "hex" disposal.
Soil samples from the east road, as well as the "hex" storage area,
old landfill and the current landfill area all show much higher levels
of HCB than those detected on the west road. The relative concentrations
of the air samples followed the same pattern.
Water Samples
Ten water samples were collected: two from ditches within the plant
area, three from the nearby creek, one from the settling pond, two from
the solar pond, and two from the two brine ponds (strong and weak).
59
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Table 17. HCB CONCENTRATIONS IN SOIL AND SEDIMENT
OLIN CORPORATION, MCINTOSH, ALABAMA
Concentration (ug/g)
Samples HCB
Soil
S-l Northern boundary road 3,200
S-2 Old landfill (northeastern boundary) 480
S-3 Brine pond area 0.98
S-4 Center road (running north/south) 72 •
S-5 High-lift route (organic plant to storage
area) 4,100
S-6 Southeast landfill 53
S-7 "Hex" storage area 13%
S-8^.' Old "Hex" dump area Not analyzed
S-9 East road 400
S-10 West road 1.1
S-ll South road 350
Sediments
Strong brine pond sediment 12
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.
60
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The results are shown in Table 18. The highest level of HCB, 159
|j,g/liter, was detected in the spent brine pond. Concentrations ranged
from nondetectable to less than 10 |j,g/liter in the other samples.
The relatively close agreement of the HCB concentrations deter-
mined in the single grab sample (5.0 |j,g/liter) versus the 24-hr com-
posite sample (2.5 p,g/liter) of the creek water collected 200 yd up-
stream of the basin indicates the instantaneous HCB concentration
did not vary significantly from the 24-hr average. HCB was not de-
tected in the basin water indicating that detectable amounts of HCB
were not discharged into the Tombigbee River.
Plant Summary
The results of the analysis of air, soil, sediment, and water
samples indicated that the "hex" storage area is the primary source
of HCB contamination, whereas the PCNB production area, old landfill
site, and weak brine pond are secondary sources. The chlorine produc-
tion plant is not a source of HCBD. Soil and sediment samples showed
relatively high levels of HCB—from 0.98 to 1.3 x 105 |j,g/g. All the
plant road samples contained HCB: the lowest was on the west road
(1.12 (J,g/g), the highest on the "high-lift road" (organic plant to
storage area, 4.1 x 10 (J,g/g)» Detectable quantities of HCB were not
discharged into the Tombigbee River.
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 ob-
tained during the presampling site visit. However, the wind was pre-
dominately from the east and east-southeast during sampling. Samplers
were positioned to take advantage of existing electrical outlets, also.
The sampling was conducted for an integrated 24-hr period; two Tenax®-GC
columns in tandem were used.
61
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Table 18. HCB CONCENTRATION IN WATER .FROM OLIN CORPORATION,
MCINTOSH, ALABAMA
Samples HCB concentration (ug/l)
W-l Weak brine pond 160
W-2 Strong brine pond 1.4
W-3 Settling pond ND
W-4 North/south running ditch 1.0
W-5 Southern ditch area (upper drop) 7.5
W-6^' Combined creek (200 yard before basin) 5.0
W-7-' Basin (at mouth of creek) ' ND
W-8 24-Hr composite of plant effluent 2.5
, (combined creek)
W-9^ Solar pond, west 3.8
W-10^- Solar pond, east ND
B-l Sampling bottle blank
B-2 Sampling bottle blank Average
B-3 Sampling bottle blank
0.4
a/ All water samples using Olin's sample bottles are reported after sub-
tracting blank bottle value.
62
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Sources and Levels of HCB Emission - The results are shown in Table B-8
in Appendix B. A simplified plant map with the sampling locations and the
24-hr average concentrations (Tenax®-GC plus filter) of HCB is shown in
Figure 19. HCB concentrations were from nondetectable, at Stations 8 and
9, to 1.7 |o,g/nr at Station 7. Relatively higher concentrations of HCB
were detected at Stations 4 through 7, which were located downwind of
the incinerator-production area. The presence of low concentrations of
HCB at Stations 2, 3, 9, and 10 could be due to other sources, e.g., the
old landfill site and the barges which were located upwind.
The presence of HCB beyond the northern plant boundary is probably
due to the incinerator since Station 6 is somewhat downwind. However, a
relatively high level of HCB was detected at Station 1 which is upwind
of the incinerator and plant area. The HCB level in this sample may in-
dicate a general contamination of the area south of the plant. Sampling
Station 6 was located in a sparsely populated residential area.
Physical Form of HCB - Figure 20 shows that HCB was predominantly in the
form of particulate rather than vapor (majority detected on the filter).
The occurrence of HCB in particulate form could be the results of
(a) particulates from the incinerator or (b) the production process em-
ployed by PPG for perchloroethylene and trichloroethylene. PPG uses a
catalytic oxychlorination technique, resulting in a lower reaction tem-
perature than that generated by the thermal chlorination of hydrocarbons.—
Soil Samples
Four soil samples were collected: two at the plant boundaries, one
along Mobil South Road, and one from the landfill. The results are shown
in Table 19. The levels of HCB in the soil ranged from 0.015 (J,g/g, around
Air Sampling Stations 8 through 10, to 0.10 |j,g/g, along Mobil South Road
and around Air Sampling Stations 4, 5, and 7.
The elevated levels of HCB 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 HCB. The results of sedi-
ment and water analyses discussed below support this possibility.
Sediment Samples
The three sediment samples were taken one each from the PPG canal
(near Air Sampling Station 1), the ship channel, and the main effluent
from the organic plant. HCB was detected in all three sediment samples;
the lowest level (0.01 |j,g/g) was in the ship channel, and the highest
in the sediment at the organic plant effluent (0.87 |o,g/g). The presence
of HCB in the ship channel sediment may be associated with waste load-
ing into the barges.
63
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Numbers in Parentheses Represent
Concentration (^i.g/m^) of
HCB per 24 hr Period
Immediate Plant
Boundary
Figure 19.
Average concentrations of HGB in air at 10 sampling stations
at PPG Industries, Lake Charles, Louisiana
-------
CO
O1
HCB
Tenax
Pilfer
5. 6
Station
8
10
Figure 20. Average concentrations of HCB in vapor and particulate at 10 sampling stations
around the plant (PPG Industries)
-------
Table 19. HCB CONCENTRATIONS IN SOIL AND SEDIMENT
FROM PPG INDUSTRIES, LAKE CHARLES, LOUISIANA
Concentration (ug/g)
Samples HCB
Air Stations 4, 5, 7 soil composite 0.10
Air Stations 8, 9, 10 soil composite 0.015
Mobil south road 0.10
Landfill 0.025
PPG sediments
Sediment 1 (downstream PPG canal) 4.4
Sediment 2 (main organic plant effluent) 6.9
Ship channel sediment 0.01
66
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The presence of significant amounts of HCB (4.4 |j,g/g) in the down-
stream PPG canal sediment indicates accumulation of deposits from the
organic plant effluent. This sediment was collected 1,000 ft beyond Air
Sampling Station 1, i.e., at least 4,000 ft from the organic plant.
Water Samples
Seven water samples were collected: one from the lake (incinerator
feed), one incinerator scrubber, two from the treatment canal, one from
the landfill (standing water), one from the PPG canal, and one from the
ship channel.
The results are shown in Table 20. The highest concentration of HCB
(7.1 fig/liter) was detected in the treatment canal inlet sample, and the
landfill surface water. The treatment canal outlet contained 4.1 fig/liter
HCB, indicating that the treatment removed about 40% of the HCB. The sam-
ple collected downstream of the PPG canal near Air Sampling Station 1 con-
tained 1.1 |j,g/liter HCB. This concentration in the canal water at more
than 3,000 ft downstream from the effluent point is consistent with the
levels detected in sediment collected 1,000 ft further downstream.
The lake water (incinerator feed water) contained 0.22 [j,g/liter HCB.
This level of HCB could, depending on the amount of feed water versus
"liquid bottoms" that passes through the incinerator, contribute signi-
ficantly to the HCB emission from the incinerator.
The. scrubber water from the incinerator contained a lower level of
HCB (0.09 |j,g/liter) than the feed water and the treatment canal inlet.
Plant Summary
The primary source of HCB in air is the incinerator and organic plant.
The HCB present in the incinerator feed water (0.22 ng/liter) may be a fac-
tor in HCB concentrations in air. The HCB was present predominantly as par-
ticulate in air. This plant was unique in the relative distribution of HCB
in air versus soil, sediment and water. The air concentrations were rela-
tively high at this plant when considering the relatively low concentra-
tions in the other types of samples. The distribution of HCB may be ac-
counted for by the plant production and waste disposal methods. Solid wastes
are not formed in the low temperature catalytic oxychlorination production
process. "Liquid bottoms," which contain HCB, are incinerated; process
water, which contains lighter chlorinated hydrocarbons, e.g., HCBD, is
treated and flows into the PPG channel and eventually the Calcasieu River.
Water sampled in the PPG canal at a point approximately 3,000 ft from the
organic plant effluent contained 1 ppm HCB. The HCB concentration in a
sparsely populated residential area downwind of the incinerator was 0.36
67
-------
Table 20. RGB CONCENTRATIONS IN WATER FROM PPG
INDUSTRIES, LAKE CHARLES, LOUISIANA
Concentration
Sample HCB
Incinerator feed water (lake water) 0.22
Scrubber water 0.09
Inlet (treatment canal) 7.1
Outlet (treatment canal) 4.12
Surface water (landfill) 7.1
Downstream PPG canal (Mobil Bridge No. 1) 1.1
Ship channel (next to Air Station No. 10) ND
Note: ND = none detected.
68
-------
SECTION VI
SEWAGE TREATMENT FACILITIES
Chlorination as a means of disinfecting treated sewage has been
known to result in the "in situ" synthesis of numerous halogenated hy-
drocarbons. It was not known whether HCB is produced in significant
concentrations by this process. For this reason, samples were collected
from two sewage treatment plants utilizing chlorination and analyzed for
HCB.
SAMPLING
Samples were collected from two sewage treatment facilities in the
Kansas City area. Both facilities utilize chlorination for disinfecting
the treated sewage. One-gallon samples were collected from the sewage
treatment stream immediately before and after the chlorination step. The
samples were returned to MRI and stored at 4°C until analyzed.
EXPERIMENTAL PROCEDURES
A 1-liter sample of the sewage treatment effluent was extracted
twice with 100 ml of 157» (v/v) ethylether in hexane and once with 100
ml of hexane. The extracts were combined and dried by passage through
Na2SOA. The sample volume was reduced to 5 ml by means of a Kuderna-
Danish evaporator. One milliliter was reserved and the remaining 4 ml
were reduced to 1 ml using a slow stream of N2 to evaporate the solvent.
The samples were analyzed using electron capture gas chromatography. The
column was 6 ft x 1/4 in. o.d. packed with 4.0% SE-30 and 6.0% OV-210 on
ChromosorbW HP. The operating conditions were as follows: injector tem-
perature, 220°C; column temperature, 200°C; detector temperature, 250°C;
and carrier gas, 17 ml/min.
69
-------
RESULTS
Analysis of both sewage samples collected ahead of the chlorination
facilities showed no significant peaks at the retention time of HCB. Based
upon the instrumental sensitivity toward HCB and the concentration enhance-
ment by extraction and evaporation, the sewage samples contained less than
1 part per trillion HCB.
The samples collected after the chlorination facility gave highly com-
plex gas chromatograms. Numerous peaks were present at and near the reten-
tion time of HCB. Assuming that the observed peak at the retention time of
HCB was due solely to HCB, the sewage samples contained a maximum of 4 to
8 ppt HCB. As this was undiluted sewage, it appears that chlorination of
raw sewage produces a negligible quantity of HCB.
70
-------
SECTION VII
SUMMARY AND CONCLUSIONS FOR PROGRAM TASK IA
SUMMARY
A summary of results is listed in Table 21. The high and low con-
centrations of HCB are listed for each type of sample, along with the
products and waste-disposal methods for each site.
Figure 21 shows the highest levels of HCB 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. The concentrations shown in Figure 21 should
not be compared directly because of differences in sampling distances,
meteorological conditions, etc., during sampling.
In general, higher concentrations of HCB were associated with the
production of perchloroethylene and trichloroethylene than with other
industries. However, most of the chlorinated hydrocarbon plants produced
a combination (perchloroethylene, trichloroethylene, carbon tetrachlo-
ride, etc.) of products which makes it difficult to extrapolate the re-
sults obtained at a particular plant to a single product. In the one
plant that produced only carbon tetrachloride, the HCB levels were
quite low. The HCB concentrations detected in samples from the penta-
chloronitrobenzene production plant were relatively high, i.e., |j,g/m
range in air. The levels of HCB associated with plants producing chlor-
ine and triazine herbicides were very low.
Several different waste-disposal methods were used at the perchloro-
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. Higher levels of HCB were detected in air and
soil at the plant using on-site landfill and open pit storage. The levels
of HCB detected in soil and samples taken upwind of suspected point sources
indicated a wide area of HCB contamination at this plant. Elevated HCB lev-
els were detected in loading and transfer areas at plants using off-site
71
-------
Table 21. DATA SUMMARY FOR PROGRAM TASK NO. 1
NJ
Cone any
Vulcan Hater la li Company
Wichita. Kansas
Stauffer Chemical Coopany
Louisville, Kentucky
Dow Chemical Company
Pittsburg, California
E. I. du Pont de Meraour*
Corpus Chrlstl, Texas
Diamond Shanrock
Deer Park, Texas
Olln Corporation
Kclntosh, Alabama
Clba-Ceigy Corporation
St. Gabriel, Louisiana
Products Substance
Perchloroethylene HCB
Carbon tetrachlorlde
Chlorine
Perchloroethylene HCB
Carbon tetrachlorlde
Methylen chloride
Chloroform, chlorine
Perchloroethylene HCB
Carbon tetrachlorlde
Chlorine
Carbon tetrachlorlde HCB
Trlchloroethylene HCB
Perchloroethylene
Chlorine
Pentachloronltrobencene HCB
Chlorine
Atrazlne HCB
Propazlne
Slmazine
Air (HR/m3) Water (ng/ t) Soil(ua/g> Sediment (ug/g.)
High Low High Lew High Low High Lev
24 0.53 300 0.009 5% 1.1 „
no
sample
7.0 0.24 35 0.2 3,700 0.23 280 0.008
0.08 < 0.02 Ho 2.61 0.014 H<)
': sample sample
ND ND 2.8 «D 0.39 0.013 0.11 ND
ND ND 0.1 ND 24 0.08 u
wo
sample
2.2 0.03 160 ND 13X 0.98 12.4 Only
one
sample
0.02 ND ND ND 0.01 ND
NO
sample
Vaste disposal
On-site landfill,
and deep well
Off-site landfill
Incineration
Co- site landfill
and off-site
disposal
Off-site
incineration
Solid wastes (in
blocks) stored in
open field covered
with plastic
Off-site
incineration
PPG Industries
Lake Charles, Louisiana
Linden Chlorine
Linden, New Jersey
Trlchloroethylene HCB
Perchloroethylene
Vinyl chloride
Vlnylldene chloride
Chlorine, etc.
Chlorine RGB
1.7 ND 7.1 ND
0.34 ND
sample
0.10 0.013 69
0.01 Incineration, land*
fill, and treatment
canal
1.7 Only 7.6 0.10 Holding pond
one
sample
-------
7r
6 -
5 -
4 -
CO
TO
3 -
2 -
(90')
2
.
-
-
-
-
9
(2
(725')
50
')
UOO1)
1
.
LEGEND
HIGHEST LEVELS OF HCB OBSERVED
IN AIR AT 8 INDUSTRIAL PLANTS
HCB CONCENTRATIONS IN AIR
AT DOWNWIND STATIONS
(16001)
(1000') (19001)
\ / (1800')
\ / /nnAi\ N.D.
(752%\_ N.D. N.D. \ / N.D. /
(1
(1600')
ooc
>')
-
„
-
-
-
(23001)
-
7
6
5
4
3
2
1
0
VULCAN STAUFFER
DOW DUPONT CIBY-GEIGY DIAMOND
SHAMROCK
PRODUCTION PLANT
OLIN
PPG
Figure 21. Summary of HCB concentrations in air
-------
disposal methods. Lower HCB levels were detected at plants using on-site
incineration, but downwind air concentrations were elevated above back-
ground at both plants; for example, an HCB concentration of 1 (j,g/m was
detected 2,300 ft downwind of the incinerator at one site. The lowest
levels of HCB for perchloro- and trichloroethylene production plants
were detected at the plant which used off-site incineration. Waste treat-
ment at the PCNB production plant involved casting the solids into blocks
which are stored under plastic. HCB vapor was detected in the low micro-
grams per cubic meter range near the storage area.
HCB was detected as vapor and particulate in three plants. In two of
the three, the particulate HCB in air coincided with relatively high soil
concentrations in the vicinity of the air sampling stations. At the third
plant, which used a low temperature reaction process, analysis of the
incinerator scrubber water showed 0.2 ng/liter HCB. Negligible levels of
HCB were detected in samples from two sewage treatment facilities.
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 20%, based on determinations
of HCB levels from sample pairs positioned at the same distances, but
at different heights from the emission source. Good agreement was ob-
tained from the analysis of water samples collected by "grab" sampling
and by concentration of HCB on XAD-4 resin.
CONCLUSIONS
Industrial Sources of HCB
Considering the estimated production volumes of each of the six
industries and the concentrations detected in this study, perchloro-
ethylene and trichloroethylene production was easily the most signifi-
cant source of HCB for the industries' sampled. Although the total vol-
ume of chlorine produced was estimated to be 20 times that of perchloro-
ethylene and trichloroethylene combined, the production of chlorine did
not appear to be a significant source of HCB. Carbon tetrachloride pro-
duction alone did not appear to be a significant source of HCB 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 resulted in the detection of moderately
high levels of HCB but the total quantity of HCB released to the air was
not significant because of the relatively low estimated production vol-
ume of PCNB. Estimated triazine herbicide production volumes and the as-
sociated HCB levels determined in this study were very low; therefore,
the production of these compounds is not a significant source of HCB.
74
-------
Effects of Waste Disposal Methods
In general, methods that involve open storage (pits, lagoons, etc.)
resulted in elevated levels of HCB 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 both
particulate and vaporous HCB in air at two sites. Transportation of wastes
resulted in at least part per million levels of HCB in roadside soil within
plant areas. On-site incineration resulted in elevated air HCB levels for
750 ft and 2,300 ft, respectively, at two sites. Plastic sheets that were
used to cover solids from PCNB production were effective in reducing par-
ticulate HCB but the storage area was the major source of HCB vapor at the
plant. The HCB levels in water were reduced by approximately 50% at two
plants that passed liquid wastes through holding ponds or treatment canals.
i
Physical Form of HCB
HCB was detected in particulate and vapor form. The detection of
particulate HCB in air can be attributed to contaminated soil or blowing
waste solids in the vicinity of air sampling stations. An exception was
the incineration of wastes at the low temperature oxychlorination plant.
The particulate HCB observed at this plant was due to either the produc-
tion process or the incineration of li'quid "bottoms." The latter conclu-
sion is supported by the detection of a significant concentration of HCB
in the incinerator scrubber water.
75
-------
REFERENCES
1. Brady, M. N., and D. S. Siyali, Med. J. Aust.. _!, 158 (1972).
2. Acker, L., and E. Schulte, Naturwissenshaften. 57/10), 497 (1970).
3. Curley, A., V. W. Burse, R. W. Jennings, E. G. Villaneuva, L. Tomatis,
and K. Akazake, Nature. 242, 333 (1973).
4. EPA Report, "Environmental Contamination from Hexachlorobenzene," Of-
fice of Toxic Substances, Environmental Protection Agency, July 20,
1973.
5. Mumma, C» E., and E. W. Lawless, "Survey of Industrial Processing Data:
Task I - Hexachlorobenzene and Hexachlorobutadiene Pollution From
Chlorocarbon Processes," Final Report by Midwest Research Institute
on Contract No. 68-01-2105 for the Environmental Protection Agency,
June 1975.
6. Personal communication with Mr. G. A. Burns, Environmental Control
Specialist, PPG Industries, Lake Charles, Louisiana, November 1975.
76
-------
APPENDIX A
PRESAMPLING SURVEY AND FIELD SAMPLING
77
-------
Presarapling 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% of their anodes are graphite, the remainder being dimensionally
stabilized anodes.
78
-------
May
June
July
August September
VD
Vulcan Materials
Wichita, Ks.
Linden Chlorine
' Linden, N. J.
Stauffer 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
•• 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 from "Hex Pit" to landfill
S-5 Between old and current landfill sites
80
-------
CO
S
§
u
S
g.
1
12
13
10
11
S-3 T
QHex Pit
, /
oT
x
S-l
g Perc Plant
il
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
17 .
16 •
°P
in
S
a.
§
U
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
00
ho
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
1,500 ft north of landfill- 1st
225 ft north 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
hr of 4 hr
1,500 ft north of landfill- 1st hr of 4 hr
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-
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
( £/min)
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. U)
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.
83
-------
Upwind Air Samples
Figure A-3. Vulcan Materials Company - Wichita plant, and
surrounding areas (2.6 in. = 1 mile)
84
-------
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
Pumped "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
Norma 1
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
Normal
Normal
Normal
Normal
Normal
Normal
Rain
85
-------
Table A-3. WEATHER CONDITIONS DURING SAMPLING AT VULCAN MATERIALS COMPANY, WICHITA, KANSAS
00
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. 0"Sullivan DEP, Springfield office
Mr. William A. McGough
Mr. Richard pills
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:
87
-------
Sample type Sample location
Water Holding pond, inlet
Water Holding pond, outlet
Water Gaf weir, upstream of Cl2 plant
Water Waste stream, downstream of Cl2 plant
Water Tap water (control)
Solids From holding pond, settled and suspended
Solids Dredged solids adjacent to holding pond
Sludge Waste stream, downstream of C^ 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 ^resampling 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.
88
-------
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 RGB 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
89
-------
\D
O I
L
4 R-2 Sediment Sample
I (700 Meters Upstream)
Solvent
Chlorine Stora9e
uilding
Settling
Pond
Outflow
R-3
Sediment
Sample
Main Rood
S-2 Soil Composite
S-l 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
General area
Upwind
Upwind
East of "Perc Plant"
Northeast of "Perc
Plant"
Downwind
Downwind
Northwest of "Perc
Total
Sample Sampling sampling
No. Exact location period time (hr)
1
2
3
4
5
6
7
450 ft south southwest of T'Perc 1st 2 hr of 4 hr 12.3
Plant" area
500 ft south southeast of "Perc 1st 2 hr of 4 hr 11.8
Plant" area
340 ft east of "Perc Plant" area 1st 2 hr of 4 hr 10.6
250 ft northeast of "Perc Plant" 1st 2 hr of 4 hr 12.5
area
300 ft north of "Perc Plant" area 1st 2 hr of 4 hr 12.9
400 ft north of "Perc Plant" area 1st 2 hr of 4 hr 13.1
330 ft northwest of "Perc Plant" 1st 2 hr of 4 hr 13.2
Total
Sampling Sample Sampler
rate vol. height
U/min) (H) (ft)
3.5 2,588 4
3.5 2,626 4
3.5 2,221 4
3.5 2,768 4
3.5 2,787 4
3.5 2,662 4
3.5 2,850 4
Plant"
West of "Perc Plant"
north of settling
pond
Southwest of "Perc
Plant," northwest
of settling pond
area
420 ft west of "Perc Plant" area 1st 2 hr of 4 hr 13.3 3.5 2,872
9 540 ft southwest of "Perc Plant" 1st 2 hr of 4 hr 13.5
area
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.
92
-------
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.
93
-------
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
94
-------
DOW CHEMICAL COMPANY, PITTSBURG, CALIFORNIA
PRESAMPLING 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 Antioch, 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.
95
-------
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.
96
-------
vO
«;ok
H*f 4^
BROWNS
ISLAND
^Ofijf SLOUGH
\
\
Pittstaurg
--f-e Poi"»-....>?tPer'c
,.rf<
Plont Area
gv:
^j/ ""! .7,
Y //
} s *
^ ..
Solar Pond
f;>:.:.xf
( : ^
\Jtfte.
®
/
7^;
.A
Plant
.N^^
*. .
Soundary oeh
'•"•"ev'eE -.
TOPEK A/. / '
"«
Point
' N
n \s
9&S
"\ X
']--.. ^^
' '"'-:
\ A
i / ' 'N
AHD , /
'\
\
"\.
\
ur<(<~- J
yo-
^
r^
JM/-VT
^r=4
'0 ^
L £_j=i
= =J.. ^^r^- —*»-• - ;.
. ,• CiK i*.. '
*r~ ==•- --=
JlJ'phn'pSr-^^
l(Z]""9<;hi
-------
Table A-7. AIR SAMPLING DATA AT DOW CHEMICAL COMPANY, PITTS BURG, CALIFORNIA
00
General area
Upwind
Upwind
Near downwind
Near downwind
Near downwind
Far downwind
Far downwind
Far downwind
Sample
No.
Exact location
2,630 ft west-northwest of
"Perc Plant"
2,780 ft west of "Perc Plant"
900 ft east-northeast of
"Perc Plant"
830 ft southeast of "Perc
Plant"
1,280 ft south-southeast of
"Perc Plant"
2,550 ft east of "Perc Plant"
3,600 ft southeast of "Perc
Plant"
5,100 ft south-southeast of
"Perc Plant"
Total Sampling Sample Sampler
sampling rate vol. height
Sampling period time (hr) (l/min) (j) (ft)
24 hr continuous 20.7
24 hr continuous 2.0-
24 hr continuous 19.8
24 hr continuous 18.4
24 hr continuous 17.7
24 hr continuous 20.5
24 hr continuous 4.6-
24 hr continuous 18.9
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
3.5
3.963
a/ Generator failure.
-------
Table A-8. WEATHER CONDITIONS AND PLANT ACTIVITIES DURING
SAMPLING AT DOW CHEMICAL COMPANY, PITTSBURG, 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
(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
Wind
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
Norma 1
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Normal
Incinerator feed
rate reduced
Normal
Normal
Normal
Normal
Possible event
Normal
Normal
Normal
aj No precipitation during sampling period.
99
-------
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.
100
-------
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
101
-------
O'
STORM SEWER
PROCESS SEWER
I" - 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
Total Sampling
sampling rate
No. Exact location Sampling period time (hr) (£/min)
1 675 ft south
2 700 ft south
tion area
3 640 ft north
tion area
4 64- ft north
tion area
5 640 ft north
tion area
of production area 24 hr continuous 22.8 3.5
southeast of produc- 24 hr continuous 19.5 3.5
northwest of produc- 24 hr continuous 21.2 3.5
northwest of produc- 24 hr continuous 21.2 3.5
northwest of produc- 24 hr continuous 21.3 3.5
Sample Sampler
vol. height
(£) (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.
104
-------
Table A-10. PLANT ACTIVITIES DURING SAMPLING AT E. I. 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
105
-------
Table A-11. 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
106
-------
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.
107
-------
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^-GC, 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.
108
-------
'•-.. c
N
PRODUCTION
AREA
I
Figure A-7. Sampling locations at Diamond Shamrock Corporation,
Deer Park, Texas
109
-------
Table A-12. AIR SAMPLING DATA AT DIAMOND SHAMROCK CORPORATION, DEER PARK, TEXAS
General area
Far upwind
Near upwind
Near. upwind
Near downwind
Near downwind
Near downwind
Far downwind
Far downwind
Sample
No. Exact location Sampling period
1 1,300 ft south of "Perc Plant" area 24 hr continuous
2 510 ft southwest of "Perc Plant" 24 hr continuous
area
3 420 ft southeast of "Perc Plant" 24 hr continuous
area
4 1,200 ft northeast of "Perc 24 hr continuous
Plant" area
5 1,300 ft northwest of "Perc 24 hr continuous
Plant" area
6 1,860 ft north northeast of 24 hr continuous
"Perc Plant" area
7 2,850 ft north northwest of 24 hr continuous
"Perc Plant" area
8 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
U/min)
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
Sample
vol.
(I)
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 tat ion Speed
7 66 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 l
765
765
765
766
766
766
766
766
766
\
1
1
1
1
1
1
1
1
1
1
766 > 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
111
-------
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.
112
-------
u>
. r~-\
I 3j.
4200
':!! — | i MJ ill i ««, jjjjte^^
i L^ ii 111 Jji—J
iii woo i II=^F—^"-^jir^i
I I ! 7100 7200 7300 I j I
: i 1 , 1 r ill
,1+SON s
_, i l3 ; 4: ™ U i 260° 'fi< *°° ! l^^p-^'^^l! n|iL_zii!r_--jjp_z]ji
f 1 ! ; ' i 800 e=±=}!=ss=5 I i ; I i ! ! 740° ! II I
\ (l—rf_ ! 'Rn^""1 ' I ' PT ^ I ' ! 7K» i 7200 7300 || I 76OO I: 77OO I TWO \\\
^'^s^M^^^Sy^^ "T """"ir^T'T""! I
_: .if L"^°: nil __J~l:£lvjUI»°° 0iL~J .r~"j .-'z:J.ii L=^l.L-i3.^r^.-i^jl -~
in""r':"i°1[p±s^®i!'; r^n^ !;^ ff^fl f iii r iiin^n s r^ ' iii n'^n I
:l I 1=3. . i' o -o: ' LJ J- K •""«-— f1' i | ill I !i I ;i;i !i
I ,.. zzoo-^ j aoo •. ._... 2100 !• U 2'100 III ' 9IO° 'Ii 9ZO° ! I ' 93O° ! ii1 | 9*°° '! 95O° ! I /
PCTOfECTTV (.IME---4-. Q. 00 N—\7 J . ^ >- i /f
._. ~*T Process Water Outflow into Mississippi River ~ 1 7 '" ., , 3 '
B uj ij i_i i i E F G H I .J K.
ZOMXJE » "" J 3I«»E 37«OOE 42«5OE CIBA — GEIGY
To Stouffer IbStauffw ' TOO..i-? "^ *? cow«uw)«
Figure A-8. Sample locations at Ciba-Geigy Corporation, St. Gabriel, Louisiana
-------
Table A-14. AIR SAMPLING AT CIBA-GEIGY CORPORATION, ST. GABRIEL, LOUISIANA
Sample No
1
2
3
4
5
6
7
Exact location Sampling period
2,200 ft nortWwest of produc- 1st 2 hr of 8 hr
tion area
920 ft north of production area 1st 2 hr of 8 hr
1,600 ft northeast of produc- 1st 2 hr of 8 hr
tion area
800 ft east southeast of produc- 1st 2 hr of 8 hr
tion area
2,200 ft southeast of production 1st 2 hr of 8 hr
area
950 ft south of production area 1st 2 hr of 8 hr
1,600 ft southwest of production 1st 2 hr of 8 hr
Total sampling
time (hr)
7.6
8.8
6.8
6.3
6.4
Lost
6.1
Sampling Sample Sampler
rate (£/min) vol. (4) height (ftl
3.5 1,772 4
3.5 2,164 4
3.5 1,630 4
3.5 1,442 4
3.5 1,561 4
3.5 Lost 4
3.5 1,277 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.
115
-------
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 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
116
-------
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 pentachloronitrobenzene is by chlorination and
nitration of isomeric chlorobenzenes. The production process results in
o
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.
117
-------
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
118
-------
Chlorine
Production
Area
H-l
Figure A-9. Sampling locations at Olin Corporation, Mclntosh, Alabama
119
-------
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
production area
f~~*
N)
° 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 Sample
rate ' vol.
(4/min) (i)
3.5 2,103
3.5 1,100
3.5 1,204
3.5 1,445
3.5 1,473
3.5 1,472
3.5 1,630
3.5 1,525
Sampler
height
(ft)
4
4
4
20^
20S/
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.
121
-------
Table A-17. WEATHER CONDITIONS DURING SAMPLING AT
OLIN CORPORATION, MCINTOSH, ALABAMA
Time
August 18
1500s/
1600s-/
1700s/
1800
1900
2000
2100
2200
2300
24002/
August 19
0100—'
0200S/
O300i/
0400
0500
0600
0700
OSOO3-/
09002/
1000s/
1200S/
Tempera-
ture
37
37
36
26
23
23
23
25
27
29
32
35
Barometric
pressure
(mm 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.
122
-------
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
123~
-------
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 bid 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, soil, 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
~ 124
-------
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
125
-------
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
9
10
Total
Location Sampling period sampling time (hr)
4,700 ft south of production 24 hr continuous 21.6
area
2,500 ft south southeast of 24 hr continuous . 21.4
production area
1,550 ft south of production 24 hr continuous 21.3
area *•
2,300 ft west northwest of 24"'hr continuous 21.0
production area
2,000 ft northwest of produc- 24 hr continuous 19.0-'
tion area
3,500 ft north northwest of 24 hr continuous 22.0
production area
1,250 ft north of production 24 hr continuous 20.7
area
1,250 ft northeast of production 24 hr continuous 21.8
area
2,250 ft east of production 24 hr continuous 21.9
area
2,700 ft east southeast of 24 hr continuous 21.9
production area
Sampling
rate (A/min)
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
Sample Sampler
vol. (A) height (ft)
1,180 4
1,170 4
1,210 4
1,170 4
950^ 4
1,250 4
1,180 4
1,190 4
1,250 4
1,130 4
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.
128
-------
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 1
East-7
a/ Rain.
129
-------
APPENDIX B
ANALYTICAL DATA
130
-------
Table B-l. HCB 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
1935r
0120-0227
0430-0523
0841-0941
1320-1424
1945-2045
0110-0220
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
30
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
Filter
Tenax
Filter
Tenax
Filter
Tenax
Filter
Tenax
HCB
Total ng pg/m3g/
5 0.6
10
< 2 0.2
7
< 2 0.2
6
< 2 0.3
10
4 0.4
10
167 11.3
25
< 2 0.6
18
< 2 1.6
45
< 2 0.3
7
< 2 1.0
32
< 2 0.1
5
< 2 0.2
6
< 2 0.2
8
65 1.7
25
275 11.5
35
2.5 0.6
18
< 2 0.8
20
270 9.7
30
144 5.0
36
131
-------
Table B-l. (continued)
Samp 1 log
gtation
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
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
RGB
Total ng
100
40
38
15
2.2
12
50
16
75
3.3
< 2
38
< 2
18
<2
14
900
21
119
20
<2
250
<2
125
<2
142
< 2
150
< 2
275
<2
116
< 2
46
<2
66
< 2
66
<2
88
pg/m3
3.4
1.1
0.4
1.4
1.5
1.1
0.5
0.4
23.6
3.0.
1.7
0.8
1.0
0.9
1.5
0.6
0.2
0.3
0.3
0.4
132
-------
Table B-l. (continued)
Sampling
station
9
\
10
11
12
Sampling
time
1950-2050
0103-0202
0458-0600
0908-1010
1308-1420
1910-2310
0005-0330
0340-0728
0737-1117
1124-1433
1910-2310
0005-0330
0340-0728
0737-1117
1124-1433
1919-2315
2350-0315
0325-0712
0721-1101
1113-1433
Volume sampled
(liter)
227
223
234
242
272
809
691
768
741
637
856
732
814
785
675
863
738
817
792
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
Filter
Tenax
Filter
Tenax
HCB
Total ng
7
167
<2
65
< 2
114
< 2
87
7
135
< 2
250
< 2
150
< 2
134
<2
91
< 2
97
< 2
278
< 2
109
< 2
75
< 2
78
Sample lost
106
14
850
< 2
300
815
190
875
210
18
260
0.8
0.3
0.5
0.4
0.5
0.3
0.2
0.2
0.1 .
0.2
0.3
0.2
0.1
0.1
0.2
1.0
0.4
1.2
1.4
0.4
133
-------
Table B-l. (continued)
Sampling
station
13
14
15
16
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
2005-0010
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
862
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
Filter
Tenax
Filter
Tenax
Filter
Filter
Tenax
Filter
Tenax
HCB
Total na
5
950
91
320
950
200
900
180
980
280
< 2
40
< 2
< 2
60
< 2
85
< 2
225
< 2
25
< 2
60
< 2
97
< 2
81
5
200
4
330
< 2
138
< 2
160
21
230
< 2
440
1.0
0.5
1.3
1.3
1.7
0.1
0.1
0.1
0.1
0.3
0.03
0.1
0.1
0.1
0.2
0.4
0.2
0.2
0.3
0.8
134
-------
Table B-l. (concluded)
Sampling
station
17
18
Tena™GC
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
HCB
Total ng
NDb/
420
< 2
200
950
130
21
350
925
330
9
395
< 2
230
935
280
3
490
10
320
Hg/m3
0.6
0.3
1.6
0.8
2.1
0.7
0.3
1.6
0.6
0.7
ND
ND
a/ Concentration based on the sum of ng found on the filter and Tenax.
bV ND - None detected.
135
-------
Table B-2. RGB CONCENTRATIONS IN AIR SAMPLES FROM STAUFFER
CHEMICAL COMPANY, LOUISVILLE, KENTUCKY
Concentration
Sampling
station
1
2
3
4
5
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
Type of
sample
Tena«®-GC
Tena^-GC
Tena^5)-GC
Tenaj^-GC
Tenax®-GC
TenaxSSi-GC
Filters
Tenax®-GC
Tenax@-GC
Tenax@-'GC
Tenaj^-GC
Tena^B^GC
Tenax@-GC
Filters
Tenax®-GC
Tenax®-GC
Tenax<®-GC
Tena*5*-GC
Tenaxl^GC
Tenax@-GC
Filters
Tena^GC
Tenaji®-GC
Tena^GC
TenaxiSi-GC
Tenax@-GC
Tenax@-GC
Filters
Tena^SLGC
Tenax!®-GC
Tenaj<®-GC
Tena^-GC
Tenax®-GC
Tenax®-GC
Filters
Volume sampled
(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
(U»g/m3)
HCB
0.04
0.07
0.12
0.05
0.05
0.08
< 0.01
0.08
0.04
0.04
0.03
0.07
0.05
< 0.01
1.1
1.4
0.35
0.35
—
0.19
0.07
2.56
2.06
0.62
0.42
0.16
0.13
1.0
0.85
1.03
0.71
0.36
0.20
0.34
0.09
136
-------
Table B-2. (concluded)
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
Tena*®-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
Concentration
(Ug/m3)
HCB
0.69
0.71
0.45
0.31
0.11
0.19
0.20
0.57
0.53
. 0.24
0.23
0.12
0.28
<0.01
0.32
0.20
0.07
0.16
0.05
0.06
0.01
0.05
0.06
0.02
0.05
0.02
0.03
< 0.01
137
-------
Table B-3. RGB 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®GC (front)
Tenax®GC (back)
Filter
Tenax®bc (front)
Tenax®GC (back)
Filter
Tenax®GC (front)
Tenax^GC (back)
Filter
Tenax®GC (front)
Tenax®GC (back)
Tenax®GC (front)
Tenax®GC (back)
Filter
(R)
Tenax^GC (front)
Tenax®GC (back)
Filter
Vo lume
sampled
(liter)
4,336
427
4,166
3,870
3,713
4,314
962
3,963
Concentration
(ug/m3)
HCB
0.02
ND
ND
< 0.02
ND
ND
0.05
ND
ND
0.08
ND
ND
0.02
ND
ND
< 0.02
ND
ND
< 0.02
ND
ND
< 0.02
ND
ND
Note: ND = none detected.
138
-------
Table B-4. HCB CONCENTRATIONS IN AIR SAMPLES FROM E. I. DU PONT
DE NEMOURS AND COMPANY, CORPUS CHRIST!, TEXAS
Sampling
station Type of
1 Tenax®-GC
Tenax®-GC
Filter
2 TenaxfSLGC
TenaxS^-GC
Filter
3 Tenax^-GC
Tenax1?)-GC
Filter
4 Tenax^-GC
Tenax@-GC
Filter
5 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)
HCB
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
139
-------
Table B-5. RGB CONCENTRATIONS IN AIR SAMPLES FROM DIAMOND
SHAMROCK CORPORATION, DEER PARK, TEXAS
Sampling
station
I
2
3
4
5
6
7
8
Type of sample
Tenax®-GC,
Tenax®-GC,
Filter
Tenax®-GC,
Tenaj^-GC,
Filter
Tenax®-GC,
Tenax®-GC,
Filter
Tenax®-GC,
Tenax®-GC,
Filter
Tenax®-GC,
Tenax®-GC,
Filter
Tenax^-GC,
Tena^-GC,
Filter
Tenax®-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
Volume sampled
(£)
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 (ug/m3)
HCB
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
140
-------
Table B-6. HCB 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
Filter
Tena^-GC
Filter
Filter
Filter
Lost
Filter
Filter
Volume sampled
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
«%
Concentration (ug/nr)
HCB
0.02
ND
0.01
ND
0.02
ND
0.01
ND
0.01
ND
Lost
ND
ND
ND
ND
141
-------
Table B-7. RGB CONCENTRATIONS IN AIR SAMPLES FROM
OLIN CORPORATION, MCINTOSH, ALABAMA
Sampling
station
1
2
3
4
5
6
7
8
Volume sampled
Type of sample
Tenax®-GC,
Tenaxi^GC,
Filter
Tenax@-GC,
Tenax®-GC,
Filter
Tenax®-GC,
Tenax®-GC,
Filter
Tenax®-GC,
Tenax@-GC,
Filter
Tenax®-GC,
Tenax@-GC,
Filter
Tenas®-GC,
Tenax®-GC,
Filter
Tenax®-GC,
Tenax@-GC,
Filter
Tenax®-GC,
TenaxS®-GC,
Filter
front
back
front
back
front
back
front
back
front
back
front
back
front
back
front
back
U)
2,103
2,103
2,103
1,100
1,100
1,100
1,204
1,204
1,204
1,445
1,445
1,445
1,473
1,473
1,473
1,472
1,472
1,472
1,630
1,630
1,630
1,525
1,525
1,525
Concentration (ug/m3l
HCB
0.26
ND
ND
0.06
ND
ND
0.04
ND
ND
0.48
0.08
ND
0.24
ND
ND
0.03
ND
ND
2.22
ND
ND
1.11
ND
ND
142
-------
Table B-8. HCB CONCENTRATIONS IN AIR SAMPLES FROM PPG
INDUSTRIES, LAKE CHARLES, LOUISIANA
Sampling
station
1 .
2
3
4
5
6
7
8
9
10
Volume sampled
Type of sample
Tenaj^-GC, front
Tenaa@-GC, back
Filter
Tenaj@-GC, front
Tenaji®-GC, back
Filter
Tenax®-GC, front
Tena3@-GC, back
Filter
Tenax®-GC, front
Tenax®-GC, back
Filter
Tena^§X-GC, front
Tena*®-GC, back
Filter
Tenaj@-GC, front
Tena^5)-GC, back
Filter
Tena2$-GC, front
Tena3®-GC, back
Filter
Tenaj@-GC, front
Tena3®-GC, back
Filter
Tena^-GC, front
Tena^-GC, back
Filter
Tena^-GC, front
Tena^-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 (ug/nr)
' HCB
0.02
ND
0.42
0.02
ND
0.07
0.03
ND
0.13
ND
ND
1.30
ND
ND
1.47
0.03
ND
0.33
0.03
ND
1.63
ND
ND
ND
ND
ND
ND
ND
ND
0.02
143
-------
APPENDIX C
METHOD DEVELOPMENT FOR SAMPLING AND ANALYSIS
144
-------
LITERATURE SEARCH
A search of the literature to 1967 revealed that there was no specific
method for sampling RGB 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.JLli' HCB
in water samples is concentrated by extraction with appropriate organic
solvents. In some cases, HCB is concentrated by passing the water sample
through a column filled with an appropriate trapping medium. Gesser et al.ft/
used a glass column with two polyurethane plugs, and found that HCB, along
with a number of polychlorinated biphenyls, could be absorbed on the column.
These compounds were then extracted by treating 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 pesticides, '
Sampling of HCB in air is generally carried out by trapping the com-
pound either in an appropriate organic solvent or in an appropriate organic
resin. Columns of wood-charcoal cigarette-filter in series as well as silica
gel have been used to trap HCB in air.H-lft/ The HCB is recovered by appro-
priate solvent extraction. Organic resins such as Chromosorb A and Chromosorb
101 have been used to trap HCB and other chlorinated pesticides.J^il^./ A
nylon-chiffon cloth (0.25 or 0.5 wr~) 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.±Z/
Another organic resin, Tenax®-GC, has been reported to be an efficient trap-
ping 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 HCB was suspected to be low, an Amberlite XAD-4 column
would be used to concentrate the two substances. Both sampling techniques
were evaluated prior to actual field sampling.
Hexane Extraction
Table C-l shows the results of recovery studies for ri-hexane extrac-
tion of HCB from water samples fortified with 1 to 30 p,g/liter. Each of the
water samples (1 liter) was extracted with three 10-ml aliquots ii-hexane,
made up to the mark of a 100-ral volumetric flask, and analyzed for HCB by
gas chromatography. The average recovery was over 100% for HCB. The slightly
positive error observed in the HCB recovery studies was probably due to the
fact that the fortified HCB samples and the standard HCB solution used for
calibration were prepared from two different stock solutions.
145
-------
Table C-l. RECOVERY STUDIES OF RGB BY n-HEXANE EXTRACTION
Sample
1
2
3
4
5
6
7
Blank
Amount in 1 liter
of water
1
2
3
5
10
20
30
None
Amount found in
n-hexane
1.1
2.2
3.4
5
11
22
32
None
% Recovery
110
110
113
100
110
110
106
Elution from Amberlite XAD-4
Water samples fortified with 1 to 30 Vig/liter of RGB 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 ji-hexane. Table
C-2 shows that the average recovery of HCB was greater than 70% (first
five runs).* Recoveries of HCB with either a closed or open system showed
no significant difference, indicating volatilization of HCB is not a problem
over short time periods.
Table C-2. RECOVERY OF HCB FROM WATER BY CONCENTRATION ON XAD-4
Run (U.R/4)
1 (30)
2 (30)
3 (1 )
4 (5 )
5 (30)
6 (30) I/
Flow rate
(ml/min)
2
2
2
2
8
10 1
Recovery from
ii-hexane
elution (%)
65
63
85
73
80
77
Recovery from
Soxhlet
extraction
0
0
0
0
0
0
Recovery from
water
extraction (%)
13
17
0
0
3
14
a/ Closed elution system.
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 extrac-
tion.
146
-------
Evidence of volatilization loss of RGB was demonstrated by the re-
sults of the following experiment. Five 250 ml water samples fortified with
5 y,g/liter of HCB were placed in five 250 ml separatory funnels. Three of
the funnels were left uncapped overnight while the remaining two funnels
were capped. Each water sample was then extracted and analyzed for HCB.
The results, shown in Table C-3, indicate that measurable amounts of HCB
were lost due to volatilization from the open system.
Table C-3. LOSS OF HCB DUE TO VAPORIZATION
Run Separatory funnel HCB recovery (%)
1 Capped 94
2 Capped 94
3 Uncapped 58
4 Uncapped 55
5 Uncapped 51
AIR SAMPLING AND RECOVERY STUDIES
Chromosorb 101 and Tenax®-GC were tested for their trapping efficiency
utilizing a device shown in Figure C-l. This device was initially designed
to check the recovery of HCB from water by vaporization at reduced pressure.
The results also indicate efficiency for collecting HCB from water-saturated
air.
One liter of water, fortified with 1 to 30 jig/liter of HCB, was placed
in a one-neck 24/^0 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
ii-hexane in an ultrasonic bath, then by overnight Soxhlet extraction. The
remaining water was also extracted with ja-hexane. All the extracts were
analyzed for HCB 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 HCB concentrations. In general, under these experi-
mental conditions, the trapping and recovery of HCB with Tenax®-GC is more
effective than with Chromosorb 101.
147
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00
.6 in.
Trapping Column
•18/7
Ball Joint
Thermometer
Pit
Heating
Mantle
To Meleod Gauge
T Pinch
Of- v Clamp
n 1
Cold Trap
To Water Aspirator
or Mechanical Pump
Figure C-l. Apparatus for recovery of RGB from water by vaporization
at reduced pressure
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Table C-4. RECOVERY OF HCB FROM WATER-SATURATED AIR
Run Column
1 Chromosorb 101
2 Tenax®-GC
3 Tenax®-GC
4 Tena:x®-GC
5 Tena*®-GC
6 Tenax®-GC
7 Tenax®-GC
Total HCB
in sample
(y.g)
30
30
1
1
5
30
30
7
10
Recovery
from
ultrasonic
extraction
7
10
Recovery
from
Soxhlet
extraction
None de-
tected
100
94
85
102
90
86
None de-
tected
Trace
Trace
Trace
Trace
2
2
% Recovery
from
extraction
of water
46
6
5
2
4
3
9
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 HCB 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-
TM
mental Research Center, USEPA. A Florisil column was used for sample
cleanup and 67o ethyl ether in petroleum ether was used for the elution of
HCB.
Two different procedures were used to prepare fortified sediment sam-
ples. In the first method, HCB was added to known amounts of sediment prior
to evaporation of moisture from the sediment; in the second method, HCB 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 HCB 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 HCB improved significantly. Therefore, direct Soxhlet extraction
of the sediment was chosen as the standard method. However, if interferences
from other impurities were present, FlorisilM cleanup would be used. The
amount of HCB determined in the sample analysis was reported on dry weight
basis.
149
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Table C-5. RECOVERY OF HCB FROM SEDIMENTS
Run Sample weight (g) Amount HCB added (p,g) % Recovery (HCB)
Li/ 50 5 59
2£/ 50 5 64
3k/ 50 5 73
4k/ 50 5 67
5 50 Control ND
6£/ 50 5 95
7£/ 50 5 98
a/ HCB added before moisture in sample was almost evaporated to dryness.
b/ HCB added after moisture in sample was almost evaporated to dryness.
c/ Direct Soxhlet extract of sample.
150
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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., 6(7):36 (1974).
4. Gesser, H. D., et al., Anal. Letter, 4_(12):883-886 (1971).
5. Hyndshaw, A. Y., J.A.W.W.A., 64j309 (1972).
6. Buelow, R. W., J. K. Carswell, and J. M. Symons, J.A.W.W.A., 65j57 (1973).
7. Ibid., 65jl95 (1973).
8. Burnham, A. K., G. V. Calder, J. S. Fritz, G. A. Junk, H. J. Svec, and
R. Willis, Anal. Chem., 44j 139 (1972).
9. Kennedy, D. C., Environ. Sci. Technol., 7(2):138 (1973).
10. 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).
11. Lebedeva, T. A., et al., Metody Anal. Pestits.. pp. 57-59 (1970) in
Russian.
12. Dranovskaya, L. M., and A. G. Gul'ko, Ostsillogr. Peremen. Polyarografiya,
pp. 163-167 (1971).
13. Gul'ko, A. G., L. M. Dranovskaya, and V. F. Chernokan, Aktual. Vop. Gig.
Epidemiol.. pp. 71-73 (1972).
14. Grob, K., and G. Grob, J. Chromatogr., 62(1):1-13 (1971).
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.. 62J1): 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 at the
25th Pittsburgh Conference on Analytical Chemistry and Applied
Spectroscopy (1974).
151
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TECHNICAL REPORT DATA
(Please read Insinii'tions on the reverse before completing)
1. REPORT NO.
EPA 560/6-76-001
2.
3. RECIPIENT'S ACCESSION-NO. •
4. TITLE AND SUBTITLE
Sampling and Analysis of Selected Toxic Substances
Task 1A - Hexachlorobenzene
5. REPORT DATE
June 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
R. T. Li, J. L. Spigarelli and J. E. Going
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 1975
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Nine industrial plants were sampled to determine hexachlorobenzene (HCB) levels
in air, water, soil and sediment. The plants represent six major industries: per-
chloroethylene, trichloroethylene, carbon tetrachloride, chlorine, triazine herbicides
and pentachloronitrobenzene. In general, higher levels of HCB were associated with
the production of lower chlorinated hydrocarbons than with the production of other
chemicals. HCB levels in soil and air at the pentachloronitrobenzene plant were rela-
tively high. The levels of HCB associated with plants producting chlorine and tri-
azine herbicides were very low. Several different waste-disposal methods were used at
the perchloro-and trichloroethylene plants that were sampled. The highest level of
HCB was detected in air and soil at the plant using on-site landfill and open pit
storage. High HCB levels were detected in loading and transfer areas at plants using
off-site disposal methods.
The highest level of HCB found in the air on plant property was 24 ug/m3. The
HCB level in an open waste treatment pond was 306 ug/liter. The level of HCB in soil
within the plant area'was over 1,000 ug/g at three plants. The maximum concentration
^_ . (continued) ,
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Monitoring - Air, Water, Soil, Sediment
Hexachlorobenzene
Organic
Chemistry
3. DISTRIBUTION STATEMENT
Release Unlimited
16. SECURITY CLASS (This Report/
Unclassified
21. NO. OP PAGES
20. SECURITY CLASS (THIS page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
152
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TECHNICAL REPORT DATA
16. Abstract
of HCB in air sampled off plant property was 0.36 jig/m . A level of 3
was detected at the boundary of another plant. Soil taken from a cornfield
adjacent to one plant contained 1.1 ug/g, and over 3,000 ug/g were detected
along a boundary road of another. HCB levels in water sampled beyond the
plant property exceeded 1 ug/liter at two plants.
Samples were collected from two sewage treatment plants; negligible
quantities of HCB were detected.
153
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