EPA-600/2-74-009a
March 1975
Environmental Protection Technology Series
State-of-The-Art For
The Inorganic Chemicals Industry:
Inorganic Pesticides
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20480
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
Environmental Protection 7\gency, have been grouped into five
series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface
in related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed
to develop and demonstrate instrumentation, equipment and
methodology to repair or prevent environmental degradation
from point and non-point sources of pollution. This work
provides the new or improved technology required for the
control and treatment of pollution sources to meet environmental
quality standards.
This report has been reviewed by the Office of Research and
Development. Approval does not signify that the contents
necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
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EPA-600/2-74-009a
March 1975
STATE-OF-THE-ART FOR THE INORGANIC CHEMICALS
INDUSTRY: INORGANIC PESTICIDES
By
James W. Patterson, Ph.D.
Project R-800857
Program Element 1BB036
ROAP 21 AZR Task 006
Project Officers
Mr. Elwood E. Martin
Office of Water and Hazardous Materials Programs
Washington, D. C. 20460
and
Dr. Robert R. Swank
Industrial Pollution Branch
Southeast Environmental Research Laboratory
. Athens, Georgia 30601
for the
Office of Research and Development
United States Environmental Protection Agency
Washington, D. C. 20460
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ABSTRACT
A literature and field study of the manufacture of inorganic
pesticides revealed that many inorganic formulations are still widely
used for agricultural purposes. The inorganic pesticide industry is a
small but distinct segment of the total agricultural chemical industry.
Its manufacturing processes and wastewaters contrast sharply with those
associated with organic pesticides. The inorganic pesticide market is
dominated by eight products, each of which is discussed in this report
with respect to its manufacturing effluent characteristics and applicable
pollution control technology. Based upon field studies, it has been
demonstrated that five of the eight products can be manufactured without
generating any process wastewater. Aqueous effluents from the manu-
facture of the remaining three inorganic pesticides appear to be directly
controllable by previously demonstrated in-plant control and/or wastewater
treatment technologies.
iii
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CONTENTS
Section
I. Conclusions
II. Recommendations
III. Introduction
IV. Scope of Study
V. Description of Industry
VI. Description of Waste Characteristics
VII. Pollution Control Technology
VIII. Acknowledgements
IX. References
X. Append ix A
XI. Appendix B
Page
1
3
5
7
9
25
51
55
57
59
63
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FIGURES
Page
1 Annual Mercury Consumption 13
2 Annual Copper Sulfate Shipments 14
3 Annual Inorganic Pesticide Production 15
4 Distribution of Manufacturing Facilities 24
5 Arsenic Acid Production 28
6 Production of Lead and Calcium Arsenate 29
7 Sodium Chlorate Production Schematic 35
8 Annual Evaporation Rate 42
9 Annual Precipitation 43
10 Sodium Monobor Production Schematic 44
11 Sulfur Pesticide Production 46
12 Sulfur Grinding Unit 47
vi
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TABLES
Page
1 Pesticide Classification 10
2 Principal Inorganic Pesticides 10
3 Producers of Inorganic Pesticides 18
4 Location of Pesticide Plants 21
5 Rank of Inorganic Pesticides 26
6 Products of Plants Visited 26
7 Copper Carbonate Effluent Character 31
8 Tri-Basic Copper Sulfate Effluent Character 32
9 Sodium Chlorate Effluent Character 37
10 Sodium Chlorate Plant Discharge 39
11 Sodium Chlorate Process Water Budget 39
12 Discharge Characteristics of Sodium Chlorate Plant 40
13 Sodium Chlorate Effluent to Evaporative Pond 40
14 Cost of Control Program 40
15 In-Plant Pollution Control Results 52
16 Comparison of Copper Pesticide Effluents 52
vii
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I. CONCLUSIONS
1. The inorganic pesticide industry is a small but distinct segment of
the total agricultural chemicals industry.
2. Of the nineteen inorganic pesticides identified in this study, eight
dominate the agricultural use market. Sulfur, sodium chlorate and
copper sulfate lead these eight.
3. Most inorganic pesticides are manufactured by only two or three
companies, often at a single site for each company.
4. Many companies often associated with the sale of inorganic pesti-
cides do not manufacture them, but purchase them in bulk from the
primary producers, and repackage under their own label.
5. Several inorganic pesticides of former wide use have declined in
popularity, while others continue to be used at previous levels.
Included among the former are the mercury chlorides, most inorganic
herbicides and calcium arsenate. Sulfur, sodium chlorate, copper
sulfate and lead arsenate use has held steady or only slightly de-
clined, while zinc sulfate use has increased in recent years. Zinc
sulfate is used primarily as a plant nutrient however, and secondarily
as a fungicide.
6. Of the eleven pesticides studied, including the eight major products,
there is a manufacturing capability to produce seven of the eleven
without any associated wastewater effluent. These seven are arsenic
acid, calcium arsenate, copper sulfate, lead arsenate, sodium arsenite,
sulfur and zinc sulfate.
7. Of the remaining four products, all had significant wastewaters associated
with their manufacture. Sodium chlorate and sodium borate effluents
are predominately cooling water. In-plant process modifications can
reduce mass pollutant discharges associated with sodium chlorate
production by more than 99 percent.
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8. Copper carbonate manufacturing wastewaters appear directly
treatable by conventional precipitation techniques, with effluent
quality equivalent to that achieved by other heavy metal processing
industries.
9. Tri-basic copper sulfate wastewater is difficult to treat, due to
the complexing nature of the wastewater.
10. In general for the products and plants studied, there appears to
be a significant capability for the inorganic pesticide industry to
totally eliminate or greatly reduce pollutant discharge.
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II. RECOMMENDATIONS
1. Although capabilities exist within the majority of the inorganic
pesticide industry to reduce or eliminate pollutant discharge,
several problems require further study. Perhaps most critical is
the problem of treating metallic wastewaters, such as those associated
with tri-basic copper sulfate production. These metals are in a
complexed form and cannot be removed by conventional means. This is
a problem not only of the inorganic pesticide industry, but also of
many other industries having complexed metal wastewaters (11).
2. Another problem area involves the cleanup of reusable shipping con-
tainers. Even when process changes eliminate effluent from the
manufacture of inorganic pesticides, container cleanup can yield
wastewaters containing significant pollatants. In the absence of
acceptable cleanup procedures, these containers are frequently stock-
piled as a temporary expediency. Guidelines and methodologies for
container cleanup are a critical need of the inorganic pesticide
industry.
3. This study has revealed no control technology utilized for effluents
of sodium chlorate manufacture, other than evaporative ponds. These
are applicable, however, only within limited geographical regions.
The pollutants associated with sodium chlorate manufacture are not
particularly critical insofar as specific contaminants, but fall more
into the general and undifferentiated category of dissolved salts
(i.e. total dissolved solids). Control of these types of materials
is a problem shared by many other industries, and one which has not
yet yielded to engineering controls. Further development and demon-
stration of processes with the potential to control dissolved solids
is important.
4. Finally, this study covered only a portion of the total number of
inorganic pesticides, although all major products and more than half
of all inorganic pesticides identified in the study were investigated.
It is probable that some of those not studied, such as ammonium sulfa-
mate, sodium cyanide and cadmium chloride might produce locally signi-
ficant pollutional sources. Therefore, supplemental study is recommended
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to both broaden the information base of the pesticides considered in this
study, and expand it to the remainder of the inorganic pesticide industry,
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III. INTRODUCTION
In recent years, a great deal of effort has been directed toward
identifying and controlling pollution associated with the pesticide
industry and the manufacture of its products. As a part of this effort,
several studies have been performed to characterize the wastewaters of
the industry, and assess the types and levels of treatment technology
applicable to those wastewaters (1-6). In recognition of the persis-
tence of organic pesticides in the environment (2,3), and of the trend
in the pesticide manufacturing industry to concentrate on organic at the
expense of inorganic pesticides (5,6), these studies have essentially
been limited to organic pesticides and their associated wastes.
The inorganic pesticide industry is a small but viable segment of
the overall industry, and has wastewaters associated with its products
which are significant from a pollutional standpoint. These wastes are
distinctly different in character and treatability, as compared to wastes
of the organic product segment. Further, the inorganic segment may be
expected to maintain and perhaps expand its share of the market, as organic
pesticide use is increasingly controlled.
Thus a program of wastewater characterization and treatment tech-
nology assessment for the inorganic pesticide industry, parallel to that
for the organic pesticide industry, is required. As a first step in this
effort, this study has been made of the effluents of the major products
of the inorganic pesticide industry.
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IV. SCOPE OF STUDY
This study represents a preliminary assessment of the pollution
potential of the inorganic pesticide industry, the extent of pollution
control utilized by that industry, and the data base available within
the industry to characterize its wastewaters and effectiveness of pollu-
tion control. Primary sources of information included the published
literature, those RAPP permit applications received by the EPA for the
subject industries at the time of this study, and a limited number of
plant visits.
The plant visits included discussions with plant operating person-
nel, inspection of the manufacturing and treatment facilities, and
review of such data on wastewater character and pollution control as
were available from the plant. No independent sampling or analyses were
undertaken during the study, and data presented within this report were
taken only from the previously described sources. Due to the limited
scope of the study, relatively few plants could be visited, and selection
of plants was based upon an attempt to visit at least one plant manufac-
turing each significant inorganic pesticide.
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V. DESCRIPTION OF INDUSTRY
Generally, pesticides are classified either on the basis of their
chemical nature (e.g. inorganic vs. organic - organophosphorus, chlori-
nated hydrocarbons, etc.) or according to their use. Table 1 represents
a typical "use" classification. On the basis of use, Table 2 lists the
inorganic formulations most commonly classified as pesticides (4-7).
In recent years, inorganic compounds have been displaced by organic
pesticides in many applications. However, they are still a mainstay of
the pesticide industry, representing approximately 20% of the industry's
output (4). Prior to 1940, the industry produced essentially only
inorganic pesticides. By 1960 the inorganic segment had decreased and
stabilized at its present level.
A recent study of the pesticide industry (8) reported a total of 79
inorganic and metallic-organic pesticide products in use. Of these, 28
were mercury-based compounds, 17 arsenic-based, 11 copper-based, 6 other
metal-based, and the remainder other inorganic compounds.
Among the inorganic insecticides, the arsenates are most effective
and widely used. The lead arsenate commonly used is an acid lead arse-
nate, PbHAsO,. Calcium arsenate is cheaper than lead arsenate, but its
lack of adherence properties renders it less effective. Its use has
been greatly reduced by the availability of organic insecticides. The
commercial calcium arsenate product is usually a mixture of tricalcium
arsenate (Ca_(AsO,)~) and lime, called basic calcium arsenate.
Fluorine compounds are stomach-poison insecticides, frequently used
as substitutes for the arsenicals. They are extremely poisonous to man
and too water-soluble for use on plants, but sodium fluoride is widely
employed to control roaches and poultry lice. Sulfur and sulfur compounds
are employed to some extent as contact insecticides, but their primary use
is as fungicides. The lime sulfurs have been widely used for control of
scale insects and to control diseases of tree fruits. The compounds are
formed by slaking a dry mixture of lime and sulfur to form among other
products, the pentasulfide (7). The use of lime sulfur has declined in
favor of organic fungicides, due to its toxicity to plant foliage.
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Table 1. Pesticide Classification on Basis of Use
(7)
Insecticides and Mi ticides
Herbicides
Fungicides and Seed Disinfectants
Rodenticides
Fumigants
Table 2. Principal Inorganic Pesticide Formulations
Insecticides
Herbicides
Fungicides
Calcium Arsenate
Calcium Cyanide
Lead Arsenate
Sodium Cyanide
Sodium Fluoride
Ammonium Sulfamate
Arsenic Acid
Borates
Magnesium Chlorate
Potassium Chlorate
Sodium Arsenite
Sodium Chlorate
Cadmium Chloride
Copper Carbonate
Copper Chloride
Copper Oxide
Copper Oxychloride Sulfate
Copper Sulfate
Mercuric Chloride
Mercurous Chloride
Sodium Polysulfide
Sulfur
Zinc Oxide
Zinc Sulfate
10
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Inorganic sulfur, and compounds of heavy metals, are still widely used
as fungicides. Among the inorganic metallic compounds are mercuric and
mercurous chloride, which have declined to very limited usage. Elemental
sulfur, plus a variety of copper salts, now constitute the bulk of the
inorganic fungicide market.
Prior to the introduction of hormone-type weed killers in the early
1940's, the herbicide market was dominated by borate and chlorate com-
pounds, and included potassium and sodium arsenite. Sodium chlorate
continues as a major herbicide (non-selective), and another inorganic,
ammonium sulfamate has also assumed importance. This is a foliage spray
which retards woody growths, but does not effect grassy plants. Although
of lesser importance today, the borate compounds and the arsenites con-
tinue to hold a small share of the market. Arsenic acid is used (decreas-
ingly)as a defoliant. Use declined by 81% between 1964 and 1966 alone
(9), due to reductions in cotton acreage and development of organic
substitutes. Since 1962, herbicide production has increased its share
of the total pesticide market at an average annual rate of approximately
4% per year. The fungicide share of the market has held essentially
constant, while insecticides have decreased insofar as percent of total
pesticide production. These trends represent the total (organic plus
inorganic) pesticide market.
Trends in Inorganic Pesticide Usage
Herbicide use is becoming more prevalent by farmers, as they
increasingly substitute for more expensive mechanical weed control mea-
sures (9). Use of inorganic herbicides appears to be rapidly diminishing
however, dropping by more then 50 percent between 1964 and 1966. In 1966,
inorganic formulations represented only 4 percent of the total herbicide
use by farmers.
The inorganic herbicide market is dominated by sodium chlorate,
followed by various borate formulations. Borax was among the earliest
inorganic herbicides used. The U.S. Department of Agriculture estimates
that sodium chlorate pesticidal usage has held essentially constant (at
15,000 tons/yr) since the mid - 1960's, although its relative share of
11
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the market is continually dwindling as more selective weed killers take
over (10). Approximately 10 percent of the total U.S. sodium chlorate
production is used in agriculture. Other herbicides listed in Table 2
have a very limited market, and like sodium chlorate and the borates,
are declining in importance.
Fungicides have been used in agriculture for many years, particu-
larly in fruit and vegetable production. While substantial quantities
of fungicides are used by farmers, such use has been relatively constant
for some years. There has been a trend of shifting from inorganic to
organic forms. One of the earliest effective fungicides was Bordeaux
mixture (copper sulfate plus slaked lime), which is still used to a
limited extent (9). Many other inorganic products were later found to
be effective fungicides, including sulfur, and copper salts. Mercuric
and mercurous chlorides, as well as organo-mercury compounds, proved to
be particularly effective fungicides, although their use declined
rapidly from 1967 (Figure 1).
Among the inorganic heavy metal fungicides in current use, copper
sulfate predominates. It is widely used on citrus crops, among others,
with these citrus crops representing 64 percent of the total domestic
copper sulfate fungicide use in 1966 (9). However, copper sulfate
represented (on a tonnage basis) only 27 percent of the total inorganic
copper salts used as fungicides in that year, and 22.6 percent of the
total inorganic fungicide use (excluding sulfur). Other copper salts
include the oxychloride sulfate, carbonate, oxide and chloride. No
information is available on the relative significance of these latter
copper salts, although there is some evidence from this study that
copper oxychloride sulfate may be among the more important.
Of the total domestic usage of copper sulfate, approximately 40
percent is used in agriculture (Figure 2), with 31.1 million pounds used
in 1971 (10). An estimated 60 percent of the agricultural copper sulfate
is used as a fungicide, 20-25 percent as an algacide, 10-15 percent as
an animal nutrient and 4-5 percent as a plant trace nutrient (10). For
the ten year period 1962-1971, agricultural copper sulfate use has held
fairly constant, as shown in Figure 3.
12
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(0
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Figure 1. Annual Mercury Usage in Pesticide Manufacture (10)
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1963
1964
1965
1966
1967
1968
1969
1970
1971
Figure 2. Annual Domestic Shipments of Copper Sulfate (10)
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60,000 |-
40,000
20,000
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Figure 3. Annual Inorganic Pesticide Production (4, 103
15
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Both zinc sulfate and zinc oxide are also used as fungicides,
although their primary agricultural use areas plant nutrients. During
the past ten years, 30-40 percent of the domestic zinc sulfate usage
was for agricultural purposes, although the proportion specifically
utilized for fungicidal purposes is unknown (10). Total agricultural
usage has been fairly constant (Figure 3), since 1965.
Sulfur has long been the most widely used fungicide product,
accounting for nearly twice as many pounds as all other fungicides com-
bined. Sulfur has been widely used (87% of total agricultural sulfur
use) on peanut and deciduous fruit crops, although its use has declined
somewhat due to short supply, price increases and the availability of
organic substitutes. Current estimates of sulfur usage as a fungicide
are 150 million pounds per year (10). This is comparable to the 137
million pounds used in 1964 (9). In that year, sulfur constituted 93
percent of all inorganic fungicide usage, and 82 percent of all inorganic
pesticides used, on a tonnage basis. It thus represents a major portion
of the total inorganic pesticide market.
The inorganic insecticide market is dominated by lead arsenate,
with calcium arsenate a poor second (Figure 3). Inorganic insecticides
represent less then 5 percent of the total insecticide usage (9). Lead
arsenate is particularly used in apple orchards, and it's market has
held relatively stable for several years (Figure 3). With the exception
of 1970, it's usage has increased since 1965 at an average annual rate
of 3.2 percent (10). Calcium arsenate production is rapidly declining,
down 56 percent in 1971 over the previous 5-year average.
However, the U.S. Department of Agriculture reports the declining pro-
duction is matched by declines in stockpiles, and that agricultural
demand is fairly steady. Other inorganic insecticides occupy a minor
position in the market.
Manufacturers of Inorganic Pesticides
Due to the sensitive nature of pesticide manufacturing, it is dif-
ficult to determine which companies actually produce inorganic pesticides
and which merely purchase in bulk and repackage under their own label.
16
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After identifying which inorganic products were utilized for pesticidal
purposes (Table 2), a detailed search was made of chemical producer
directories and manufacturing catalogs, such as the Stanford Research
Institute "Directory of Chemical Producers" (1972), to identify suppliers
of chemicals falling into the inorganic pesticide category. Since many
of the inorganic compounds have uses other than as pesticides, not all
manufacturers are actually pesticide sellers, per se. For example,
sodium chlorate is'used in the metallurgical, textile, dye and pulp and
paper industries, as well as for an agricultural herbicide.
As a result of the review of chemical product directories, plus
discussions with the Manufacturing Chemists Association and National
Agricultural Chemicals Association, fifty companies were tentatively
identified as producing inorganic chemicals for pesticidal use. Each
of these companies was contacted to determine if they did produce the
particular inorganic chemical, and if they sold it as a pesticide. Of
the fifty companies contacted (Appendix A), twenty responded in the
affirmative, that they did produce and market inorganic pesticides.
These twenty, and their pesticide products, are listed in Table 3.
The remaining thirty companies either did not produce the chemicals,
produced them but did not merchandise them as pesticides, or purchased
pesticide in bulk from the twenty primary manufacturers and repackaged
under their own label. This latter category included several of the
larger companies frequently identified as major pesticide manufacturers.
Inorganic pesticides listed in Table 2, for which producers were not
identified, include
sodium fluoride
ammonium sulfamate
potassium chlorate
zinc oxide
sodium cyanide.
With the exception of zinc oxide, whose primary agricultural use is as
a plant nutrient, and possibly ammonium sulfamate, these five compounds
are very minor insofar as their agricultural and/or pesticidal use and
17
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Table 3. Producers of Inorganic Pesticides
Company
Allied Chemical Corp.
American Cyanamid Co.
Chemetron Corp.
Chevron Chem. Co.
Cities Service Co.
FMC Corporation
Harshaw Chem. Co.
Hooker Electrochem. Co.
Kerr-McGee Chem. Co.
Los Angeles' Chem. Co.
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Table 3. (Continued)
Company
Pennwalt Corp.
Phelps Dodge
So. Calif. Chem. Co.
Stauffer Chem. Co.
U.S. Borax
Van Water & Rogers
Ventron Corp.
Volunteer Purch. Group
W. A. Cleary Corp.
Woolfolk Chem. Works
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as such constitute only a small fraction of the pesticide market.
Many of the companies identified in Table 3 have plants at several
locations. Plants, products and locations are given in Table 4, and
their geographical distribution shown in Figure 4. With the exception
of those plants concentrated in California, the facilities are fairly
evenly distributed throughout the north, north central and southern
sections of the country. Distribution, to a large extent, appears to
be influenced more by the product market (ie. agriculture) then other
factors, although a few are located adjacent to sources of their raw
materials. One example is the Cities Services plant in Copperhill,
Tennessee, located near copper mines owned and operated by that company.
In general, the plants fall into two categories: (1) those in
which pesticide production represents only a portion of the total pro-
duction and, (2) those facilities devoted solely to pesticide manufacture.
Plants in the first category either produce other chemicals not marketed
as pesticides, or only a portion of the pesticidal-type chemicals are
sold for pesticide use; the remainder being marketed for other purposes.
Examples are the plants manufacturing sodium chlorate, copper sulfate
and similar compounds of wide general industrial application.
The inorganic pesticide industry is a small and readily identified
segment of the total industry, typically consisting of one or a few
plants within each company which produce inorganic pesticides. Although
not previously well characterized as to pollutional impact, it is by
nature an industry which is amenable to direct study.
20
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TABLE 4. Producers of Inorganic Pesticides
Company
1. Allied Chemical Corp.
2. American Cyanamid Co.
3. Chemetron Corp.
4. Chevron Chemical Co.
5. Cities Service Co.
6. FMC Corporation
7. Harshaw Chemical Co.
8. Hooker Electrochemical Co.
Plant Location
Baltimore, Maryland
Linden, New Jersey
Cleveland, Ohio
Maryland Heights, Missouri
Richmond California
Copperhill, Tennessee
Middleport, New York
Richmond, California
Modesto, California
Fresno, California
Jacksonville, Florida
Richmond, California
Elyria, Ohio
Niagara Falls, New York
Columbus, Mississippi
Taft, Louisiana
Products
Arsenic acid
Calcium arsenate
Sodium arsenite
Calcium cyanide
Copper chloride
Sodium arsenite
Calcium arsenate
Copper sulfate
Lead arsenate
Copper carbonate
Copper sulfate
Tri-basic copper sulfate
Lead arsenate
Copper chloride
Sodium polysulfide
Sulfur
Sulfur
Sulfur
Copper chloride
Sodium chlorate
Sodium chlorate
Sodium chlorate
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TABLE 4. (continued)
ISJ
hi
Company
9. Kerr-McGee Chemical Corp.
10. Los Angeles Chemical Co.
11. Perm wait Corp.
12.
13.
Fhelps Dodge
Plant _Loc a t i on
Henderson, Nevada
Hamilton, Mississippi
Powder Springs, Georgia
Trona, California
South Gate, California
Portland, Oregon
Bryan, Texas
Laurel Hill, New York
El Paso, Texas
Southern California Chemical Co. Los Angeles, California
14. Stauffer Chemical Co.
Compton, California
Dayton, New Jersey
N. Portland, Oregon
Richmond, California
Tampa, Florida
Products
Sodium chlorate
Sodium chlorate
Tri-basic copper sulfate
Copper oxide
Borax
Pentahydrate borax
Sodium pentaborate
Arsenic acid
Calcium arsenate
Copper oxychloride sulfate
Lead arsenate
Sodium arsenite
Magnesium chlorate
Sodium chlorate
Arsenic acid
Copper sulfate
Copper sulfate
Copper sulfate
Copper chloride
Copper oxychloride sulfate
Copper oxide
Zinc sulfate
Sulfur
Sulfur
Sulfur
Sulfur
Sulfur
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TABLE 4. (continued)
u>
Company
15. U.S. Borax Co.
16. Van Water & Rogers
17. Ventron Corp.
18. Volunteer Purch. Groups
19. W. A. Cleary Corp.
20. Woolfolk Chemical Works
Plant Location
Columbus, Mississippi
Wilmington, California
Boron, California
Midvale, Utah
Wallace, Idaho
Metaline Falls, Idaho
Woodridge, New Jersey
Bonham, Texas
New Burnswick, New Jersey
Ft. Valley, Georgia
Products
Sodium metaborate
Polybor chlorate
Sodium tetraborate
Copper sulfate
Copper sulfate
Copper sulfate
Mercuric chloride
Mercurous chloride
Arsenic acid
Cadmium chloride
Calcium arsenate
Lead arsenate
Sodium arsenite
Zinc sulfate
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Figure 4. Geographical Distribution of Inorganic Pesticide Manufacturing Facilities
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VI. DESCRIPTION OF WASTE CHARACTER
Information on the nature of wastewaters associated with manufacture
of inorganic pesticides was initially assessed as being available from
(1) published literature, (2) RAPP discharge permit applications, and (3)
direct contact with the manufacturers by plant visits. An intensive
search of the literature failed to reveal any wastewater characterization
or treatment reports specifically pertaining to the subject industry,.
In light of subsequently developed information revealing the limited
nature of the industry, this absence of published data is not surprising.
The only published references to wastewaters were contained in reports
of two plant visits previously undertaken by contractors to EPA, and
neither report included quantitative data0 These reports were for a
mercury chloride plant (5), and a sulfur facility (6).
Somewhat better success was encountered in reviewing permit applica-
tions. Several applications were available for plants which produced
inorganic pesticidal chemicals, and limited information within this
report was extracted from those applications. However, many plants
which produce only inorganic pesticides have not submitted permit appli-
cations, because they have no discharge or possibly because they discharge
to municipal facilities. Most plants for which applications were avail-
able were larger facilities, only partially devoted to inorganic pesticide
manufacture. The reliability of data from these applications is questionable,
since in most cases the effluents represented combined discharges for both
inorganic pesticide plus other product lines.
In recognition of the limited information available, other than
through direct plant visits, six plants were selected to visit on the
basis of products manufactured. In order to assess which products were
most significant, major inorganic pesticides were listed in decreasing
tonnage of usage and total market value, as shown in Table 5. Tonnage rank
is based upon values previously reported in Chapter V. The market value
ranking, although somewhat outdated, is generally comparable to the current
tonnage ranking.
25
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Table 5. Ranking of Major Inorganic Pesticides
Pesticide
Sulfur
Sodium Chlorate
Copper Sulfate
Zinc Sulfate
Sodium Borates
Lead Ar senate
Calcium Ar senate
Sodium Arsenite
Tonnage
Rank
1
2
3
4
5 (est.)
6
7
8
Market Value
Rank (7)
1
3
2
6
5
4
8
7
Table 60 Inorganic Pesticide Products of Plants Visited
Arsenic Acid Lead Arsenate
Calcium Arsenate Sodium Arsenite
Copper Carbonate Sodium Chlorate
Copper Sulfate Sodium Borates
Copper Sulfate, Sulfur
Tri-basic Zinc Sulfate
26
-------
Table 6 lists products produced by those six plants visited. The
products include all listed in Table 5, plus arsenic acid and copper
carbonate, and incompass more than half of the products listed in Table 3.
Of six plants visited, four had submitted discharge permit applications,
and two had no process wastewater discharge. The six plants visited
(insofar as the ten products investigated) appear to employ average to
excellent production and wastewater control technology. The manufacture,
wastewater character and treatment technology employed for each product
is described in the following sections.
Arsenic Acid
At the plant visited, arsenic acid is produced on a batch basis, as
an intermediate in the manufacture of arsenate pesticides. A schematic
of the arsenic acid manufacturing process is shown in Figure 5. Nitric
acid is mixed with arsenic trioxide to form arsenic acid. Unspent
nitric acid is recovered. Arsenic acid is stored, to be utilized in the
manufacture of calcium and lead arsenate. The arsenic acid reaction
produces nitrous oxide fumes, which are scrubbed in a raschig ring packed
tower, with countercurrent (recycled) water flow. The water is returned
to a storage tank, where a portion is employed for processing and vat
cleanup. The remainder is reused in the NO scrubber tower. The por-
.At
tions used for processing and vat cleanup are evaporated to dryness in
rotary gas-fired driers, to recover product. There is thus no wastewater
associated with this process.
Calcium Arsenate
Both calcium and lead arsenate are produced by similar reaction
processes. Lime or lead oxide is mixed with arsenic acid to produce
calcium or lead arsenate, respectively (Figure 6). The products are piped
to drum driers. Water vapor fron the driers is collected and vented to
stacks. Cleanup water from the batch mix vats is either saved to mix
with the next batch, or evaporated in the drum driers to recover product.
All product spills are caught in spill-pans below each processing unit.
Spilled liquids are recycled back to the processing line. There is thus
27
-------
Fresh
Nitric
Acid
Vent
.NJ
00
Nitric
Acid
Storage
Tank
Arsenic
Trioxide
HNO,
Arsenic
Acid
Reactor
Recovered Nitric
t
Counter Current
Water Flow
Packed
Raschig
Ring
Tower
Make-up
Water
Water
Storage
Tank
NO
Scrubber Water
Water Used in
Processing
Acid
Arsenic
Acid
Storage
Tank
To Production Use
Figure 5. Arsenic Acid Production
-------
Arsenic
Acid
Storage
to
Lime
or
Lead Recycle
Oxide Water
Measuring
Tank
Batch
Mix Vat
Water
Vapor
Drier
55-gal
Drums
Figure 6. Production of Lead and Calcium Arsenate
-------
no wastewater associated with the manufacture of either calcium or lead
arsenate at this plant.
Copper Carbonate
Copper shot is reacted on a batch basis with steam-heated sulfuric
acid, to form a concentrated copper sulfate solution. To manufacture
copper carbonate, soda-ash is mixed with the copper sulfate concentrate in
a batch reactor. Lime is then added to neutralize the mix to pH 6.3-6.5,
thereby precipitating copper carbonate. The precipitate is settled, vacuum
filtered and dried. The supernatant from the precipitation tank, and the
filtrate are discharged as wastewater. Average wastewater flow is approxi-
mately 11,000 gallons per ton of copper carbonate product. Of this,
approximately 7,000 gallons is vacuum filter wash and water pump flow.
Table 7 presents wastewater characteristics and pollutant discharge from
the copper carbonate manufacturing process. The metals, aside from copper,
shown in Table 7 represent impurities in the copper shot employed in the
process.
Currently, discharge is to a holding pond and thence into a nearby
waterway. Plans are presently being formulated, in cooperation with the
appropriate state regulatory agency, to design and construct a precipi-
tation treatment plant to remove copper and other heavy metals from the
wastewater. This will also likely include provision for reductions in
suspended solids.
Copper Sulfate
Copper shot is reacted on a batch basis with steam-heated sulfuric
acid to form a supersaturated copper sulfate solution. When the solution
is allowed to cool, copper sulfate crystals form. The supernatant
"mother liquor" is decanted and either reused for the next batch of
copper sulfate crystals, or used in the production of tri-basic copper
sulfate or copper carbonate. Any washwater used in cleanup is retained
in the crystallization vats, and used in the copper sulfate production
process. Steam to heat the solution is produced on site, from chemically
softened creek water. Sludge from the softening process, plus boiler
30
-------
Table 7. Effluent Characteristics from Copper Carbonate Production
Parameter
PH
Copper
Iron
Magnesium
Manganese
Nickel
Lead
Zinc
Chr ornate
Sulfate
Chloride
NH_-N
Diss. Solids
Susp. Solids
Concentration ,
mg/1*
6.3-6.5
13
3.6
1.0
0.1
0.1
0.7
1.3
<0.5
NA
16
10
36,650
59
Discharge,
Ibs/ton Product
~
1.21
0.33
0.09
0.01
0.01
0.06
0.12
<0.05
NA
1.48
0.93
3,398
5.47
*except pH
blowdown, constitute the only wastewaters associated with the copper
sulfate process. These are discharged directly to a holding pond,
where the sludge settles. Pond overflow is to an adjacent waterway.
Copper Sulfate, Tri-basic (TBCS)
Production involves addition of 10 percent ammonium hydroxide
solution to copper sulfate mother liquor. Lime is added to adjust the
pH to 6.3-6.5, with TBCS precipitating from solution. The settled
precipitate is vacuum filtered and dried. The supernatant from the
precipitation vat, and the filtrate are discharged as wastewater.
Average wastewater flow, including vacuum filter flow, is approximately
7,000 gallons per ton of product. Of this, approximately 50 percent is
filter backwash and water pump effluent.
Table 8 presents effluent data from the TBCS production line. The
31
-------
Table 8. Effluent Characteristics of TBCS Production
to
"ft
Concentration, mg/1
Parameter
PH
Copper
Iron
Magnesium
Manganese
Nickel
Lead
Zinc
Chr ornate
Chloride
Sulfate
NH3-N
Diss. Solids
Susp. Solids
minimum
5.9
131
4.9
0.8
0.05
0.1
--
1.3
<0.3
2.5
3,840
14
average
6.4
136
38
1.5
0.17
0.9
0.12
1.4
<0.4
3.4
24,000
4,800
35,400 r.
240
max imum
7.0
150
84
2.2
0.20
2.5
--
1.7
<0.5
5.5
814
Discharge
ave. Ibs/ton product
--
7.77
2.17
0.09
0.01
0.05
0.01
0.08
<0.02
0.19
1,371
274
2,023
13.71
*
except pH
-------
effluent is high in ammonia, which acts to complex metals and hold them
in solution. For this reason, the wastewater contains higher levels of
metals than would be normal for the pH shown. Except for copper, the
effluent metals shown in Table 8 represent impurities in the copper shot
used to form the copper sulfate solution. Due to the ammonia complexes
formed, simple precipitation treatment is not expected to be effective
for this wastewater, insofar as heavy metals removal, and the plant is
currently evaluating means to either substitute other raw materials for
the ammonia hydroxide, or strip ammonia from the wastewater prior to
»
precipitation treatment.
Lead Arsenate
Lead arsenate is manufactured by a batch process, similar to that
previously discussed for calcium arsenate (see Figure 6). Lead oxide
is mixed with arsenic acid on a batch basis. The precipitate slurry is
drum dried and packaged. Water vapors are collected and vented, and
all spills are caught and returned to the process. At the particular
plant visited, there are thus no wastewaters associated with lead
arsenate production. However, it has been reported that other producers
of lead arsenate filter the precipitate slurry prior to drying, to remove
undesirable (soluble) reaction side products. For those producers, this
filtrate liquid may require treatment prior to discharge, for removal
of lead and arsenate.
Sodium Arsenite
Sodium arsenite is manufactured as a liquid product, by batch mix-
ing caustic, water and arsenic trioxide. The product is sold in the
liquid form, and there is thus no liquid waste associated with the
process. All cleanup water from the batch mix vats is saved to mix with
the next batch.
*„
Sodium Chlorate
Two sodium chlorate manufacturing facilities were visited, and the
following discussion represents the processes used by both. Difference
33
-------
in processing between the two plants are indicated. Additional effluent
data from the RAPP permit application of a third plant is included in
the discussion of wastewater character.
Sodium chlorate production basically involves electrolysis of con-
centrated sodium chloride solution to produce a mixture of sodium
chlorate, sodium hypochlorite and residual sodium chloride. As shown
in Figure 7, rock salt plus makeup water is added to a "mother liquor"
representing recycled electrolyte solution from which sodium chlorate
has been crystallized. The brine solution is decanted to the electroly-
tic cells. At one plant, muriatic acid, is added for pH control, and
sodium dichromate to improve cell efficiency. The cells are cooled by
a once-through non-contact water flow. After completion of electrolysis,
the sodium chlorate "mother liquor" is decanted to a hypochlorite decay
tank, where (at one plant) barium chloride is added to precipitate
(as barium sulfate) sulfate impurities in the mother liquor. The solution
is then pumped to a precipitation tank, where soda-ash is added. This
precipitates calcium as CaCO_, and excess barium as BaCO_. At the second
plant, sulfate impurity in the sodium chloride is removed by lime addition
to the mother liquor to precipitate calcium sulfate, with residual calcium
precipitated as calcium carbonate by addition of soda-ash. In both
plants, the solution is then pressure filtered to remove the mixture of
precipitates previously formed, plus graphite fragments from the cell
electrodes. The pressure filter is backwashed several times daily, with
cooling water, and the backwash discharged.
At one plant, the filtrate then goes to a steam heated evaporator,
to drive off water vapor and precipitate NaCl. The sodium chlorate-rich
supernatant is decanted to a chlorate crystallization process, while the
NaCl slurry is vacuum filtered. Crystalline NaCl is returned to the
dissolver, and filtrate pumped to the chlorate crystallizer. The chlorate
solution is cooled by refrigeration, or by reducing the pressure, with
water vapor released. This vapor, plus that driven off in the steam
heated NaCl crystallization chamber is condensed using cooling water at
2,500 gpm, and returned to the dissolver, along with a portion of the
cooling water for makeup.
34
-------
Sodium
Chloride
Sludge
Make-up
Water
Mother Liquor
i
Filter
Filter
Wash
Water
Electrolysis
Cooling
Water
Discharge
Decay
Tank
Cooling
Water
Recovery
f
Treatment
Chemicals
Discharge
Crystalline
NaC100
Figure 7. Sodium Chlorate Production Schematic
35
-------
The sodium chlorate slurry is then centrifuged to separate the
crystals from the mother liquor. The mother liquor is returned to the
electrolytic cells, and the crystalline sodium chlorate dried in rotary
driers. This completes the manufacturing process, and the product is
loaded into drums or tank cars for shipping.
The primary wastewater discharged from sodium chlorate plants is
uncontaminated cooling water, plus sludges formed through precipitation of
rock salt impurities. Spills of mother liquor are fairly frequent, but
are normally caught in spill sumps and returned to the process. Table 9
summarizes the raw wastewater properties for the three plants for which
data were available. Plants 1 and 2 were visited during this study, and
data for Plant 3 were taken from the permit application. Table 10 pre-
sents additional data on the discharge characteristics. Flows shown for
Plants 1 and 3 represent total plant flows, including process lines other
than sodium chlorate manufacture. The flow for Plant 2 is only for the
sodium chlorate facility.
Plant 2 has developed and will implement a plant-wide pollution
control plan involving total containment of all wastewaters, through a
system of process changes, effluent reuse and evaporative ponds. A
current and proposed water budget for the sodium chlorate process, only,
is presented in Table 11. As a result of these process changes and reuse,
Plant 2 anticipates a reduction in water use by 88 percent. Changes in-
clude separation and recycle of weak and strong effluents, elimination of
once-through cooling water, and reduction in filter washwater.
There is little information on the specific nature of the effluent
from the sodium chlorate facility at Plant 2. Data contained in Table 9
represent the combined plant discharge, of which the sodium chlorate dis-
charge represents only about 30 percent. Current data are available, as
presented in Table 12, on volume and sodium chloride content of the dis-
charge. Based upon other information provided by the plant, it is estimated
that the sodium chlorate discharge is on the order of 35 Ibs/ton product.
In addition, there are two to three spills of mother liquor each
year, totaling 20,000-30,000 gallons per spill. As a part of the
36
-------
Table 9. Sodium Chlorate Effluent Character
Parameter
BOD5
TDS
TSS
NH3-N
Sulfate
Chloride
Barium
Plant 1
mg/1
12
240
10
1.5
25
55
8
Ibs/ton
prod.
12.73
254.47
10.62
1.59
26.47
58.24
8.47
Plant 2
mg/1
NA
3822
216
7
1700
1200
NA
Ibs/ton
prod.
NA
217.04
12.27
0.40
96.59
68.18
NA
Plant 3
mg/1
6.7
952
14
6.8
42.3
276
NA
Ibs/ton
prod.
8.52
960.2
17.90
8.69
54.08
352.84
NA
Range
mg/1
6.7-12.0
240-3822
10-216
1.5-7.0
25-1700
55-1200
8
Ibs/ton
prod.
8.52-12.73
217.0-960.2
10.62-17.90
0.40-8.69
26.47-96.59
58.24-352.84
8.47
Average
mg/1
9.35
1671.33
80.0
5.10
589.1
510.33
8
Ibs/ton
prod.
10.63
477.24
13.60
3.56
59.05
159.75
8.47
u>
-J
-------
Table 9. (Continued)
Parameter
Calcium
Sodium
Plant 1
mg/1
10
100
Ibs/ton
prod.
10.59
105.88
Plant 2
mg/1
400
1000
Ibs/ton
prod.
22.73
56.82
Plant 3
mg/1
118
142
Ibs/ton
prod.
150.85
181.53
Range
mg/1
10-400
100-1000
Ibs/ton
prod.
10.59-150.85
56.82-181.53
Average
mg/1
176.0
414.0
Ibs/ton
prod.
61.39
114.74
u>
00
-------
Table 10. Sodium Chlorate Plant Discharge
Parameter
PH
Temperature, F
Winter
Summer
Flow, MS/ ton Prod.
Plant 1
6.0-8.0
90
90
0.123
Plant 2
6.0-10.0
65
75
0.0023
Plant
6.4-7
50
83
0.150
3
.3
Table 11. Sodium Chlorate Process Water Budget - Plant 2
Evaporative Loss, MG/Yr.
Discharge, MS/Yr.
Total Use, MG/Yr.
Present
6.0<1>
74.0
80.0
Proposed
7.2<2>
2.5<3>
9.7
(1) Process evaporation
(2) Process + evaporative pond
(3) Reused elsewhere in plant
39
-------
Table 12. Discharge Characteristics of Sodium Chlorate Plant 2
Flow, gal/day 191,000
NaCl Discharge, Ibs/ton Product 11.0
Table 13. Anticipated Sodium Chlorate Plant Discharge to Evaporative
Pond - Plant 2
Flow
gal /day
Flow 1,370
NaCl
NaCl03
NaClO,
Na2Cr20
CaC03
Total Diss. Solids
Concentration,
mg/1
1,000
3,000
400
1,400
50
500
6,350
Table 14. Cost of Sodium Chlorate Wastewater Control Program - Plant 2
Process Changes - Material $56,000
Process Changes - Labor 27,000
Evaporative Pond* - Materials 12,000
Evaporative Pond* - Labor 2,000
Total Cost $97,000
*l-acre lined pond
40
-------
Plant 2 implementation plan, such spills will be caught and retained
in evaporative ponds.
The anticipated sodium chlorate plant effluent from Plant 2, after
in-plant modification, is shown in Table 13. This wastewater will flow
to an evaporative pond, thus providing complete wastewater containment.
The economics of the implementation plan, as estimated by Plant 2 for the
sodium chlorate production line only, are summarized in Table 14.
Evaporative ponds, together with process changes and recycle, appear to
be a valuable and effective pollution control technique in those geo-
graphical regions where evaporation sufficiently exceeds rainfall to
allow their use. A comparison of Figures 8 and 9 indicate that their
use is essentially limited to the west and southwest regions of the
country, however.
Sodium Borates
The plant visited produces monobor chlorate, a mixture of sodium
metaborate and sodium chlorate. Monobor chlorate is manufactured by
mixing caustic solution, borax and crystalline sodium chlorate. The
reaction is exerthermic, and the resultant slurry is cooled on water-
chilled rollers, to form flakes. The flakes are sized by screening.
Dust (collected by bag collectors) and fines are returned to the
continuous mixer. Oversized flakes are granulated, and returned to the
screening operation. Figure 10 is a production schematic. The con-
tinuous mixer, chill rollers and granulator are cleaned by washing,
once per shift.
There are two sources of process discharge from the plant; a
continuous cooling water flow from the chill rollers, and cleanup water.
The cooling water is non-contact once-thru well water. Based upon
average operation, this cooling water flow constitutes 7200 gal/ton
product. Cleanup water results from washing the mixer, granulator and
chill rollers each shift. The quantity of water involved is 200-300
gal. per cleanup.
Both cooling and cleaning water are discharged to a common sewer
of an adjacent industrial plant. This sewer is sampled only after
41
-------
N)
Figure 8. Mean Annual Inches of Lake Evaporation
-------
CO
Figure 9. Mean Annual Inches of Precipitation
-------
Caustic
Storage
Tank
Borax
Hopper
Sodium
Chlorate
Hopper
Continuous
Mixer*
Slurry
Chill Rollers*
Granulator*
Bag
Dust
Collector
Oversize
Dust
Fines
Cooling
Water
Screen
Separator
*Clean-up wash once/shift.
Discharge to sewer.
Bagging
Figure 10. Monobor Chlorate Production Schematic
44
-------
mixing of the two plants wastes. The combined flow of this sewer is
10.58 MGD. The borate process flow represents 1.36 percent of the
total, with cleanup water being diluted (on an average daily basis)
almost 500-fold by cooling water. The total sewer discharge consists
of 99.9 percent cooling water and 0.1 percent combined process waste-
water» Of the combined process (only) wastewater, the borate flow
averages 22,7 percent of the total process flow,, The wastewater will
contain as industrial waste constituents sodium, chlorate and metaborate,
and is expected to have a high pH. However, due to the high dilution
factor, and batch (once/shift) discharge of borate wastewater it was not
appropriate to extrapolate its character from data available on the com-
bined discharge.
Sulfur
Bulk sulfur, brought in by hopper cars, is crushed by teethed
rollers to 10 mesh size, and transported by conveyor belts to holding
bins. Additional processing is shown in Figure 11. The crushed sulfur
is placed, in charges of 750-800 Ibs., into a batch mixer. Clay, if
required, is added at 7-50 percent of the finished product. Wetting
agents may also be added to allow field spraying of the pesticide as a
liquid suspension.
After batch mixing, the preparation is conveyed to an enclosed
grinding mill (Figure 12) to further reduce the size of the sulfur.
In order to prevent explosions, an oxygen-lean atmosphere must be main-
tained in the grinding mill. This is accomplished by using C02 rich
flue gas from the plant steam boiler. After grinding, the mixture goes
to a final post-blender, and then is bagged for shipment.
When shifting from one product to another, it is necessary to clean
out the mix and grinding system. As a first step, the caked material
in the units is chipped out by hand. Then,charges of clay are run
through the batch mixer, grinding mill and post-blender. This clay is
stockpiled, and later used when the same product is again being formu-
lated.
Plant wastes include sanitary sewage, shower drainage, laundry
45
-------
Crushed
Sulfur
Holding
Bin
Wetting
Clay Agents
(Opt.)
Batch
Mixer
Steam to
other Plant Uses
Slowdown
to Ditch
\
Boiler
0)
Grinding
Mill
Flue Gas
Scrubber
Exhaust
t f
CO
<&
O
Post -
Blender
J
Flue Gas
Scrubber
Water
Discharge
to Ditch
To Bagging
Operation
Figure 11. Sulfur Pesticide Production
-------
PRESSURE
RELIEF VENTS
VENT TO
BAGHOUSE
CYCLONE
COLLECTOR
FINISHED
PRODUCT
DISCHARGE
RETURN AIR LINE
VENT STACK
INERT GAS INLET
SEPARATOR
! FEED
HOPPER
*
ROLLER MILL
EXHAUSTER
Figure 12. Typical Sulfur Grinding Unit(6)
47
-------
waste-waters, gas scrubber water and boiler blowdown (see Figure 11).
All sanitary waste including shower and laundry discharges, go to a
company-owned septic tank. Gas scrubber water, estimated at 250,000
gal/month, and boiler blowdown (twice/year discharge) flow to an open
ditch and thence into a roadside drainage ditch. The company is under
the impression that a discharge permit is not required, and has there-
fore not submitted an application. No information is available on the
character of the boiler blowdown or gas scrubber cooling water. With
the exception of these two product-associated processes, there is no
wastewater involved in production.
Zinc Sulfate
Basic zinc sulfate is manufactured by first adding metallic zinc
to concentrated sulfuric acid, to form zinc sulfate solution. Lime is
then added to neutralize, and the precipitate slurry is decanted by
pipe into drum driers. Water vapor from the driers is collected and
vented to stacks. Cleanup water from the batch mix vats is either
saved to mix with the next batch, or evaporated in the drum driers to
recover product. As a result of the processing methodology employed
at this plant, there is no wastewater effluent associated with the
manufacture of zinc sulfate. All product spills are caught in spill-
pans below each processing unit. Spilled liquids are recycled back
into the processing line.
General Problems
Among producers of inorganic pesticides, one problem appears com-
mon. This relates to the cleanup of returnable containers used to ship
their products. Normally, these are drums or tank cars, and to avoid
contamination from shipment of one product to the next, cleanup proce-
dures are required. In those plants which already have a wastewater
associated with their manufacturing process, container cleanup water
is added to other plant effluents, and handled as a part of that flow.
However, one major inorganic pesticide manufacture of heavy metal
products has recently completed a process modification program which
48
-------
has eliminated all process-associated wastewaters. The major pollutional
concern remaining is how to clean out and reuse the 55-gallon drums in
which they ship their products, without producing difficult-to-treat
wastewaters. This problem has not been resolved, and several thousand
used drums are currently stockpiled in a storage yard, awaiting the
development of a cleanup procedure which will avoid the generation of
wastewater.
49
-------
VII. POLLUTION CONTROL TECHNOLOGY
Seven of the eleven Inorganic pesticides investigated in this study
had no effluent associated with their manufacturer, as a result of the
specific production technology used. These seven are,
arsenic acid sodium arsenite
calcium arsenate sulfur
copper sulfate zinc sulfate
lead arsenate
The remaining four did have wastewaters, ranging from predominantly
cooling water (sodium chlorate and sodium borate) to complex process
waste effluent (copper carbonate and tri-basic copper sulfate). One
sodium chlorate plant has developed a program for zero effluent, based
upon extensive process changes, recycle and discharge to an evaporative
pond.
Of the six sodium chlorate plants identified in this study (Table 4),
three are located in the south, one in the southwest, one in the north-
west and one in the northeast. A comparison of annual evaporative
(Figure 8) and annual rainfall (Figure 9) reveals that use of evapora-
tive ponds is only feasible for that plant located in the southwest.
For all other locations, rainfall equals or exceeds evaporation.
However, one plant also plans to implement in-plant process
controls, which will greatly reduce mass pollutant discharge. Select
data from Table 13, as compared with current discharge levels (Table 9)
are presented in Table 15. The implementation of process controls will
thus reduce mass pollutant discharges in excess of 99 percent. At the
subject plant, this residual effluent will discharge to an evaporative
pond.
Effluent from the copper carbonate facility (Table 7) is high in
copper (13 mg/1), and dissolved and suspended solids. In addition, it
contains 0.62 Ibs. of other heavy metals per ton of product, due to
impurities in the copper used. Of particular significance is the lead
(0.7 mg/1) and zinc (1.3 mg/1) in the effluent. Plans to install a
51
-------
Table 15. Effect of In-Plant Controls an Mass Pollutant Discharge
IS)
Parameter
Sodium
Calcium
Sulfate
Chloride
Tot. Diss
Table 16.
. Solids
Comparison
Parameter
PH
Copper
Iron
Magnesium
Manganese
Nickel
Lead
Zinc
NH3-N
Current
mg/1 Ibs/ton prod. mg/1
1000 56.8 1579
400 22.7 200
1700 96.6 946
1200 68.2 607
3822 217.0 6,350
of Copper Carbonate and TBCS Effluent Concentrations
CuC03, mg/1
6.5
13
3.6
1.0
0.1
0.1
0.7
1.3
10
Proposed
Ibs/ton prod.
0.49
0.06
0.30
0.19
1.99
TBCS, mg/1
6.4
136
38
1.5
0.17
0.9
0.12
1.4
4,800
-------
precipitation treatment system at this plant are now under development.
Based upon data developed by Patterson and Minear (11) in an extensive
study of treatment technology for pollution control, precipitation treat-
ment appears most applicable for this waste. By proper pH control and
efficient solids removal, copper should be reduced to 0.2-0.5 mg/1 in
the process wastewater. Assuming no process changes to reduce total
effluent flow, this would result In a copper discharge of 0.02-0.05
Ibs/ton product, or a reduction of 96 to 98 percent. Effluent levels
for lead and zinc, based upon the same report, should be reduced to
0.02-0.20 and 0.1-0.5 mg/1 respectively, depending upon the efficiency
of solids removal (11).
Treatment of the tri-basic copper sulfate waste is also proposed,
by the plant manufacturing that product. However, treatment of this
waste is more difficult then the copper carbonate waste, due to the
presence of ammonia which acts as a complexing agent to prevent effec-
tive precipitation. The ammonia results from the addition of ammonium
hydroxide to copper sulfate solution, to form the tri-basic copper
sulfate. The pH values of the effluent from both the copper carbonate
and tri-basic copper sulfate are comparable, and except for complexation
effects, the heavy metal solubility (and therefore effluent metal levels)
would be expected to be similar. This is not true, as shown in Table 16.
Data from Table 16 is extracted from Tables 7 and 8.
Ammonia-nitrogen is present in the TBCS effluent at 4800 mg/1.
Although not as strong a complexing agent as for example cyanide, at
that concentration ammonia does exert a significant effect upon residual
metal solubilities. Copper, iron and nickel levels are up to ten times
greater in the TBCS effluent, while other metals are comparable to the
copper carbonate wastewater. In order to effectively treat this waste,
the ammonia must be removed. Two alternatives are (1) to replace the
ammonia hydroxide by some other base in the process, or (2) remove the
ammonia from the wastewater prior to metal precipitation. The plant
having this wastewater is currently assessing methods of pollution con-
trol. However, they feel that it is not feasible to substitute another
base for the ammonium hydroxide, and are currently investigating the
53
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possibility of stripping the ammonia from solution prior to heavy metal
precipitation. This potentially creates an air pollution problem.
In summary, with the exception of the complexation problem for TBCS
wastewater, pollution problems associated with all of the inorganic
pesticides of this study are either non-existent, or greatly alleviated
by in-plant modifications and/or implementation of well established
treatment technology. A caution must be observed relative to those
products which, in this study, exhibited no discharge. Each of the
seven products is manufactured by two or more producers, and it was
only at the specific plants visited that zero effluent was observed.
It is probable that other producers may, in fact, have wastewaters
associated with their manufacture of these products and, at least for
lead arsenate, quite likely. However, the studies reported here demon-
strate that process technology is available and currently in use to
achieve zero effluent for those seven products.
54
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VIII. ACKNOWLEDGEMENTS
The cooperation of E. Martin and D. Becker of the Effluent Guide-
lines Division, and personnel the Regional Offices of the Environmental
Protection Agency, the Manufacturing Chemists Association and the
National Agricultural Chemicals Association greatly assisted the per-
formance of this study.
55
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IX. REFERENCES
1. National Agricultural Chemicals Association, "Manual on Waste
Disposal," Washington, D.C., June, 1965.
2. Nicholson, H. P., A. R. Grzenda and J. I. Teasley, "Water Pollution
by Insecticides. A Six and One-Half Year Study of a Watershed,"
Proc. Symp. Agr. Wastewater, 132 (1966).
3. Edwards, C. A., Persistent Pesticides in the Environment, Chem.
Rubber Co., Cleveland, Ohio (1970).
4. Atkins, P. R., "The Pesticide Manufacturing Industry - Current
Waste Treatment and Disposal Practices," Water Pollution Control
Research Series 12020 FYE 01/72 EPA, January, 1972.
5. Lawless, E. W0, R. Van Rumker and T. L. Ferguson, "The Pollution
Potential in Pesticide Manufacturing, "EPA Technical Studies Report
TS-00-72-04, July, 1972.
6. Ferguson, T. L., "Pollution Control Technology for Pesticide Formu-
lators and Packagers" EPA Technical Studies Report, Grant #R-801577,
(in preparation).
7. Shreve, R. N., Chemical Process Industries, 3rd Ed., McGraw-Hill
Book Co., N. Y.
8. Lawless, E. W. et al. "Methods for Disposal of Spilled and Unused
Pesticides," Report on EPA Project #15090 HGR, (in press).
9. "Quantities of Pesticides Used by Farmers in 1966,"
USDA Agricultural Economic Report No. 179, April, 1970.
10. Fowler, D. L. and J. N. Mahan, "The Pesticide Review - 1972," U.S.
Department of Agriculture, June, 1973.
57
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11. Patterson, J. W. and R. A0 Minear, "Wastewater Treatment Technology"
2nd ed., State of Illinois Institute for Environmental Quality
Report IIBQ 73-1, February, 1973.
58
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Appendix A
59
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Companies Contacted on Inorganic Pesticides
Allied Chemical
American Cyanamid Company
American Smelting and Refining
Company
Amvac Chemical Corporation
Anaconda American Brass Company
Apache Chemicals, Inc.
Chem Met. Corporation
Chemetron Corporation
Chempar Chemical Company
Chemtech Corporation
Chevron Chemical Company
Cities Service Company
Diamond Shamrock Chemical Company
Dow Chemical Company
Filo Color and Chemical Corporation
FMC Corporation
P.O. Box 2120
Houston, Texas 77001
P.O. Box 400
Princeton, New Jersey 08540
120 Broadway
New York, New York 10005
4100 E. Washington Blvd.
Los Angeles, California 90023
P.O. Box 747
Waterbury, Connecticut 06720
P.O. Box 17
Rockford, Illinois 61105
10 E. Erie Street
Chicago, Illinois 60611
1250 Terminal Tower
Cleveland, Ohio 44113
260 Madison Avenue
New York, New York 10016
7882 Folk Avenue
St. Louis, Missouri 63143
200 Bush Street
San Francisco, California 94120
3445 Peachtree Road, N.E.
Atlanta, Georgia
1100 Superior Avenue
Celveland, Ohio 44114
200 Main Street
Midland, Michigan 48640
347 Madison Avenue
New York, New York 10017
100 Niagra Street
Middleport, New York 14105
60
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Freeport Minerals Company
Great Lakes Chemical Corporation
The Harshaw Chemical Company
Hooker Electrochemical Division
Kerr-McGee Chemical Corporation
Lobel Chemical Company
Los Angeles Chemical Company
Mallinckrodt
Merck & Company
Nor-Am Agricultural Products, Inc.
Olin Corporation
Pennwalt Corporation
Phelps Dodge Refining Corporation
PPG Industries, Inc.
Rhodia Inc., Chipman Div.
Rohm and Haas Company
Rona Pearl Company
161 East 42 Street
New York, New York 10017
P.O. Box 2200, Hwy. 52 N.W.
West Lafayette, Indiana 47906
1945 East 97th Street
Cleveland, Ohio 44106
Niagara Falls, New York 14302
Kerr-McGee Center
Oklahoma City, Oklahoma 73102
100 Church Street
New York, New York 10007
4545 Ardine Street
South Gate, California 90280
Second & Mallinckrodt Streets
St. Louis, Mo. 63160
126 E. Lincoln Avenue
Rahway, New Jersey 07065
20 N. Wacker Drive
Chicago, Illinois 60606
120 Long Ridge Road
Stamford, Connecticut 06904
1713 S. California Avenue
Monrovia, California 91016
300 Park Avenue
New York, New York 10022
New Albany Road
Moorestown, New Jersey 08057
120 Jersey Avenue
New Brunswick, New Jersey 08903
Independence Mall West
Philadelphia, Pa. 19105
E. 21st & 22nd Street
Bayonne, New Jersey 07002
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The Shepherd Chemical Company
Southern California Chemical -Co.,
Inc.
Stauffer Chemical Company
Tenneco Chemicals
Texas Gulf, Inc.
Triangle Chemical Company
U.S. Borax & Chem Company
United Chemicals Company
Van Waters & Rogers
Ventron Corporation
Vineland Chemical Co., Inc.
Vistron Corporation
Volunteer Purchasing Groups, Inc.
W. A. Cleary Corporation
Woolfolk Chemical Works, Ltd.
5000 Poplar Street
Cincinnati, Ohio 45212
8851 Dice Road
Santa Fe Springs, California 90670
Westport, Connecticut 06880
Turner Place, P.O. Box 2
Piscataway, New Jersey 08854
200 Park Avenue
New York, New York 10017
P.O. Box 4528
Macon, Georgia 31208
3075 Wilshire Blvd.
Los Angeles, California 90005
401 Delaware
Kansas City, Missouri
Box 3200
San Francisco, California 94119
2400 Congress Street
Beverly, Mass. 01915
P.O. Box 745
Vineland, New Jersey 08360
Midland Building
Cleveland, Ohio 44115
P.O. Box 460
Bonham, Texas 75418
P.O. Box 749
New Brunswick, New Jersey 08903
Fort Valley, Georgia 31030
62
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APPENDIX B
Metric Conversion Factors
English Unit
lb.
ton
gal.
MG
Ibs/ton
Ibs/MG
Metric Equivalent
0.454 kg
0 908 kkg
3.785 liters
-3 3
3.785 x 10 meters
3.785 x 106 liters
3 3
3.785 x 10 meters
0.500 kg/kkg
0.120 mg/1
0.120 x 10"3 kg/m3
63
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SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
1.
4. Title
State-of-the-Art For The Inorganic Chemicals Industry:
Inorganic Pesticides
James W. Patterson, Ph.D.
9 Dep^rtlnent of Environmental Engineering
Illinois Institute of Technology
Chicago, 111. 60616
12. Sponsoring Organization
15. Snpfrlemrriary Notes
Environmental Protection Agency report number, EPA-600/2-7^-009a, March 1975
5. Report Date
Organization
10. f'r>.jectNo.
PE 1BB036 R/T 21 AZR 06
13. Type of Report and
Period Coveted
16. Abstract
A literature and field study of the manufacture of inorganic pesticides revealed
that many inorganic formulations are still widely used for agricultural purposes.
The inorganic pesticide industry is a small but distinct segment of the total
agricultural chemical industry. Its manufacturing processes and wastewaters
contrast sharply with those associated with organic pesticides. The inorganic
pesticide market is dominated by eight products, each of which is discussed in
this report with respect to its manufacturing effluent characteristics and
applicable pollution control technology. Based upon field studies, it has been
demonstrated that five of the eight products can be manufactured without
generating any process wastewater. Aqueous effluents from the manufacture of the
remaining three inorganic pesticides appear to be directly controllable by pre-
viously demonstrated in-plant control and/or wastewater treatment technologies.
17a. Descriptors
17b. Identifiers
17c. COWRR Field & Group
18. Availability
19. Security Class.
(Report)
30. Security Class.
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 2O24O
'SIT 10?
"IN - 1371.
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