U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-253 051
Survey of Methods Used to
Control Wastes Containing
Hexachlorobenzene
TRW Systems Group
Prepared For
Environmental Protection Agency
1976
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BIBLIOGRAPHIC DATA
SHEET
I. Report No.
EPA/530/SW-120C
PB 253 051
4. Tide and Subtitle
SURVEY OF METHODS USED TO CONTROL WASTES CONTAINING
HEXACHLOROBENZENE
5. Report Date
November 1975
6.
7. Author(s)
S. Quinlivan, M. Ghassemi. H. Santy
& Performing Organization Kepi.
No.
9. Performing Organization Name and Address
TRW Systems, Inc.
One Space Park
Redondo Beach, CA 90278
10- Task no.
68-01-3203
II. Contract/Grant No.
68-01-2956
12. Sponsoring Organisation Name and Address
Office of Solid Waste Management Programs
U.S. Environmental Protection Agency
Washington, D.C. 20460
13. Type of Report & Period
Covered
14.
15. Supplementary Notes
16. Abstracts
stuc|y presents the results of a survey of methods used to control wastes
containing hexachlorobenzene (HCB). The specific objectives were to identify the
sources and characteristics of manufacturing wastes containing HCB, to document
methods used for treatment and disposal of HCB wastes, and to evaluate the environ-
mental adequacy of the treatment and disposal methods.
17. Key Words and Document Analysis. 17a. Descriptors
Hexachlorobenzene (HCB), disposal, environmental control, hazardous wastes,
industry survey.
17b. Idemiflers/Opin-Lndcd Terms
Chemical waste survey, chemical waste control and disposal.
17c. COSATI Fie Id/Group
18. Availability Statement
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
21. No. of PJRCS
I f"+
Pai
'8=
Ul
'NCLASSIFIED
FORM NTIS-35 (REV. 3-721
USCOMM-DC 14gs2-P72
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SURVEY OF METHODS USED
TO CONTROL WASTES CONTAINING HEXACHLOROBENZENE
This final report (Sti-12Qo) describes work performed
for the Federal solid waste management programs under contract No. 68-01-2956
and is reproduced as received from the contractor
U.S. ENVIRONMENTAL PROTECTION AGENCY
1976
i-fl
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This report has been reviewed by the U.S. Environmental Protection
Agency and approved for publication. Approval does not signify that
the contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency, nor does mention of commercial products
constitute endorsement by the U.S. Government.
An environmental protection publication (SW-120c) in the solid waste
management series.
ii
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PREFACE AND ACKNOWLEDGEMENTS
This report presents the results of a survey of methods used to
control wastes containing hexachlorobenzene {HCB). The survey was
conducted by TRW Systems under Contract BOA 68-01-2956, Task Order
68-01-3203, for the EPA Office of Solid Waste Management Programs,
(OSWMP). The project is deeply indebted to the EPA Project Officer,
Mr. Thomas Leshendok, Hazardous Waste Management Division, OSWMP,
for his continuing advice and guidance during the course of the study.
Thanks are also due to other staff members of the Office of Solid Waste
Management Programs for their critical review of the draft final report.
TRW wishes to express its sincere gratitude to the technical and
management personnel at industrial facilities and company headquarters
who participated in the survey and arranged for site visits and/or
provided information for use in the study. The assistance received from
various State agencies (in particular, Louisiana State Health Department,
Section of Solid Waste and Vector Control, and Air Control Section) and
non-industrial organizations are acknowledged. Special thanks are due to
Dr, W. Farmer of the University of California at Riverside for discussing
recent research findings on control of HCB volatilization at land disposal
sites.
iii
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TABLE OF CONTENTS
Page
PREFACE AND ACKNOWLEDGEMENTS 111
LIST OF TABLES vi
LIST OF FIGURES vlii
1. SUMMARY 1
2. CONCLUSIONS 7
3. INTRODUCTION 9
4. METHODOLOGY 11
5. RESULTS AND DISCUSSION 13
5.1 HCB WASTE GENERATION SURVEY 13
5.2 INDUSTRIAL OPERATIONS PRODUCING HCB WASTES 16
5.2.1 Basic Production of HCB 16
5.2.2 Chlorinated Solvents Production . 17
5.2.3 Pesticide Industry 17
5.2.4 Electrolytic Chlorine Production 20
5.2.5 Ordnance and Pyrotechnics Production 22
5.2.6 Sodium Chlorate Production 25
5.2.7 Aluminum Manufacture 25
5.2.8 Seed Treatment Industry 28
5.2.9 Pentachlorophenol (PCP) Production 29
5.2.10 Wood Preservative Industry 29
5.2.11 Electrode Manufacture 31
5.2.12 Cyanogen Chloride Production 33
5.2.13 Vinyl Chloride Monomer (VCM) Production 33
5.2.14 Synthetic Rubber Production 35
5.3 CHARACTERISTICS OF HCB-CONTAINING WASTES 35
5.4 ESTIMATED HCB WASTE QUANTITIES 37
5.4.1 Total Waste Quantities and Comparison of
Estimates with Those Made in an Earlier
Study 37
5.4.2 Chlorinated Solvents 40
iv
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TABLE OF CONTENTS (CONT'D)
Page
5.4.3 Pesticide Industry 42
5.4.4 Electrolytic Chlorine Production 44
5.5 WASTE HANDLING, TREATMENT AND DISPOSAL 47
5.5.1 Waste Handling (Storage and Transportation) . . 47
5.5.2 Waste Treatment 55
5.5.3 Ultimate Disposal 56
5.5.3.1 Land Disposal 58
5.5.3.2 Deep-Well Injection . '. 62
5.5.3.3 Drying Pond 63
5.5.3.4 Incineration 63
5.5.3.5 Miscellaneous Disposal Methods .... 67
5.5.4 Resource Recovery 68
5.6 ULTIMATE DISPOSAL TECHNOLOGY CLASSIFICATION AND
EVALUATION 68
5.7 WASTE HANDLING AND DISPOSAL COSTS 71
6. REFERENCES 76
7. APPENDIX 80
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LIST OF TABLES
Page
Table No.
1 HCB Waste Generation Survey, Number of Firms
Contacted and Responses Received 15
2 Companies, Domestic Sites and Production Rates
or Capacities for Carbon Tetrachloride,
Perch!oroethylene, Trichloroethylene and
Dlchloroethylene 18
3 Producers, Formulators and the Number of
Distributors for Mi rex, Dacthal, Simazine,
Atrazlne, Propazine and PCNB 21
4 Electrolytic Chlorine Producers Using Graphite
Anodes and Production Sites ... .... 23
5 Electrolytic Chlorine Producers Using DSA's or
Other Non-Graphite Electrodes, and Production
Sites 24
6 Sodium Chlorate Producers, Production Sites and
Type of Anode Used 26
7 Aluminum Manufacturers (Smelters) and Company
Headquarters 27
8 Pentachlorophenol (PCP) Producers and Production
Sites 30
9 Electrode Manufacturers and Company Headquarters ... 32
10 Vinyl Chloride Monomer Producers and Production
Sites 34
11 General Characteristics of HCB-Containing Waste
Streams for Chlorinated Solvent and Pesticide
Manufacturing Industries, Based on Data for
Specific Production Sites . 36
12 HCB Waste Quantities 39
13 Production Sites and HCB Waste Quantities for
Chlorinated Solvents Production 41
14 Chlorinated Solvents Producers Reporting no HCB
Waste Generation or Having No Analytical Data .... 43
vi
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LIST OF TABLES (CQNT'D)
Page
Table No.
15 Quantities of HCB Hastes from Pesticide
Manufacture 45
16 Electrolytic Chlorine Producers Using Graphite
Anodes Which Were Contacted in This Survey 46
17 Methods of HCB Waste Treatment, Handling and
Transport Based on Data for Specific Production
Sites 4*a
18 Prevalence of Methods Used for Ultimate Disposal
of HCB Wastes , 57
19 Methods and Sites for Land Disposal of HCB Wastes ... 59
20 Sites for the Incineration of HCB Wastes 64
21 Resource Recovery Methods for Processing HCB-
Containing Wastes ' 69
22 Disposal Technology Classification 72
23 Costs for Off-Site Disposal of HCB Wastes 74
24 Costs for On-Site Disposal of HCB Wastes 75
25 Costs for HOC Tars Concentration and Storage
System at Plant Site D 75
A-l Key to Plant Sites, Their Locations and Sources
of Wastes 80
A-2 Key of Off-Site Waste Disposal Contractors Handling
HCB Wastes, Their Locations and Plant Sites Serviced . 82
A-3 General and Hazardous Characteristics of HCB 83
A-4 HCB Waste Data Requested From Some Industries/
Plants 84
A-5 Non-Industrial Agencies Contacted for Data
Acquisition . 87
vii
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LIST OF FIGURES
Figure No.
1 Photographs of Drummed HCB Wastes at a
Sanitary Landfill 52
2 Tar Concentration and Storage Facility
At Plant Site D 53
viii
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1. SUMMARY
Under a contract with the EPA Office of Solid Uaste Management Pro-
grams, Hazardous Waste Management Division, TRW conducted a survey of
methods used to control wastes containing hexachlorobenzene (HCB). The
specific objectives of the study were to identify the sources and charac-
teristics of manufacturing wastes containing HCB, to review and document
methods used for treatment and disposal of HCB wastes, and to evaluate the
environmental adequacy of the treatment and disposal methods.
The data collected and used in this study were obtained from the
following sources: (a) published literature; (b) telephone contacts and
formal correspondence with industrial firms; (c) visits to production sites
and waste disposal facilities; and (d) discussions and interviews with
technical staffs in academic institutions, research establishments, trade
organizations, and State and Federal agencies. The initial phase of the
program concentrated on the identification of all possible sources for the
generation of HCB wastes. Based on a literature search and some contact
with industry, the following fourteen industries/operations were initially
identified as possible sources of HCB wastes.
Industry/Operation Potential Origin of HCB Wastes
Basic HCB production HCB production operation
Chlorinated solvents production Reaction side-product in the production
of chlorinated solvents, mainly,
carbon tetrachloride, perchloro-
ethylene, trichloroethylene, and
dichloroethylene
Pesticide industry Reaction side-product in the production
of Dacthal, simazine, mirex, atrazine,
propazine, and pentachloronitrobenzene
(PCNB)
Electrolytic chlorine production Chlorine attack on the graphite anode
or its hydrocarbon coating
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Industry/Operation
Potential Origin of HCB Waste
Ordnance and pyrotechnics
production
Sodium chlorate production
Aluminum manufacture
Seed treatment industry
Pentachlorophenol production
Use of HCB in the manufacture of pyro-
technics, and tracer bullets and
other ordnance items
Similar to electrolytic chlorine pro-
duction, where graphite anodes are
used
Use of HCB as a fluxing agent in
aluminum smelting
Use of HCB in seed protectant formu-
lations
Reaction by-product of PCP production
by chlorination of phenol
Wood preservative industry
Electrode manufacture
Cyanogen chloride production
Vinyl chloride monomer
production
Synthetic rubber production
Use of HCB as a wood preserving agent
Use of HCB as a porosity control in
the manufacture of graphite anodes
Cyanogen chloride production process
By-product in the manufacture of vinyl
chloride monomer
Use of HCB as a peptizing agent in
the production of nitroso and
styrene rubbers for tires
Subsequent to the identification of the above listed industries, a
number of firms in each industry were contacted and inquiries made regard-
ing HCB waste generation and quantities. Of the total of 232 firms reported
for the above listed industries, 80 firms (34 percent) were contacted in
this survey. Of these 80 firms, 21 (26 percent) indicated that their waste
streams contained HCB, 40 (50 percent) indicated that their waste streams did
not contain HCB, and 19 (24 percent) either indicated that they did not know or
that they preferred not to discuss the matter. The percentage distribution
of the three types of response varied for the various industries. Based
on the survey results, chlorinated solvents and pesticide industries were
identified as the major sources of HCB wastes and were subsequently subjected
to in-depth evaluation from the standpoint of waste generation and treatment
and disposal methods.
2
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Based on the data collected In this survey, of the estimated 3,900
metric tons of HCB waste* which is generated annually in this country,
2,400 metric tons (2,650 tons) is produced as a by-product waste in the
production of chlorinated solvents. Of the 16 companies manufacturing
chlorinated solvents, 5 representing 7 production sites and accounting for
an estimated 37.3 percent of the total U.S. chlorinated solvents production
capacity, indicated that HCB was a constituent of their waste streams and
provided data (in some cases very limited) on waste quantities and treat-
ment and disposal methods. These production sites are designated in this
report as Plant Sites A, B, C, D, E, F and J.f HCB waste quantities
generated at three production sites (Plant Sites G, H, and I) were esti-
mated based on data provided by an off-site disposal contractor which had
previously handled HCB waste from Plant Site G and the data collected for
similar production operations at other plant sites. Plant Sites G, H and
I account for an estimated 21.2 percent of the total U.S. chlorinated solvents
production capacity.
Five additional chlorinated solvents production plants representing
an estimated 41.5 percent of the total U.S. chlorinated solvents production
capacity responded in one of the following ways: (a) they use the CS2 pro-
cess which does not generate HCB waste; (b) they have not detected HCB in
their waste streams; and (c) they have not analyzed their waste stream for
HCB content. For the plants surveyed, HCB-containing waste streams are
usually in the form of heavy ends waste liquids from various distillation
or purification processes within the manufacturing operation. Two plants
Except when noted as "HCB-Containing Waste", throughout this report
all quantitative data on HCB wastes refer to the HCB content of the
wastes (i.e., the amount of HCB contained in the waste stream).
Many of the companies participating in the present study submitted
data to TRW on a proprietary basis. To protect the proprietary
interests, where appropriate the participating companies (plant
sites and waste disposal contractors) are referred to in this
report by designated letters of alphabet (e.g., Plant Site A or off-
site waste disposal contractor OC-1, etc.). Tables A-l and A-2 in
the Appendix identify the states in which the production sites and
off-site contractors are located.
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recover HCB from chlorinated solvents wastes. Each year approximately
240 metric tons (265 tons) of HCB is recovered for sale. This quan-
tity, however, accounts for only 10 percent of the total HCB generated
by the chlorinated solvents industry; the other 90 percent is dis-
charged in the waste streams which are disposed of on land or are
incinerated.
In the pesticide industry, the production of Dacthal, PCMB, nn'rex
simazine, atrazine, and propazine result in the generation of HCB wastes.
At the present, Dacthal, PCNB, and mirex each is produced at only one pro-
duction site and by a different company. Simazine, atrazine and propazine
are produced at one site by one company. Pesticide production sites are
designated as Plant Sites Q, R, S and T. The estimated total quantity of
HCB waste generated in the pesticide industry is 1,499 metric tons (1,655
tons) per year with wastes from Plant Sites R and Q accounting for 84.5
percent and 15.1 percent of the total, respectively, The HCB is present
mainly in tars and still bottoms from manufacturing operation.
For a total of 2,870 metric tons (3,168 tons) per year of HCB waste
for which data were obtained from industry on waste handling methods, the
currently used waste storage methods and the percentage of waste handled
by each method are: storage of solid cubes under plastic cover, 44.2 per-
cent; water-covered open storage lagoons, 33.1 percent; drums which may
or may not be lined, 14.3 percent; insulated and heated storage tanks,
8.2 percent; and nitrogen-blanketed steel tank, <0.1%. Methods used for
waste transportation and the percentage of waste handled by each method
are: truck, 38.4 percent; forklift, 35.7 percent; pipeline, 19.1 percent;
heated tank trucks, 6.6 percent; and rail, 0.1 percent. Loading, storage
and transportation of waste can result in environmental contamination if
the operation is not managed properly or in cases of accidents and spills.
At some HCB waste generation and disposal sites some form of treatment
is utilized prior to ultimate waste disposal. These treatment methods
include use of storage lagoons to effect settling of HCB solids, distillation
to effect waste volume reduction and material recovery, heating to effect
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fluidization during storage and bulk transportation by pipeline and trucks,
solidification and shaping into cubes for storage, dewatering for waste
concentration, and dilution and suspension by mixing with other wastes
prior to deep well injection.
Methods currently used for the ultimate disposal of HCB wastes include
land disposal (sanitary landfill* industrial landfill, deep well injection
and drying ponds), incineration (with or without by-product recovery), open
pit burning, resource recovery, discharge to municipal sewage treatment
plants, and emission to the atmosphere. Both on-site disposal and off-site
contract disposal are used. Based on a total waste quantity of 2,444 metric
tons (2,64? tons) for which data were obtained on waste disposal methods,
land disposal is currently the most prevalent method for ultimate disposal of
HCB wastes. Nine of the 22 sites surveyed use land disposal; approximately
1,389 metric tons (1,483 tons) of HCB wastes (56 percent of the total) are
disposed of by this method each year. Among land disposal methods,
industrial landfill is the most widely used method, accounting for the dis-
posal of 39.7 percent of all HCB wastes. Ranked next to land disposal is
incineration which is used at nine of the sites surveyed for the destruction
of 1,055 metric tons (1,164 tons) per year of HCB wastes. One incineration
site handling 680 metric tons (750 tons) of HCB waste per year, recovers
hydrochloric acid as a by-product. No data were available on the quantity of
HCB wastes which is used at one site as a chemical feedstock for the pro-
duction of low-molecular weight aliphatic halogenated hydrocarbons. Compared
to land disposal and incineration, the quantities of waste discharged to
sewage treatment plants and to the atmosphere appear to be very small.
Of the 22 sites surveyed, 6 use the services of commercial off-site dis-
posal contractors for the disposal of a total of 655 metric tons (723 tons)
per year of HCB wastes.
Methods for the ultimate disposal of HCB wastes were evaluated in terms
of three levels of technology representing the prevalent practice (Level I),
the best technology available in current commercial practice (Level II),
and technology currently known and assessed as providing adequate health
and environmental protection (Level III). Based on the quantity of HCB
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wastes handled, Industrial landfill on a suitable geological formation and
with a cover consisting of 1.2 to 1.8 m (4 to 6 feet) of soil and a 0.025
cm (10-mil) thick polyethylene film placed at approximately mid-depth of
the soil cover would be the Level I technology. However, based on the
number of sites which use a disposal method, incineration without by-
product recovery but with emission control would be the Level I technology.
Incineration with emission control and by-product recovery is considered
as Level II and Level III technology. Data for operating sites indicate
that HCB can be effectively destroyed by incineration with little emission
of pollutants to the atmosphere. An incineration system of proprietary
design at Plant Site G is reported to effect 99.94 percent destruction of
HCB and allows for recovery of HC1 as a by-product.
Not all industries and waste disposal facilities which were contacted
furnished information on the costs for handling and disposal of HCB wastes.
Some of the companies and waste disposal facilities indicated that they
cannot break down their total cost to arrive at any meaningful estimate of
the portion of the cost which can be attributed to the handling of HCB
wastes, which accounts for a small fraction of the total waste handled. The
cost charged to waste generators by four off-site waste disposal contractors
employing landfill, incineration and deep-well injection range from $22 to
$35 per metric ton ($20 to $32 per ton) of HCB-containing wastes. At one
plant site, the cost for the operation of a pretreatment lagoon, removal
and transport of waste from the lagoon to an industrial landfill, and equip-
ment maintenance is estimated at $11 per metric ton ($10 per ton).
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2. CONCLUSIONS
Of the 14 industries/operations identified as possible sources
for HCB waste generation, chlorinated solvents production and
pesticide manufacturing are the two major sources of HCB wastes
accounting for nearly all of the reported HCB waste generation
quantities.
t HCB has been detected in waste effluents from electrolytic
chlorine production, pyrotechnic and ordnance manufacture and
seed treatment industries. Adequate analytical data are not
available to assess the magnitude of HCB generation and spe-
cific operations resulting in HCB production in these
industries.
The largest current use of HCB is as a peptizing agent in the
manufacture of nitroso and styrene rubber for tires. The use
of large quantities of HCB in the manufacturing of synthetic
rubber is very new and quantitative and qualitative data are
not available on waste generation possibilities and environ-
mental implications associated with such a usage.
Based on contacts with a number of firms/plants in the aluminum
manufacturing, pentachlorophenol production, electrode manu-
facture, and vinyl chloride monomer production industries, HCB
wastes are not associated with these industries »
Adequate data are not available to assess the magnitude of HCB
problem in the wood preservative industry, cyanogen chloride
production, and sodium chlorate production.
The hauling of HCB wastes in open drums and the dumping of the
drums in a normal sanitary landfill operation can present a
significant potential for contamination of air, land, water
and wildlife.
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Disposal of HCB in sanitary or industrial landfills can be
environmentally acceptable if an adequate soil cover which
includes an intermediate layer of plastic is provided and
the geology of the site is suitable for waste and leachate
containment.
Incineration with emission control and by-product recovery
appears to be the most desirable and environmentally accept-
able technology for the destruction of HCB wastes. Design
data, operating conditions and cost data are not available
on the only unit of this kind currently in operation at one
plant site.
Very limited actual disposal cost data are available on
existing facilities handling HCB wastes.
At most facilities which generate HCB wastes, these wastes
account for only a fraction of the total waste effluent.
At these facilities, the handling of HCB wastes cannot be
considered as an isolated problem requiring a separate
solution, but rather should be viewed as an element in the
total waste management plan for the facility.
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4. METHODOLOGY
The data collected and used in this study were obtained from the
following sources: (a) published literature; (b) telephone contacts and
formal correspondence with industrial firms; (c) visits to production sites
and waste disposal facilities; and (d) discussions and interviews with
technical staffs in academic institutions, research establishments, trade
organizations, and State and Federal agencies. In the body of the report,
the source or sources of data are identified, where appropriate.
The first step in data gathering was a preliminary literature survey
in which industries, plants, and operations suspected of generating HCB
wastes were identified. This was then followed by telephone inquiries and
submission of formal requests for data to the company headquarters and
plants. The specific data which were requested from some industries/plants
contacted are illustrated in the questionnaire form shown as Table A-4 in
the Appendix. The requested data included information on source(s) of HCB
wastes; commodity production and HCB generation rates; physical and chemical
characteristics of waste streams containing HCB; and waste handling, treat-
ment, and disposal methods and associated costs. Overall, a total of 80
companies (some operating more than one production site) were contacted. A
listing of the non-industrial agencies contacted are presented in Table A-5
in the Appendix.
Six site visits were made for data collection. These included visits
to two major waste generation sites (designated as plants B and F in
Table A-l in the Appendix), two visits to waste disposal sites (designated
as OC-1 and OC-4 in Table A-2 in the Appendix), one trip to New Orleans,
Louisiana, for discussions with the personnel at the Louisiana State Health
Department (Section of Solid Waste and Vector Control, and Air Control
Section), and one trip to the University of California at Riverside
(California) to discuss research findings on control of HCB volatilization
at land disposal sites.
11
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The data which were collected In the survey were collated and
evaluated, and are presented (in summary form) and discussed in the
sections of this report which follow.
12
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5. RESULTS AND DISCUSSION
This Chapter presents and discusses the data obtained on industries
and operations which produce HCB-containing wastes, quantities and charac-
teristics of the wastes, and methods and procedures used for handling, treat-
ment, and disposal of the wastes. A discussion of the environmental
adequacy of waste treatment/disposal methods is also presented in the per-
tinent sections of this Chapter.
5.1 HCB WASTE GENERATION SURVEY
The following 14 industries/operations were identified as possible
sources for the generation of HCB wastes:
(1) Basic HCB production
(2) Chlorinated solvents production
(3) Pesticide industry
(4) Electrolytic chlorine production
(5) Ordnance and pyrotechnics production
(6) Sodium chlorate production
(7) Aluminum manufacture
(8) Seed treatment industry
(9) Pentachlorophenol production
(10) Wood preservative industry
(11) Electrode manufacture
(12) Cyanogen chloride production
(13) Vinyl chloride monomer production
(14) Rubber manufacturing
A number of firms in each of the industries listed above were contacted
and Inquiries were made regarding the presence of HCB in their waste streams.
The number of firms in the first 13 industries listed above which were
13
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contacted, the estimated number of firms in each industry, and the number
of responses received from the firms contacted are summarized in Table 1.
(It is only very recently that large quantities of HCB have been used in
the manufacturing of synthetic rubber. Very little data are available on
HCB use, and waste generation and treatment in the rubber manufacturing
industry. Although identified here as a possible source of HCB wastes, the
synthetic rubber industry was not included in this survey.) Relative to
the estimated total number of firms in the various industries, the number
of firms contacted in general represent an adequate sampling of the indus-
tries reviewed. Indeed, for some industries, more than 50 percent of the
estimated total number of firms were contacted (e.g., for chlorinated
solvents production and vinyl chloride production). Some of the firms con-
tacted own and operate more than one plant; some of these firms provided
information on more than one or all of their facilities. Of the total of
80 firms surveyed, 21 (26 percent) indicated that their waste streams con-
tained HCB, 40 (50 percent) indicated that their waste streams did not
contain HCB, and 19 (24 percent) either indicated that they did not know
or that they preferred not to discuss the matter. The percentage distri-
bution of the three types of response varied for the various industries.
Thus, for chlorinated solvents production, of the 11 firms contacted, 6
(55 percent) indicated that they generated HCB-containing wastes, and 5
(45 percent) indicated that they did not generate HCB-containing wastes;
whereas for electrolytic chlorine production, 2 (14 percent) of the 14
firms contacted indicated that they generated HCB-containing wastes and
7 (50 percent) indicated that they did not know or that they preferred not
to discuss the matter. The survey results shown in Table 1 indicate that
not all plants (firms) within a given industry generate HCB wastes. This
may be explained in a number of ways including:(a) that there are differ-
ences in processes/operations utilized, and (b) not all plants monitor their
waste streams for HCB or utilize the analytical procedures with the same
detection levels.
Based on the survey results and the data on waste quantities (which
are presented and discussed in Section 5.4), the chlorinated solvents and
pesticide industries are the major sources of HCB wastes. The electrolytic
chlorine industry can be considered as a minor source of HCB wastes. (See
14
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TABLE 1
HCB WASTE GENERATION SURVEY, NUMBER OF FIRMS
CONTACTED AND RESPONSES RECEIVED
Industry
Basic production/
Distribution
Chlorinated
Solvents Production
Pesticide Industry'
Formulatl on/Distribution
Electrolytic Chlorine
Production
Ordnance and Pyrotechnics
Production
Sodium Chlorate Production
Aluminum Manufacture
Seed Treatment
Industry
Production
Formulation/
Distribution
Seed Treatment
Houses. Nurseries
PCP Production
Uood Preservatives
Industry
Electrode Manufacture
Cyanogen Chloride
Production
VCH Production
(Total )
Mo of
firmi
Contacted
in Each
Industry
3
11
4
2
14
7
5
4
3
3
1
5
2
5
0
11
(80)
Total No
of Firms
Repoi ted
For the
Indus try"1
3
11
4
46
34
i
9
10
8
8
4
6
52
23
2
12
(232)
No Of
Contacted
Firm
Generating
HCB Waste-.
1
6
4
2
2
3
0
1
0
1
0
0
0
1
n.a.
0
(21)
No Of
Contained
Finns Not
Generating
HCa Wastes
2
5
0
0
7
1
0
3
3
2
0
3
2
4
n.a.
8
(10)
No of
Contacted
Firms Not
Sure /Would
Hot Disclose
0
0
0
0
5
3
5
0
0
0
1
2
0
0
n.a.
3
(19)
Some of the firms operate more than one production facility.
t Based on data in references 9 through 1?.
< Includes only those firms involved in production/formulation of Dacthal, mirrx, sunazine,
atrazlne. propo?inc and PCIIO. These t>cs tic ides and operations related to their production/
formulation arc Suspected sources of HCB waste.
> No exact estimates available due to fluctuations in munitions needs whfcn involve
activation and dcactivation of many military production sites.
n.e. Indicates not applicable.
15
-------
also the discussion below for the Individual industries.) Because of this
consideration, only these three industries were subsequently subjected to
1n- depth evaluation from the standpoint of waste quantities generated and
treatment/ disposal methods employed.
The following section briefly reviews the industries which were sur-
veyed as possible sources of HCB wastes. The information presented is
based on (a) response to inquiries which were directed to various companies,
(b) literature search and (c) in some cases, field visits and discussions
with plant technical personnel.
5.2 INDUSTRIAL OPERATIONS PRODUCING HCB WASTES
5.2.1 Basic Production of HCB
Although there are known methods for direct synthesis of HCB (e.g.,
by chlori nation of benzene or treatment of isomers of hexachlorocyclohexane
with sulfuryl chloride), the current industrial production of HCB involves
recovery of HCB from wastes generated in the production of chlorinated sol-
vents (see below).
The 1975 Stanford Research Institute Directory of Chemical Producers' '
and the Oil, Paint and Drug Chemical Buyers Directory1 ' list Dover
Chemical Company (Dover, Ohio) and Hummel Corporation (South Plalnfield,
New Jersey) as manufacturers of HCB. In 1974, the Dover facility in Ohio
f 1 A \
produced approximately 50 metric tons (55 tons) of HCB.^ ' The produc-
tion process involves recovery of HCB from chlorinated solvent wastes.* '
Hummel is only an HCB supplier/distributor, handling primarily Dover's
product. ^^
wastes in the production of HCB are expected to originate from the
actual manufacturing operations and from equipment and spill clean-up acti-
vities. Using a carbon absorption/solvent extraction method for sample
concentration, followed by gas chromotographic analysis of the concentrate,
no HCB has been detected in the aqueous waste streams from the Dover plant
at a detection level of 0.1 ppm; '
16
-------
5.2.2 Chlorinated Solvents Production
Based on industry-furnished data (see Section 5.4), over half of the
3,909 metric tons (4,316 tons) of HCB which is generated annually in the
country is produced as a by-product waste in the production of chlorinated
solvents (mainly, carbon tetrachloride, perchloroethylene, trichloroethylene,
and dichloroethylene). In the production of chlorinated solvents, HCB is
formed as a reaction side product in the course of thermal chlorination,
oxychlorination and cracking operations. HCB-containing waste streams are
usually heavy ends waste liquids from various distillation or purification
processes within the manufacturing operations. As will be discussed in
Section 5.4.2, because of differences in the manufacturing processes, not
all chlorinated solvent producers generate HCB in their waste streams.
Table 2 lists companies, domestic sites and annual production capaci-
ties (or quantities) for the production of carbon tetrachloride, perchloro-
ethylene, ethylene dichloride and trichloroethylene. Carbon tetrachloride
is produced by seven companies at 12 different locations; perchloroethylene
is produced by eight firms at 11 different production sites; ethylene di-
chloride is manufactured by 12 firms at 18 sites; and trichloroethylene is
produced by 5 companies at 5 different sites. Of the total of 16 companies
manufacturing chlorinated solvents, only one recovers HCB from its waste
streams at one of its facilities (Plant Site A). Each year approximately
190 metric tons (210 tons) of HCB is recovered at this site for sale. When
this quantity of HCB is added to the 50 metric tons (55 tons) per year of
HCB produced at the Dover Plant (see Section 5.2.1), the total quantity of
HCB recovered from chlorinated solvent waste is 240 metric tons (265 tons)
per year which accounts for only 10 percent of the estimated 2401 metric
tons (2650 tons) per year of HCB waste which is generated annually in the
production of chlorinated solvents. The other 90 percent of HCB which is
not recovered is discharged in the waste streams which are disposed of on
land or are incinerated (see Section 5.5).
5.2.3 Pesticide Industry* (Excluding Seed Treatment Industry)
Based on the data collected in this study, approximately 38.6 percent
of the total HCB generated annually in the U.S. is produced by the pesticide
*See Section 5.2.8 for a discussion of the seed treatment industry.
17
-------
TABLE 2
COMPANIES, DOMESTIC SITES AND PRODUCTION RATES OR CAPACITIES
FOR CARBON TETRACHLORIDE, PERCHLOROETHYLENE,
TRICHLOROETHYLENE, AND DICHLOROETHYLENE
Company
Carbon '« trachltiride
Allied Chemical Corp.
Do* Chcinicel U.S.A.
Dow Chemical U.S.A.
Dm Chemical U.S.A.
E. I. duPont de Nemours t Co.. Inc.
FMC Corp.
Inland Chemical Corp.
Stauffer Chemical Co,
Stauffer Chemical Co.
Stauffer Chemical Co.
Vulcan Material? Co.
Vulcan Materials Co.
Perch lorocUiylenc
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Dew Chemical U.S.A.
Oow Chemical U.S.A.
E. I. duPont de Nemours t Co., Inc.
Ethyl Corp.
Hooter Chemical Co., Subs id.
Occidental Petroleum Corp.
PPG Industries. Inc.
Stauffer Chemical Co.
Vulcan Materials Co.
Vulcan Materials Co.
Site
'Moundsville, U.V.
freeport, 7x.
Pittsourg, Ca.
Plaqueminc, La.
Corpus Chris tl, Tx
So. Charleston. U.V.
Kjnati , P.R.
Louisville, Ky.
LeHoyne. Al.
Niagara Falls, N.r.
Geismar, La.
Wichita, Ka.
Deer Park, Tx.
Freeport, Tx.
PHtsburg, Pa.
Plaquenine, La.
Corpus Chris t1 , Tn.
Baton Rouge, La.
Taft. La.
Lake Charles, La.
Louisville. Ky.
Gefsmar, La.
MichiU, Ks.
PruducCiorr Hjte or Capacity*
Maine Tons/Vu.ir [Ions/Year]
3,630, (4,000)
5^,000, (65.000)
20,400, (22,500)
45.400, (50,000)
22J.ODO. (P50.DOO)
136.000, (150,000]
(Not available)
2?,700. (25,000)**
90,600, (100.000)
68,000, (75,000}
16,000, (17,500)
IB. 000, (20,000)
73,100, (10,500)**
54.500. (60.000)
9,100, (10,0"1)
68,100, (75.00C)
72,600, (80,000)
22,900, (25,000)
2Z.900. (25,000)
91.000, (100,000)
25.000, (27.500)
60.000, (75,000)*
Z2.900, (25. COO:
Reference
10
10
10
10
10 &
10 I
10
17
10
10
10
10
..
"
10
10
10
10
10
10
17
10
10
* Unless marked by ** these figures are the production capacities reported in Reference (10);
the figures marked by are the actual production rates as supplied by the industry.
18
-------
TABLE Z
COMPANIES, DOMESTIC SITES AND PRODUCTION RATES OR CAPACITIES
FOR CARBON TETRACHLORIDE, PERCHLOROETHYLENE,
TRICHLOROETHYLENE, AND DICHLOROETHYLENE (CONT'D)
Company
Tricnloroetliylenc
Diamond Shamrock Corp.
Dou Chemical JJ.S A.
Ethyl Corp
Hooker Chemical Co , Subsld
(Occidental Petroleum Corp. )
PPG Industries, Inc.
Dichloroethylene
Allied Chemical Corp.
Continental Oil Co.
(Conoco Chemicals)
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Ethyl Corp.
Ethyl Corp.
B. F. Goodrich Co.
PPG Industries, Inc.
PPG Industries, Inc
Stauffer Chemical Co.
Shell Chemical Co.
Shell Chemical Co.
Texaco, Inc.
Union Carbide Corp.
Union Carbide Corp.
Vulcan Materials Co.
Site
Deer Park. Tx.
Freeport. Tx.
Baton Rouge, La.
Taft, La.
Lake Charles, Li.
Baton Rouge. La.
West lake, La.
Deer Park, Tx.
Freeport, Tx.
Oyster Creek, Tx.
Plaquemlne, it.
Baton Rouge. La.
Pasadena, Tx.
Calvert City, Ky.
Lake Charles, La.
Cuayanflla. P.R.
Carson, Ca.
Deer Park, Tx.
Norco, La.
Port Heches, Tx.
Taft. La.
Texas City. Tx.
Geismar. La.
Production Rate or Capacity
.'It'lnr Tons/Y<>
-------
industry, primarily in the manufacturing of Dacthal, mirex, simazine,
atrazine, propazine, and pentachloronitrobenzene (PCNB). HCB is produced
as a waste product and is also present in the product as an impurity.
Based on industry-furnished data, it is estimated that 99.4 percent of the
estimated 1,509 metric tons (1,666 tons) per year of HCB associated with
the pesticide industry is contained in the process waste streams (tars,
still bottoms, etc.) from production operations, and 0.6 percent (9 metric
tons or 10.5 tons per year is contained in the product as an impurity.
HCB contained in the wastes from the manufacturing of simazine, propazine,
and atrazine has been attributed to the presence of HCB impurities in the
cyanogen chloride which is used as a raw material. Direct use of, and for-
mulation operations involving HCB-containing pesticides can result in the
introduction of HCB into the environment. Table 3 lists the producers,
production sites, formulators and the number of distributors for each of
the above-mentioned pesticides. The list of formulators and the number of
distributors are based on the data published in the Farm Chemicals Handbook.^ '
Some of the formulators operate more than one formulation site.
5.2.4 Electrolytic Chlorine Production
The electrolytic processes for the production of chlorine (diaphragm
and mercury cells) generate HCB (and other hydrocarbon wastes) in the crude
chlorine gas when graphite electrodes are used as the anode. HCB produc-
tion is believed to result from direct attack of chlorine on the graphite
and/or from the reaction of chlorine with the hydrocarbon oils (e.g., linseed
oil) which are used as anode coatings. When crude chlorine is liquified and
purified by distillation, most of the chlorinated hydrocarbons (including
HCB) are separated from chlorine and remain as components of the "heavy ends."
Some HCB may also be present in the recycled spent brine and in the brine
purification mud. Some manufacturers do not purify chlorine on site. The
undistilled product is used in a number of industrial applications (e.g.,
as a flux in aluminum smelting) not requiring a highly pure chlorine gas.
When the unpure liquified chlorine is vaporized at the application site
orior to use, HCB and other hydrocarbon impurities remain as residuals in
the storage tank and/or vaporization equipment. Thus, industrial sites
vJhere unpurified chlorine is used may be regarded as secondary potential
sources for HCB waste generation.
20
-------
TABLE 3
PRODUCERS, FORMULATORS AND THE NUMBER OF DISTRIBUTORS FOR MIREX,
DACTHAL, SIMAZINE, ATRAZINE, PROPAZINE AND PCNB (10, 11)
Pesticide
Dacthal
PCNB
Mi rex
Simazine
Atrazine
Propazine
Producer
Diamond Shamrock
Corporation
01 in Corporation
Nease Chemical
Ciba-Geigy
Corporation
Production
Site
Greens Bayou,
Tx.
Me In tosh, Al.
State College,
Pa.
St. Gabriel,
La.
Formula tor
Agway, Inc.
Brockville Chemical
Industries, Ltd.
Lebanon Chemical
Company
Uoodbury Chemical
of Homestead
Wool folk Chemical
Works, Ltd.
Hooker Chemical
Company
Allied Chemical
Company
Location of
Company
Headquarters
Syracuse, N.Y.
Montreal ,
Quebec
Lebanon, Pa.
Princeton,
N.J.
Ft. Valley,
Ga.
Niagara Falls,
N.Y.
Morris town,
N.J.
"
Number of
Distributors*
22
10
2
33
ro
* A complete listing of these distributors and their locations can be found in the Farm Chemicals
Handbook (11)
-------
Electrolytic chlorine production operations which use metallized
anodes, such as the so-called dimensionally stable anodes (DSA's), do not
generate HCB. Since about 1969, many modern plants have been converted to
the use of the DSA's. In the present survey, 67 plants were identified as
sites for the electrolytic production of chlorine; graphite anodes are cur-
rently used at 32 of the sites (see Table 4); the remaining 35 sites (see
Table 5) currently use or are scheduled to use DSA's or other types of non-
graphite electrodes.
5.2.5 Ordnance and Pyrotechnics Production
HCB is used in the manufacture of various pyrotechnics (e.g., signal
flares) for military and civilian use and in the production of certain
ordnance items (e.g., tracer bullets). Some HCB-containing wastes are thus
expected to be generated at pyrotechnic and ordnance manufacturing/loading
facilities which handle HCB-containing raw materials or products. Except
for the major facilities which are identified below, all of the pyrotechnic/
ordnance production sites which may generate HCB wastes could not be ideni-
fied because of the limited data available (mainly due to the classified
nature of munitions production operations).
HCB has been used in the manufacture of Navy Mark 13 Day and Night
Distress Signals, Mark 99 Marine Markers, Army hand signals (eliminators)
and commercial highway emergency flares by Kilgore Corporation (Toone,
Tennessee). Between 1962 and 1975, approximately 2.7 metric tons (3 tons)
of HCB was loaded for Army hand signals, 0.6 metric tons (0.65 tons) HCB
for commercial flares, and an additional undisclosed quantity for the Navy
Marine Mark Series at this site.^20* Mark 99 Marine markers have also
been loaded at the Crane Naval Ammunition Product Engineering Center (Crane,
Indiana). Three other pyrotechnic and ordnance manufacturers (Apache,
Benson, Arizona; Aerojet-General, El Monte, California; and Security Signals,
Cordova, Tennessee) which are involved in the production of similar items
may also generate HCB wastes. Longhorn Army Ammunition Plant (Marshal,
Texas) and Crane Naval Ammunition Center are reportedly using or have used
(21 22)
HCB in pilot scale testing of certain ordnance/pyrotechnic iterns.v
22
-------
TABLE 4
ELECTROLYTIC CHLORINE PRODUCERS USING GRAPHITE ANODES AND PRODUCTION SITES
Company
Site(s)
Allied Chemical Corp.
BASF Wyandotte Corp.
Champion International Corp.
Dow Chemical U.S.A.
E. I. duPont de Nemours & Co., Inc.
Ethyl Corp.
Ft. Howard Paper Co.
Hooker Chemical Corp., Subsid.
(Occidental Petroleum Corp.)
Hooker-Sobin Chemicals, Inc.
Inland Chemical Corp.
Jefferson Chemical Co.
Linden Chlorine Products, Inc.
Mobay Chemical Corp.
01 in Corp.
Oregon Metallurgical Corp.
PPG Industries, Inc.
RMI Company
Stauffer Chemical Co.
Vicksburg Chemical Co.
Brunswick, Ga., Baton Rouge, La.,
Syracuse, N.Y., Acme, N.C.
Wyandotte, Mi.
Houston, Tx.
Midland, Mi., Plaquemine, La.,
Freeport, Tx., Pittsburg, Ca.
Niagara Falls, N.Y., Memphis, Tn.
Baton Rouge, La., Houston, Tx.
Green Bay, Wi.
Montague, Mi., Taft, La., Tacoma,
Wa.
Niagara Falls, N.Y.
Newark, N.J.
Port Neches, Tx.
Linden, N.J.
Cedar Bayou, Tx.
Augusta, Ga., Mclntosh, Al., Niagara
Falls, N.Y., Charleston, Tn.
Albany, Or.
Barberton, Oh., Corpus Christi, Tx.
Ashtabula, Oh.
Henderson, Nv.
Vicksburg, Ms.
li
L
I
* Based on data in Reference 9, supplemented by direct contact with
industry; seven of the companies listed were contacted in the survey.
23
-------
TABLE 5
ELECTROLYTIC CHLORINE PRODUCERS USING DSA'S OR OTHER
NON-GRAPHITE ELECTRODES, AND PRODUCTION SITES*
Company
Site{s)
Aluminum Company of America
Allied Chemical Corp.
BASF Wyandotte Corp.
Brunswick Pulp and Paper Co.
Champion International Corp.
Diamond Shamrock Corp.
Detrex Chemical Industries, Inc.
Georgia-Pacific Corp.
B. F. Goodrich Co.
Hercules, Inc.
Hooker Chemical Corp.,Subsid.
(Occidental Petroleum Corp.)
Kaiser Aluminum & Chemical Corp.
Monsanto Co.
Pennwalt Corp.
FMC Corp.
PPG Industries, Inc.
Shell Chemical Co.
Sobin Chemicals, Inc.
Stauffer Chemical Co.
Vulcan Materials Co.
Weyerhaeuser Co.
Ft. Comfort, Tx.
Moundsville, W.V.
Fort Edwards, Wi., Geismar, La.
Brunswick, Ga.
Canton, N.C.
Painesville, Oh., Deer Park, Tx.,
Delaware City, De., Muscle Shoals,
AT.. Mobile, Al.
Ashtabula, Oh.
Billingham, Wa.
Calvert City, Ky.
Hopewell, Va.
Niagara Falls, N.Y.
Gramercy, La.
E. St. Louis, II., Pisgah Forest,
N.C.
Calvert City, Ky., Tacoma, Wa.,
Portland, Or., Wyandotte, Mi.
S. Charleston, W.V.
New Martinsville, W.V., Lake
Charles, La.
Deer Park, Tx.
Orrington, Me.
LeMoyne, Al., St. Gabriel, La.
Denver City, Tx., Wichita, Ks.,
Geismar, La.t
Longview, Wa.
* Based on data in Reference 9, supplemented by direct contact with
industry; nine of the companies listed were contacted in this survey.
t Not yet on stream.
24
-------
HCB wastes generated by the ordnance/pyrotechnic industry are relatively
small in quantity and are primarily in the form of HCB scrap and contami-
nated containers. At the Kilgore plant in Toone, Tennessee, approximately
1.5 percent of drummed dry scrap waste generated in the manufacturing of
HCB-containing products 1s HCB. The total amount of scrap generated is
not known.
5.2.6 Sodium Chlorate Production
Sodium chlorate is manufactured by the electrolysis of saturated brine
solutions containing sodium dichromate and acidified with hydrochloric acid.
As with the electrolytic chlorine production, two types of electrodes are
commonly used as the anode: graphite and metallized anodes (such as the
DSA). Because of the use of graphite anode, sodium chlorate production by
the electrolytic process can be a potential source of HCB production. Waste
streams from the process which may contain HCB are the mud wastes (graphite
stub residue) from spent cell liquor.
Table 6 presents a list of the 15 sodium chlorate manufacturing facili-
ties in the U.S. Five companies representing seven sites (four sites using
graphite anodes and three sites using non-graphite anodes) were contacted
in this survey and inquiries were made about HCB production. The companies
contacted indicated that they had not tested their waste streams for HCB
and had no qualitative or quantitative data available on HCB. Based on
contact with industry and the information contained in a recent publica-
tion^ ', all sites which currently use graphite electrodes will soon convert
to DSA's or other types of non-graphite electrodes. Accordingly, the sodium
chlorate industry is expected to be eliminated as a potential source of HCB
production.
5.2.7 Aluminum Manufacture
HCB has been reported to be used as a fluxing agent in the smelting
operating associated with the primary manufacture of aluminum. In the
present survey, four of the ten major aluminum manufacturing companies which
were contacted (see Table 7 for a complete list of domestic aluminum
25
-------
TABLE 6
SODIUM CHLORATE PRODUCERS, PRODUCTION
SITES AND TYPE OF ANODE USED*
Company
Site
Type of
Anode Used
Brunswick Pulp and Paper
Company
Huron Chemicals of America,
Inc.
Georgia-Pacific Corp.
Kerr-McGee Chemical Corp.
Hooker Chemical Corp., Subsid.
of Occidental Petroleum Corp.
Pacific Engineering and
Production Company of Nevada
Penn-Olin Chemical Co.
Pennwalt Corp.
PPG Industries, Inc.
Riegel Paper Corp.
Brunswick, Ga.
Butler, AT.
Bellingham, Wa.
Hamilton, Ms.
Henderson, Nv.
Columbus, Ms.
Niagara Falls, N.Y.
Taft, La.
Henderson, Nv.
Calvert City, Ky.
Portland, Or.
Wyandotte, Mi.
Lake Charles, La.
Naheola, Al.
Riegelwood, N.C.
Graphite
N.A.
DSA
Graphite
Graphite
N.A.
DSA
N.A.
Graphite
DSA
DSA Scheduled
Not Disclosed
N.A.
N.A.
N.A.
*Based on the data in References 9 and 10, supplemented by direct
contact with industry; five of the companies listed were contacted in this
survey.
N.A. indicates not available.
26
-------
TABLE 7
ALUMINUM MANUFACTURERS (SMELTERS)
AND COMPANY HEADQUARTERS
Company
Headquarters
Kaiser Aluminum & Chemical Corp.
Howmet Corp.
01 in Corp.
Satchelder, Charles E.
Manufacture Systems Inc.
Martin Marietta
Revere Copper and Brass
Ormet
Reynolds Metals
Aluminum Co. of America
Oakland, Ca.
Brunswick, Ct.
Stanford, Ct.
Newton, Ct.
Great Lakes, Mn.
New York City, N.Y.
New York City, N.Y.
Hannibal, Oh.
Richmond Va.
Pittsburgh, Pa.
;i
* Based on data in Reference 12; four of the companies
listed above were contacted in this survey.
27
-------
manufacturers) indicated that they do not use HCB as a fluxing agent and
they envisioned no likelihood for the generation of HCB in the smelting or
fabrication of aluminum by the currently used technology. Alcoa is cur-
rently conducting pilot plant tests on a new proprietary smelting process.
To date, tests conducted on waste streams from the pilot plant have failed
to indicate the presence of HCB.
As was indicated above in Section 5.2.4, aluminum manufacturing plants
which use impure chlorine (alone or in combination with other gasses as a
flux in smelting) may be a source of HCB waste, since any HCB present in
the liquified chlorine feed tank may accumulate as residue which may
require disposal.
5.2.8 Seed Treatment Industry
In the past, the principal use of HCB has been as a seed protectant or
as an ingredient in seed protectant formulations for the control of wheat
bunt and smut fungi of other grains. ' (Currently, HCB is mainly used as
a peptizing agent in the manufacturing of certain types of synthetic rubber.)
In 1971, an estimated 6.2 metric tons (6.9 tons) of HCB were used as a grain
fungicide primarily in California, Washington and Oregon."' HCB is also
(23)
used in quarantine centers and in seed certification.* ' Seed treatment
formulation houses which formulate HCB-contaim'ng seed protectants, and
quarantine and seed treatment houses, as well as the use of treated seeds
(particularly the cotton seed) are sources for HCB waste generation and
introduction of HCB into the environment.
According to the Farm Chemicals Handbook/ ' there are at least eight
major seed treatment formulators in the country (and at least four seed
treatment nurseries* '). Each of the companies and nurseries presumably
formulate and operate at more than one site. Three of the seed treatment
formulators were contacted in the present survey. Two of the formulators
indicated that they do not use HCB in any of their seed treatment formula-
tions. One formulator (Production Site AD) indicated that it uses HCB in
two formulations but declined to identify the products or provide data on
28
-------
their compositions. This formulator formulates about 45.3 metric tons
(50 tons) per year of each product. According to California State Depart-
ment of Food and Agriculture/ ' HCB is also an ingredient of Grannox,
a specific seed treatment formulation, which is imported from United Kingdom
and distributed for use in this country by ICI America. ICI reports no
(25)
waste generation in the distribution of the product. '
5.2.9 Pentachlorophenol (PCP) Production
According to one report, ' HCB is produced as a by-product in the
production of pentachlorophenol (PCP). This assertion, however, is not
supported by the industry-furnished data collected in this survey.
There are six reported major domestic producers of PCP.^ ' These are
(26 27)
listed in Table 8. Based on the plant analytical data/"' ' HCB is not
generated at two sites (Vulcan Materials Co., Wichita, Kansas; and Reichold
Chemicals, Inc., Tacoma, Washington) which produce PCP by the chlorination
of phenol. This same PCP synthetic route is also used by Monsanto Co. at
its Sauget, Illinois plant and by Dow Chemical U.S.A. at its Midland,
Michigan facility. No analytical data have been obtained at the Sauget
plant to assess the presence of HCB in the waste streams. ' The fifth
producer of PCP, Dover Chemical Company, which is also an HCB producer,
may produce PCP through hydrolysis of HCB. As discussed in Section 5.2.1,
at a detection level of 0.1 ppm, no HCB has been detected in the effluent
discharges from the Dover plant. The sixth reported domestic producer of
PCP, Sonford Chemical Company, has indicated it is only a representative
/2Q}
for PCP manufacturers.* '
5.2.10 Wood Preservative Industry
(9)
HCB has been reported to be used as a wood preservative.* ' There are
at least 52 domestic sites for wood preservation treatment. * ^ Two com-
panies (J.H. Baxter Co., San Mateo, California, and Honolulu Wood Treatments
Company, Honolulu, Hawaii) which were contacted in this survey, reported
that HCB is not used at any of their treatment sites and that to the best
of their knowledge HCB is not in use domestically, at least not in large
29
-------
TABLE 8 *
PENTACHLOROPHENOL (PCP) PRODUCERS AND PRODUCTION SITES
Company
Site
Dover Chemical Company
(Subsidiary of Ansul Company)
Dow Chemical U.S.A.
Monsanto Company
Reichhold Chemicals, Inc.
Sonford Chemicals Company
Vulcan Materials Company
Dover, Oh.
Midland, Mi.
Sauget, II.
Tacoma, Wa.
Houston, Tx.
Wichita, Ks.
With the exception of one, all of the above
companies were contacted in this study.
30
-------
wood treatment centers. *' According to one industry contact, °' the
apparent confusion regarding the use of HCB as a wood treatment agent may
stem from the fact that HCB is often confused with t-BHC (gamma-benzene
hexachloride or gamma-hexachlorocyclohexane) which has been used both in
this country and in Europe as a wood preservative. (Note: the British
Wood Society Register of Mood Preservatives, also does not list HCB as a
wood preservative.^ ')
Pentachlorophenol (PCP) is used as wood preservative in this country.
If it is assumed that technical grade PCP produced by hydrolysis of HCB
contains HCB as an impurity, the use of PCB for wood preservation may con-
stitute a source for the generation of HCB wastes. However, no analytical
data are available on the HCB content of technical grade PCP to test the
validity of this assertion.
In wood treatment operations, the wood is steamed in the presence of
treatment chemicals or is pressure-treated with solutions containing such
chemicals. The wood is then drained and the residual liquid is removed by
the application of a vacuum. If PCP contaminated with HCB is used in these
processes, probable sources of HCB-containing wastes may include the non-
recyclable spent liquor, mechanical losses, spills and overflows, equipment
clean-up, etc.
5.2.11 Electrode Manufacture
HCB has been reported to have been used as a porosity control agent in
io\
the manufacture of graphite anodes for industrial uses. ' There are 23
domestic manufacturers of carbon and graphite products, including electrodes
(see Table 9). Five of the electrode manufacturers were contacted in this
survey. One manufacturer (Stackpole Carbon Company, St. Marys, Pennsylvania)
indicated that the company has stopped using HCB in its electrode manufac-
turing operations.* ^ Two other companies (Carborundum Corporation,
Sanbornne, New York and Airco-Speer Corporation, St. Marys, Pennsylvania)
indicated that they do not use HCB in their operations, but suggested that
HCB may be an ingredient of the heat transfer materials, primarily chlori-
nated organic compounds, such as chlorinated biphenyls, which are used by
the industry.(33»34) These sources, however, added that the use of
31
-------
TABLE 9 *
ELECTRODE MANUFACTURERS AND COMPANY HEADQUARTERS
Company
Headquarters
Airco Speer Co., Carbon-Graphite Division
Becker Bros. Carbon Co.
Carbone Corp.
Carborundum Co.
Electro-Nite Co.
Great Lakes Carbon Corp.
Helwig Carbon Products, Inc.
Kennametal Inc.
Keystone Carbon Co.
Kirkwood Comnutator Co.
Lukens Steel Co.
Morganite Incorporated
Ohio Carbon Co.
Pure Carbon Co., Inc.
Saint Marys Carbon Co.
Stackpole Carbon Co.
Superior Carbon Products, Inc.
Teeg Research, Inc.
Textool Products, Inc.
Ultra Carbon Corp.
Union Carbide Canada Limited
Union Carbide Corp.
United States Graphite Co.
St. Marys, Pa.
Cicero, II.
Boonton, N.Y.
Sanborne, N.Y.
Philadelphia, Pa.
New York, N.Y.
Milwaukee, Wi.
Milwaukee, Wi.
St. Marys, Pa.
Cleveland, Oh.
Coatesville, Pa.
Dunn, N. C.
Cleveland, Oh.
St. Marys, Pa.
St. Marys, Pa.
St. Marys, Pa.
Cleveland, Oh.
Easton, Md.
Irving, Tx.
Bay City, Mi.
Toronto, Canada
New York, N.Y.
Saginaw, Mi.
Five of the companies listed were contacted in this survey.
32
-------
chlorinated organic compounds as heat transfer materials is apparently
becoming outdated in the industry. Of the remaining two firms, one
(Keystone Carbon Company, St. Marys, Pennsylvania) indicated that it now
makes metal anodes, rather than graphite anodes. ' The other firm (Helwig
Carbon Products, Inc., St. Marys, Pennsylvania) indicated that it is not
involved in the manufacturing of electrodes.* '
5.2.12 Cyanogen Chloride Production
As discussed in Section 5.2.3, HCB contained in the wastes from the
manufacture of three pesticides (simazine, atrazine, and propazine) has
been attributed to the HCB impurities in the cyanogen chloride which is
used as a raw material. At one site, HCB emission was significantly reduced
when a higher purity cyanogen chloride was used in the process. The presence
of HCB in cyanogen chloride suggests that cyanogen chloride manufacturing
may be a potential source of HCB generation. This possibility for HCB gen-
eration was not discussed with the two reported domestic manufacturers of
cyanogen chloride (Nilok Chemicals Inc., Memphis, Tennessee^ ' and DuPont
(37)
and Co., Inc., Wilmington, Delaware)/ ;
5.2.13 Vinyl Chloride Monomer (VCM) Production
/Q\
According to one report/ ' HCB may be produced as a by-product in the
production of vinyl chloride monomer (VCM). The industry-furnished data
collected in this study, however, do not support such a possibility.
There are 12 major producers of VCM and 17 production sites in this
country (see Table 10). Based on industry-furnished analytical data (and
some independent testing by one state laboratory), tests with ppm (parts
per million) sensitivities, have indicated no detectable amount of HCB in
the waste streams at 5 of the 17 sites. At four of the sites HCB has been
detected in waste streams containing VCM wastes, but in these cases the VCM
wastes are in combination with wastes from chlorinated solvent production
which may be the real sources of HCB. The data supplied by one company for
two production sites indicate that at a detection level of 10 ppm, no HCB
was found in its waste streams.
33
-------
TABLE 10 *
VINYL CHORIDE MONOMER PRODUCERS AND PRODUCTION SITES
(10)
Baton Rouge, La.
Carson, Ca.
Allied Chemical Corp.
American Chemical Corp.
(Stauffer Chemical Co.)
Westlake, La.
Continental Oil Co.
Dow Chemical U.S.A.
Oyster Creek, Tx.
Freeport, Tx.
Plaquemine, La.
Baton Rouge, La.
Pasadena, Tx.
Ethyl Corp.
Calvert City,
B. F. Goodrich Co.
PPG Industries, Inc
Lake Charles, La.
Guayanilla, P. R.
Deer Park, Tx.
Norco, La.
Shell Chemical Co.
Houston, Tx.
Texas City, Tx.
Geismar, La.
Geismar, La.
Tenneco, Inc.
Union Carbide Corp.
Borden, Inc.
Monochem, Inc.
* Except for one, all companies listed
survey.
were contacted in this
34
-------
Of the remaining six VCM production sites, two reported they are
phasing out of production. Information was not available for the remaining
two companies representing four production sites.
5.2.14 Synthetic Rubber Production
According to a 1975 publication,^ the largest supplier of HCB in the
U.S., has committed its entire HCB production output on a multi-year con-
tract basis for use as a peptizing agent in the production of nitroso and
styrene type rubber for automobile tires. The use of HCB on such a large
scale in the manufacture of synthetic rubber is very new and very little
information is available on sites using HCB, processes involved, and pollu-
tant emission quantities.
5.3 CHARACTERISTICS OF HCB-CONTAINING WASTES
Table 11 summarizes the data collected in this survey on HCB waste
characteristics. As indicated in this table, in most cases HCB is present
as a constituent of the distillation residue and heavy ends (tars) from
product purification operations. The HCB content of the waste mixtures
varies, depending on the nature of the operation and the specific products
produced. In general, as discharged from the process, HCB-containing wastes
are viscous organic fluids containing little or no water. When cooled to
ambient temperature, HCB solidifies and separates from the mother liquor.
Depending on the nature of the liquid component, some HCB may remain in
solution in the liquid phase. (See Table A-3 in the Appendix for properties
of HCB.)
As indicated in Table 11, HCB-containing wastes from chlorinated
solvents production also contain hexachlorobutadiene (HCBD) as a major
ingredient. Indeed, HCBD for commercial use was formerly produced as a
/ Q \
recovered by-product in the production of perchloroethylene. (In 1974,
all commercial quantities of HCBD, 91 to 227 metric tons or 100 to 250 tons
per year, were imported from Germany^9'). HCBD is liquid at ambient tem-
perature (melting range -19 to 22°C; boiling range 210 to 220°C), is con-
siderably more volatile than HCB (vapor pressure 1.5 mm Hg at 40°C) and
35
-------
TABLE 11
GENERAL CHARACTERISTICS OF HCB-CONTAINING WASTE STREAMS
FOR CHLORINATED SOLVENT AND PESTICIDE MANUFACTURING
INDUSTRIES, BASED ON DATA FOR SPECIFIC PRODUCTION SITES
Industry (and Products)
Carbon tetrachlonde,
ps cMcroethyieie.
cnlc'oretnane solvents
Carbon tetrachlonde,
perchloroethy 1 ene,
ethy'iene dichloride
Perchloroethy lens,
tnchloroethylene,
ethylene dichloride
Perchloroethylene,
tnchloroethylene
Ethylene dichloride
Pesticides
Pesticides
Pesticides
Pesticides
Site
Designation
A
F
D
Q
R
S
T
Process Waste Source
Heavy ends from solvent
recovery system (recy-
cle, stripping)
Heavy ends from purifi-
cation stills
Still bottoms,
("heavies") from purifi-
cation stills
Heavy ends
Distillation tars and
residue
Distillation residue
Liquid still bottoms
Distillation tars
Stack emissions
HCB-Contalnlng '
Waste Composition
74r, HCB, K- hexachloro-
butadiene (HCBD), 102 hexa-
chloroethane (HCE)
15% HCB,* 75X HCBD. 10%
HCE
1.65 HCB. 791 HCBO, 3.5t HCE,
3.51 tetrachlorobutadiene,
3.4t pentachlorobenzene.
3.3Z trichlorobenzene.
2.4% perchloroethylene,
0.9X tetrachlorobenzene.
0.8% pcntachlorobutadiene.
1.62 sand and carbon
6* HCB, 20-901 HCBD, 4-14%
C4-Cg chlorinated organic
conpounds
10-40 ppm HCB. 15% 1,2-
trichloroethylene, 41S
chlorinated C4.Cs, compounds
4% miscellaneous solids
75% HCB, ?S% product
80% HCB. 20% lower
chlorinated benzenes
IS HCB
No data available
Miscellaneous Waste Stream Characteristics
Grayish or whitish in color
Grayish-white solid settles out when cooled
(with viscous red-brown liquid supernatant
containing concentrated organics)
Viscous tars, vapor pressure <690 newtons/
m* absolute (0.1 psla) at 38°C (100"F);
viscosity (at 24°C or 75°F) » 0.025 newton-
second/ms- density =1.6 g/cr->
Viscous tar. black 1n color; density
1.8 g/cm3
Similar to above
Viscous > el low liquid when discharged (hot);
yellow crystalline solid formed at ambient
temperature
Grayish-white; HCB separates from mother
liquor as an opaque solid when cooled
No data available
No data available
OJ
Ol
* Indeoendent analysis of this waste has indicated an HCB content of as high as 758. (38)
-------
has some of the toxic and biological properties of HCB. The present survey
has concerned itself primarily with the HCB which originates in the produc-
tion of a greater number of chemicals. General information and sources and
characteristics of HCBD waste can be found in Reference 9.
In one pesticide production site, HCB is emitted from the process in
the scrubber emission which is vented to the atmosphere. These HCB emis-
sions, however, are from cyanogen chloride which is used as a raw product
and which contains HCB as an impurity (see Section 5.2.12). No data (quali-
tative or quantitative) could be obtained on possible HCB emissions to the
atmosphere for other production operations.
5.4 ESTIMATED HCB WASTE QUANTITIES
5.4.1 Total Waste Quantities and Comparison of Estimates with
Those Made in an Earlier Study
Under a contract with EPA Office of Toxic Substances, Midwest Research
Institute (MRI) conducted a study of hexachlorobenzene and hexachlorobu-
tadiene (HCBD) in U.S. industrial wastes, by-products, and products/ '
The study identified the following 11 industrial/agricultural chemicals
which contain HCB and/or their production results in the generation of HCB
With the exception of one plant site producing pesticides, the possi-
bility of direct HCB discharges to the air has not been documented. Several
of the firms contacted in this survey indicated that measurements of HCB
levels in gaseous emissions and other process waste streams have been made
and no HCB has been detected. For example, at Plant Site B, stack gases had
been monitored several times monthly since the 1973 episode of HCB contami-
nation in the Southern Lousiana area. The periodic monitoring has since
been discontinued, since only 1-2 parts per billion (ppb) HCB has been the
maximum ever detected. At Plant Site F, a spot check of miscellaneous
effluent streams showed 2.2 ppb of HCB in the "No. 3 Outfall." The firm
also indicated it does not normally check its effluent waste streams for
HCB. Thus, if HCB has been detected in miscellaneous plant effluent and
stack discharges in the chlorinated solvents and pesticide industries, it
would appear to be the exception rather than the rule, and is not likely to
be documented.
37
-------
wastes: perch!oroethylene, trichloroethylene, carbon tetrachloride,
chlorine, Dacthal, vinyl chloride, atrazine, propazine, simazine, penta-
chloronitrobenzene, and mirex. These chemicals fall into the "chlorinated
solvents production," "electrolytic chlorine production," "pesticide indus-
try", and "vinyl chloride monomer production" which were discussed in
Sections 5.2.2, 5.2.4, 5.2.3 and 5.2.13, respectively. Although in the
present survey 14 industries/operations were identified as sources of HCB
wastes, based on the discussion in Section 5.2, only three industries,
namely, chlorinated solvents production, electrolytic chlorine production,
and pesticide industry can be regarded as significant sources for HCB waste
generation. Data obtained in the present survey on the vinyl chloride
monomer industry indicate that this industry is probably not an important
source of HCB production (five production sites which were contacted indi-
cated that they had not detected any HCB in their waste streams).
Based on reported or estimated chemical commodity production capacities
for the U.S., some waste composition data obtained from selected production
sites, and assuming that the quantity of waste generated is proportional to
production capacity, estimates were made by MRI of the total quantity of
HCB waste generated in 1972 in the U.S. by each of the major HCB waste pro-
ducing industries.^ The MRI data which are reproduced in Table 12,
consist of "high" and "low" estimates with the "low" values generally
assumed to be 50 percent of the "high" estimates. The industry-furnished
data on waste quantity collected in the present survey are also presented
in Table 12. At some plant sites where more than one of the three listed
chlorinated solvents are manufactured, the waste streams are not segregated
and only the combined plant effluent is sampled and analyzed for HCB con-
tent. Accordingly, the industry-furnished waste quantity data for chlori-
nated solvents shown in the Table, represent the total for perchloroethylene,
trichloroethylene, and carbon tetrachloride production. These waste quanti-
ties are from selected sites which participated in the present survey and do
not include waste from all production sites. Comparison of the industry-
furnished data with the MRI estimate indicates that, with few exceptions,
the industry-furnished data are significantly higher than the "high" esti-
mates reported in the earlier study by MRI. Of particular interest is
pentachloronitrobenzene production for which the "high" estimate is
38
-------
TABLE 12 *
HCB WASTE QUANTITIES
(A COMPARISON OF THE EARLIER MRI ESTIMATES AND THE DATA
COLLECTED AND ESTIMATES MADE IN THE PRESENT STUDY)
Industry/Product
Chlorinated Solvents
Perchloroethylene
Trichloroetnylene
Carbon tetrachlonde
Subtota 1
Pesticides
Dae thai
Simazine,
Atrazine, and
Propazlne
PCNB
HI rex
Subtotal
Electrolytic
Chlorine Hfr
Vinyl Chloride
Total
MRI Data for 1972
Estimated Total
1972 Production HCB Quantity
Rate
High Low
332,000 (367.000)
193,400 (213,500)
151,600 (498,500)
977.000 (1,079,000)
900 (1,000)
50,700 (56.000)
1,350 (7,500)
450 (500)
53,400 (59,000)
8,940,000 (9,668,000)
2,305,000 (2,544,000)
-
1,585 (1.750)
204 (275)
181 (200)
1,970 (2,175)
45 (50)
4.1 (4 5)
2 7 (3)
0.9 (1)
53 (59)
180 (195)
12 (13)
2.215 (2,442)
793 (875)
104 (115)
91 (100)
988 (1,090)
36 (40)
2 3 (2.5)
1 4 (1 5)
0.4 (0.5)
40 (45)
72 (BO)
0
1,100 (1,215)
1975 Production
Rate
1,530,000 (1,689,000)
2,300 (2,500)
**
N A.
t
1,532.000 (1,692,000)
10,872,000 (12,000,000)
3,162,000 (3,490,000)
Indjs try-Furnished
Waste Quantities
HCB
Waste
2,401 (2,650)
226 (250)
25 kg (55 lb)
1,268 (1.400)
5 0 [5 5)
1,499 (1,555)
2 7 kg (6 lb)
0
3,900 (4.305)
HCB-Containlng
Haste
21,440 (23.665)
302 (131)
N.A.
1,585 (1.750)
500 (550)
2.387 (2,633)
141 (156)
0
(23 ,'968 (26,454
Projected
Waste
Quanti ty
for the U S
3,937 (4,345)
226 (250)
25 kg (55 lb)
1,268 (1.400)
5 0 (5.5)
1 499 (1,651)
t
i
5.323 (6.000)
Projected Waste
Quantity Adjusted
to 197Z Products
Level
2,514 (2.775)
91 000)
N C
N C
N.C.
91 (100)
t
*
Z.605 (2,875)
U)
* Except as noted, values not enclosed in parenthesis are metric tons, those enclosed in parenthesis are tons AD HCB waste values indicate the
amount of HCB contained in the waste and not the total waste stream quantities which would be significantly larger.
' Production data is not available, since U S Tariff data does not cover products manufactured at only one site
* Production of Mi rex at the one domestic production site (Nease Chemical Co ) was stopped In mid-1974.
t No valid projection can be made from the one available data point.
N A indicates Not Available N C Indicates Not Calculable from the given data
-------
2.7 metric tons (3 tons) per year of HCB whereas the Industry-furnished
data indicate an HCB waste generation rate of 1,268 metric tons (1,400 tons)
per year. Since a greater number of plants were surveyed in the present
study and the industry-furnished data represent those collected through
actual sampling and waste analysis, the industry-furnished waste quantities
shown in the table, are probably closer to actual values than those esti-
mated in the earlier study. Indeed much higher values would be obtained,
if, using the earlier approach, the industry-furnished waste data are pro-
jected to a national level using the total estimated national production
capacity and assuming that the quantity of waste generated is proportional
to production capacity, (see the last two columns in Table 12).
The present survey indicates that approximately 3,909 metric tons
(4,316 tons) per year of HCB is produced at major industrial plants and
that major sources of HCB are chlorinated solvents production (2,401 metric
tons or 2,650 tons per year), pentachloronitrobenzene manufacture (1,268 metric
tons or 1,400 tons per year) and Dacthal production (226 metric tons or
250 tons per year). A more detailed description of the data collected in
this survey on waste quantities and waste generation rates follows.
5.4.2 Chlorinated Solvents
In the present survey, seven companies representing 10 chlorinated
solvents production sites indicated that HCB was a constituent of their
waste. These plant sites which are designated as Sites A through J and the
reported or estimated waste quantities for these sites are listed in
Table 13. With the exception of Plant Site D, where only one product
(ethylene dichloride) is manufactured, more than one type of chlorinated
solvent are manufactured at the production sites listed in Table 13. Since
at most sites waste streams from all chlorinated solvent production opera-
tions are combined and the combined effluent is tested for HCB, HCB waste
quantities shown in the table are not broken down for the individual products.
Although ethylene dichloride is included in the HCB waste data for the
majority of the sites, based on the data for Site D, ethylene dichloride
production is not a significant source of HCB wastes.
40
-------
TABLE 13
PRODUCTION SITES AND HCB WASTE *
QUANTITIES FOR CHLORINATED SOLVENTS PRODUCTION
Site
Designation
Products
Quantity of HCB Waste
Metric Tons/Year
(Tons/Year)
I
J
Carbon tetrachlonde, 378 (418)
perch!oroethylene, (methyl
chloride, chloroform, d1-
chloromethane)
t
Carbon tetrachlorlde, 734 (810)
perchloroethylene, ethylene
dichloride (EDC)
Carbon tetrachlorlde, 217 (240)
perch1oroethy1ene
Ethylene dichloride 0.35 (0.39)
Perchloroethylene, tri- 0.14* (0.16)
chloroethylene. ethylene
dichloride
Perchloroethylene, tri- 236 (260)
chloroethylene, ethylene
dichloride
Carbon tetrachlorlde 6805 (750)
perchloroethylene, ethylene
dichloride
Carbon tetrachloride, 7701 '850)
perchloroethylene, trichloro-
ethylene. ethylene dichloride
Carbon tetrachlorlde, 3171 (350)
perchloroethylene
Ethylene dichloride, perchloro- 157 (173)
ethylene, trichloroethylene
Total 3.489 (3.851)
* All waste quantities refer to the amount of HCB contained in
the waste and not the total waste mixture which would be significantly
larger.
t Based on industry-furnished data that waste contains 15% HCB. (33)
However, a recent independent analysis of the waste has found 75% HCB.
Estimated based on waste generation data for Plant Site D.
i Based on 1971 data on the quantity of waste hauled away from the
site.
i Estimated based on plant production capacity and the calculated
waste generation factor for Plant Site G.
41
-------
The data in Table 13 indicate that approximately 2,401 metric tons
(2,650 tons) of HCB wastes are generated each year at plant sites for which
industry has supplied waste generation quantities. For Plant Sites H and I,
for which no industry-supplied data were available, estimates were made of
the waste generated based on production capacities. When the estimates for
these two major production sites are included, the total industry-supplied
and estimated waste quantities would be 3,489 metric tons (3,851 tons) per
year of HCB. The plant sites listed in Table 13 represent an estimated
total chlorinated solvents production capacity of 892,000 metric tons
(985,000 tons) and account for 58.5 percent of the total U.S. production
capacity for 1975.
Table 14 lists a number of additional plant sites for which data on
HCB waste production quantities were solicited in the present survey.
These sites represent 41.5 percent of total U.S. chlorinated solvents
production capacity. Three of the sites representing a production capacity
294,500 metric tons (325,000 tons) per year of carbon tetrachloride use the
CS2 process which reportedly does not generate HCB as a by-product. *9'
One small plant (production capacity 3,624 metric tons or 4,000 tons per
year of carbon tetrachloride) has not detected any HCB in its waste stream.
According to the company representing Plant Site L, the waste from this
plant probably contains HCB at parts per million (ppm) concentration levels;
the waste, however, has not been tested for HCB content. No quantitative
data were available on wastes from Plant Site P, which, according to one
(37}
source,v°'y contains "small quantities" of HCB.
5.4.3 Pesticide Industry
Pesticide industry is the second most important source of HCB wastes.
As was indicated in Section 5.2.3, production of Dacthal, PCNB, mirex,
simazine, atrazine and propazine result in the generation of HCB wastes.
At the present, simazine, atrazine and propazine are produced at one pro-
duction site by only one company and each of the remaining three pesticides
is produced by a different company at only one production site. The four
production sites, designated as Plant Sites Q through T, and industry-
furnished data on HCB waste quantities generated at these sites, are
42
-------
TABLE 14
CHLORINATED SOLVENTS PRODUCERS REPORTING NO HCB WASTE GENERATION OR HAVING NO ANALYTICAL DATA
Site
Designation
K
L
M
N
0
P
Product
Carbon
tetrachloride
Carbon tetra-
chloride
Perch! oro-
ethylene
Carbon tetra-
chloride
Carbon tetra-
chl ori de
Carbon tetra-
chloride
Perch lo ro-
ethylene
Trichloro-
ethyl ene
,
Production Capacity" '
Metric Tons/Year
(Tons/Year)
3,624 (4,000)
226,500 (250,000)
72,500 (80,000)
135,900 (150,000)
90,600 (100,000)
67,950 (75,000)
22,650 (25,000)
18,120 (20,000)
-r .-i"-5 . j'i.r. .:'.. .r.-1.1 r ssii..*---" "E-~- .: .-<
Comments
None detected
HCB may be generated
in ppm quantities;
wastes have never
been analyzed
Uses CS2 method
Uses CS2 method
Uses CS« method
Produces HCB in /,7v
"small quantities"^''
co
-------
presented in Table 15. The data indicate a total HCB waste quantity of
1,499 metric tons (1,655 tons) per year with wastes from Sites R and Q
accounting for 84.5 percent and 15.1 percent of the total, respectively.
As was discussed in Section 5.2.3, both Dacthal and PCNB contain HCB
as an impurity (estimated at 9 metric tons or 10.5 tons per year in the
final products) which should be considered as a potential source for the
introduction of HCB in the environment. No quantitative data were obtained
in this study on the HCB content of wastes generated at formulation plants
which handle these products.
5.4.4 Electrolytic Chlorine Production
As indicated in Section 5.2.4, electrolytic chlorine production using
graphite anodes generate HCB wastes. Of the 67 domestic electrolytic
chlorine production sites, 32 have been identified as using graphite anodes
(see Table 4). Table 16 lists eight sites which use graphite electrodes
and which were contacted during this survey.
As indicated in Table 16, HCB has been detected in the waste stream
from at least two sites (designated as U and U). At Plant Site U, HCB has
been determined to be close to the 20 ppm level in the still bottoms from
chlorine distillation operation. Because of the small volume of the waste,
however, the quantity of HCB generated is very small (2.7 kg/year or 6 lb/
year). At Plant Site W, HCB has been detected in the product chlorine which
is not purified but sold directly. No qualitative data are available on
HCB waste for this site. No HCB has been detected in waste from two other
*
plant sites (V and X). The waste from Plant Site Y has never been analyzed
for HCB. Three other plants (G, H and I) which did not discount the possi-
bility for the presence of HCB in their waste stream did not submit data
on HCB quantities.
Based on the waste generation data for Site U, the HCB produced in the
electrolytic chlorine industry should be very small relative to the waste
quantity in the chlorinated solvents and pesticide industries. Since data
were not available on production capacities for the 32 plants which use
44
-------
TABLE 15
QUANTITIES OF HCB WASTES FROM PESTICIDE MANUFACTURE
Site
Designation
Quantity of HCB in
Discharged Wastes
(Tons/Year)
Q
R
S
T
226 (250)
1,268 (1,400)
5 (5.5)
0.02 (0.03)
45
-------
TABLE 16
ELECTROLYTIC CHLORINE PRODUCERS USING
GRAPHITE ANODES WHICH WERE CONTACTED
IN THIS SURVEY
Site Designation
Industry-Furnished Data
I
H
G
W
X
Y
20 ppm HCB in distillation
tars (2.7 kg/yr or 6 Ib/yr)
No HCB detected using gas
chromatography
No data submitted
No data submitted
No data submitted
HCB detected in unpurified
chlorine product. No quanti-
tive data submitted
No HCB detected using infrared
spectroscopy
Never analyzed for HCB
46
-------
graphite anodes, no projection could be made of the total quantity of HCB
produced on a nation-wide level. Some of the sites which currently use
graphite anodes plan to convert to DSA anodes which do not generate HCB
wastes.
5.5 WASTE HANDLING, TREATMENT, AND DISPOSAL
5.5.1 Waste Handling (Storage and Transportation)
Loading and temporary storage of HCB wastes in containers, tank trucks
and lagoons, and .the transportation of HCB wastes from the point of waste
generation to loading/storage or ultimate disposal facilities provide poten-
tial for environmental contamination through possible accidental spills,
mismanagement of the operation and use of inadequate environmental safe-
guards. Accordingly, as part of the present survey, data were collected on
methods of HCB waste storage and transportation. These data which are sum-
marized in Table 17, are briefly discussed below. (The information con-
tained in Table 17 on methods of waste treatment will be discussed in
Section 5.5.2.)
Based on the data in Table 17, for the total of 2,870 metric tons
(3,168 tons) per year of HCB waste for which data were obtained from industry
on waste handling methods, the currently used waste storage methods and the
percentage of waste handled by each method are as follows:
Storage of solid cubes under plastic 44.2 percent
cover
Water-covered open storage lagoons 33.1 percent
Drums which may or may not be lined 14.4 percent
Insulated and heated storage tanks 8.2 percent
Nitrogen-blanketed steel tank <0.1 percent
This quantity of HCB represents 74.4 percent of the estimated total
national HCB waste production quantity based on data furnished by industry
(see Table 12).
47
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TABLE 17
METHODS OF HCB WASTE TREATMENT, HANDLING, AND TRANSPORT'
BASED ON DATA FOR SPECIFIC PRODUCTION SITES
00
Site Designation
A
B
C
0
Z
E
HCB Quantity
metric tons/year
(tons/year)
188 (208)*
734 (810)
217 (240)
0.35 (0.39)
Not Disclosed
0.14 (0.16)
Treatment
No pre- treatment for bulk
HCB wastes; spills washed
to a collection pit
Storage lagoon for solid-
liquid separation
Distillation for waste
concentration and
resource recovery; heat-
Ing to effect waste
fluldlzatlon
Distillation for waste
concentration and
resource recovery
Distillation for waste
concentration and
resource recovery
Handling and
Storage Methods
Drums covered with plastic
bags; drums stored in a
metal truck body with other dry
trash
Open concrete pit with water
cover; waste dredged with a
crane or clan-type shell
equipment
Nitrogen blanketed steel storage
tank
Storage tank
Not known
Transportation
Method
Trucks used to haul truck
body containing druimed
waste to a dispose! site
16 kilometers (10 miles)
away
Trucks used to haul waste
to an on-site burial site
Waste hauled to Site E In
tank trucks
Waste hauled by ship to
Site E
Piped to Incinerator (prior
to pipeline construction,
trucks were used to trans-
port waste to onslte
storage tank, then to
Incineration)
* Does not Include 190 metric tons (210 tons) per year which Is recovered and sold.
-------
TABLE 17
METHODS OF HCB WASTE TREATMENT, HANDLING, AND TRANSPORT
BASED ON DATA FOR SPECIFIC PRODUCTION SITES (CONT'D)
Site Designation
F
G
Q
R
s
AA
AB
HCB Quantity
metric tons/year
(tons/year)
236 (260)
680 (750)
227 (250)
1,268 (1.400)
5 (5.5)
Not available
Not available
Treatment
Distillation for waste
concentration; heating
to effect fluldlzatlon;
spills washed off to a
collection sunp; waste
dilution and suspension
by the off-site disposal
contractor prior to deep
well Injection
Not disclosed
Not disclosed
Solidification and
shaping Into cubes
Distillation for waste
reduction and notarial
recovery
Not disclosed
Dewatertng by filtration
Handling and
Storage Methods
Heated, Insulated storage tank,
with 3-ro (10- ft) pipeline for
truck hook-up
Not disclosed
113-liter (30-gal) "fiber-
pale" drums
Cubes stored under plastic
cover
Not disclosed
Drums
Not disclosed
Transportation
Ceihod
Heated tank trucks
Piped to Incinerator; metal
truck bodies were used 1n
1970-71 to haul the waste
to off-site disposal
Truck transport to off-site
disposal site
Waste 'orkllfted to storage
area
Rail and/or truck transport
to a neighboring state. 'by
an off-site disposal
contractor
Truck transport
Not disclosed
-------
At pesticide production Site R, heavy still bottom tars containing
80 percent HCB from the distillation operation are discharged into a 1-cubic
yard mold and allowed to cool to the ambient temperature. The cooling
results in the solidification of the waste into 1-ton blocks which are then
removed and transported by a forklift to a storage area. As of the date of
this survey, approximately 3,171 metric tons (3,500 tons) of the HCB-
containing waste blocks (2,537 metric tons or 2,800 tons of HCB) have been
accumulated at this storage site. The blocks are covered with a plastic
tarpaulin sheet as a rain cover. The company is currently evaluating a
number of possible alternatives, including incineration and material
recovery, for disposal of the accumulated wastes. The handling and storage
of the waste blocks can involve some environmental contamination (e.g.,
resulting from possible fragmentation and dust formation during handling,
and volatilization through sublimation during handling and storage).
Three-meter (10-foot) deep rectangular concrete lagoons are used for
temporary storage of HCB-containing wastes at Plant Sites B and C. At these
sites waste discharges from process operations enter the lagoons through
steam-jacketed fiber-cast pipes. The waste is not pumped and flows through
the pipe by means of process-generated pressure. The waste is distributed
along the length of the lagoon by a submerged mobile discharge pipe.
Ordinarily, a water cover of 0.3 to 0.6 meter (1 to 2 feet) is maintained
above the waste to minimize volatilization. Periodically, a portion of the
HCB waste is "scooped" and removed from the lagoon (using a crane or a clam-
type shell equipment) and transported by a dump truck to an on-site land-
fill location. Since some water is also scooped out with the waste, this
water acts as a seal in the dump truck during transportation.
The operation of lagoons at Sites B and C provides some potential for
environmental contamination. Although compared to soil and polyethylene
film, a water cover has been shown to be most effective to reduce HCB vola-
/3o\
tilization and loss to atmospherev , it is difficult to maintain an
effective layer of water cover at all times. Moreover, HCB is soluble to
some extent in the aqueous cover (6.2 ug.l for distilled water at 23.5°Cr
and can be lost to atmosphere through evaporation and wind action. Mass
balance calculations around the lagoon at Plant Site B have indicated
(38)
leaching into the subsurface soil, ' possibly due to deterioration of
concrete lining.
-------
Both lined and unlined drums are used for temporary storage/
transportation of HCB wastes. In some cases, a drum containing HCB is
placed in a thin plastic bag which also serves to cover the open drum.
During handling, transportation and land disposal of these drums, there is
a strong possibility for spillage, generation of dust, and volatilization.
Some actual photographs of the drums containing HCB wastes as delivered to
a sanitary landfill are shown in Figure 1.
At Plant Site F, HCB waste is stored on-site in a 41,600-liter (11,000-
gal) insulated and steam-jacketed tank. The waste is maintained in a fluid
state by heating to 116°C (240°F). The waste is removed from the tank and
transferred to heated tank truck via 3-meter (10-foot) discharge pipe to
which the trucks can connect their intake. The 3-meter (10-foot) distance
between the storage tank and the tank truck intake pipe is considered an
adequate safety measure. The tank sits on a concrete base and any spillage
flows to a collection sump and the contaminated area is washed with water
which also flows to the collection area. The material collected in the
sump is removed, the organic material is recovered by steam stripping and
the aqueous portion is discharged to an on-site waste treatment facility
which discharges its treated effluent to a receiving water.
Figure 2 presents a schematic flow diagram for the HCB waste concentra-
tion and storage at Site D. The storage tank at this facility is a nitrogen
blanketed 226,800-liter (60,000-gal) steel tank. Environmental safeguards
provided include: (a) use of dike around the storage tank, (b) return of
truck loading vent to the storage tank, (c) collection and discharge of all
the surface drains which might accidentally contain tars to plant secondary
waste treatment system, and (d) use of personnel safety equipment including
full-face shield and rubber gloves by personnel while handling the tars.
As indicated in Table 17, the methods currently used for the transpor-
tation of HCB wastes include trucks (for drummed or bulk solid waste),
heated tank trucks {for bulk liquid), pipeline (for in-plant transportation
and transfer to handling trucks), forklift (for solidified blocks of HCB
waste), ship (for bulk fluid), and rail (for tars). Based on the data
bl
-------
Figure 1. Photographs of Drummed HCB Wastes at a Sanitary Landfill
52
-------
to
FROM EOC PURIFICATION
(EDC + HEAVY CHLORINATED
HYDROCARBONS)
STEAM
CONDENSATE
VAPOR
EDC RECYCLE
TO WASH
SYSTEM
LIQUID
TAR STILL
COLUMN
C-104
10 TRAYS
2'6" 9 x 25'0" TT
STEEL
N2
BLANKET
PRESSURE
VACUUM VENT
STIRRED
STEAM JACKETED
VESSEL
VINYL
TARS
HEAVY CHLORINATED
HYDROCARBONS TO STORAGE
T-405
TRANSFER
PUMP
EDC TAR
STILLS
S-104 A/B
(TWO VESSELS)
6'6" 0 x 7'6" TT
STEEL
HEAVY CHLORINATED
HYDROCARBON
STORAGE TANK
60,000 GAL.
STEEL
LOADING
VENT RETURN
-IV'/Vt
TRUCK
LOADING
LOADING
PUMP
Figure 2. Tar Concentration and Storage Facility
At Plant Site D
-------
shown in Table 17, for the total of 3,555 metric tons (3,924 tons) per
year of HCB wastes for which data were obtained from industry on waste
*
transportation method, the percentages of the total HCB waste quantity
handled by the above-listed methods are as follows:
Truck 38.4 percent
Forklift 35.7 percent
Pipeline 19.1 percent
Heated tank trucks 6.6 percent
Rail 0.1 percent
Although no documented incidents of accidents involving transportation
of HCB by the above methods have been reported, the possibility of such
accidents occuring in the future cannot be ruled out. Because of the haz-
ardous nature of the HCB-containing wastes, precautions should be taken to
avoid spillage and losses due to wind action during transportation. During
site visits in this survey, it was observed that some waste haulers use
open trucks to transport open drums or drums enclosed in loose plastic bags
containing HCB waste. This method of transportation presents a definite
potential for environmental contamination. A major episode of HCB contami-
nation in cattle occurred in southern Louisana in 1973 due partly to the
spillage of HCB from the sides of open dump trucks as the trucks crossed
railroad tracks, hit bumps in the country roads, etc., on the way to a
landfill.^7' Pipelines used to transport HCB waste are usually heated to
permit fluid flow. Any malfunction in the heating system can result in
waste solidification and accidental discharge (flow-back-up) due to system
failure.
This quantity of HCB represents 91.1 percent of the estimated total
national HCB waste production quantity based on data furnished by industry
(see Table 12).
54
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5.5.2 Waste Treatment
A number of sites for which data were collected in this survey utilize
some form of treatment prior to ultimate disposal of HCB wastes. These
treatment methods which are listed in Table 17 include use of storage lagoons
to effect solidification and settling of HCB (Sites B and C), distillation to
effect waste volume reduction and material recovery (Sites D, E, F, S, Z);
heating to effect fluidization during storage and bulk transportation by
pipeline and trucks (Sites D and F); solidification and shaping into cubes
for storage (Site R); dewatering for waste concentration (Site AB); and
dilution and suspension by mixing with other wastes prior to deep well injec-
tion (Site OC-3, see Section 5.5.3.3).
The use of storage lagoons, solidification, and heating systems were
discussed above in connection with waste handling. At one off-site disposal
site (OC-3, see Section 5.5.3.3) HCB waste from Plant Site F is mixed with
a range of liquid wastes (chlorinated solvents, acids, alkali, rinse waste,
etc.) from other industrial clients prior to deep well injection. At an
electrolytic chlorine production facility (Plant Site AB), the mud from
brine purification operation which contains graphite stub residues is
dewatered by vacuum filtration prior to contract disposal. Based on the
data in Table 17, for the total of 2,649 metric tons (2,924 tons) per year
of HCB for which data on waste treatment were obtained from industry, the
percentage of total HCB waste quantities handled by the above-mentioned
methods are as follows:
Solidification and shaping into cubes 47.9 percent
Storage in lagoons to effect solidification and settlina 35.9 percent
Distillation to effect volume reduction and material 9.0 percent
recovery and/or heating to effect fluidization
No treatment 7.1 percent
This quantity of HCB represents 68.7 percent of the estimated total
national HCB waste production quantity based on data furnished by industry
(see Table 12).
55
-------
No data were available on methods of pretreatment (if any) used at Site G
where approximately 680 metric tons (750 tons) per year of HCB waste is
disposed of by incineration.
5.5.3 Ultimate Disposal
Based on the industry-furnished data, methods currently used for the
ultimate disposal of HCB-containing wastes include land disposal (sanitary
landfill, industrial landfill, deep well injection and drying ponds),
incineration, open pit burning, resource recovery, discharge to municipal
sewage treatment plants, and emission to atmosphere. Both on-site disposal
and off-site contract disposal are used. The prevalence of various disposal
methods are shown in Table 18 in terms of the quantity of HCB (and HCB-
containing wastes) handled and the number of facilities (on-site and off-
site) which utilize the disposal methods.
The data in Table 18 indicate that based on the total quantity of
waste handled, currently land disposal is the most prevelant method for
ultimate disposal of HCB wastes. Nine of the sites surveyed use land dis-
posal; approximately 1,389 metric tons (1,483 tons) of HCR waste (56 percent
of th« total) which is contained in a waste mixture of 17,362 metric tons
(19,164 tons) is disposed of by this method each year. Among land disposal
methods, use of industrial landfills is the most prevalent method, account-
ing for the disposal of 39.7 percent of all HCB wastes. Ranked next to land
disposal is incineration which is used at nine of the sites surveyed for the
destruction of a minimum of 1,055 metric tons (1,164 tons) per year of HCB
contained in a waste mixture in excess of 4,763 metric tons (5,257 tons) per
year. Compared to land disposal and incineration, the quantities of waste
discharged to sewage treatment plants and to atmosphere are very small. No
data were available on the quantity of HCB waste which is used at one site
(Site L) as a chemical feedstock for the production of low-molecular weight
aliphatic halogenated hydrocarbons. Of the 22 sites listed in Table 18,
six use the services of off-site disposal contractors, which handle 655
metric tons (723 tons) per year of HCB wastes. A discussion of the various
disposal methods follows.
56
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TABLE 18
PREVALENCE OF METHODS USED FOR ULTIMATE
DISPOSAL OF HCB WASTES
Disposal Method
Land Disposal
Sanitary Landfill
Industrial Landfill
Deep Well
Drying Pond
(Subtotal )
Incineration
Without by-product
recovery
With by-product
recovery
(Subtotal )
Open Pit Burning
Resource Recovery
(excluding
Incineration)
Discharge to Haste
Treatment Plants
Emission to
atmosphere
Total
HCB Waste
Quantity
metric tons/year X of Total
(tons/year)
188 (208) 78
997 (1,050) 39.7
204 ( 225) 8 5
Not available
1,389 (1.483) 56 0
375* ( 414) 15 6
680* ( 750) 28.3
1.055 (1,164) 43 9
13 kg (29 Ib) <0 1
Not available
Small, data on
exact quantity
not available
25 kg (55 Ib) <0.1
2.444S(2.647) 100X
HCB - Containing Haste
Quantity
metric tons/year I of Total
(tons/year)
254 ( 281) 1.1
6.544 ( 7,223) 29 6
10,564 (11,660) 47.7
Not available
17.362 (19.164) 78.4
3.857*( 4.257) 17.4
906' ( 1.000) 4.1
4.763(5.257) 21.5
165 kg (365 Ib) <0.1
Not available
Not available
Not available
22.1255(24.421) 100S
Plant Sites
Number 1 of Total
1 4 5
5 22.7
2 9 1
1 4.5
9 40.8
'I
8f 36.4
1 4 5
9 40 9
1 4 5
1 4 5
1 4 5
1 4.5
22 100X
Includes an estimated 0.50 metric tons (0.55 tons) per year of HCB from plant sites D and E.
These wastes are extremely dilute (10 to 40 ppm HCB content) and were not Included in the total waste
quantities to avoid gross distortion of percent of "HCB-Contalning Waste" handled by Incineration.
t Includes sues H and I for which data on actual waste quantities were unavailable
i Waste quantities is for 1970-71, data supplied by the off-site waste disposal contractor then
handling the waste Waste assumed to contain 75 percent HCB based on data for other plants.
§ Does not Include 1,268 metric tons (1,400 tons) per year of HCB waste (1,586 metric tons or 1,750 tons
of HCB-containinn waste) temporarily stored under cover at Plant Site R. Also does not Include 190 metric tons
(210 tons) of HCB vhich is recovered for sale from 257 metric tons (284 tons) of HCB-conta1n1no wastes at Plant Site A.
57
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5.5.3.1 Land Disposal
The data collected In this survey on sites employing land disposal and
the quantity of HCB wastes handled at each site are summarized in Table 19.
As used in this report, sanitary landfills are those off-site landfills
which accept both municipal refuse and industrial wastes. Industrial land-
fills are those which accept only industrial wastes. Industrial landfills
may be located on-site or off-site. The American Society of Civil Engineers
defines sanitary landfill as: "a method of disposing of refuse on land
without creating nuisance or hazards to public health or safety, by utiliz-
ing the principles of engineering to confine the refuse to the smallest
practical area, to reduce it to the smallest practical volume, and to cover
it with a layer of earth at the conclusion of each day's operation or at
(39)
such more frequent intervals as necessary."x ' Not all landfills which
are commonly referred to as sanitary landfills conform to this definition
or meet the high operating standards which are implied. Industrial land-
fills are generally waste burial sites consisting of pits or trenches which
are excavated in suitable ground and into which the waste is deposited and
subsequently covered with dirt. To provide protection against possible
infiltration of leachate into the subsurface soil and contamination of
groundwater, the burial sites may be lined with impervious materials such
as dense clay, concrete or plastic liners.
The data collected in this survey on sites using sanitary landfills,
industrial landfills, deep well injection, and drying ponds are presented
below.
Sanitary Landfill
HCB wastes from Plant Site A are handled by an off-site contractor
(designated as OC-1) which operates a 603-hectare (244-acre) sanitary
landfill and handles household refuse and manufacturing wastes from
a metropolitan area. Approximately 255 truck loads of wastes are
received at the site each day, including seven to ten loads of HCB wastes
per month from Plant Site A which is located about 16 kilometers (10 miles)
58
-------
TABLE 19
METHODS AND SITES FOR LAND DISPOSAL OF HCB WASTES
Method of
Land Disposal
Sanitary Landfill
Industrial Landfill
Deep Well Disposal
Drying Pond
Disposal Site
Designation
Off -site: OC-1
Off-site: OC-2
On-site: B
On-site: C
On-site: P
On-site: U
Off -site: OC-3
On-site: J
On-site: AC
Quantity of
HCB Waste
metric tons/year
(tons/year)
188 (208)
45 (50)
734 (810)
217 (240)
Not available
2.7 kg (6 Ib)
47 (52)
157 (173)
Not available
MMMMMHiMH
Source of Waste ;
(Plant Site .
Designation) .
i
4
A i
Q ':
B i
'»
P P
IF'
U '
F ^
J
i
AC 'i
3
59
-------
away from the landfill. The HCB wastes are received in open drums, some
enclosed in plastic bags. The disposal contractor's haul trucks containing
the drums merely "dump" their loads at the site. These drums along with
other loads of refuse and industrial trash are then compacted on a 4.7
meter (15-foot) high slope by a bulldozer. A 15-centimeter (6-inch) earth
cover is provided at the end of each working day. Since the plastic bag
enclosures for the drums do not provide a tight seal, in some cases the
wastes are spilled from the drums and physically mixed with other wastes
during the dumping and bulldozing operation. Because of the powdery nature
of the waste, some of the HCB material may be blown away by wind action
and this constitutes a potential health hazard to the equipment operators
and presents possibilities for the contamination of air and adjacent land.
(See Figure 1 and discussion in Section 5.5.1). HCB wastes from Site A
have been hauled to this landfill since early 1974; it is estimated that
about 282 metric tons (311 tons) of HCB has been deposited at this landfill
to date.
The operation at the OC-1 waste disposal site was started about 24
years ago. The area was originally an uncleared swamp which has since
been cleared and filled with dirt and sections of it used for waste dis-
posal. The section which is in operation currently has an anticipated
service life of 3-5 more years. The drainage ditches which pass through
the property provide water for waste compaction and dust suppression during
the operation. A hydrogeological study conducted by an independent con-
sulting engineering firm has indicated that the site is suitable for use as
a sanitary landfill and that the soils and bedrock are essentially imper-
meable to water (run-off) infiltration. The State Department of Health has
been conducting periodic sampling of the ambient air in the vicinity of the
site and of the drainage ditches above and below the operating dump.
Industrial Landfills
Based on the data collected in this study, five industrial landfills
accept HCB wastes. Four of the sites are on-site landfills and one is
operated by an off-site disposal contractor. The off-site disposal facility
(designated as OC-2) receives HCB wastes from Plant Site Q. Prior to the
60
-------
current use of landfill, HCB wastes were incinerated at OC-2 disposal site
along with other industrial wastes. However, because of certain operational
difficulties and high cost of supplementary fuel, the incineration as a
method of ultimate disposal was abandoned in favor of landfill operation.
The site is located on a 593-hectare (240-acre) parcel and is classified
as a Texas Class I site which, under Texas Water Quality Control Board
regulations, is suitable for the disposal of hazardous chemicals. Approxi-
mately 20 percent of the HCB waste from Plant Site Q is hauled to this
facility by the disposal contractor. (The other 80 percent is sent to
another off-site facility, OC-5, for incineration; see below.) Since Plant
Site Q is expected to join a regional waste disposal authority which will
use incineration as the disposal method, no HCB waste will be taken to the
OC-2 site after about 1976.
Although the practice has been stopped, during 1970-71, approximately
680 metric tons (750 tons) of HCB waste from Plant Site G was disposed
of in an off-site disposal facility (OC-4). The waste was originally de-
posited in two 38 x 38 meter (125 x 125 foot) pits. One of the pits, which
had become full, was subsequently covered with 0.61 meter (2 feet) of soil
and 0.61 meter (2 feet) of dry trash. The other pit in which HCB had been
deposited was still active receiving other industrial wastes. During the
HCB contamination episode in Louisiana in 1973 (see Section 3), the opera-
tion at this site was suspected as a possible source for environmental con-
tamination. This suspicion was later confirmed when samples of the soil
from selected locations at the site were tested. A cleaning operation
which was financed by the company representing Plant Site G was then ini-
tiated which included removal of the dirt and trash covers from the first
pit and their replacement with a new cover consisting of a total of 1.9
meters (6 feet) of fresh soil with a 0.025-centimeter (10-mil) sheet of
polyethylene film placed approximately at the middle of the soil cover.
On-site industrial landfill is used for the disposal of HCB wastes at
Plant Sites B and C. The HCB wastes are scooped from the settling lagoons
and brought to the burial site in dump trucks. The disposal sites at the
two facilities are essentially identical. The landfill at Plant Site B,
which is the larger of the two landfills, was visited during this survey.
61
-------
HCB wastes are deposited in excavated pits 3.1 to 3.7 meters (10 to 12 feet)
deep and roughly 6.2 x 9.3 meters (20 x 30 feet) in size. Each pit is of
sufficient capacity to handle all the waste which is scooped from the set-
tling pond in a lagoon emptying operation. The deposited waste is covered
with 1.2 to 1.9 meters (4 to 6 feet) of soil and a 0.025-centimeter (10-mil)
thick polyethylene film placed approximately at the mid-depth of the soil
cover. The subsurface structure at the site includes impermeable strata
which are considered adequate to prevent groundwater contamination. Soil
boring tests have indicated that the top soil down to a depth of about
19 meters (60 feet) consists of a clay-silt mixture with very little sand.
Periodic sampling and analysis of water from several wells in the area have
indicated no contamination of groundwater with HCB.
Prior to the use of on-site land disposal, HCB wastes from Plant Site B
were handled by a private off-site contractor and deposited in a nearby
sanitary landfill. The landfill received 500 to 600 m3 of material every
three months for 2.5 years ending in January 1973. During much of this time
the HCB waste was spread in a thin coat over the entire dump to serve as a
fly repellent. This operation was later identified as the major source of
environmental contamination in the Louisiana HCB contamination episode of
1973 (see Section 3). The site has since been closed and the wastes buried
under polyethylene sheeting in an isolated section of the landfill.
Two other sites which utilize on-site landfills for the disposal of
HCB wastes are Plant Sites P and U. According to the Louisiana State Health
Department/37^ the on-site facility at Plant Site P has been in operation
for a number of years. The quantity of HCB waste generated at this site is
considered very small. Tars and still bottoms from the chlorine purifica-
tion operation at Plant Site U contain a very small quantity of HCB (20 ppm
or 2.7 kg/yr). These wastes are buried on-site in the desert land.
5.5.3.2 Deep-Well Injection
At the off-site waste disposal facility OC-3, deep-well injection is
used for the disposal of certain types of industrial wastes. Among the
wastes handled is approximately 780 metric tons (860 tons) per year of tars
62
-------
containing 6 percent HCB from Plant Site F. The waste is hauled to the site
by the contractor in 18,900-liter (5000-gallons) vacuum tank trucks. The
HCB-containing tars are mixed and diluted with wastes from other industrial
sources prior to deep-well injection. The disposal stratum is about 1.6
kilometers (1 mile) below the surface and the average injection rate is
522 liters per minute (138 gpm). Depending on the nature and quantity of
the wastes, some wastes are injected underground as soon as received at
the site; other wastes may be stored for a period of several days prior
to injection. The injection operation meets all requirements for deep-well
disposal set by the Texas Water Quality Board and is carried out under a
Board permit.
Deep-well disposal is also employed at an on-site facility (Plant Site
J) in Louisiana for the disposal of HCB wastes from a chlorinated solvents
production plant. No data are available on the actual disposal operation
at this site.
5.5.3.3 Drying Pond
At Plant Site AC, the graphite stub residue from the electrolytic
sodium chlorate production is dewatered by filtration and the filter cake
which consists of the graphite stub loss, perl He filter aid, and insoluble
calcium sulfate is taken to on-site drying ponds. In addition to the filter
cakes, these ponds receive a number of other process wastes. When a pond
is full, the operation is transferred to a new pond. Although the dried
material in some of the abandoned ponds Is not currently covered, the com-
pany plans to cover the dried material with dirt in the future.
5.5.3.4 Incineration
Incineration as a method for ultimate disposal of HCB wastes is used
at six facilities listed in Table 20, along with the sources and quantity
of waste handled at each site. The largest quantity of HCB wastes is han-
dled at Plant Site G, which uses an on-site incinerator of proprietary
design. The system reportedly effects 99.94 percent destruction of HCB
and recovers hydrochloric acid as a by-product. The incinerator is equipped
63
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TABLE 20
SITES FOR THE INCINERATION OF HCB WASTES
Disposal Site
Designation
On-site: G
Off-site: OC-5
On-site: E
Off -site:* OC-6
On-site: AD
On-site: Y
^^^^^^^^^^^i
Quantity of Waste
metric tons/year
(tons/year)
680 (750)
189 (208)
182 (200)
Min 0.45 (0.5)
5.0 (5.5)
Not available
Not available
Source of Waste
(Plant Site
Designation)
G
F
Q
E, D, Z
S
AD
Y
^^^^^^^^^^^^^^^^^^^^^^^^^^^^BMH
^^^^^^^^^^^^^^^^^^^^^"^
No HCB waste has been hauled to the site since mid-1974.
64
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with scrubbers to minimize emissions to the atmosphere. Prior to the
installation of the incinerator, HCB wastes were stored in metal drums;
the stored wastes are now fed to the incinerator. The company plans to
install similar incinerators at its facilities at two other locations.
The OC-5 off-site disposal contractor handles HCB wastes from Plant
Sites F and Q. The wastes are hauled from these plants in heated tank trucks
and stored in storage tanks prior to incineration. The incineration is
essentially a destruction operation and does not include any by-product
recovery. The solid and semi-solid wastes are handled in a Bartlett Snow
rotary kiln incinerator which has a rated capacity of 1.8 metric tons (2
tons) per hour and operates at a temperature of 816 to 1,093°C (1,500 to
2,000°F) or higher. Low to medium viscosity waste liquids are fed at a
rate of up to 3,780 liters (1,000 gallons) per hour to a Loddby liquid
incinerator which operates at a burner temperature close to 1,093°C
(2,000°F). All exhaust gases from the rotary kiln incinerator and the
liquid waste burner are mixed and passed through an afterburner which
operates at 1,316°C (2,400°F). The combustion gases are then cooled in
a water quench chamber, scrubbed with an alkali solution and discharged
to the atmosphere through a stack. Gases exist the stack at 77°C (170°F)
and at a linear velocity of 539 meters (1770 fpm) per minute. When Plant
Sites Q and F join a regional waste disposal authority (possibly in 1976),
they will no longer use the services of the off-site contractor (OC-5) for
the disposal of the HCB wastes.
The incinerator at Plant Site E handles HCB-containing wastes from
chlorinated solvents production at this site and at two other production
sites (D and Z). The incinerator is a Thermal Research unit having two
trains, one for the destruction of gases and one for the combustion of
liquids. The liquid train was designed to incinerate 19 metric tons (22
tons) per day of waste tars containing 98.5 percent chlorinated hydrocar-
bons. The gas train was designed to incinerate 48 metric tons (53 tons)
per day of waste gases containing 20 percent chlorinated hydrocarbons.
The incinerator is equipped with water and alkali scrubbing systems for
the removal of acids from combustion gases. The scrubbed gases are exited
to the atmosphere through a 1.2-meter (4-foot) diameter stack at a
65
-------
temperature of about 57°C (135°F) and an exit velocity of 3 meters per
second (10 fps). Monitoring of stack gases has indicated the following
emission rates:
Emission Rate,
Pollutants kg/hr (Ib/hr)
HC1 2.8 (6.2)
CO 1.5 (3.2)
NOX 5.7 (12.6)
C12 0.3 (0.6)
Particulates 3.3 (7.2)
Up until mid-1974, the off-site contractor OC-6 in New York, handled
approximately 5.0 metric tons (5.5 tons) per year of HCB from Plant Site S
in Pennsylvania. No HCB wastes have since been handled at this site because
of the discontinuation of the production of an HCB waste producing chemical
at Plant Site S.
At Plant Site AD, liquid waste from formulation of HCB-containing
pesticides are destructed, along with wastes from some other process sources,
in an incinerator designed for pesticide wastes. The incinerator is bottom-
fed, refractory-lined, and of up-right design. The dimensions for the lower
section of the combustion chamber are 2.4 m I.D. x 7.5 m long (8 x 25 feet).
Above this, the combustion chamber tapers to 1.2 meters (4 feet) I.D. at the
top. The exhaust gases are quenched to less than 121°C (250°F) by means of
water sprays and are scrubbed in a Venturi scrubber which normally operates
with a pressure drop of about 1.4 x 10 Newtons/m (2 psi). The incinerator
is pressurized with a forced air feed (125 percent excess air) and is de-
signed for a heat release of 3.2 x 1010 Joules/hr (30 x TO6 Btu/hr). There
are two spray nozzles at the bottom of the incinerator for introducing
wastes and a gas burner at the pilot flame level. The quantitative rate at
which supplementary fuel gas is used can be adjusted to obtain desired tem-
peratures. Ordinarily, the incinerator is operated at 871°C (1600°F). The
residence time in the combustion chamber is 2 to 3 seconds, based on an
exit gas volume of 1,528 actual cubic meters per minute (54,000 ACFM) at
the operating peak load. Under normal operating conditions, the exit gas
flow rate is 764 actual cubic meters per minute (27,000 ACFM) and the gas
66
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exits at 85°C (185°F). The residence time is reduced to 1 to 1.5 seconds
under maximum loadings. From the Venturi, the gases pass through a
"disengager" where the scrubbing solution is separated and recycled to the
quench tower and the Venturi scrubber. A sodium hydroxide solution is
used as make-up which also adjusts the pH to 9.5 to 10.0.
All brine wastes from the electrolytic production of chlorine at Plant
Site Y are destroyed in an on-site incinerator. Detailed information on
this incinerator was not available.
5.5.3.5 Miscellaneous Disposal Methods
Miscellaneous methods which are currently in use for the disposal of
HCB wastes include resource recovery (discussed in Section 5.5.4), open-
pit burning, discharge to sewage treatment plants, and stack discharge to
the atmosphere. Except for resource recovery, the quantity of HCB wastes
handled by these miscellaneous methods is very small.
As at most munitions manufacturing sites, the combustible production
wastes generated at Plant Site AA, are disposed of by open-burning; the
scrap containing HCB is placed in waste cans which are covered with fuel
and burned in an open pit. The open pit burning at this site is conducted
under a State permit.
At Plant Site AE wastewater from the clean-up of equipment used for
pesticide formulation enters a local sewage treatment plant which discharges
its treated effluent to a receiving water. Beacuse of the refractory (resis-
tant to biodegradation) nature of HCB/ ' it is doubtful that biological
treatment per se can result in destruction of HCB in wastewaters.
At Plant Site T, a small amount of HCB (25 kg/year or 55 Ib/year)
which originates from the use of impure raw material (see Sections 5.2.3
and 5.2.12) is emitted to the atmosphere through stack discharges.
67
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5.5.4 Resource Recovery
If a waste can be processed to recover energy or salable products,
or If it can be directly used as a chemical feedstock in the production
of commercial products, such resource recovery methods would be preferred
to waste disposal such as incineration aimed solely at the destruction of
organic wastes or landfilling. Table 21 lists a number of resource recovery
methods which are currently used in connection with processing HCB-containing
wastes. Because of the proprietary nature of the resource recovery opera-
tions currently in use, detailed information could not be obtained on raw
material requirements, operating conditions, system efficiencies, and costs
associated with various resource recovery methods. In general, the appli-
cability of a specific resource recovery method to the processing of HCB-
containing wastes would be dependent on the waste characteristics (HCB con-
centration, nature of other constituents, and total waste quantity) and
should be evaluated on a case-by-case basis. As indicated in Table 21, at
two Plant Sites (A and AF) HCB is recovered for sale from processing HCB-
containing wastes generated in the manufacturing of chlorinated solvents.
The recovered HCB is now largely used as a peptizing agent in the manufac-
ture of nitroso and styrene rubber for tires. The incineration system at
Plant Site 6 reportedly effects 99.94 percent destruction of HCB and recovers
hydrochloric acid as a by-product. At Plant Site L, the wastes from chlori-
nated solvent production are used as a raw material in a process for the
production of freon. The freon process apparently includes recovery of
HC1 as a salable product. The inorganic waste from freon production
operations (silica gel, metallic salts, etc.) are encapsulated in concrete
in a landfill.
5.6 ULTIMATE DISPOSAL TECHNOLOGY CLASSIFICATION AND EVALUATION
The technology of waste disposal for the management of hazardous wastes
is often described on the basis of the following classification standards:
Level I Technology: The typical broad average practice for the
industry or product group (i.e., prevalent
practice).
Level II Technology: The best technology available in current
commercial practice.
68
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TABLE 21
RESOURCE RECOVERY METHODS FOR PROCESSING HCB
CONTAINING WASTES
Resource Recovery
Method
Plant Site Where
Method Used
Quantity of HCB
Handled
metric tons/year
(tons/year)
Recovery of HCB for sale
from chlorinated solvent
wastes
Use of recovered HCB for
seed treatment
Use of recovered HCB
in the manufacture of
synthetic rubber
Incineration including
recovery of HC1
Use in production of
freon, including HC1
recovery
A
AF
Seed treatment
houses
Data not
available
190 (210)
50 (55)
6.2 (6.9)
190 (210)
680 (750)*
Not available
This method is also scheduled for use at Plant Sites H and I which
generate 770 metric tons (850 tons) and 317 metric tons (350 tons) of HCB
waste, respectively.
69
-------
Level III Technology: Technology currently known and assessed
as providing adequate health and environ-
mental protection.
Depending on the technology and the nature of the industry or specific waste
stream, in some cases the three levels of technology may be the same or
there may not be significant differences between Level I and Level II, or
Level II and Level III technologies.
The quantitative data on the prevalence of various methods used for the
disposal of HCB wastes are presented in Table 18 and were discussed in
Section 5.5.3. Land disposal and incineration appear to be of equal preva-
lence from the standpoint of the total number of sites using each of the
two disposal methods. However, based on the quantity of HCB waste handled,
a greater quantity of waste (56.0 percent of the total) is disposed of on
land, as compared to that destroyed by incineration (43.9 percent of the
total). When the land disposal method is subdivided and considered as
four separate technologies (sanitary landfill, industrial landfill, deep
well injection and drying pond), and the incineration is considered as
technologies with and without by-product recovery, incineration without
by-product recovery (but with emission control) is the most prevalent
method in terms of its usage at different plant sites. In terms of the
quantity of HCB wastes handled, however, a greater quantity of HCB wastes is
handled by industrial landfills than by an other single disposal method.
The industrial landfills at Plant Sites B and C are designed and operated
with due consideration to abatement of environmental contamination. The
subsurface structure at the sites includes impermeable strata which are
considered adequate to prevent groundwater contamination. Subsequent to
waste deposition, the wastes are covered with 1.2 to 1.8 meters (4 to 6 feet)
of soil with a 0.025-centimeter (10-mil) thick polyethylene film placed
approximately at the mid-depth of the soil cover.
Incineration with emission control and by-product recovery is considered
to correspond to both Level II and Level III technologies as defined above.
The incinerator at the Plant Site G is reported to effect 99.94 percent des-
truction of HCB and to permit recovery of HC1 as a by-product. The system
is of a large capacity and handles about 680 metric tons (750 tons) per year
70
-------
of HCB. Based on the very limited data which are available on the operation
of this particular incinerator, the applicability of the system for handling
smaller quantities of HCB wastes (at other production sites) cannot be deter-
mined. The incinerator used at Plant Site E handles 7,112 metric tons (7,350
tons) per year of tars containing 314 pounds of HCB. Based on the stack
monitoring data presented in Section 5.5.3 for this incinerator, emissions of
HC1, CO, NOX, C12 and participates are estimated at 0.002, 0.001, 0.005,
0.0002, and 0.003 kg/kg of tar input, respectively.
Table 22 summarizes the technology levels identified for the disposal
of HCB wastes. The technology classification levels identified in this
table are subject to certain limitations which should be considered in
interpretation of the data and in developing regulations for the control
of HCB wastes. The wide variety of systems which are in current use for
the disposal of HCB-containing wastes reflect the differences in: (a) waste
stream characteristics; (b) manufacturing and formulating methods; (c) size
and geographic location of the plants; and (d) applicable environmental reg-
ulations. Because of the differences in waste quantities of characteristics
and in plant locations and operations, it is almost impossible to arrive at
a "broad average" HCB waste disposal method representative of the current
practice at a "typical" plant. An equally impossible task is to define or
prescribe a disposal system which would be applicable to the management of
wastes at all HCB waste generation sites. At some large chemical production
facilities or at off-site disposal sites, HCB wastes are only a very small
portion of the total waste handled. In such facilities, the management of
waste from a specific production operation Is not usually an isolated
problem requiring a separate solution, but rather an element in the total
waste management plan for the facility.
5.7 WASTE HANDLING AND DISPOSAL COSTS
Not all industries and waste disposal facilities which were contacted
in this survey furnished information on the costs for handling and disposal
of HCB wastes. In some cases where cost data were supplied, the information
71
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TABLE 22
DISPOSAL TECHNOLOGY CLASSIFICATION
Technology
Level
Technology
Level I
Industrial landfills with a 1.2 to 1.8 m (4 to 6 ft) of
soil cover and a 0.025 cm (10-mil) thick polyethylene
film placed approximately at mid-depth of the soil cover
(based on the quantity of HCB handled)
Incineration without by-product recovery but with
emission control (based on the prevalence of number of
sites)
Level II
and
Level III
Incineration with emission control and by-product
recovery
72
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was fragmented and Inconclusive. Some of the companies and waste disposal
facilities indicated that although they can probably provide data on their
overall cost of waste handling and disposal, they cannot break down the
cost to arrive at any meaningful estimate of the portion of the cost which
can be attributed to the handling of HCB waste which accounts for a small
fraction of the total waste handled.
Table 23 presents the cost charged to waste generators by four off-
site waste disposal contractors employing landfill, incineration and deep-
well injection. The data indicate a disposal fee ranging from $22 to $35
per metric ton ($20 to $32 per ton) of HCB-containing wastes. The range
in the disposal fee is understandable in the light of differences in the
quantities of waste handled, method of disposal, haul distance, and labor
costs in different locations.
Table 24 presents the very limited data which were furnished by two
Plant Sites (B and E) on on-site waste disposal by landfill and incinera-
tion. The $T1 per metric ton ($10 per ton) operating cost at Plant Site B
includes costs for the operation of pretreatment lagoon, removal and trans-
port of waste from the lagoon to the landfill site and equipment maintenance.
No data were available on the cost of lagoon construction, and value of
land used for lagooning and landfill ing. The waste which is incinerated at
Plant Site E is a chlorinated solvent waste containing a very small con-
centration of HCB (10-40 ppm).
The most comprehensive cost data collected in this study are for the
ethylene dichloride (EDC) waste concentration and storage facility at Plant
Site D (see Figure 2 for schematics of the operation). The system handles
8,833 metric tons (9,750 tons) per year of waste containing 40 ppm of HCB.
The concentrated tar is hauled by tank trucks to Plant Site E for incinera-
tion. A breakdown of the cost for the EDC concentration and storage system
are shown in Table 25. The system was installed in 1967, and the cost data
are in 1967 dollars.
73
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TABLE 23
COSTS FOR OFF-SITE DISPOSAL OF HCB WASTES
Disposal Method
and
Disposal Contractor
Source of Waste
(Plant Site)
Quantity
metric tons/year
(tons/year)
$/metric ton ($/ton)
of HCB Waste
$/metric ton ($/ton)
of HCB-
Containing Waste
Landfill: OC-1
Landfill: OC-4
Deep Well Injection: OC-3
Incineration: OC-5
F,Q
188 (208)
680 (750)
47 (52)
371 (408)
$57 ($52) [$33 ($30)
for users fee, and
$24 ($22) for con-
tainer rental]
$40 ($36)
$35 ($32) [$20 ($18)
for users fee, and
$15 ($14) for con-
tainer rental]
$30 ($27)
$22 to $33 ($20 to
$30) for all chlor-
inated solvent wastes
including those
containing HCB.
$22 ($20) for all
chlorinated solvent
wastes
* Data are for 1971 operation and the costs were adjusted to 1975 dollars assuming
an escalation factor of 8% per year.
-------
TABLE 24
COSTS FOR ON-SITE DISPOSAL OF HCB WASTES
Plant
Site
B
E
Disposal
Method
Industrial
Landfill
Incineration
metrl c
tons/year
1 tnn*i
734 (810)
142 (157)
Costs
Operating Cost: $11 /metric ton
($10/ton) of HCB waste
$2,000,000 investment cost for
incinerator
TABLE 25
COSTS FOR EDC TARS CONCENTRATION AND STORAGE SYSTEM
AT PLANT SITE D (SEE FIGURE 2)
Major Equipment
EDC Tar Stills (S-104A and B)
Tar Still Column and Condenser (C-104)
Transfer and Loading Pumps
Tars Storage Tank (T-405)
1967 Major Equipment Cost
Installed Cost (Estimated: 3X Major Equipment Cost)
Utilities Requirements
Steam (1.03 x 106 Newtons/m2 gage; 150 psig) -
634 kg (1400 pounds) per hour
Cooling Water - 794 liters per minute (210 gpm)
Pumps (2) - 3.7 kW (5 hp) each
Agitators (2) - 15 kW (20 hp) each
Maintenance (Estimated at 6% of Installed Cost Per Year)
Insurance and Taxes (1.535 of Installed Cost)
Operating Labor
1967 Cost
$28,562
13,294
14,000
15,000
$70,856
$213,000
$12,800
$2,700
$6,000
75
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G. REFKRENCES
1. National Research Council, Ocean Affairs Board. Assessing potential ocean
pollutants. Washington, National Academy of Sciences, 1975. 438 p.
2. Booth, N. H., and J. R. McDowell. Toxicity of hexachlorobenzene and asso-
ciated residues in edible animal tissues. Journal of the American Veteri-
nary Medical Association. 166(6);591-595, Mar. 15, 1975.
3. Beck, J., and K. E. Hansen. The degradation of quintozene, pentachloroben-
zene, hexachlorobenzene and pentachloroaniline in soil. Pesticide Science,
5(l):41-48, Feb. 1974.
4. Taylor, I. S., and F. P. Keenan. Studies on the analysis of hexachlorobenzene
residues in foodstuffs. Journal of the Association of Official Analytical
Chemists. 53(6):1293-1295, Nov. 1970.
5. Siyali, D. S., and P. Strieker. Hexachlorobenzene and other organochlorine
pesticides in milk. Australian Journal of Dairy Technology, 28(2):55-58,
June 1973.
6. Siyali, D. S. Hexachlorobenzene and other organochlorine pesticides in human
blood. Medical Journal of Australia, 2(19):1063-1066, Nov. 4, 1972.
7. Burns, J. E., and F. M. Miller. Hexachlorobenzene contamination: its effects
in a Louisiana population. Archives of Environmental Health, 30(l):44-48,
Jan. 1975.
8. Hexachlorobenzene (HCB) emissions in Geismar, Louisiana vicinity, 4 June 73;
status report. [New Orleans], Louisiana Air Control Commission and
Louisiana Division of Health Maintenance and Ambulatory Patient Services,
1973. 33 p. (Unpublished report.)
9. Mumma, C. E., and E. W. Lawless [Midwest Research Institute]. Survey of
industrial processing data. Task I-hexachlorobenzene and hexachloro-
butadiene pollution from chlorocarbon processes; final report. Washington,
U.S. Environmental Protection Agency, Office of Toxic Substances, June
1975. (Distributed by National Technical Information Service, Springfield,
Va., as PB-243 641.)
10. 1975 directory of chemical producers - United States of America. Menlo Park,
Calif., Stanford Research Institute, Chemical Information Services, 1975.
1050 p.
76
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11. Farm chemicals handbook - 1972. Willoughby, Ohio, Meister Publishing Co.,
1972. 424 p.
12. Dun & Bradstreet million dollar directory - 1975. New York, Dun & Bradstreet,
Inc., 1975. 7089 p., app.
13. Oil, paint and drug reporter. 1975-76 OPD chemical buyers directory. 63d ed.
New York, Schnell Publishing Company, Inc., 1975. 1616 p.
14. Personal communication. B. Cohen, Dover Chemical Company, to S. Quinlivan,
TRW Systems, Inc., Sept. 19, 1975.
15. Personal communication. Mr. Schultz, Hummel Chemical Company, to
M. Ghassemi, TRW Systems, Inc., Dec. 4, 1974.
16. Personal communication. B. Cohen, Dover Chemical Company, to S. Quinlivan,
TRW Systems, Inc., Feb. 7, 1975.
17. Data supplied to TRW Systems, Inc., by Stauffer Chemical Company in connec-
tion with EPA Contract 68-01-2919: Gruber, G. I., and M. Ghassemi.
Assessment of industrial hazardous waste practices, organic chemicals,
pesticides and explosives industries. Washington, U.S. Environmental
Protection Agency. (In preparation; to be distributed by National Technical
Information Service, Springfield, Va.)
18. Personal communication. H. E. Everson, Diamond Shamrock Corporation,
to S. Quinlivan, TRW Systems, Inc., July 8, 1975.
19. Personal communication. J. D. Lunn, Jr., Continental Oil Company, to
S. Quinlivan, TRW Systems, Inc., Mar. 5, 1975.
20. Personal communication. A. Jordan, Kilgore Corporation, to S. Quinlivan,
TRW Systems, Inc., Feb. 19, 1975.
21. Personal communication. D. Maley, Longhorn Army Ammunition Center, to
S. Quinlivan, TRW Systems, Inc., Feb. 21, 1975.
22. Personal communication. Mr. Fitch, Crane Naval Ammunitions Center, to
S. Quinlivan, TRW Systems, Inc., Feb. 15, 1975.
23. Personal communication. B. Rollins, Dept. of Food and Agriculture, State of
California, to S. Quinlivan, TRW Systems, Inc., Feb. 25, 1975.
77
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24. Standard & Poor's register of corporations, directors and executives. New
York, Standard & Poor's Corporation, 1975. 3 v.
25. Personal communication. Mr. Hanson, ICI America, to S. Quinlivan, TRW
Systems, Inc., Feb. 28, 1975.
26. Personal communication. Messrs. Vlacos and Gilbert, Vulcan Materials Com-
pany, to S. Quinlivan, TRW Systems, Inc., July 7, 1975.
27. Personal communication. B. Walker, Reichhold Chemicals, to S. Quinlivan,
TRW Systems, Inc., Feb. 21, 1975.
28. Personal communication. C. F. Buckley, Monsanto Company, to S. Quinlivan,
TRW Systems, Inc., Feb. 24, 1975.
29. Personal communication. Sonford Chemicals Company, to S. Quinlivan, TRW
Systems, Inc., Feb. 24, 1975.
30. Personal communication. C. Bests, J. H. Baxter Company, to S. Quinlivan,
TRW Systems, Inc., Feb. 1975.
31. Personal communication. D. Nicholas, Honolulu Wood Treatment Company, to
S. Quinlivan, TRW Systems, Inc., Feb. 10, 1975.
32. Personal communication. Mr. Raleigh, Stackpole Carbon Company, to
S. Quinlivan, TRW Systems, Inc., Feb. 11, 1975.
33. Personal communication. R. Newman, Carborundum Corporation, to
S. Quinlivan, TRW Systems, Inc., Feb. 13, 1975.
34. Personal communication. F. Fier, AirCo-Speer Corporation, Niagra Falls
Research Center, to S. Quinlivan, TRW Systems, Inc., Feb. 11, 1975.
35. Personal communication. Mr. O'John, Keystone Carbon Company, to
S. Quinlivan, TRW Systems, Inc., Feb. 11, 1975.
36. Personal communication. Mr. Konitzer, Helwig Carbon Products, to
S. Quinlivan, TRW Systems, Inc., Feb. 11, 1975.
37. Personal communication. G. von Bodungen, Louisiana State Department of
Health, to S. Quinlivan, TRW Systems, Inc., July 8, 1975.
78
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38. Farmer, W. J. A study of volatilization and vapor phase transport of hexa-
chlorobenzene from industrial wastes deposited on land; progress report -
Jan. 16, 1975-Apr. 13, 1975. Cincinnati, U.S. Environmental Protection
Agency, Solid and Hazardous Waste Research Laboratory, 1975. 13 p.
(Unpublished report.)
39. Baum, B., and C. H. Parker. Solid waste disposal, v. 1. Incineration and
landfill. Ann Arbor, Mich., Ann Arbor Science Publishers, Inc., 1973.
397 p.
79
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7. APPENDIX
TABLE A-l
KEY TO PLANT SITES, THEIR LOCATIONS
AND SOURCES OF WASTES
1 Plant Site
Designation
A
"
c
D
E
F
IG
R
1
J
K
L
M
N
0
P
Location
(State)
Ky.
La.
Ks.
La.
La.
Tx.
La.
Tx.
Ca.
La.
W.V.
Tx.
W.V.
Al.
N.Y.
La.
Operations Producing or Likely to I
Produce HCB Waste [
Chlorinated solvents production E
Chlorinated solvents production; electro- jj
lytic chlorine production E
P
L
Chlorinated solvents production; PCP pro- E
duction; electrolytic chlorine I
production f
Chlorinated solvents production; VCM ;
production '
Chlorinated solvents production; electro- !
lytic chlorine production; sodium chlorate
production
Chlorinated solvents production; electro-
lytic chlorine production
Chlorinated solvents production; electro- 1
lytic chlorine production; VCM production |
Chlorinated solvents production; electro- |
lytic chlorine production; VCM production jj
Chlorinated solvents production; electro- 0
lytic chlorine production n
Chlorinated solvents production; electro- 3
lytic chlorine production; VCM production |
Chlorinated solvents production; electro- I
lytic chlorine production |
Chlorinated solvents production; electro- |
lytic chlorine production i
Chlorinated solvents production B
Chlorinated solvents production; electro- jj
lytic chlorine production |
Chlorinated solvents production 3
Chlorinated solvents production; electro-
lytic chlorine production; sodium chlorate |
production |
80
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TABLE A-1
KEY TO PLANT SITES, THEIR LOCATIONS
AND SOURCES OF WASTES (CONT'D)
Plant Site
Designation
Q
R
S
T
U
V
W
X
Y
Z
AA
AB
AC
AD
AE
AF
Location
(State)
Tx.
Al.
Pa.
{La.
Nv.
Oh.
Al.
Wa.
J0r.
P.R.
Tn.
Or.
Ms.
Ca.
N.Y.
Oh.
Operations Producing or Likely to
Produce HCB Waste
Pesticide production
Pesticide production
Pesticide production
Pesticide production
Electrolytic chlorine production
Electrolytic chlorine production
Electrolytic chlorine production
Electrolytic chlorine production
Electrolytic chlorine production
Chlorinated solvents production
Ordnance and pyrotechnics production
Sodium chlorate production; electrolytic
chlorine production
Sodium chlorate production
Seed treatment chemicals formulation
Pesticide production; electrolytic chlorine
production; sodium chlorate production
HCB production; PCP production
81
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TABLE A-2
KEY TO OFF-SITE WASTE DISPOSAL CONTRACTORS HANDLING
HCB WASTES, THEIR LOCATIONS
AND PLANT SITES SERVED
Contractor
Disposal Site
Designation
OC-1
OC-2
OC-3
OC-4
OC-5
OC-6
Location
(State)
Ky.
Tx.
Tx.
La.
Tx.
N.Y.
Waste Disposal
Method Used
Sanitary landfill
Industrial landfill
Deep well injection
Industrial landfill
Incineration
Incineration
Plant
Site(s)
Served
A
Q
F
G
F, Q
S
82
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TABLE A-3
GENERAL AND HAZARDOUS CHARACTERISTICS OF HCB
Synonym: percnlorobenzene
Appearance (Pure HCB): monoclinic prisms (white needles)
Formula: CCC1C
(Q\
Physical constants:* ;
Molecular weight: 284.80
Melting point: 230°C
Boiling point: 326°C
Flash point: 116. 7°C
Density: 1.5 j.
Vapor pressure: 1.089 x 10"D mm Hg, 20°C
1 ran Hg, 114. 4°C
Vapor density: 9.8
Stability: highly stable and unreactive; is not hydrolyzed in aqueous
solutions(9)
Volatility: sublimes readily and evaporates readily when exposed to air(9)
Vapor pressure of HCB: ^8)
Temperature (°C) Vapor Pressure (mm Hg)
15 4.47 x ID'6
25 1.91 x 10'5
35 6.36 x 10"5
45 2.09 x 10"4
Heat of vaporization: 23.4
Solubility
(i) in distilled water: 6.2 yg/1 at
(ii) in landfill leachate: 5.1 pg/1 at 23.5°C'l
Bioaccumulation: accumulative in aquatic and terrestrial organisms^1 >
Environmental persistence: resistant to biological degradation^'9'
Experimental results on volatilization of HCB at 25°C through various
types of cover materials :(38)
Volatilization Rate
Type of Cover kg/ha/yr _
No cover 317
Polyethylene film, 0.15 ram 255
Soil, 1.9 cm 4.56
Composite soil and polyethylene film, 1.915 cm 3.29
Water, 1.43 cm 0.38
Soil, 60 cm 0.13 (calculated)!
83
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TABLE A-4
HCB WASTE DATA REQUESTED FROM SOME INDUSTRIAL PLANTS
CHARACTERISTICS OF WASTES
1. General Information
a. Quantities of HCB/HCB-containing wastes handled
b. Sources of waste (company and location)
c. Characteristics of wastes:
physical description
concentration
chemical composition/analysis (BOD, COD, pH, etc.)
d. Quantities and characteristics of other types of wastes (non-HCB)
handled (in conjunction with HCB wastes).
2. Waste Pretreatment Facilities and Processes
a. Process types (sedimentation, chemical treatment, filtration,
etc.). Describe.
b. Costs associated with waste pretreatment (i.e., capital invest-
ment costs, direct and indirect operating costs).
3. Materials Recovered
a. Form, characteristics, quantities, etc.
b. Residues generated (quantities, characteristics)
c. Cost analysis of resource recovery methods:
capital investment costs
direct operating costs
t indirect operating costs
4. Waste Handling and Storage Facilities and Methods
a. Description of methods and facilities
b. Costs associated with waste handling and storage
DISPOSAL METHODS
1. Incineration of Wastes
a. Historical background (start-up date, etc.)
b. Type of incinerator used
84
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TABLE A-4
HCB WASTE DATA REQUESTED FROM SOME INDUSTRIAL PLANTS (CONT'D)
c. Process and equipment description (copies requested, if
available)
process flow diagram
sketch or picture of incinerator layout
controls schematic
sampling points
d. Safety provisions used
, Equipment, controls, interlocks, etc.
Standard operating procedures. Description.
e. Equipment or methods for controlling pollution from off-gases
afterburner? Describe.
t stack gas cleaning? Describe.
characteristics and treatment/disposal of scrubber solutions.
f. Sampling and instrumentation capabilities
has any HCB been determined in burner off-gases?
t has any HCB been detected in other sampling positions?
g. Costs associated with incineration
capital investment costs (i.e., equipment, facilities, land,
etc.)
direct operating costs (i.e., power, labor, chemicals,
equipment for related pollution abatement methods)
indirect operating costs (equipment depreciation, taxes,
insurance, etc.)
2. Landfill Operations Associated with HCB-Containing Wastes or Residues
a. Site characteristics and historical background (size, depth,
location, topography, geological formation, distance to ground-
water, start-up date, etc.)
b. Quantities of wastes handled
85
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TABLE A-4
HCB WASTE DATA REQUESTED FROM SOME INDUSTRIAL PLANTS (CONT'D)
c. Costs associated with landfill
0 capital Investment costs (i.e., equipment, land, facilities,
etc.)
direct operating costs (i.e., power, labor, chemicals,
equipment)
t indirect operating costs (equipment depreciation, taxes,
insurance, etc.)
d. Disposal fee associated with waste handling
e. Safety provisions: shower, eyewash, etc.
f. Registration (reporting requirements to regulatory agencies)
g. Environmental safeguards: leachate collection? monitoring
systems, etc.
3. Any other disposal processes associated with HCB-containing wastes:
deep well injection, lagooning, ocean dumping, etc.
a. Description
b. Cost analysis, as above.
86
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Q
to
o
TABLE A-5
NON-INDUSTRIAL AGENCIES CONTACTED FOR DATA ACQUISITION
Agency Naiie
EPA.
Pesticide and Toxic Effects Laboratory
Louisiana State Health Dept.
Chlorine Institute
State of California.
Dept. of Food and Agriculture
Aluminum Association of America
Midwest Research Institute
Cdgewood Arsenal
Frankford Arsenal
Plcatlnny Arsenal
Surgeon General ,
"icdical R&3 Command.
SanUary Engineering Research Branch
Crane Naval Ammunition Center
Lone Star Amy Amnunltlon Plant
Naval Ship Parts Control Center
Naval Civil Information Laboratory
Longhorn Army Amnunltlon Center
ARKCOH.
Installation and Services Group,
Rock Island Arsenal
Texas Hater Quality Board
Location
Research Triangle Park. N.C.
New Orleans. La.
New York City. N.Y.
San Francisco, Ca.
New York City. N.Y.
Kansas City. Mo.
Baltimore. Hd.
Philadelphia, Pa.
Dover, N.J.
Washington, D.C.
Crane, In.
Texarkana, Tx.
Nechanlcsburg, Pa.
'Port Huenene, Ca.
Cornak. Tx.
Rock Island, 11.
Houston, Tx.
Person(s) Contacted
J.B. Mann
G. Von Bodungen
Nr. Lowbush
Hr. Col strum;
B. Rollins
Dr. Balgord
Or. Splgarelll
A. Hlllsmeyers
Dr. P. Brody
G. Escalln
Col. L.H. Reuter
K. Wnorral ;
Mr. Fitch.
Industrial Hygenlst
J. Alexander
0. Wagner
T. Culbertson
D. Maley, Chief Engineer
T. Walsh
Chief of Environmental Group
B. Taylor
Tel ephone
(919)-549-8411
(5041-527-5115
(212J-MU2-4322
(916J-445-2742
(9161-322-5130
(212)-972-1800
(816J-561-0202
(30D-671-3133
(215)-831-6130
(201 )-328- 3906
(202)-693-8061
(812)-854-1603
(812)-854-1847
(214)-838-1626
(717)-766-8511
(865)-982-5071
(214)-679-3181
(309)-794-6244
(512)-475-2500
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