_ \ ENVIRONMENTAL PROTECTION AGENCY
\&&/ OFFICE OF WATER PROGRAMS
POLLUTION POTENTIAL IN PESTICIDE MANUFACTURING
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EPA Reviev; Notice
This report has been reviewed by the Office of Water
Programs of the Environmental Protection Agency and
approved for publication. Approval does not signify
that the contents necessarily reflect the views and
policies of the Environmental Protection Agency, or
does mention of trade names or commercial products
constitute endorsement or recommendation for use.
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PREFACE
This program (MRI Project No. 3556-C) has been under the general
supervision of Dr. A. E. Vandegrift, Head, Environmental Sciences Section
of MRI's Physical Sciences Division. The project team consisted of
Dr. Edward W. Lawless, Project Leader, Dr. Rosmarie von Rumker of RvR
Consultants, and Mr. Thomas L. Ferguson, with the assistance of Miss Anne
Aspoas, Miss Meredith Reichel and Mr. Edward Trompeter. Dr. L. Eugene
Cronin, Dr. Gordon E. Guyer and Mr. T. G. Lewton, Jr., acted as consultants
to the program. The assistance of the many members of the pesticide industry
who contributed their time and helpful comments to this study is gratefully
acknowledged.
Approved for :
MIDWEST RESEARCH
H. M. Hubbard, Director
Physical Sciences Division
10 January 1972
111
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TABLE OF CONTENTS
Page
Summary S-l
i
I. Introduction • 1
II. History of Pesticide Use and Production 3
A. Discovery of Various Classes of Pesticides 3
B. Development of Pesticide Use Patterns 20
C. Developments in Manufacture and Formulation Methods . . 26
III. Present Production Volumes and Sites 39
t
A. Estimated Production of Major Pesticides 41
B. Geographical Location of Producers and Transportation
Patterns 54
IV. Modern Manufacturing Methods. . . .' 62
A. Criteria for Selection 'of Pesticides for Case Studies . 62
B. Summary of Classes, Producers, Production, Formula-
tions, and Use Patterns for Case Study Pesticides . . 63
C. Case^Studies 71
D. Summary of Pollution Aspects Based on Case Studies. . . 188
V. Formulation of Pesticides 203
A. Formulation Facilities 204
B. Pollution Potential in Pesticide Formulation. ..... 205
VI. Marketing of Pesticides ..... 221
VII. Conclusions and Recommendations 230
Appendix A - Toxicity Data on Selected Pesticides 233
Appendix B - Emergency Procedures in Event of Fire in a Warehouse
Containing Pesticides 1 239
Appendix C - Preliminary Discharge Data Submitted by Pesticide
Producers Under the 1899 Refuse Act 243
Appendix D - List of Individual Contributors to This Study 246
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TABLE. OF CONTENTS (Continued) .
List of Tables
Table.. Title Page •
S-I' -. Production Volumes of Major .Pesticidal Ingredients. . .'". . S-3 ;'
S-II Uses, Classes'and Production Volumes of Selected
Pesticides. . . .. . . . . '. . . . • . . . ... . . . . . . S-5
S-III Summary of Manufacturing Wastes and Disposal S-ll
I . Pesticides Produced, Imported or Sold in the
United States ..:.....'.. 10
II , Estimated U.S. Pesticide'Production Volume, 1971. . .... . 42
III. United States Usage of Wood Preservative, 1965-69 . . .• . . 49
IV United States Imports of Synthetic Organic Pesticides,1 '
1965-69 . . . • 50
V United States Exports of Pesticides, 1968-69. .......... 51
VI . Summary of Production Volumes of Selected Herbicides, .
Insecticides, and Fungicides. . . • ....:.. 53
VII Major Pesticide Production Sites. . • 56
VIII Pesticide Ratings 64
IX Uses and Classes of Selected Pesticides . , .- , •. . 67
X Selected Herbicides, Estimated Production Volume,
Formulation, Uses, and Areas.of Use, 1971 ."'• • 68
XI Selected Chemical Insecticides, Estimated Production ••
Volume, Formulations, Uses, and Areas of Use, 1971. . . . 69 '
XII Selected Biological Insecticides, Fumigants, and •
Fungicides: Estimated Production Volume, Formulations,
Uses and Areas of Use, 1971 .............'.. 70
XIII Case Studies: Summary of Producers Visited ; 72
XIV Order of Presentation of Case.Studies ........... 73
XV Summary of Formulation and Warehousing Activities by Key
1 Pesticide Producers ............ 191
XVI Summary of Packaging .and Transportation Practices for
Key Pesticides. '. . 193'
XVII . Summary of Manufacturing Wastes and Disposal ; . . . . .; . . 195
XVIII Summary of Formulators, Packagers, and Distributors
Visited . . 203
XIX Aerosol Pesticide Filling Plants. . . . ... . ... ..• . . 206'
XX How Pesticides are Moving to Market 213
XXI Marketing1Outlets to the Consumer for Pesticides. . . . . . 223
XXII Major Pesticides ,-Sold in the Garden and Home Market .... 224
XXIII Types of Containers Used for Garden and Home Pesticides . . 225
XXIV Number and Types of Containers for Agricultural and
Related Pesticide Use 227
C-I Preliminary Discharge Data Submitted by Pesticide Pro-
ducers Under the 1899 Refuse Disposal Act 245
vi
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TABLE OF CONTENTS (Continued)
List of Figures
Figure Title Page
S-l Production Sites for 22 Major Pesticides .... S-6
1 Schematic Description of Pesticide Production and Move-
ment to Consumer, Indicating Potential Pollution •
Sources •.- '2
2 Classes of Pesticides According to Use .......'..» 20
3 U.S. Production of Synthetic Organic Pesticides. ..... 22
4 U.S. Producers' Sales of Synthetic Organic Pesticides. . . 22
5 Corn Harvested for All Purposes, 1964. ...... o ... 23
6 Cotton Harvested, 1964 23
7 Soybeans Harvested for All Purposes, 1964 24
8 Alfalfa Cut for Hay, 1964. . 24
9 Tobacco Harvested, 1964 ' 25
10 Tomatoes Harvested for Sale, 1964. .........'... 25
11 Synthesis of Some Chlorinated Hydrocarbons and Related '
Pesticides 28
12 Synthesis of the Diene Group of Chlorinated Insecticides —
From Hexachlorocyclopentadiene • 29
13 Synthesis of Phosphorus-Based Pesticides -. . 30
14 Synthesis of Some Carbamate Pesticides . . 31
15 Synthesis of Triazine Pesticides .... 32
16 Locations of Pesticide Production Plants 55
17 Production Distribution for 22 Major Pesticides. ...'.. 60
18 Production and Waste Schematic for. DDT . . . 75
19 Production and Waste Schematic for Aldrih '. . 81
20 Production and Waste Schematic for Dieldrin. . ...... 85
21 Production and Waste Schematic for .Chlordane -. '. ..... 89
22 Production and Waste Schematic for Toxaphene 95
23 Production and Waste Schematic for Disulfoton. ....... 100
24 Production and Waste Schematic for Malathion 105
25 Production and Waste Schematic for Phorate . 110
26 Production and Waste Schematic for -Parathion and' Methyl
Parathion (Monsanto) 114
27 Production and Waste Schematic for Carbaryl. . . . . . .' . 119
28 Production and Waste Schematic for Aldicarb. . . ,: . . .'• . 124
29 Production and Waste Schematic for 2,4-D (Dow Chemical). . 129
30 Charcoal Absorption/Filtration Plant for Treating
Phenolic Wastes. ...... J . 135'
31 Production and Waste Schematic for 2,4,5-T' 137'
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TABLE OF CONTENTS (Concluded)
List of Figures (Concluded)
Figure Title
32 Production and Waste Schematic for Atrazine 144
33 Production and Waste Schematic for Trifluralin 149
34 Production and Waste Schematic for Alachlor. 154
35 Production and Waste-Schematic for Captan. ...".... 158
36 Production-and Waste Schematic for Methyl Bromide
(Dow Chemical) ...... . . . . . 164
37 Pyrethrum Refinery and Waste Schematic (FMC Corp.) . . . 169
38 . Production and Waste Schematic for Bacillus
thuringiensis 176
39 Production and Waste Schematic for Mercury Chloride. . . 183
40 Acute Oral Toxicity 200
,41 Acute Dermal Toxicity. 201
42 Pesticide, Aerosol Filling Plants . . . - 207
.43 1969 United States Aerosol Container Production 208
44 Liquid Formulation Process 210
45 Dust Formulation Process 212
viii
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SUMMARY
The use of pesticides has become an extremely important factor in
the United States and indeed throughout the world in determining man's
quality of life. The benefits which have been obtained from this usage—
increased production of food and fiber and increased freedom from disease
and obnoxious plant and animal life--have not been without some undesirable
side effects, such as direct effects on nontarget organisms, the indirect
unbalancing of delicate ecosystems, and the environmental contamination by
persistent pesticides which may tend to be biologically accumulated in food
chains. In addition, the possible long-term effects of low levels of pesti-
cides on man himself is the cause of serious concern. Hence, the entire
subject of pesticide production and use is under intensive study by govern-
ment and nongovernment scientists in the United States and in many other
countries.
The production and use of pesticides is not new or even of recent
origin. From ancient times man has investigated the minerals, and the plant
and animal life around him for their value as medicinals, in the production
of his food, in warding off the attacks of obnoxious or dangerous insects,
and against his fellow man. A tremendous growth has occurred, however,
during the past 40 years in the number of pesticides available, the variety
of applications, and the volumes of production of the active ingredients
and their formulated products. A broad definition of "pesticides" is used
here which includes: rodenticides; insecticides;, larvacides; miticides
(acaricides); molluscicides; nematocides; repellants; synergist; fumigants;
fungicides; aligicides; herbicides; defoliants, desiccants, plant growth
regulators and sterilants. On this basis over 1,500 chemical pesticides
have been produced. About 275 pesticides are of commercial importance and
perhaps as many as 8,000 individual formulated products are prepared for
specific uses and methods of application.
The objective of this study was to survey and evaluate the environ-
mental pollution potential associated with the manufacture, formulation,
and marketing of pesticides, including such related activities as packaging,
transportation and warehousing, i.e., all of the operations up to the point
where a pesticide is placed in the hand of the normal consumer.
Pesticide Production Volumes
In order to evaluate the pollution potential of pesticide manu-
facture, knowledge of current production volumes was needed. A serious
handicap here was the unavailability of data on how much of each pesticide
is produced or even on which ones are produced in the largest quantities
S-l
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in the United States. Most of this information is in the hands of the U.S.
Tariff Commission, but it is not disclosed in a meaningful manner. The
Tariff Commission publishes partial production data for synthetic organic
compounds which includes a section on pesticides, but the data are categorized
and grouped: no data are disclosed for specific compounds unless there are
three or more producers (and not even then if one producer is dominant)
because these data are considered proprietary by the companies and are
revealed in confidence to the Tariff Commission. Under this policy, produc-
tion data are not now available on the most widely used insecticide (toxa-
phene) or herbicide (atrazine) and apparently will no longer be available
on DDT or 2,4-D after 1970 as only one or two producers of these materials
remain. We strongly recommend that public disclosure of production data
for pesticides and all hazardous materials be made mandatory, so that sci-
entists, regulatory officials, legislators and other concerned citizens
can make use of these data to make an intelligent assessment of environ-
mental impacts and of areas which require further research, new regulations,
or legislation. Furthermore, we believe a sizable percentage of the pesticide
industry would actually be agreeable to the uniform disclosure of these data,
because under the present situation most companies maintain an expensive
staff of market researchers to develop much of these data anyway. In addi-
tion, some industry members apparently feel that the availability of such
data would help relieve their companies of certain guilt--by--association
feelings toward the pesticide industry in general.
The production volumes of all pesticides have been estimated on
this program. The results for the major pesticidal ingredients are shown
in Table S-I, and show that, with the exclusion of the special category
(which will be discussed below) the 1.34 billion pounds per year pesticide
market is dominated by about 24 major products or product groupings which
account for a combined production of 862 million pounds per year or 64% of
the market, while the remaining 26% is divided between about 250 other
pesticides. Of these, 65-75 are estimated to have production volumes of
over 1 million pounds per year.
The special category includes petroleum oils (of which some syn-
thetic and refined products are used directly as insecticidal sprays, but
most of which are used more extensively as diluents and carriers and as
wood preservatives); creosote and coal tar (general wood preservatives);
aromatic solvents; and the dry carriers and diluents. These materials have
been of little environmental concern compared to the more active ingredients
in most pesticides and are not the focus of the present study (although
such materials are deserving of more attention than they have received).
S-2
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TABLE S-I
PRODUCTION VOLUMES OF MAJOR PESTICIDAL INGREDIENTS^./
Herbicides
Product
Atrazine
2,4-D
MSMA-DSMA
Sodium chlorate
Trifluralin
Propachlor
I
to Chloramben
Alachlor
CDAA
Subtotal
Total, all
pesticides
Quantity
90
45
35
30
25
23
20
20
10
298
408
Insecticides
Product
Toxaphenek/
DDT
Carbaryl
Methyl parathion
Malathion
Chlordane
Parathion
Aldrin
Methoxychlor
Diazinon
Quantity
50
45
45
45
35
25
15
10
10
12
290
406
Fungicides
Product Quantity
Sulfur (inorganic) 150
Pentachlorophenol 46
and salts£/
Dithiocarbamate 40
groupfi/
Trichlorophenol 20
and salts
Captan 18
274
297
Fumigants/Rodenticides
:antit
Product
Methyl bromide 22
Dibromochloropropane 10
Other halogenated 50
C1"C3 orSanics—I
Dichlorobenzenei/ 60
Warfarin 12
Special Category
Produc t
Petroleum oiLS'
Creosote
Coal tar
Aromatic solvents
Dry carriers and
diluents
154
200
a/ Quantity produced in million pounds per year for direct pesticidal use, excludes production for other uses except as indicated.
b_/ Includes Strobane-T.
c_/ Includes use for termite control and as herbicide.
d_/ Includes 11 products.
£/ Includes eight or more compounds.
f_/ Includes moth proofing and lavatory-space deodorant usage.
£/ Includes synthetic and refined spray oils, diluents and carriers in formulated products.
160
N.A.
N.A.
> 2,000
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Study Approach
The approach used in this survey and evaluation has been to select
pesticides, producers, formulators and packagers which would be representa-
tive of the industry.
A system was developed in which pesticides were rated on the basis
of production volume (present and projected); chemical class and production
technology; use pattern (biological activity and major crops)'; toxicity,
including human (acute and public health) and nontarget; persistence and
biomagnification; and public or legislative concern. On the basis of these
ratings, 22 representative pesticides were selected for intensive study of
the pollutional aspects of the manufacturing process. These 22 pesticides
are listed in Table S-II along with their use, chemical class, estimated
production, mammalian toxicity and relative environmental persistence.
The production sites of these pesticides are shown in Figure S-l.
Personal contacts and visits were made with the producers of
the 22 selected pesticides and also with 15 formulators and packagers and
these were supplemented by review of the literature on production, formula-
tion, packaging and marketing practices.
Special Notes from the Case Studies of Manufacturers
The case studies'developed a considerable amount of information
on the practices of the pesticide manufacturers which is related to the
overall pollution potential. Because of the diversity of processes used
for the different pesticides, and the different pollution control practices
employed, comparison is difficult, but several aspects are worthy of dis-
cussion.
1. Raw materials: The raw materials used for the synthesis of
many pesticides are hazardous materials and some pollution potential is
inherent in the transportation and handling of materials of this nature.
Some of these materials are flammable, some are corrosive and poisonous,
and some may be exceptionally toxic to fish if spilled into waters. How-
ever, the transportation of these materials are subject to close governmental
regulation and the handling practices of the pesticide manufacturers are as
good as or better than those of industry in general.
The raw material which is common to the most pesticides is ele-
mental chlorine which is used directly on-site in the production of chlor-
dane, toxaphene, 2,4-D, 2,4,5-T, atrazine, captan, carbaryl and mercuric
chloride and is used to prepare raw materials brought in for the produc-
tion of DDT, aldrin-dieldrin and perhaps also trifluralin and alachlor.
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TABLE S-II
USES, CLASSES AND PRODUCTION VOLUMES OF SELECTED PESTICIDES
CO
I
Selected Pesticides
Alachlor (Lasso)
Aldicarb (Temik)
Aldrin
Atrazinc
B. thuringiensis
Captan .
Carbaryl (Scvin)
Chlordane
2,4-D
DDT
Dieldrin
Disulfoton
Ma lath ion
Mercury fungicides
Methyl bromide
Methyl parathion
Parathion .
Phorate (Thimet)
Pyrethrins
2,4,5-T
Toxaphene (including
Strobane-T)
Trifluralin (Treflan)
Totals (22
pesticides)
(Fungicii
F
F
§-H
o
00 f4
•H ' JO
1 1
H
H
H
Fu
H
•H
JJ
U
QJ
S
I
I
I
I
I
I
I
I
I .
I
I
I'
I
I
IChlorini
1 u.. ,4 *._»*•
X
X
X
X
X
X
X
<»•>
CO O
X
X
X
t
CJ eo « co « *-4
oj 01 o ai o ^ «8
504J >r4IU >rl (0 U
(Sxmcj: o) T< no Estimated Annual
O.^CQQ. 00 C O M
"io -HI?" o 3 • "o x Production
5-g.<0
0.5
X 8
X '•' 35
X 0.2
X 22
X 45
X 15
X 8
X 0.3
6
50
X ' 25
Mammalian Toxicity
LDSQ (mg/kg)
.1,200
6.93
55
3,080
Nontoxic
10,000
540
570
500
113
60
2.0-12.5
2,800
30-200 •
21 mg/liter
9-42
6-15 '
1.6-3.7
1,500
300-800
69
> 10,000
Environmenta1
Persistence
Low
Low
High
Low
Low
Medium
Low
High
Low
High
High
Low
Low
Low
Low
Low
Medium
Medium
Low
Low
Medium
Low
14
516.5
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Figure S-l - Production Sites for 22 Major Pesticides
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The production of this chlorine formerly involved extensive use of the
mercury cells which led to the well-publicized mercury losses. Now, how-
ever, these cells are being better controlled and are being displaced by
the mercury-free diaphram cells. Only two of the pesticide producers
studied here use on-site chlorine, generation, while the other chlorine users
receive it in tank car quantities by rail with the exception of one plant
which receives it by pipeline.
Other materials of unusually hazardous nature which are transported
by rail, barge or truck include hydrogen cyanide (of which over 10 million
pounds are required for atrazine), carbon disulfide, various amines, and
the concentrated acids and caustic. The PO% use<^ ^n &H the organophos-
phorus pesticides; the 05615 used for aldrin, and numerous other materials
also pose some hazard. ' .
The raw materials may be stored on-site in bulk storage facilities,
but in many cases are drawn directly, from the shipping container (e.g., tank
car or tote bin) and used in the production processes. The handling of
materials such as chlorine are apparently in conformity with good industrial
practice codes. Accidental spills of raw materials occasionally occur which
require special clean-up and disposal procedures. In many cases scrubbers
or dust collection equipment are used in the raw material unloading areas.
2. Production.processes: The manufacturing processes for pesti-
cides vary considerably from product to product; but two characteristics
are generally present which may differentiate the pesticide industry from
many, if not all, of the large industries which are of environmental pollu-
tion concern: the ingredients handled or. produced have usually high toxicity
to some animals (e.g., man or fish) or plant-life; and the production pro-
cesses normally require only low or moderate temperatures, compared for
example,to industries producing ore- or rock-derived products. Because of
the toxicity of the'materials handled, production facilities were designed
to include a great many safety features to minimize occupational hazards.
Because of the moderate temperature, air pollution control of good efficiency
could be largely adapted from existing technology. Water pollution control,
as will be discussed in a subsequent section, poses a much more difficult
problem than air pollution in the pesticide industry.
The production plants for the 22 key pesticides studied range
from capacities of less than 1 million pounds per year to about 100 million
pounds per year and the plant equipment ranges from 1 year old to over 20
years old and in at least two cases the plant buildings are over 50 years
old. In general, the more toxic materials such as the organophosphorus
and carbamate insecticides and some of the herbicides which have undergone
rapid growth recently (such as atrazine) are produced in newer plants, while
many of the older chlorinated hydrocarbons and other products are produced
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in somewhat older equipment. However, almost none of the plants have been
designed since the advent of the recent increased consciousness of environ-
mental concern, and most of the companies interviewed have recently com-
pleted, are building, or are designing new pollution control equipment to
bring their plants into conformity with local standards.
The production equipment is used in almost every case either for
only one product or for two very similar products, i.e., two products of
the same chemical family and with similar pesticidal applications. Clean-
up of equipment is therefore minimized and is small compared to that re-
quired in a formulation plant where many products are processed through
the same equipment. In cases where solvent cleanup of process equipment
is required, the used solvent is generally reused as a matter of economics
by recycle to the process, or it may be used in formulation, or combusted
for fuel purposes.
Most of the companies interviewed have fairly extensive contingency
plans. Many of them maintain a company fire department and others state
that they work closely with local fire departments, but this cooperation
could probably be improved in nearly all cases.
Good practice dictates that production facilities be diked and
that runoff from malfunction, spills, fire extinguishment, etc., can be
contained in a holding pond or pit until treated, so that over-loading of
the conventional waste treatment plant is avoided. In many, but not all
plants, this procedure is in effect.
All the manufacturers of the 22 key pesticides have on-site quality
control laboratory facilities and frequently monitor the raw materials and
reaction intermediates as well as the final product. In almost no case, it
would seem, is a production run of such poor quality or so far "off spec."
that it cannot be used—either blended off with a higher quality batch or
reworked to remove objectionable impurities.
The efficiency of the synthesis reactions as commercially con-
ducted is generally regarded as proprietary information. Similarly, the
efficiencies of recovery of products, by-products and unreacted starting
materials are not available. The efficiency of recovery in the past has
often depended on the price of the product balanced against the difficulty
of recovery, and hence a widely and easily produced material like DDT was
previously discharged in sizable quantities. The present trend is toward
better recovery and water economy in order to minimize treatment or dis-
posal costs.
3. Storage, handling and shipping: The use of most pesticidal
products is seasonal with the major application occurring during the spring
S-8
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or summer season. Therefore, production and formulation also tend to be
seasonal in order to avoid building up undesirably large inventories. Among
the manufacturers of the key pesticides studied, several noted that their
production peaked in late winter or early spring and some stated that they
did not produce during the summer months. On the other hand, most companies
do produce the year around and also may formulate on-site so that extensive
storage facilities are required. Production site storage in bulk or tank
car quantities is sometimes practiced, but long-term storage appears to be
more often in drums.
Good storage practices dictate that different pesticides be stored
separately, or at least in well-marked locations within a warehouse. In
cases where a company handles more than one pesticide at a given location,
special care is usually taken to keep herbicides well segregated from fungi-
cides and insecticides, but pesticides which are similar chemically and in
activity may be produced in the same equipment and stored in the same area.
The storage facilities of the major producers appear to be generally
well regulated to prevent accidental losses of pesticides during handling
and storage and well equipped with fire protection. These facilities, how-
ever, are not as frequently diked as are the production areas. Similarly,
most companies appear to specify such fire protection equipment as automatic
sprinklers when they use public warehouses, but few of these warehouses are
diked. Thus, warehouse fires which require use of large amounts of water
are a serious potential source of pesticide pollution. The further the
warehouse is from the control of the primary producer, the greater the po-
tential in an estimated majority of cases.
The mode of transportation of pesticides away from the production
sites to the customer, distant storage facility or formulator varies widely
because of the variations in location of production sites and use areas.
The products are shipped by various combinations of rail and truck, depending
on the nature of the material, packaging practices and the marketing struc-
ture. Shipping containers range in size from gallon cans and small bags
to 6,000 gal. tanks.
The packaging and transportation practices generate different
pollution potentials for different products. Most of the highly toxic
organophosphates such as disulfoton and the parathions are never shipped
in tanks—only drums. Similarly, the toxic carbamates are shipped as 50-
Ib bags, in the case of carbaryl, and in two specially-modified tank trucks
in the case of the extremely toxic aldicarb. The shipment of liquid pesti-
cides (and particularly toxic organophosphates) in drums reduces the poten-
tial for a large spill of hazardous material, but the handling and disposal
of the emptied drums is a serious problem. On the other hand, most of the
toxaphene is shipped in tank cars and trucks and transferred directly into
S-9
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company-owned bulk storage tanks at the formulators1 location and no used
drums are generated in this step,
A significant difference in pollution potential exists between
transport in tank cars and tank trucks. Tank cars are either company-owned
or leased by the company from the railroad, and are used over and over for
the same or a similar product. If the tank car requires cleaning between
shipments or before return to the railroad (as during the slack season),
cleanup is done at the production site and wastes go to the company's
detoxification or disposal system. Tank trucksj on the other hand, normally
are received from the trucking firm in a clean and dry condition, are filled,
then transported to the destination and unloaded by the trucker, who then
has the responsibility for cleanup before the truck goes to another customer.
The trucking firm, however, normally does not have the detoxification and
decontamination equipment nor the technical expertise available at the manu-
facturer. Washings are probably most often disposed in the most convenient
manner.
Pesticides which are packaged in cans, drums and bags are very
often shipped from the manufacturers only in truck load or car load lots.
In many cases, however, as the distribution system fans out, consignment
becomes less than car load or truck load lots and the pesticides become
part of mixed lot shipments. In such cases the manufacturer loses some
control over the product and it may be shipped together with flammable sol-
vents or other material which might increase the pollution potential.
4. By-products and wastes: Virtually every pesticide production
process produces aqueous or gaseous streams and frequently solid wastes
which contain unreacted ingredients, unrecovered products and solvents, and
unavoidable or undesired by-products. Extensive efforts are usually made
to minimize by-products and to recover, recycle, or otherwise prevent these
process losses from occurring. For each process, however, a balance point
is eventually reached between the expense of recovery and the value of the
recovered product. In the past, the economic considerations were frequently
dominant and process losses were included as unavoidable costs. Under the
recent emphasis on environmental contamination further efforts have been
made to recover many previously lost materials—even when economics indi-
cated that it was more expensive to do so--and most pesticide manufacturers
have invested in or are in the process of building extensive waste treat-
ment facilities wherein those wastes which cannot be recovered are degraded
to acceptable levels or disposed by state approved methods. A summary of
the principal wastes generated and the disposal methods employed by the pro-
ducers of the key pesticides is shown in Table S-III.
S-10
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TABLE S-III
SUMMARY OF MANUFACTURING WASTES AND DISPOSAL
Liquid Wastes
Solid or Other Wastes
Pesticide
DDT
Aldrin
Dieldrin
Chlordane
Toxaphene
Disulfoton
Malathion
Phorate
Parathions
Carbaryl
Aldicarb
2,4-D
2,4-D
2,4,5-T
2,4,5-T
Atrazine
Trifluralin
Alachlor
Captan
Methyl bromide
Pyrethrin
Bacillus _t.
Bacillus J:.
HgCl2 - Hg2Cl2
Source
Processing solutions
Floor washings, etc.
Process solutions
Process solutions
Pinene-camphene plant
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
As per 2,4-D
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Aqueous still bottoms
Process solutions
Process solutions
Process solutions
Disposal
Evaporative basin
Evaporative basin
Evaporation bas in
Deep well
Bio-treatment plant
Neutralize, hold, discharge
Secondary treatment 'plant
Barge to deep sea
Barge to deep sea
Waste treatment plant
Secondary waste treatment
Neutralize, secondary waste
treatment
Trickling filter, biological
waste treatment plant
Charcoal absorption/
filtration treatment
Oxidation pond, discharge
Most to river; some to
deep well
Biological waste treatment
Discharge
Hold, discharge
Sewer
Sterilized, biological
waste treatment
Evaporation pond
Hg-recovery;
Discharge to sewer
Source
Reactor solutions
Lime slurry
Filter solids
Filter solids
Filter solids
Filter solids, etc.
H2S
Filter solids
Filter solids
Mercaptan losses
H2S, S
H2, COC12, amine
Heavy residues
Process vents
Filter solids and
still bottoms
Solids
Solvent
Gas streams
Gaseous wastes
Process solids
Filter solids
Process air
Filter solids
Disposal
County dump
Lime pit
Incinerate
Clay pit
Solid waste
Commercial landfill
Flare
Landfill (with lye)
Landfill
Flare
Flare, incinerate
Flare
Incinerate
Flare
Incinerate, scrub
Landfill
Scrubber
Fuel
Scrub, vent
Scrub, waste treatment
plant
Storage
Landfill
Incinerate or filter
Hg recovery
Rccovcrv?
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While most of the companies interviewed indicated that they are
presently in conformity with local standards, a quantitative picture of
the overall pollution potential could not be developed during this program.
Under the 1899 Refuse Act Permit program, those companies which discharge
to navigable water have been filling discharge data with the Corps of Engi-
neers, but unfortunately, these data started to become available only very
late in our study. These data which we have seen, however, indicate that
production processes as presently employed for several product lines lead
to surprisingly large losses of active ingredients, and toxic raw materials
or by-products.
The producers of the persistent chlorinated hydrocarbons use:
an evaporative basin, in part* for DDT; an evaporative basin for aldrin
and dieldrin; and deep well disposal for chlordane. Therefore, these plants
have no discharges subject to the 1899 Act. The evaporative basins require
a word of further comment: evaporative and wind blown losses from these
facilities require evaluation and the long-term future of the basin should
be considered, e.g., what happens if the production site is closed 25 years
from now and converted to other uses?
Deep well disposal is used by several pesticide producers in
states where that practice is permitted and deep sea disposal is practiced
by a number of producers in the eastern seaboard area.
The air pollution aspects of pesticide production are essentially
without quantitative data* A small amount of information on levels of
certain pesticides in ambient air samples have been reported, but almost
no emissions data on specific pesticides from a given plant have been pub-
lished. These data are much needed.
A number of minor sources of pesticide losses were noted during
the interviews. One which has received the attention of a few companies
is the small amounts which collect on workers clothing, wipe cloths, etc.
Good data on losses on shoes, etc., are simply unavailable, although one
company noted that they had reduced miscellaneous losses from 150 to 2 lb/
day by increased vigilance to small details. Some companies furnish all
production workers with clothing which is then collected and washed or pre-
washed in a company-run laundry from which the wastewater goes to detoxifica-
tion treatment. On the other hand, some pesticide producers utilize com-
mercial laundries which may wash the company's materials separately from
all others, but do not use any special detoxification treatment. The use
of disposal clothing and cloths also requires attention to see that these
materials are incinerated rather than go to a landfill if the contaminant
is a persistent pesticide.
C-containing liquids to go to an approved county Class 1 dump,
DDT-
S-12
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Another potential pollution source is contaminated solvents which
might be sent to a so.lvent reclamation service. None of the major manu-
facturers -appear to do this but small producers or fprmulators may (par-
ticularly with solvents used for cleanup purposes). The pesticide content
of the solvents may be concentrated in still bottoms or.on filter media
which are not detoxified.
For some plants the pollution caused by; loss of active ingredients
is apparently less significant than that caused by unrecovered by-products
such as H2S, which is flared to SC>2, or particulates from fuel combustion,
e.g., a plant which produces 10 million pounds per year of most thioorgano-
phosphates could emit over 2 million pounds of SQ2 which would compare
with that emitted from a small electric power plant. Depending on the fuel
used for process heat and the air pollution controls installed, such a
plant might also produce 5 to 10 million pounds per year of particulate
pollutants (fly ash, etc.). By comparison, the amount of active ingredient
discharged through the waste treatment plant would probably be less than
10,000 Ib/year. .
The by-product which is common to many pesticide production
processes (including chlorinated hydrocarbons, organophosphates, triazines,
carbamates, captan, and others) is salt. A large production plant may
generate several million pounds per year of salt which with few excep-
tions is not recovered and is discharged to the river or through waste
treatment plants. The effects of these discharges are probably small, but
may require further evaluation.
5. Cleanup and decontamination of equipment: Equipment cleanup
is an integral part of pesticide manufacture. This operation is both
time consuming and expensive, and therefore, is kept to an absolute minimum.
Equipment cleanup is generally required for one of two reasons: (1) for
equipment maintenance, or (2) for quality control purposes.
Repair and preventive maintenance of production equipment is a
continuing process not only because of the types of equipment used, but
also in many cases because of the age of the production facility. Corporate
philosophy on maintenance varies from scheduled shutdowns of the complete
production unit to only unscheduled shutdowns of .specific items of equip-
ment for needed, repair. Generally, continuous processes require a scheduled
shutdown whereas batch operation can be maintained on a less ridged schedule.
In either case, the equipment must be emptied of toxic material before it
can be opened for inspection or repair.
Quality control necessitates the cleanup of production equipr
ment when the same facility is used for production of different active in-
gredients to prevent possible cross-contamination. Production scheduling,
S-13
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that minimizes the number of product changes is used to reduce this type
of cleanup as much as possible. Product changeover usually involves clean-
up of only that portion of the process that would contain potential con-
taminants. Cleanout procedures generally involve flushing the production
system with a solvent or in some cases, with steam. Wastes from these
cleaning operations normally go into the plant's process-waste system.
The pollution potential associated with equipment decontamination
and cleanup is not particularly significant. First of all, only a small
quantity of active material is involved in this operation, much less than
1% of the equipment capacity. Of more importance is the fact that wastes
generated by equipment cleanup in most cases goes to the plant waste treat-
ment system or in some cases can be recycled to the production unit. Thus,
the pollution that could result from discharge of these wastes is primarily
dependent on the efficiency of the waste handling system.
• e
6. Safety practices; Safety practices in the pesticide produc-
tion industry are designed for both the protection of the workers and the
containment of highly toxic or dangerous chemicals. The degree and sophis-
tication to which safety measures are used are primarily dependent on the
hazard involved.
Two types of pesticides require special environmental control:
(1) the organophosphates, and N-alkyl carbamate because of their anti-
cholinesterase activity; (2) the chlorinated hydrocarbons, and inorganics
such as mercury because of their stability and persistence. Effects from
these, as well as other toxic pesticides, may be produced by swallowing,
breathing, or absorption through the skin. Personnel protection measures
and devices are designed to minimize exposure.
Coveralls, boots, gloves, goggles, and a variety of respiratory
devices are used to protect production workers. In addition, exhaust
ventilation systems are used where there is a potential for atmospheric
vapor, spray, or dust containing active ingredients, for a hazardous raw
material or intermediate. These devices seem to protect personnel from
respiratory and dermal routes of intoxication. Protection against inges-
tion of toxic materials is dependent on demanding high standards of per-
sonal hygiene of the individual worker.
The facility for manufacturing aldicarb, one of the most toxic
pesticides made in the United States, utilizes highly refined precautions,
including air suits for maintenance and decontamination, and glove-cabinets
at toxic sample points. Respirators are issued to all personnel who come
on the plant site. Less toxic pesticides, such as carbaryl, only require
the use of standard personnel safety equipment.
S-14
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The containment practices and equipment used are also commensurate
with the hazard involved. Fire, explosion, and toxicity risks are con-
sidered. Control devices commonly used for containment include diking the
production area, vacuum operation of process vessels, and caustic scrubbing
of process vents.
Medical facilities are a part of the overall safety program found
at pesticide plants. Both preventive medicine and first aid services are
provided. Typical medical services include a periodic physical examina-
tion, first aid for minor cuts or burns, and periodic cholinesterase tests
for employees potentially exposed to anticholinesterase pesticides (organo-
phosphates and carbamates).
The potential for environmental damage resulting from inadequate
safety equipment and procedures apparently does exist for some facilities;
better contingency plans specifically designed to handle emergency situa-
tions: fires, explosions, or vandalism are needed for some pesticide produc-
tion plants.
General Conclusions
1. The major pesticide producers have, on the whole, extensive
wastewater treatment facilities. Many of these are new or newly-modified
and many are under construction or in design, but some still have little
or no effective treatment procedures at some facilities. The disposal of
liquid wastes from pesticide manufacture varies widely with different
companies, different products, and different geographical locations. Methods
being used include: many varieties of neutralization, oxidation, settling,
and holding ponds and also secondary and biological waste treatment plants
(all of which are followed by discharge to a stream or lake); evaporation
basins (which have no outfall); deep well disposal; deep ocean disposal;
and incineration. Unfortunately, data on the discharge of effluents to
navigable waters are only beginning to become available under the "1899
Refuse Act" for disposal of materials into navigable waters. Pesticide
producers were scheduled to submit discharge data to the Corps of Engineers
at a time when this study was nearing completion and very little data be-
came available in time to be evaluated. Preliminary review, however, in-
dicates that production processes as presently employed for several product
lines do lead to sizable losses of active ingredients, toxic raw materials,
by-products, etc., and that these are often not detoxified by the waste
treatment facilities, e.g., discharges of active ingredients range from a
few pounds per day to over 1,000 Ib/day for some products. These data
clearly show the need for a systematic study of the scope and effects of
these discharges for all producers. On the other hand, four of the major
persistent chlorinated hydrocarbon insecticides are now produced in facilities
S-15
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which do not discharge liquid wastes to a river, i.e., they are using
evaporative basins, deep well, etc. The evaporative basins pose two prob-
lems which we recommend receive further study: (a) what are the long-term
losses of persistent pesticide by evaporation and wind? and (b) what is
the disposition of the slowly accumulating sediment or sludge (which is
probably highly contaminated with pesticide) in event of periodic cleanout
over the years, or in event that the pesticide production is discontinued
and the area used for other purposes? In the case of one major chlorinated
hydrocarbon, toxaphene, better analytical techniques are needed to establish
whether it is persistent, because wastes from this production plant are
discharged.
2. The production processes have numerous potential sources of
pollution in addition to the primary liquid waste streams, including air
emissions, solid wastes, and miscellaneous liquid wastes. The major producers
appear to be cognizant of these sources and exercise controls to satisfy
local requirements. In a number of cases solid or liquid wastes contain-
ing active ingredients go to approved landfills or other burial sites with-
out detoxification, e.g., a liquid waste which apparently contains DDT goes
to an approved Class 1 dump in California. At a few facilities high ef-
ficiency incinerators are used to dispose of such wastes and we recommend
this practice.
Data on air emissions of pesticides are not yet available from
production plants and are much in need. The major producers have expended
much effort to install baghouses, scrubbers, and other air pollution con-
trols, but data on loss of active ingredients through these devices are
needed.
3. Some of the biggest sources of pollution from the major manu-
facturers are not from the active ingredient (i.e., the pesticide) but
from unrecovered by-products such as H2S (which may be flared to SC^).
Particulate or gaseous pollutants from incomplete combustion of fossil fuel
may be bigger sources of pollution than loss of active ingredient for some
plants.
4. Nearly all of the basic facilities and equipment now in use
for pesticide manufacture and formulation were designed and built prior to
the present age of intense concern about environmental quality. Even in
the case of one large, completely new facility which has just recently come
on stream, additional pollution control procedures and systems had to be
added on after the basic plant was designed in an attempt to meet new and
higher standards. This situation is not unique to the pesticide industry,
but prevails with most manufacturing facilities and processes currently in
use. However, this problem is of special importance in the pesticide in-
dustry because this industry produces biologically active chemicals which
are apt to have higher potential for causing environmental damage than do
the effluents discharged from most manufacturing processes.
S-16
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Numerous examples were noted wherein companies have recently
modified their production and waste disposal facilities to decrease the
amounts of wastes generated or lost; e.g., improved recycle, recovery and
decontamination of by-products, use of lined settling basins to avoid
seepage, etc.
Most of the production equipment is dedicated to one product or
to two very similar products so that cleaning wastes are minimal.
A host of smaller potential pollution sources were noted some
of which have received attention by some producers, but not by others,
e.g., carryout of pesticides on shoes and clothes are prevented by sending
company-provided work-wear along with wipe cloths, etc., to special laundries,
followed by recycle or detoxification of the wash liquid; wash basin or
lavatory wash water is sent to the waste treatment plant rather than dis-
charged with sanitary wastes; and the proper disposal of "bottoms" from
solvent recovery operations.
5. The formulation of pesticides is probably a larger source of
environmental pollution than is the initial production. The formulation is
done in some cases by the manufacturer at the production site, but in most
cases it is not. A host of formulators process hundreds of pesticides into
thousands of finished products. By the nature of this arrangement many of
the formulators have relatively small facilities and many of the formula-
tion runs are relatively short. The combined result is that formulators
with few exceptions have less extensive waste treatment facilities than
do the manufacturer, but they generate considerably more wastes from equip-
ment cleanup. However, the majority of the formulators probably send liquid
wastes to municipal sewer systems so that no data are becoming available
on the amounts discharged. These smaller businesses are also more apt to
send pesticide-containing solvents to commercial solvent reclamation services
(where the fate of the pesticide is uncertain) than is the manufacturer.
One problem faced by pesticide formulators wishing to improve
their pollution abatement systems and procedures is the lack of authorita-
tive, practical information on how to accomplish this. Several formulating
companies whom we interviewed expressed disappointment and dissatisfaction
with engineering firms to whom they had turned for help in developing
practical systems and procedures which would meet the environmental quality
standards set by local, state and/or federal regulatory and enforcement
agencies.
A closely related problem is that of dealing with catastrophes.
While most basic pesticide manufacturers (especially those where the pesti-
cide production is integrated into a larger chemical manufacturing complex)
have emergency procedures, contingency plans on how to handle emergencies
S-17
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such as fires, explosions, floods, etc., were inadequate or absent in most
independent pesticide formulating plants and also in many public warehouses
which handle concentrated pesticides. Recent history indicates, however,
that emergencies in which large quantities of toxic materials are suddenly
released into the environment can and do occur.
We therefore conclude that there.is an urgent need for the de-
velopment of principles and procedures by which pesticide formulating and
warehousing enterprises can minimize or completely eliminate the release
of toxic chemicals into the environment, especially into waterways. Such
information is needed (1) for their normal operations, and (2) for emergen-
cies. We recommend that early steps be taken to develop and furnish this
type of information to the pesticide formulating industry and to those in-
volved in warehousing large quantities of pesticides.
6. The transportation of pesticides, as with many other products,
causes increased chances of accidental breakage, spills and losses. The
potential is probably higher in the case of concentrated active ingredient
than it is with more dilute formulated products, but varies with the
packaging and shipping practices. Overall, the pesticide industry has had
relatively few major spills, but the potential remains inherent in the
transportation of hazardous materials.
Of smaller scope, but of importance we believe, is the increased
pollution potential of tank trucks over railroad tank cars in regard to
cleanout procedures: cars are frequently dedicated, require only occasional
cleanout, and this is done at the manufacturer's site with wastes going to
treatment; the trucks are most often leased one-way and are cleaned by the
operator at a point remote from detoxification facilities.
Another important pollution point related to the need to trans-
port pesticides is the inability to empty the standard 5 and 55 gal. metal
drums completely. These drums may often be reused for formulated products,
etc., and losses at the manufacturer/formulator/packager level are not
nearly so large as those at the consumer level; but new designs are needed
which permit complete drainage.
7. The warehousing of finished pesticidal products and the
marketing of pesticides are a smaller source of pollution, but losses in
this area are frequently disposed to the nearest sewer or trash can.
8. Overall the environmental impacts from pesticide manufacturing/
formulating/packaging/marketing activities appear to be small compared to
those resulting from consumer use of these products; but those negative
impacts of the former activities have zero benefit/cost ratios and should
be minimized. On the other hand, the costs of reducing all pollutants
S-18
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to zero are very large; regulations and legislation in this area must con-
sider that unrealistic standards in this area will drive many small producers
from the industry and preclude the entry of others who would previously
have entered. The large producers generally already have a very large in-
vestment in pollution control equipment, will be best able to meet the most
stringent control regulations, and will probably do so (with added costs
passed on to the buyer) if the product involved is much in demand by the
public.
S-19
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I. INTRODUCTION
The use of pesticides has become an extremely important factor
in the United States and indeed throughout the world in determining the
quality of life of man. The benefits which have been obtained from this
usage — increased production of food and fiber and increased freedom from
disease and obnoxious plant and animal life—have not been without some
undesirable side effects, such as direct effects on nontarget organisms,
the indirect unbalancing of delicate ecosystems, and the environmental
contamination by persistent pesticides which may tend to be biologically
accumulated in food chains. In addition, the possible long-term effects
of low levels of pesticides on man himself is the cause of serious concern.
Hence, the entire subject of pesticide production and use is under inten-
sive study by government and nongovernment scientists in the United States
and in many other countries.
The Environmental Protection Agency of the United States is cur-
rently conducting numerous studies on aspects of the production, use and
effects of pesticides of which the study performed under the present con-
tract is one. The objective of this study was to survey and evaluate the
environmental pollution potential associated with the manufacture, formu-
lation, and marketing of pesticides, including such related activities as
warehousing, transportation and testing, i.e., all of the operations up
to the point where a pesticide is placed in the hand of the normal con-
sumer. Emissions of pesticides or other pollutants from these sources to
the environment are without the benefits accompanying normal use patterns;
they may have detrimental effects and should be minimized. The scope of
this study is illustrated in Figure 1.
In the present study, a broad definition of "pesticides" has
been used which includes: rodenticides; insecticides; larvacides; miti-
cides (acaricides); molluscicides; nematocides; repellants; synergist; fumi-
gants; fungicides; aligicides; herbicides; defoliants, desiccants, plant
growth regulators and sterilants.
Over 275 pesticides are of commercial importance and perhaps as
many as 8,000 individual formulated products are prepared for specific
uses and methods of application. The brevity of the present study (6 months)
precluded, of course, the investigation of all of these pesticides, formu-
lations and products. The approach has, therefore, been to select examples
which are representative of the diverse production, properties and use
patterns and to investigate these in as much detail as time and resources
would permit.
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Raw
Materials
Handling
Losses
Manufacturing
Site
Process Water
Air Vents
Solid Wastes
and Landfills
By-Product
Disposal
Stockpile Losses
Handling Dusts
and Mists
Testing
Program
Equipment
Cleaning
1
Formulation
Site
Transportation
and Handling
Losses
Mixing Losses
Packaging Losses
Equipment
Cleaning
Marketing
Site
Transportation
and Handling
Losses
Warehousing
Losses
Other Breakage
and Spillage
Consumer
Figure 1 - Schematic Description of Pesticide Production and Movement
to Consumer, Indicating Potential Pollution Sources
-------
II. HISTORY OF PESTICIDE USE AND PRODUCTION
The production and use of pesticides are not new or even of re-
cent origin, but a tremendous growth has occurred during the past 40 years
in the number of pesticides available, the variety of applications, and
the volumes of production of the active ingredients and their formulated
products.
A. Discovery of Various Classes of Pesticides
From ancient times man has investigated the minerals, and the
plant and animal life around him for their value as medicinals, in the
production of his food, in warding off the attacks of obnoxious or danger-
ous insects, and against his fellow man.!—!L' Rotenone (the active ingre-
dient in the roots of Derris and other members of the Leguminosae family)
was used for many centuries in the Far East and South America to kill fish
for easier harvest and against insects. Pyrethrum (from the flowers of
Chrysanthemum cinerariaefolium) used in the Middle and Near East as an
insecticide, Sabadilla (from the bulbs of sea onion) used in South America
to kill lice, red squill (from the seeds of Schoenocanlum officinale). a
rodenticide, and numerous other minor pesticides have been used since
ancient times.
The advent of global navigation and travel brought knowledge of
many of these pesticides for the first time to Europe, where coincidentally
the study of chemistry was developing. White arsenic (As20o) was apparently
introduced to Europe from China in the 16th Century as a rat poison and a
1681 text described the use of arsenic as an ant poison. A method of pre-
paring elemental arsenic was published as early as 1649. (Arsenic poison-
ing of humans was also practiced during this time and may have been used
much earlier.) Tobacco was introduced from the New World in about 1550
and a tobacco extract was used as an insecticide on plants by 1690. Nico-
tine, the active ingredient, was of chemical interest as early as 1571 and
was isolated in 1828. Pyrethrum was introduced to Europe in 1828 (or
earlier by some accounts) and Rotenone was recognized by 1848 as an effec-
tive insecticide on caterpillars. Petroleum oil as an insecticide was
mentioned as early as 1787, but the general use of distillates of oil,
wood and coal did not develop until 75-100 years later. The use of copper
sulfate as a fungicide dates to about 1807.
The latter half of the 19th century saw considerable development
in the use of pesticides. In 1854, the insecticidal properties were de-
scribed of carbon disulfide, apparently the first fumigant. Paris Green,
a copper acetate arsenite and probably the first organometallic, and the
first example of a "second generation" pesticide, was introduced in
-------
1865-1867 for control of the Colorado potato beetle which was invading the.
Midwest. A number of other pesticides containing heavy metals was intro-
duced in the late 1800's: London Purple, a complex calcium arsenate mixture
with Rosanilline dye, Bordeaux mixture (copper sulfate plus slaked lime)
was introduced as an improved fungicide in 1885; copper sulfate was used
as a selective herbicide in 1895; mercuric chloride was first used for
crop protection in 1891; lead arsenate was introduced in 1892 against the
gypsy moth in Massachusetts; sodium fluoride was introduced in 1896 for
use on ants and cockroaches (and was subsequently used on many insects and
rodents); and borax was apparently introduced as a mild antiseptic and
fungicide. Lime sulfur (palcium polysulfide), which was probably present
in an insecticidal mixture used as early as 1833, was introduced as a
fungicidal solution in 1851 in France and was introduced in California
as a sheep-dip and in 1886 as a spray insecticide against-San Jose, scale.
Kerosene, which had become widely used as an illuminant, was
used in 1865 (and in the form of an emulsion with soap in 1877) as an
insecticide. Crude oil was used as dormant and summer spray oils in 1897,
although the highly refined oils of low phytotoxicity soon, became preferred.
The creosotic tar oils were used as wood preservatives asi early as 1890.
The first synthetic organic insecticide, dinitro ortho-cresol (as
the potassium salt), was described in 1892 in Germany.
Hydrogen cyanide,was used as .an insecticidal fumigant in 1886 and
formaldehyde, which was introduced as a disinfectant in 1888, was described
as a seed disinfectant (insecticidal and fungicidal) in 1896. A host of
natural and synthetic organics was apparently examined as pesticides during
l ' • '
this period. The most important pesticides during this period appear to
have been the arsenicals and nicotine.
The first three decades of the 20th century saw an extension of
and building dn the developments of the late 19th century, with some
emphasis on fumigants and herbicides. Naphthalene (which had been isolated
from coal tar in 1820) came into use as a moth-proofing fumigant followed
by paradichlorobenzene in 1913. Carbon tetrachloride, described in 1908 as
a fumigant for nursery stock, was the first chlorinated hydrocarbon insec-
ticide. Propylene dichloride, (1925), ethylene dichloride (1927), and di-
chloroethyl ether (1929) were also described as insecticidal fumigants
for stored crops. Calcium cyanide, introduced in 1923, as a solid source
of HCN, is used as an insecticidal and rodenticidal fumigant. Sulfuric
acid (1909), sodium chlorate (1910), and calcium cyanamide (which has been
introduced in 1905 as a fertilizer) were used as total herbicides.
-------
A number of complex fluorides were described as pesticides during
the early 1900's including the naturally occurring cryolite in 1929. Chlorp-
picrin was patented in 1908 as an insecticide, as was a rotenone extract in
1912. The use of the first organomercury pesticide,chlorophenol mercury,
dates from wheat bunt application in 1914, and methoxymethyl mercuric
chloride (1928) and mercurous chloride (1929) were introduced as replace-
ments for the highly toxic mercuric chloride. Copper napthenate became
used as a wood preservative during this time. A trend toward chemical
modification of the original pesticide was evident.
The 1930's saw several significant developments which set the stage
for the explosive growth of the pesticidal industry which followed.' The 'in-
secticidal activity of methyl bromide was reported in 1932 (it is now a widely
used fumigant for soil and stored products) and illustrated the use of sub-
stitutive organic chemistry to yield a product of greater activity and
improved physical properties. Aluminum phosphide, introduced in the early
1930's as an insecticidal fumigant for stored grains (it hydrolyzes in
moist air to give phosphine 'gas), and zinc phosphide, a rodenticide bait
poison (it hydrolyzes in the rodent's stomach), were the first pesticidal
phosphorous containing compounds. In about 1934, research was also start-
ing by Schrader in Germany on the organophosphorous chemistry which would
lead to the organophosphate class of pesticides.' In the early 1930's also
the Du Pont company introduced Ziram (zinc dimethyldithiocarbamate) the
first example of a new class of fungicides. Another significant develop-
ment was the introduction of the pentachlofophenol as a wood preservative
in 1936 followed by applications of chloranil (fungicidal crop protection)
in 1937 and pentachloronitrobenzene fungicide. Dinitro ortho-cresol (DNOC)
was also introduced in 1932 as a herbicide (a forerunner of the 2,4-D
family), and pentachlorophenol was introduced as a'herbicide by 1940. The
first organic thiocyanate insecticide was introduced in 1932 (as Lethane
384) by the Rohm and Haas Company. Phenothiazine, first synthesized in
1883, was discovered to have insecticidal properties in,1934 (plus fungicidal
properties a few years later). By 1944, the organic thiocyanates and pheno-
thiazine were being produced'in quantities of 6 and 3.5 million pounds per
year, respectively. Several other organosulfur and organonitrogen compounds
were evaluated during this period, including the first anilide (salicyl-
anilide) introduced as a selective fungicide (mildew) in 1931. Finally,
the introduction in about 1939 of the dialkyl phthalates (long known as
plasticizers) as repellants for biting insects represented another new
step. The total sales of synthetic organic pesticides in the U.S. in
1940 was only 287,150 Ib.
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A host of heavy metal salts and compounds were also examined
during this era, many of which received some pesticidal use, including
compounds of thallium, zinc, selenium, barium, chromium and antimony.
The chlorate, arsenite and thiocyanate herbicides also came into use
during this period as did borax for mold prevention. Of considerable
interest in light of current environmental concern was the introduction
in Sweden in 1938 of the organomercury compound, Panogen, for seed treat-
ment (although this material was not used in North America until 1949).
Modern Insecticides
In 1939, the Swiss chemists Paul Muller and coworkers at J. R.
Geigy A-G discovered, during a search for moth-proofing chemicals, the
remarkable insecticidal properties of 2,2-bis(p-chlorophenyl)trichloro-
ethane, a compound which had been first synthesized in 1874. This dis-
covery of DDT, for which Muller was awarded the Nobel Prize in 1948,
followed by the development of low-cost production methods in 1943, and
the wartime needs, led to an unprecedented acceptance and growth of a
pesticidal product. The production of DDT reached 180 million pounds
in 1963 in the United States and it was also produced in Europe, in India
(where production passed 35 million pounds in 1967),£/ and apparently in
the USSR and in China. Yet, this very volume was, of course, to lead to
trouble as DDT residues persisted long after use and spread throughout the
world to the extent that a gala centennial in 1974 seems improbable, to say,
the least.
The discovery and success of DDT also spurred intensive research
of similarly structured chemicals, and of chlorinated hydrocarbons in
general. Insecticidal properties were discovered in 1941 in France and
in England in 1942, for benzene hexachloride, which had been known since
1825. The discovery that the y-isomer (four isomers had been known since
1912) had exceptional- potency lead to methods of its synthesis (lindane)
and to a focusing by organic chemists of the study of structure-activity
relationships. Production of BHC also reached over 11.0 million pounds in
1951, but production declined rapidly after 1956. Methoxychlor, the most
widely used of the DDT analogs and a compound known since 1893, was dis-
covered to have insecticidal properties in 1944, along with ODD and with
the difluoro-analog (DFDT) at about the same time in Germany. Numerous
other DDT relatives were synthesized and tested during the late 1940's and
early 1950's and a dozen or so were produced commercially. With the sub-
sequent decline in popularity of DDT itself, interest has been revived in
the present day in finding active derivatives which are not persistent and
which do not biomagnify in the environment.
-------
The second major family of pesticides which emerged from wartime
research was the phenoxyalkanoic acid herbicides of which 2,4-D became the
most widely used. An analogue, 2-methyl-4 chlorophenoxyacetic acid (MCPA),
discovered at about the same time, was apparently used in England in 1941-
1942 and was produced commercially by Imperial Chemical Industries in 1945.
The 2,4-D, apparently held under secrecy for military reasons, was patented
as a growth stimulant, interestingly enough, in 1943 and as a herbicide in
1945. Production was started in 1944 by Amchem, passed 20 million pounds
in 1949, and over 100 million pounds per year (acid equivalent of esters
and salts) by the late 196Q's. Of the dozen or more other chlorophenoxy
herbicides that have been developed only 2,4,5-T (introduced in 1944) has
reached large production volume, although Silvex and 2,4-DB are of com-
mercial importance. Unlike DDT and BHC, the 2,4-D family is nonpersistent
in the environment.
1
Several other pesticides worth noting also were developed during
the war including: the rodenticides, sodium fluoroacetate (extremely toxic
to mammals, but a natural constituent of some African plants), and warfarin,
an anticoagulant of low acute toxicity (1944); the herbicides; the metal-
dithiocarbamate ( =NC(S)S- group) fungicides; Ferbam, Nabam and Zineb; sev-
eral halogenated fumigants; the repellant, ethyl hexanediol (6-12); the
synergist, piperonyl butoxide (1947); and the herbicides trichloroacetic
acid, TCA (1944); and ammonium sulfamate (1945).'
Immediately following the end of World War II several new classes
of pesticides became available including: the aldrin-toxaphene group of
highly chlorinated organics; the o>rganophosphates; the carbamates; and the
substituted ureas.
i
In 1945-1946, chlordane and heptachlor, the first two of the
highly chlorinated organic insecticides derived from hexachlorocyclopenta-
diene, were announced by Hyman of the Velsicol Company and discovered in-
dependently by Riemschneider in Germany. These were quickly followed by
numerous related compounds including aldrin, dieldrin and endrin in 1948
and the structurally related toxaphene, which was prepared by chlorination
of camphene at Hercules in 1947. About 16 members of the toxaphene-aldrin
group have been produced commercially. About 35 other chlorinated aromatics
and aliphatics are produced.
A major new class of insecticides which became available at the
end of World War II were the organophosphorus compounds, a "development
assisted considerably by German research tinder Gerhard Schrader on anti-
cholinesterase chemical warfare agents. The first of these (patented as
an insecticide in 1942, in Germany, and surprisingly enough in 1943 in the
U. S.) was identified, after some early confusion, as TEPP (tetraethylpyro-
phosphate) a compound first prepared in 1854. This relatively simple ester
-------
was rapidly followed by the synthesis and commercialization in the U. S.
and Europe of a number of phosphorus compounds which incorporated dif-
ferent structural features: the phosphoramide, (P-N bonds), Schradan;
the thiophosphates (P=S bonds), parathion (1947), methyl parathion (1949),
diazinon (1953), and demeton; the dithiophosphate, malathion (1950); the
thiophosphono compound (C-P=S grouping), EPN (1950); and the alkyl thio-
dithioate, phorate (1953). Over 80 organophosphorus pesticides have been
described to date.
Several classes of nitrogenous pesticides have been produced
since 1945. Herbicidal activity was discovered in 1946 for substituted
ureas and a series of "urons" were introduced subsequently (largely by
Du Pont), including: monuron (1952); diuron (1954), fenuron (1957),
chloxuron (1960), and noruron (1962). Included in this general category
also might be a number of (a) herbicides: hydrazides, e.g., MH (1948 by
U. S. Rubber), amides, e.g., CDAA (1956, Monsanto); anilines, e.g., pro-
panil (described in 1951, commercialized in 1960); and alachlor (1966);
and uracils, e.g., bromacil (1963, Du Pont); (b) fungicides: imides,
e.g., cycloheximide (1949, Upjohn) and the two trichloromethylthio imides
captan and folpet (1949, Standard Oil); a guanidine, dodine (1956, American
Cyanamide); and (c) repellants: an amide, diethytoluamide (1955, Hercules).
About 50 pesticides are included among these. In addition, about 35 other
compounds which contain amine, amidine, diazo, azole, imidazole, pyridine,
quinoline, diazine, thiazine or nitrile functions have been produc-ed as
pesticides (most are herbicides or fungicides; a few are insecticides).
Of these picloram with a production of about 5 million pounds per year is
probably the most significant commercially. About six herbicidal quaternary
ammonium salts are available of which the imported diquat and paraquat
(introduced in 1958) appear to be most popular. Three other classes of
nitrogenous compounds require special mention because of the production
volumes and variety: the carbamates, the triazines and the nitroaromatics.
The carbamates have about the broadest range of biological activ-
ity known for any chemical class of compounds. The toxicity to mammals and
plant growth regulating properties of some members of this family were
known before 1930. The N-aryl carbamate (Ar-NH-C(O)-OR group) ester,
propham (IPC) was commercialized in 1945 as a selective herbicide (grasses),
followed by the chloro derivative in 1951. A series of thiocarbamate
herbicides such as EPTC was introduced by Stauffer Chemical in 1954, and
several other herbicidal and fungicidal carbamates of various structures
have been introduced more recently. The insecticidal (chlorinesterase
inhibiting) N-alkyl carbamates were patented first in 1952, but the most im-
portant today are carbaryl (1956), propoxur (1959), aldicarb (1965), methomyl
(1966), carbofuran (1967), and Bux Ten (1968). About 32 carbamates, eight
thiocarbamates and eight dithiocarbamates (including the metal complexes)
have been produced.
8
-------
The first example of the triazine class of pesticides was a fungi-
cide introduced experimentally in 1955 by Ethyl Corporation and now known
as Dyrene. The major entries in the field, however, are the herbicides
introduced by the Geigy Company including: simazine (1956), atrazine (1958),
propazine (1960), ametryne (1969) and others. Production of atrazine in
the U. S. may soon pass 100 million pounds yearly.
As previously noted, DNOC has long been known to have insecticidal
and herbicidal properties. Several other nitrophenol derivatives have been
developed as pesticides including the herbicide, dinoseb (1945 et. seg.,
Dow) and the acaracides dinocap (1946, Rohm and Haas), binapacryl (1960),
dinobuton (1963), nitrofen (1964), fluorodifen (1968), and others. The
nitroaniline herbicides, dichloran (1959), trifluralin (1960), benefin
(1965), and nitralin (1966) have been of more commercial importance with
total production of perhaps 40 million pounds.
The chlorinated benzoic acid family of herbicides was introduced
in 1954 with the 2,3,6-TBA of Heyden Chemical and the polychlorinated acid
of Du Pont. The amino dichloro derivative, chloramben introduced by Amchem
Products in 1958 is the leader in the field today, with an estimated yearly
production of 20 million pounds, followed by dicamba (1965), dacthal (an
ester, 1959) and the acetic acid analogue of 2,3,6-TBA, chlorfenac (1959).
jOther herbicides of interest include the organic arsenicals in-
troduced by Ansul Chemical in 1958 and the host of organic mercurials intro-
duced primarily as fungicides, although phenyl mercury acetate was used as
a selective herbicide (crabgrass) as early as 1947. Certain organotiri com-
pounds have also been recently introduced.
Considerable interest has recently developed in newer methods of
pest control which do not center on synthetic organic chemicals. These
include Bacillus thuringiensis, which has been known since 1915, but intro-
duced as a microbial insecticide (Lepidoptera larvae) in 1960, polyhedrosis
virus, juvenile hormone, and other experimental pesticides.
The pesticides and related products which are currently produced
in or imported into the United States are listed in Table I. The pesticides
are grouped by use class (herbicide, insecticide, fungicide, etc.) and arrange-
ment is alphabetical by common name or in some cases, by tradename.
-------
TABLE I
PESTICIDES PRODUCED. IMPORTED OR SOLD IN THE UNITED STATES^./
A. Herbicides and Plant Growth Regulators
Pesticide
Producer^'
Alachlor (Lasso®)
Ametryne^ ^
Ammonium Sulfamate
Arsenicals, organo
DSMA
MS MA
MAMA
CMA
Dimethylarsinic acid
(cacodylic acid)
Arsenic acid
Atrazine (AAtrex®)
Bandane®
Barban
Benefin
Bensulide
/B\
Bentanar2' (phenmediphan)
Borax (sodium tetraborate)
Bromacil (Hyvar®)
Bromoxynil
Butylate
CDAA (Randox®)
CDEC (Vegadex®)
Chloramben (Amiben®)
and derivatives
Chloroxuron
Chloropropham
Cycloate
Monsanto
Geigy
Du Pont
Ansul, Cleary, Diamond, Dow
Ansul, Diamond, Vineland
Ansul
Vineland
Ansul, Vineland
Pennsalt, FMC
Geigy
Velsicol
Gulf
Lilly
Stauffer
Imported
Am. Pot., U. S. Borax
Du Pont
Imported ;
Stauffer
Monsanto
Monsanto
Am. Chem.
Geigy
PPG
Stauffer
a/ Based on U. S. Tariff Commission data for 1970, on 1969 data from the
Pesticide Review. 1970, and other sources.
b_/ For complete company names see page 56 .
10
-------
TABLE I (Continued)
A. Herbicides and Plant Growth Regulators (Continued)
Pesticide
2,4-D (acid, esters, and salts)
Dalapon
DCPA (Daethai®)
Def®
2,4-DEP
Diallate
Dicamba
Dichlobenil
Dinitrobutylphenol (and derivatives)
Dinitrocresol
Sodium salt (DNOC)
Dinoben (acid and derivatives)
Diphenamid
Diquat
Diuron
DMSA (N-dimethylamine succinamic
acid)
Endothal
EPTC (Eptam®)
EXD (ethylxanthogen disulfide)
Fenuron
Fluometuron
Folex® .
Gillerellic acid
Indolebutyric acid
Lenacil (Venzar®)
Linuron
Machete®
Magnesium chlorates
MCPA
MCPA, Potassium salt
MCPP
Metobromuron
MH (maleic hydrazide)
Producer
Dow, Chipman
Dow
Diamond
Chemagro
Uniroyal
Monsanto
Velsicol
Imported
Dow, FMC
Imported
FMC
GAF
Arapohoe, Upjohn
Imported
Du Pont
Uniroyal
Pennsalt
Stauffer
Roberts
Du Pont
Ciba
Mobil
Abbott, Merck
Merck
Du Pont
Du Pont
Monsanto
Allied, Chevron, Dow, Pennsalt
Cleary, Rhodia
Guth
Imported
Imported
Am. Cy., Ansul, Chem. Form.,
Fairmont, Uniroyal
11
-------
TABLE I (Continued)
A. Herbicides and Plant Growth Regulators (Concluded)
Pesticide
Producer
Molinate
Monuron
Monuron-TCA
Stauffer
Du Pont
Allied
Naptalam
Napthaleneacetic acid and derivatives
Neburon
Nitralin (Planavin®)
Nitrofen
Norea
Uniroyal
Am. Chem., Thorn. Hay., Berkeley
Imported
Shell
Rohm and Haas
Hercules
Paraquat
Phosphon®
Picloram (Tordon®)
Preforan®
Prometryne
Propachlor (Ramrod®)
Propanil
Propazine
Propham (IPC)
Pyrazon
Siduron
Silvex
Simazine
Sodium arsenite
Sodium borate (metaborate)
Sodium chlorate
2,4,5-T (acid, salts, and esters)
TCA (sodium salt)
Terbacil
Terbutol
Triallate
Trichlorobenzoic acid,
dimethylamine salt
Trifluralin (Treflan®)
Vernolate
Imported
Mobil
Dow
Geigy
Geigy
Monsanto
Monsanto, Rohm and Haas
Geigy
PPG
Imported
Du Pont
Dow, Thorn. Hay., Hercules
Geigy
Chem Ins., Chev., Chip., FMC, Pennsalt
U. S. Borax
Am. Potash., Chipman, Hooker,
Pennsalt, PPG
Dow, Thorn. Hay.
Dow
Du Pont
Hercules
Monsanto
Du Pont
Elanco
Stauffer
12
-------
TABLE I (Continued)
B. Insecticides (including Miticides and Nematocides)
Pesticide
Producer
Abate
Acaralate
®
Aldicarb (Temik®)
Aldrin
Aramite®
Arsenates, calcium and lead
Aspon
Axinphosmethyl (Guthion )
Azodrin
.®
American Cyanide
Geigy
Union Carbide
Shell
Uniroyal
Several Companies
Stauffer
Chemagro
Shell
Bacillus thuringiensis
Baygon^1 (propoxur)
Bidrin®
Binapacryl (Morocide^
Bromophos
2-(p_-tert-Butylphenoxy)cyclohexyl-2-
propynl sulfite
Bux Ten®
Carbaryl (Sevin®)
Carbofuran (Furadan®)
Carbophenothion (Trithion®)
Chlordane
Chlorobenzilate
Ciodrin®
Coumaphos (Co-Ral®)
ODD (IDE)
DDT
Demeton (Systox®)
Diazinon
Dichlorvos (DDVP, Vapona®)
Dicofol (Kelthane)
Dieldrin
Dilan®
Dimethoate
2,6-Dimethyl-3,5-dichloro-4-
pyridinol
0,0-Dimethyl S-phthalimidomethyl-
phosphorodithioate
Abbott, Nutralite, IMC
Imported
Shell
FMC
Imported
Uniroyal
Chevron
Union Carbide
FMC
Stauffer
Velsicol
Geigy
Shell
Chemagro
Allied, Rohm and Haas
Montrose
Chemagro
Geigy
Shell
Rohm and Haas
Shell
Com. Solv.
American Cyanide
Dow
Stauffer
13
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TABLE I (Continued)
B. Insecticides (Including Miticides and Nemotocides) (Continued)
Pesticide
Producer
Dioxathion
Disulfoton (Disyston®'
IF?)
Dursban^
Endosulfan (Thiodan®)
Endrin
Ethion
Hercules
Chemagro
Dow
Hooker
Velsicol
FMC
Fensulfothion (Dasanit^
Fenthion
Gardona
,®
Chemagro
Chemagro
Shell
Heptachlor
Isopropylphenyl N-methylcarbamate
Kepone®
Lethane 384
Lindane
Velsicol
Ott
Allied
Rohm and Haas
Hooker
Ma lathion
Metaldehyde
Me thorny1
Methoxychlor
Methyl Demeton (Meta Systox 0
Methyl Parathion
Mevinphos (Phosdrin )
Mirex
(R)
Morestan (oxythioquinox)
Naled (Dibrom®)
Nemacide (dichlofenthion)
Nicotine and derivatives
Parathion
Perthane®
Petroleum spray oils
N- (Phenyl-2-nitropropyl)piperidine
American Cyanide
Com. Solv.
Du Pont
Chem. Form., Du Pont, Nease
Chemagro
Am. Pot., Monsanto, Stauffer, Shell
Shell
American Cyanide
Imported
Chevron
Mobil
Chem. Form,
Am. Pot., Monsanto, Stauffer, Shell
Rohm and Haas
Humble, several other companies
Merck
14
-------
TABLE I (Continued)
B. Insecticides (Including Miticides and Nematpcides) (Concluded)
Pesticide
Phorate
Phosphamidan
Prophos (Mocap®)
Pyrethrum, extract
Ronnel
Rotenone, roots
Ruelene® (Cruformate)
Sodium fluoride
Sumithion® (Fenitrothion)
TEPP
Tetradifon
Thanite
2-Thiocyanoethyl laurate
m-Tolyl-N-methylcarbamate
Trichlorfon
Toxaphene (including strobane-T)
Zinophos® (Thionazin)
Producer
American Cyanide
Geigy, Mobil
Mobil
Imported
Dow
Imported
Dow
Allied, Alco, United
Imported
Am. Pot.
FMC
Ott Chemicals
Rohm and Haas
Ott Chemicals
Chemagro
Hercules, Tenneco, Sonford
American Cyanide
C. Fungicides
2-Aminobutane Carbonate
Benomyl
Bis-l,4-Bromoacetoxy-2-butene
2,6-Bis(dimethylaminomethy1)-
cyclohexane
2'-Bromo-4'hydroxacetophenone
Cadmium succinate
Captan®
Chloranil
5-Chloro-2-mercaptobenzothiazole,
laurylpyridinium salt
Chloroneb
Copper carbonate, basic
Copper chloride, basic
Lilly
Du Pont
Vineland
Merck
Buckman
Mallinckrodt
Stauffer
Imported
Vanderbilt Chemicals
Du Pont
Mallinckrodt, Tenneco
FMC, Harshaw
15
-------
TABLE I (Continued)
C. Fungicides (Continued)
Pesticide
Copper napthenate
Copper 8-quinolinate
Copper sulfate
Cyanodithioimidocarbonate,
disodium salt
Cyanomethylthiobenzothiazole
Dazomet (DMTT)
DCNA
Dexon®
Dichlone
Difolatan (captafol)
Dimethyldithiocarbamic acid
Mn salt
K salt
Dimethylthiocarbonyl
Diphenylammonium propionate
Dodine
Dyrene^
Ethylene bis(dithiocarbamic acid,
diammonium salt)
Ferbam
Folpet
Glyodin®
2-Hydroxypropylmethanethio sulfonate
Kara thane®
Lanstan® (Korax)
Maneb
Metham (SMDC)
Mercurial organics (~ 20)
Mercurial chlorides
2-Mercaptobenzothiazole, zinc and
ethanolamine salts
Producer
Harshaw
Fisher, Nuodex, Mer.ck
Calumet, Harshaw, Phelps Dodge,
Tenneco
Buckman
Buckman
Merck, Ott, Stauffer, Wood Ridge
Upjohn
Imported
Imported
Chevron
FMC
Buckman
Cleary
Merck
American Cyanide
Chemagro
Roberts
Du Pont, FMC, Vanderbilt, Wood Ridge
Stauffer
Union Carbide
Buckman
Rohm and Haas
FMC
Alco, Du Pont, Rohm and Haas
Stauffer
Mallinckrodt, Cleary, Vineland
Mallinckrodt
Vanderbilt
16
-------
TABLE I (Continued)
C. Fungicides (Concluded)
Pesticide
Producer
Nabam
PCNB (pentachloronitrobenzene)
PGP (pentachlorophenol) and
sodium salt
Piperalin (Pipron®)
Plantvax® (oxycarboxin)
Polyethylenethiuram disulfide
Sulfur and inorganic sulfides
2,3,4,6-Tetrachlorophenol
Thiram
2,4,5-Trichlorophenol
Sodium salt
Ethanolamine salt
2,4,6-Trichlorophenol
Zinc sulfate
Zineb
Ziram
FMC, Rohm and Haas, Uniroya'.
Olin
Several Companies
Lilly
Imported
Buckman
Stauffer, FMC, Olin
Dow
Du Pont
Dow, Hooker, Hercules
Dow
GAF
Dow
Several Companies
Du Pont, FMC, Rohm and Haas
Du Pont
D. Wood Preservatives
Coal tar
Creosote
Acid copper chromate
Chromated copper arsendte '
Osmosalts®
Tanolith® (Wolman's Salts®)
Chromated zinc chloride
PCP (pentachlorophenol and Na salt)
Petroleum oils
Several Companies
Several Companies
Several Companies
Several Companies
Osmose
Koppers
Several Companies
Dow, Monsanto
Several Companies
17
-------
TABLE I (Continued)
E. Fumigants (Soil, Stored Products, Structural, Sterilants)
Pesticide
Acrylonitrile
Azobenzene
Calcium cyanide
Carbon disulfide
Carbon tetrachloride
Chloroform
Chloropicrin
DBCP (dibromochloropropane)
£-Dichlorobenzene
£-Dichlorobenzene
Ethide® (dichloronitroethane)
Ethylene dichloride
Ethylene oxide
Ethyl formate
Formaldehyde
Hydrogen cyanide
Methyl bromide
Sulfuryl fluoride
Producer
Stauffer, Union Carbide, Monsanto,
American Cyanide
Eastern Chemical
American Cyanide
FMC, PPG, Stauffer
Dow, Diamond, FMC, Stauffer
Several Companies
Dow, IMC
Am. Pot., Dow, Occidental, Shell
Dow, Shell
Dow, Monsanto, Hooker
Allied, Monsanto, Dow, PPG
Com. Solv.
Five Companies
Dow, Jefferson, Union Carbide,
Wyandotte
Com. Solv.
Allied, Celanese
American Cyanide
Am. Pot., Dow, Great Lakes, Michigan,
Vulcan
Dow
F. Insect Attractants. and Repellants
Deet (diethyltoluamide)
Ethyl hexandiol (6-12®)
MGK repellant 326 (di-n-propyl
isocinchomeronate)
Trimedlure
Chem. Form., Hercules, Uniroyal
Union Carbide
MGK
Union Oil Products
18
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TABLE I (Concluded)
G. Synergists
Pesticide
Producer
MGK 264
Piperonyl butoxide
Tropital
®
MGK
FMC, Alpha, Berkeley
MGK
H. Rodenticides
Antu^
Diphacinone
Norbormide (Raticate®)
Pival® (pindone)
Sodium fluoroacetate
Strychnine
Penick
Nease
Pitman-Moore
Motomco, Pierce
Roberts Chem.
Imported
I. Miscellaneous Pesticides
- -.«£. . • - J . -
... -I • »
Hexachlorophene, a bacteriocide,
and fungicide' ....
3-Trif luoromethyl-4-nitroph.enpl
(TFM), lamphreycide
4-Aminopyridine (Avitrol®, bird
repellant
Imported
Maumee
Phillips Petroleum Company
J. Dry Carriers and Diluents
Bentonite
Fuller's Earth
Kaolin
Pyrophyllite
Talc and Soaps tone
Several
Several
Several
Several
Several
Companies
Companies
Companies
Companies
Companies
19
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B. Development of Pesticide Use Patterns
) : .
The pesticide industry developed as a result of pest control
needs in agricultural, structural, home arid garden, recreational and other
areas. The general classes of pesticides according to the type of pest
controlled is shown in Figure 2.
Raw Materials:
90% Organic
(95 % Synthetic)
Fungicides
Organo-Metallic Organic
Herbicides
V
Total Killers Selective Killers
Pre-Emergent
Raw Materials:
1.0 % Inorganic
(5% Natural)
Rodenticides
Agaricides
Sterilants
Post-Emergent
Insecticides \
Killers Attractants
. ! Systemic Contact
t I
Growth Regulators !
Repellents
Figure 2 - Classes of Pesticides According to Use—
6/
The total use of pesticides has grown rapidly over the past 20
years and the use patterns of pesticides have changed appreciably since
these products were first introduced. These changes have not been very
drastic from one year to the'next, but they have occurred and go on con-
tinually, and their accumulative effects are considerable.
20
-------
During the last 10 years, the production and use of fungicides
has increased very little. The total volume of insecticides has grown
somewhat, while by far the greatest increase has occurred in the herbicide
field. The growth of the various classes of the pesticide market is illus-
trated by the production and sales data shown in Figures 3 and 4.
The major agricultural crops of importance to the pesticide
market are cotton, corn, soybeans, the various fruit and vegetable crops,
hay and pasture, and tobacco, followed by a host of smaller animal and
plant uses. The distributions of acreage for major field crops are shown
in Figures 5 through 10.Z/ The distribution of use for many nonagricultural
pesticides more nearly reflects the population distribution except that usage
generally increases as one goes to more southerly latitudes.
The changes which have been occurring in the use patterns of
pesticides are significant and are worthy of further comment. These
changes are being brought about.by several factors, including the follow-
ing.
Increased general use of pesticides. As the steadily in-
creasing volume of pesticide production and sales indicate,
the use of pesticides has increased significantly over the last
10 years. Agricultural uses of pesticides have increased
by application of pesticides, especially herbicides, to a
larger number of acres. In addition, the rates of applica-
tion per acre of a number of pesticides, especially insec-
ticides, have increased gradually in response to the
development of resistance in the pests to be controlled.
Nonagricultural consumption of pesticides has also grown
through increased use of pesticides by government agencies,
home owners, suburban gardeners, and for a variety of in-
dustrial and other purposes.
Replacement of pesticides by competitive products. In pest
control as in many other fields, the "better" product tends
to replace what is only "good." In many instances, more
effective or less expensive pesticides have replaced older
products in the market place. In general, only pesticides
offering more control at the same cost, or the same control
at lesser cost, or both, have been successful in replacing
other products. Greater safety to humans, to other non-
target species, or to the environment have not been equally
rewarded in the market place, at least not up to the present
time.
21
-------
I I Fungicides
E^xtt;:*:) Insecticides, Fumigants, Rodenticides, Soil Conditioners
1 500r- ^"^-^ Herbicides and Plant Hormones
c
I 1,000
u-
o
c
:=' 500
0
1960 1965 1970 1975 Est.
(MRI)
Source: U.S. Tarriff Commission (1960 Data Adjusted for Fumigants)
Figure 3 - U.S. Production of Synthetic Organic Pesticides
1,500
!2
_o
;§ 1,000
I 500
0
Fungicides
l::::x:x:x:::::l Insecticides, Fumigants, Rodenticides, Soil Conditioners
_ l::XyXv::::::j Herbicides and Plant Hormones
1960 1965 1970 1975
(Est.) (Est.)
Adapted from Chemical Week, p. 34, May 27, 1970
Figure 4 - U.S. Producers' Sales of Synthetic Organic Pesticides
22
-------
UNITED STATES
TOTAl
63,514,906
MAP NO. 6JA.M64
U.S. DEPARTMENT OF COMMERCE
BUREAU OF THE CENSUS
Figure 5 - Corn Harvested for All Purposes, 1964
UNITED STATES
TOTAl
13,916,648
MAP NO. 64A.M7I
U.S DEPARTMENT OF COMMERCE
BUREAU OF THE CENSUS
Figure 6 - Cotton Harvested, 1964
23
-------
UNITED STATES
TOTAL
30,351,24*
ma NO. MA.KTO
US. DEPARTMENT OF COMMERCE
IUMAU Of TMC CENSUS
Figure 7 - Soybeans Harvested for All Purposes, 1964
UNITED STATES
TOTAL
28,211,434
US. DEPARTMENT Of COMMERCE
IUMAU Of THE CINSUS
Figure 8 - Alfalfa Cut For Hay, 1964
24
-------
UNITED STATES
TOTAL
1,026,240
ttAf NO. 64A.M74
U.S. DEPARTMENT OF COMMERCE
tUMAU Of THI CCNSUS
Figure 9 - Tobacco Harvested, 1964
MAP NO 64A.MIJ
US DEPARTMENT OF COMMERCE
BUBEAU OF THE CENSUS
Figure 10 - Tomatoes Harvested For Sale, 1964
-------
Regulatory Actions. Cancellation of the registration of
certain pesticides or pesticide uses have removed some products
from the market, and have restricted the available uses of
other products. In the great majority of these instances,
other pesticides have quickly replaced the products or uses
which were withdrawn.
The chlorinated hydrocarbon insecticides illustrate this point.
In line with the worldwide concern about detrimental effects
of DDT on the environment, followed by the cancellation of
many DDT registrations in the U. S., the annual production
volume of this insecticide and its domestic use have dropped
considerably. We estimate that "only" about 15 million
pounds of DDT were used in the United States in 1971.
The "aldrin-toxaphene group" (including aldrin, chlordane,
dieldrin, endrin, heptachlor, Strobane, and toxaphene) has
also experienced some decline in production and sales. The
use of aldrin for the control of"soil insects on corn has
decreased somewhat. This is at least in part due to a
"secondary" regulatory problem, i.e., widespread appearance
of illegal residues of dieldrin, an aldrin metabolite, in
food, feed and animal products in areas where aldrin had
been in heavy use for many years. (Development of insect
resistance has been another factor contributing to the
slowly declining use of aldrin on corn.) On the other hand,
it appears that larger quantities of products like chlordane
and toxaphene are used for many purposes where DDT, aldrin
or dieldrin were previously the products of choice. Where
chlordane or toxaphene are used as replacements for aldrin
or dieldrin, much higher rates of application per acre are
usually required. At the same time, analytical methods of
sufficient sensitivity and specificity for monitoring chlor-
dane or toxaphene residues in the environment are lacking.
It is therefore questionable whether this type of replace-
ment represents an improvement from the standpoint of environ-
mental contamination.
C. Developments.in Manufacture and Formulation Methods
The manufacture and formulation of pesticides acquired a tremen-
dous amount of sophistication during the last 25 years as the types of
pesticides, the use patterns and the methods of application have changed.
26
-------
1. Pesticide manufacture: The synthetic chemistry required for
the production of the pesticides is generally well known and various aspects
are described widely through the technical literature, including the texts,
"Organic Insecticides" by Metcalf^.' and "The Chemistry of Pesticides" by
Melnikov;^' certain references such as "Pesticide Manual" by Martini./ and
the "Herbicide Handbook"?/ and special reviews such as that by Riemschneider,±-z.'
The "The Chemical Process Industries" by Shreeve,!!/ and "Industrial Chem-
icals" by Faith, Keyes and Clarkli./ describe the production processes for
a number of better known pesticides and Sittig'sil/ "Pesticide Production
Processes" covers the patent literature on the manufacture of about 85 active
ingredients. Schematic depictions of the synthesis of some of the more
important chemical classes of pesticides are shown in Figures 11 through
15.
The technology for the production of pesticides varies widely
depending on the properties of the compounds and the position of the com-
pany in terms of raw materials, patent position and sales structure. Pro-
duction of the early inorganic pesticides was essentially by batch processes
and since most of the ingredients were nonvolatile solids or handled in
aqueous media, precautions to avoid occupational exposure or environmental
pollution were probably minimal. The rise of the petrochemical industry
brought an increasing capability to conduct continuous process manufactur-
ing and much of this technology was drawn upon by the synthetic organic
pesticide industry, and semicontinuous operations are common. In fact, a
number of the petrochemical companies had the raw materials and technical
know how to move rapidly into the pesticides field.
The production of synthetic organic pesticides in general, how-
ever, involved the use and handling of more hazardous materials (e.g.,
chloral and chlorobenzene for DDT) than did the inorganics and in many
cases the production systems were more carefully controlled or enclosed to
avoid occupational exposure. The advent of the chloinesterase-inhibiting
organophosphate and carbamate insecticides lead, of necessity, to almost
completely enclosed or controlled production systems. While many of the
early organic pesticides could be produced with relative ease, many of the
highly effective or specific recently developed materials require consider-
ably more sophisticated production chemistry and technology so that the
product is quite expensive and more care is exercised to recover the prod-
uct from waste streams.
In summary, then, one can say that prior to the recently developed
consciousness of environmental pollution, the most poorly controlled pro-
duction processes were those in which the raw materials and product were
least toxic to humans and the product could be produced at a low cost.
Unfortunately, the persistent DDT fills both of these criteria rather well
and one result is that the sediments in the sewer lines below one long-
time producer were found to contain 9% DDT--a total of 4,500 Ib in 0.5
million pounds of sediment were removed.
27
-------
00
METHOXYCHLOR
CCI3
DDT
CH3O
NaCI
(CCI3)2CO
HEXACHLOACETONE
CICH2COOH
CHLOROACETIC ACID
CH3OCO
DACTHAL CAPTAN
CHLORAMBEN
Cl Cl
HEXACHLOROPHENE
Figure 11 - Synthesis of Some Chlorinated Hydrocarbons and Related Pesticides
-------
ISODRIN
ENDRIN
N>
DIELDRIN
, EPOXIDATION
\H2O2 OR PER ACIDS
, SiO2 OR FULLERS
EARTH IN CCU OR
SO2CI2+ BENZOYL
PEROXIDE IN C6H6
HEXACHLOROCYCLOPENTADIENE
Clo PARTIAL
CS-HYDROCARBONS —^> CHLORINATION
C)0H|2
DICYCLOPENTA
DIENE
PENT AC
H2
BROMODAN
Perchlorinated Ring
MIREX KEPONE
Figure 12 - Synthesis of the Diene Group of Chlorinated Insecticides—From Hexachlorocyclopentadiene
-------
(C2H5O)2 PSH
Delnav
Disyston
Malathion
'CH3OH
Methyl Parathion
CH3OH
C9H5OH
—— +• (C2H5O)2 PCI »• Demetox
Meta-Systox
Bayer 25141
VC2H5OH Coumaphos
Parathion
(CH30)3P
DDVP
Naled
Phosdrin
Trichlorfon
TEPP
Figure 13 - Synthesis of Phosphorus-Based Pesticides—
30
-------
Reactions
Examples
A. N-Alkyl Carbamates
1. ROH(ArOH) + CoCl2 NaOH> ROCOCl 2.> RO-CO-NHR
O-CO-NVICII,
CO
Carbaryl
2. ArOH.+ ClCO-NHR > ArO-CO-NHR
3. ArOH, ROH or =NOH + CH3NCO > RO-CO-NHR
0-CO-NHCH3
OCH(CH3)2
Baygon
C5H11"(( JVO-CO-NHCH
3
Bux
CH
NO,
1. Reduce
~2~.Diazotize
CH3NCO
(CH3)2
OH
CO-:
NHCH,
Carbofuran
(CH3)2C=CH2
1. NaN02 + HCl^
2. CH3SNa
CH3SC(CH3)2CH=NOH
CH->NCO
CH3SC(CH3)2-CH=NO-CO-NHCH3
Aldicarb
B. N-Aryl Carbamates
1. ArNCO + ROH > Ar-NH-CO-OR
NH-CO-OCH2CECCH2C1
Barban
2. ArNH2 + C1CO-OR >ArNH-CO-OR
*-NH-CO-OCH(CH..)2
Propham (IPC)
Figure 14 - Synthesis of Some Carbamate Pesticides
31
-------
Dyrene
"9
NH
A
Cl
Simazi.ne
Cl
xk
Cl
C2H5NH IT NHC2H5
Cl
A
,H crflrXN.''Sffl -CH (CH, )
CH3SH
3'2
Atrazine
Cl " Cl
Cyanuric
Chloride
C2H5NH2 N Cl
(CH3)2CHNH2
Cl
(CH3)2CHNH ^' NHCH(CH3)2
Propazine
CH3Cfl
OCH,
"IT NHC(CH3)3
Terbutryne
SCH,
JL
(CH3)2CHNH XNX NHCH(CH3)2 . (CH3)2CH-MT^N^NHCH(CH3)2
Prometon Prometryne
SCH3
Ametryne
Figure 15 - Synthesis of Triazine Pesticides
32
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2. Pesticide formulations: The technical product or concentrate
produced by the prime manufacturer is usually converted into another form
that is both more effectively used as a pesticide and safer for the
applicator to use. The effectiveness of a pesticide is dependent upon
adequate distribution on the target. Applicator safety is largely dependent
on the toxicity of the material being used. These characteristics are
obtained by diluting the concentrated pesticide and converting it into a
conveniently usable formulation. Dusts, wettable powders, granules, emul-
sifiable concentrates, and aerosols are the formulations most commonly used.
In many cases, two or more active ingredients are used in a formulation to
increase its effectiveness and market potential.
The type of formulation manufactured for a specific application
is dependent on many factors. Cost and biological efficiency are the most
important.—' Other factors that must be considered are: (1) the biology
of the pest and host; (2) the host-pest -relationship; (3) the characteris-
tics of available production and application equipment; and (4) the toxic-
ity of the pesticide in relation to plants, animals, and humans.is/ Most
agricultural fungicides, for example, are formulated as wettable powders
rather than dusts or emulsifiable concentrates. This is true because emul-
sions are generally more expensive and more difficult to transport, fungi-
cides are less active in the solid than in the liquid state, and because
fungicides are often phytotoxic.il.', The solubility characteristics of the
pesticide may exclude liquid formulation even where it might be preferred
from an application viewpoint. Air milled wettable powers are frequently
more expensive than an emulsifiable concentrate.
a. Dusts; Dust is frequently the cheapest and simplest way
of applying pes tic ides.ij!/ Active ingredient concentrations are generally
low, 0.1 to 20%,I2/ thus making dust relatively low in toxicity. In recent
years, dusts have become less important than the other formulations because
of the dependence of dust on climatological factors that cause variable
performance as well as drift problems.!§/ They were formerly frequently
used for soil application and seed treatment.!^'
The physical properties of the dust formulation are largely
determined by the properties of the carrier used and the particle size to
which it is ground. Some of the more commonly used carriers are organic
flours, sulfur, silicon oxides, lime, gypsum, talc, pyrophyllite, bentonites,
kaolins, attapulgite, and volcanic ash. Selection of the carrier is criti-
cal, and is based on compatibility with the active ingredient, particle
size, abrasiveness, density, absorbability, wettability and cost.lZ/
33
-------
In some cases, it is necessary that a stabilizer be added
to the dust formulation.12' Hydrolysis of some organophosphate insecti-
cides in dust formulations, for example, can be inhibited by the use of
a stabilizer.
The dust may be formulated by simply mixing or by grinding
the ingredients in a hammer, impact, vertical roller, or fluid-energy
mill.—' Another method used is to dilute the active ingredient with a
volatile solvent, and then impregnating the carrier with this solution.
Some dusts are prepared in two stages.?_£/ The first stage involves the
mixing of the concentrated active ingredient with the carrier to form a
dust concentrate, generally containing more than 25% active ingredient.Ill'
The dust concentrate is convenient to transport and store before being
processed into a field strength dust.
b. Wettable powders; Wettable or water-dispersible powders
are mixtures of active ingredients, carriers, surface-active agents, and
adjuvants that can be suspended in water for application. Wettable powders
are formulated with a high active ingredient concentration, usually from
15 to 95%. A surface-active agent is usually added at 1 to 2% to improve
the wetting and suspendibility characteristics of the powder. The use of
wettable powders has been widely accepted where emulsifiable concentrates
are unavailable and because of their greater safety to plants in some
instances.iZ/
Wettable powders are formulated by processes similar to
those used for dust production. The carriers used are similar to those
for dust formulations, but are more stringently specified for bulk density
and flowability properties.!^./
c. Granules: Granular formulations are generally prepared
by the impregnation of the active ingredient on sized granular carriers
such as clay, vermiculite, bentonite, or diatomaceous earth.iZii2' The
size of the granule normally ranges from 30 to 60 mesh (250 to 590 (j, in
diameter). Liquid active ingredients can be sprayed directly onto the
granular carrier. Solid active ingredients are either melted before being
impregnated or applied as slurry.
Granules have advantages in aerial application in that they
can penetrate vegetation canopies, they avoid the problem of drift, and con-
trol of the rate of toxicant release can often be achieved by changing the
ingredients of the formulation. The size of the carrier granule, which can
be controlled in the manufacturing process, also influences the redistribu-
tion of the active ingredient under the influence of rainfall.—' This
formulation is used primarily for mosquito larvicides and soil applications.LL'
34
-------
The impregnation is normally accomplished by using ribbon
mixers or drum blenders.
d. Emulsifiable concentrates; Emulsifiable concentrates
are solutions of active ingredients and surface-active ingredients in
water-emulsifiable organic solvents. Active ingredient concentrations
generally range from 15 to 50%IZ/ for single pesticide formulations to
as high as about 8,0% in multiple active ingredient formulations. Surfac-
tants are normally used at a concentration of only a few percent, but are
sometimes required in concentrations greater than 5%.—'
The selection of the solvent to be used is based on many
factors, including solvency, specific gravity, flash point, safety to
plants and animals, volatility, compatibility, odor, corrosiveness and
cost. *•'**•*•' Some of the most commonly used solvents are kerosene, xylenes,
methyl isobutyl ketone, and amyl acetate.IZ' Xylene, heavy aromatic, and
aliphatic type solvents are produced by a number of the major oil companies
for use in insecticide formulations.?_L/
Emulsifiable concentrates are widely used for household
insect control as well as agricultural plant protection. An example of
an agricultural concentrate are the three-way blends of toxaphene, DDT,
and methyl parathion that were introduced in the late 1950's.2_l/ These
blends, referred to as 4-2-1 or 4-2-1/2, contain. 4 Ib toxaphene, 2 Ib DDT,
and 1 or 1/2 Ib of methyl parathion per gallon.
e. Aerosols: Aerosol formulations typically contain less
than 2% active ingredient in a solvent with small amounts of auxiliary
materials. The solvents used include a wide variety of organic materials,
such as refined kerosene, and water. Many unusual solvents have been used
in specialized aerosols, such,as o-dichlorobenzene in garbage can sprays
because of its odor-masking characteristic and isoparaffinic-base oil in
livestock facefly sprays for safety of the animals mucous membranes.22/
The auxiliary materials used include a host of special pur-
pose chemicals: Chlorbisan is used in some pet sprays to suppress odor,
copper oleate is added to some roach and ant sprays to prevent mildew.22/
A very important category of auxiliary materials is the synergist added
to increase the pesticidal properties of the active ingredient. Synergists
commonly used include piperonyl butoxide, sulfoxide, and propyl isomer.22^/
35
-------
The finished aerosol formulations are packaged with a pro-
pellant into various types of pressure packs, including true aerosols for
space treatment, plant sprays, pet sprays, and repellent sprays for per-
sonal use and for use on animals.z2J Propellants used are predominantly
mixtures of dichlorodifluoromethane and trichloromethane, al.though di-
chlorodifluoromethane is widely used as the sole propellant in pressurized
sprays designed to deposit residual insecticides. Methylene chloride,
methyl chloroform, N20, CC^, and No are also used to a lesser extent.
Aerosol formulations account for only a small fraction of
the active ingredients produced in the United States: 1 to 1.5 milli9n
poundsl^/ in aerosols versus about 1 billion pounds per.year total pesti-
cide production. However, pesticide aerosol accounts for almost 470 of
the aerosol containers packaged in the United States (see Figure 43, p. 208)
36
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REFERENCES
1. Frear, D. E. H., The Chemistry of Pesticides (3rd Edition), D. van
Nostrand Company, Inc., New York (1955).
2. Martin, H., Pesticide Manual (2nd Edition), British Crop Protection
Council, Worchester, England (1971).
3. Jacobson, M., and D. G. Crosby, Naturally Occurring Insecticides,
Marcel Dekker, Inc., New York (1971).
4. Metcalf, R. L., Organic Insecticides, Interscience Publishers,
New York (1955).
5. Kearney, P. C., and D. D. Kaufman, Degradation of Herbicides, Marcel
Dekker, Inc., New York (1969).
6. Report of the Secretary's Commission on Pesticides and Their Relation-
ship to Environmental Health, U. S. Government Printing Office,
Washington (1969).
7. "1964 U. S. Census of Agriculture," Vol. Ill, Part 5, U. S. Depart-
ment of Commerce, Bureau of the Census, May 1969.
8. Melnikov, N. N., Chemistry of Pesticides, Springer-Verlag, New York
(1971).
9. Herbicide Handbook, Weed Science Society of America, Urbana, Illinois
(1970).
10. Riemschneider, R., "The Chemistry of the Insecticides of the Diene
Group," World Review of Pest Control; Vol. 4, No. 29, pp. 29-61 (1963),
11. Shreve, N., Chemical Process Industries, McGraw-Hill Book Company,
New York (1967).
12. Faith, W. L., D. B. Keyes, and R. L. Clark, Industrial Chemicals,
(3rd Edition), John Wiley and Sons, Inc., New York (1965).
13. Sittig, M., Pesticide Production Processes, Noyes Development Corp.,
Park Ridge, New Jersey (1967).
14. Anon., "Pesticides: Present and Future," Chemical Engineering,
pp. 133-140, April 7, 1969.
37
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15. Forgeson, D. C., Fungicides. Vol. 1, Academic Press, New York (1967).
16. Coombs, G., "Pesticide Formulation," Agricultural Chemicals, Vol. 15,
No. 6, pp. 47-103 (1960).
17. Kirk-Othmer Encyclopedia of Chemical Technology, (2nd Edition), Vol.
II, Interscience Publishers, New York, pp. 731-732 (1966).
18. Winchester, J. M., "Future Developments in Pesticide Chemicals and
Formulations," Chemistry and Industry, January 27, 1968, pp. 106-108.
19'. Anon., "Formulation of Pesticides," Agricultural Chemicals. Vol. 15,
No. 3, pp. 35-38 (1960).
20. Personal Communication, Mr. Jack G. Copeland, Hercules, Inc., November
17, 1971.
21. Hersey, J., "Choosing a Solvent for Insecticide Formulations," Farm
Chemicals, pp. 42-46, October 1966.
22. Herzka, A., International Encyclopedia of Pressurized Packaging.
Pergamon Press, New York (1966).
23. Personal Communication, Mr. Don Gohlson, Cook Chemical Company,
November 9, 1971.
38
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III. PRESENT PRODUCTION VOLUMES AND SITES
Nearly 100 companies in the United States are engaged in the
production of pesticidal active ingredients and possibly as many as 500
are engaged in the varied aspects of formulating the active ingredients
into final products such as liquids, dusts, and packaged aerosol. The
total number of formulators and distributors of pesticides is said to be
about 1,800 companies. Data on the production volumes of these pesticides
and their formulations are almost completely unavailable on an individual
compound basis and those which are available leave much to be desired. The
basic source of pesticide data for years has been the U.S. Tariff Commission's
"Synthetic Organic Chemicals, United States Production and Sales," which
contains a two-page tabular summary on "Pesticides and Related Products."
This report, issued annually but 2 years after the subject year, is preceded
by a preliminary issue of the "Pesticides and Related Products" section of
about 10 pages which lists the manufacturing companies who reported pro-
duction of each synthetic organic pesticidal compound, in addition to the
tabular summary. The tabular data are categorized under cyclic and acyclic
with subdivisions of (a) fungicides, (b) herbicides and plant hormones,
(c) insecticides, rodenticides and fumigants and soil conditions, plus
general totals for benzenoid and nonbenzoid chemicals. Thus, the total
production of synthetic organic pesticides is listed as 1.03 billion pounds
in 1970.y
The major limitation of the tables is that no data on an individ-
ual pesticide is published unless three or more manufacturers report, because
the data are considered proprietary by the companies and are accepted in
confidence by the Tariff Commission. The data are reported for several
subcategories such as the aldrin-toxaphene group or the organophosphates,
but the "all other" group is invariably so large (e.g., almost two-thirds
of the total) as to make meaningful deductions extremely difficult.* In
addition, the Tariff Commission data consistently show sales volumes
(domestic and exports) of 15-25% less than production volume. v
The U.S. Department of Agriculture's Agricultural Stabilization
and Conservation Service issues annually—' "The Pesticide Review," which
tabulates certain data from the Tariff Commission together with supplemental
production data on inorganics and organics from the Bureau of Mines and
The situa'tion may be getting worse as the number of producers decrease;
for example, DDT now has only one producer and 2,4-D has only two,
so that specific production data on these pesticides will become un-
available after 1970.
39
-------
industry sources. It also includes import-export data from the Tariff
Commission and Bureau of Census, certain price, transportation and use
information, and a brief commentary on aspects and trends in pesticide
usage in agriculture. However, little significant new data on production
volumes of pesticides are given and, in fact, the USDA's total for "pesti-
cidal chemicals" varies unexpectedly from the Tariff Commission's "synthetic
organic pesticides" total: e.g., from 1.5% less than in 1968 to 2.6% more
than in 1969.
Certain commercial publications such as Chemical Week and Farm
Chemicals also maintain close observation of the pesticide industry and
frequently publish reviews and surveys which include forecasts (usually
in terms of sales dollars as in Figure 4). Several commercial market
survey organizations specialize in collecting this type of information and
offer it for sale to their clients. In addition, most if not all of the
major pesticide manufacturers have their own market intelligence organiza-
tions and systems. Consequently, these groups have their own estimates of
the total volume and distribution patterns of pesticides, but this infor-
mation is closely guarded and generally not accessible to persons outside
these organizations. Industry sources have at times revealed certain data,
such as that 29 insecticides were produced in amounts of over 1 million
pound each in 1968.—'
Several states have recently started to collect pesticide use
data. Among these, California probably has the most complete and advanced
system. The California State Department of Agriculture publishes quarterly
a "Pesticide Use Report"— which details the quantities of pesticides used
by product, crop or commodity treated, number of applications of each prod-
uct on each crop, and individual and total number of acres treated. Similar,
but less complete and less sophisticated pesticide use reporting systems
were initiated in the five Great Lakes States in 1969, following increasing
concern about the contamination of the Great Lakes. The Departments of
Agriculture in the states of Illinois,— Indiana, Michigan, Minnesota—'
and Wisconsin collect and publish annual information on the farm use of
pesticides in each state. However, this information is given in terms
of number of acres treated, but not in terms of quantities of specific pes-
ticides applied.
The preceding discussion makes clear that adequate data on the
production volumes and the distribution and use patterns of pesticides are
not available to the public. Scientists, regulatory officials, legislators,
and other members of the public have become increasingly concerned about the
unavailability of these data on these and all other hazardous materials.
This information is needed for an intelligent assessment of the actual and
potential impact of pesticides on the environment, for pinpointing problems
requiring research, regulatory or other special attention, for the
40
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establishment of meaningful monitoring programs, and for many other pur-
poses. These needs have recently been pointed out emphatically by the
"Panel on Monitoring Persistent Pesticides in the Marine Environment" of
the Committee on Oceanography, National Academy of Sciences.~U The Panel
recommends that the present legal obstacles to public access to chemical
production data be removed, and we concur.
A. Estimated Production of Major Pesticides
In view of the absence of complete and reliable data on pesticide
production volumes, intensive efforts were on this program to identify all
the major pesticides and to estimate production volumes of all of over 1 mil-
lion pounds per year. This extensive effort was made to satisfy the specific
request of the present contract for "quantitative information on production
of major pesticides in recent years," and because of our need for this
information in evaluating the pollution potential of the pesticide industry.
The following methods and sources were used in arriving at these
estimates. Published data were reviewed in the light of recent changes
and trends and our own experience to prepare a tentative list of pesticide
production volumes. Subsequently, during our personal interviews with
pesticide manufacturers in the field survey phase of this study, we advised
each company of our estimates for the production volume of its product(s)
and related products and invited comments. The comments were carefully
considered, along with many other factors which came to our attention, in
our preparation of our "final estimates."
Table II summarizes our estimates of the volume of production for
over 150 different pesticides in 1971. Special categories of pesticide data
which are provided by the government-=A=/ are production of wood preservatives
shown in Table III and the import-export figures shown in Tables IV and V,
respectively.
Table II does not include every pesticide that the U.S. Tariff
Commissioni-' says was produced in 1970 (see Table I). Some smaller products
have been lumped together in the small remaining "other products" categories
under each group of pesticides. Table II does include, we believe, all
major pesticides manufactured in the U.S., and most smaller products, in-
cluding many with a manufacturing volume of less than 1 million pounds per
year. This tabulation is the most complete and detailed compilation of the
estimated volume of pesticide production which will be available to the
public in the United States. We emphasize again that the majority of the
production volume figures are our estimates, and that these were arrived at
by the use of many different sources of information of varying degrees of re-
liability. While these estimates lack the authority which could be provided
by the Tariff Commission, they are the best available.
41
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TABLE II
ESTIMATED U.S. PESTICIDE PRODUCTION VOLUME, 1971
A. Herbicides (Including Defoliants and Plant Growth Regulators)
Principal Production
Common Name
Atrazine
2,4-D
MSMA-DSMA
Sodium chlorate
Trifluralin
Propachlor
Chloramben
Alachlor
CDAA
Bromacil
Nitralin
Dicamba
Diuron
Propanil
Butylate
2,4,5-T
N.A.
EPIC
Simazine
Dalapon
Fluometuron
Propazine
Maleic hydrazide
Dinoseb
Diphenamid
Trade Name
Manufacturer
Aatrex
Several
Several
Several
Treflan
Ramrod
Amiben
Lasso
Randox
Hyvar
Ciba-Geigy
Several
Several
Several
Elanco
Monsanto
Amchem
Monsanto
Monsanto
Du Pont
Planavin
Banvel-D
Karmex
Rogue; Stam F34
Sutan
Several
^ DBF
Eptam
Princep
Dowpon
Cotoran
Milogard
Several
Premerge
Dymid, Enide
Shell
Velsicol
Du Pont
Monsanto; Rohm & Haas
Stauffer
Several
Chemagro
Stauffer
Ciba-Geigy
Dow
Ciba-Geigy
Ciba-Geigy
Several
Dow
Elanco, Upjohn
N.A.
Silvex
Picloram
Cacodylic acid
Vernolate
Folex
Several
Tor don
Several
Vernam
Mobil
Several
Dow
Ansul
Stauffer
MM Ib A.I.S/
90
45
35
30
25
23
20
20
10
8
8
6
6
6
6
6
5
5
5
5
4
4
3
3
3
3
3
3
2
2
a/ MM = million; A.I. = active ingredient.
42
-------
TABLE II (Continued)
A. Herbicides (Including Defoliants and Plant Growth Regulators) (Concluded)
Trade Name
Common Name
Naptalam
Linuron
Norea
TEA
DC PA
Endothall
Chlorpropham
Subtotal, 3% herbicides of
> 1 MM Ib production volume each
Principal
Manufacturer
Alanap
Lorox
Herban
Trysben
Dacthal
Aquathol
Several
Uniroyal
Du Pont
Hercules
Du Pont
Diamond
Pennwalt
PPG
Production
MM Ib A.I.
2
2
2
2
2
2
2
408
Acrolein
N.A.
Amitrole
N.A.
Barban
Benefin
Bensulide
CDEC
Chlorbromuron
Chlorboxuron
Cycloate
Diallate
Fenuron
Fluorodifen
Molinate
Monuron
Pebulate
Siduron
Terbacil
Terbutol
TCA
Triallate
Aqualin
Animate
Several
Bandane
Carbyne
Balan
Betasan, Prefar
Vegadex
Maloran
Tenoran
RoNeet
Avadex
Dybar
Preforan
Or dram
Telvar
Tillam
Tupersan
Sinbar
Azak
Several
Avadex BW, Far -Go
Shell
Du Pont
American Cyanamid
Velsicol
Gulf
Blanco
Stauffer
Monsanto
Ciba-Geigy
Ciba-Geigy
Stauffer
Monsanto
Du Pont
Ciba-Geigy
Stauffer
Du Pont
Stauffer
Du Pont
Du Pont
Hercules
Dow
Monsanto
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
<_1
Subtotal, 22 listed herbicides of
< 1 MM Ib production volume each
All other herbicides
Total, All Herbicides
15
5
428
43
-------
TABLE II (Continued)
B. Synthetic Organic Insecticides, Miticides, Nematocides
Common Name
Toxaphene
DDT
Carbaryl
Methyl parathion
Malathion
Chlordane
Parathion
Aldrin
Methoxychlor
Diazinon
Carbofuran
Disulfoton
Phorate
Heptachlor
N.A.
N.A.
Dicofol
Azinphos -methyl
Fensulf othion
Methomyl
N.A.
Ethion
Ronnel
Car bo ph en othion
Naled
Dimethoate
Aldicarb
Endosulf an
Chlorobenzilate
Crufomate
Trade Name
Several (incl.
Strobane-T)
Several
Sevin
Several
Cythion
Several
Several
Several
Several
Spectracide
Furadan
Di-Syston
Thimet
Several
Bux
Dursban
Kelthane
Guthion
Dasanit
Lannate
Dyfonate
Nialate
Korlan
Trithion
Dibrom
Cygon
Temik
Thiodan
Several
Ruelene
Chemical
Group3.'
CH
CH
CA
OP
OP
CH
OP
CH
CH
OP
CA
OP
OP
CH
CA
OP
CH
OP
OP
CA
OP
OP
OP
OP
OP
OP
CA
CH
CH
OP
Principal
Manufacturer
Hercules, Tenneco
Montrose
Union Carbide
Monsanto
American Cyanamid
Velsicol
Monsanto
Shell
Du Pont
Ciba-Geigy
FMC
Chemagro
American Cyanamid
Velsicol
Ortho
Dow
Rohm & Haas
Chemagro
Chemagro
Du Pont
Stauffer
FMC
Dow
Stauffer
Ortho
American Cyanamid
Union Carbide
FMC
Ciba-Geigy
Dow
Production
MM Ib A.I.
50
45
45
45
35
25
15
10
10
10
8
8
8
6
6
5
4
4
4
3
3
3
3
2
2
2
2
2
2
2
Subtotal, 30 insecticides of
> 1 MM Ib production volume each
368
§_/ CH = chlorinated hydrocarbon.
OP = organophosphate.
CA = carbamante.
44
-------
TABLE II (Continued)
B. Synthetic Organic Insecticides, Miticides, Nematocides (Concluded)
Common Name
N.A.
Coumaphos
Fenthion
Dioxathion
Dichlofenthion
Thionazin
^-Dichlorvos
Oxydemeton-me
— Mevinphos
^Phosphamidon
- Dicrotophos
"^Monocrotophos
N.A.
TEPP
N.A.
Dieldrin
Endrin
Lindane
N.A.
Chloropropylate
N.A.
Binapacryl
Trade Name
Abate
Co-Ral
Bay t ex
Delnav
VC-13
Zinophos
DDVP
Meta-Systox-R
Phosdrin
Dimecron
Bidrin
Azodrin
Aspon
Several
Mocap
Several
Several
Several
Mirex
Acaralate
Omite
Morocide
Chemical
a/
Group—
OP
OP
OP
OP
OP
OP
OP
OP
OP
OP
OP
OP
OP
OP
OP
CH
CH
CH
CH
CH
MI
MI
Principal
Manufacturer
American Cyanamid
Chemagro
Chemagro
Hercules
Mobil
American Cyanamid
American Cyanamid
Chemagro
Shell
Ciba-Geigy
Shell
Shell
Stauffer
Several
Mobil
Shell
Shell
Hooker
Allied Chemical
Ciba-Geigy
Uniroyal
FMC
Production
MM Ib A.I.
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
<_1
Subtotal, 21 listed insecticides of
< 1 MM Ib production volume each
15
All other synthetic organic insecticides, miticides, nematocides 10
Total, All Synthetic Organic Insecticides, Miticides, Nematocides 393
45
-------
TABLE II (Continued)
C. Botanical, Biological, and Inorganic Insecticides;
Attractants, Repellents and Synergists
Common Name
Type
Trade Name Product
Botanical and Biological Insecticides
Bacillus thuring.
Polyhedr. virus
Pyrethrins
Rotenone
Nicotine
Inorganic Insecticides
Pb-arsenate
Ca-arsenate
Dipel
Viron H
Several
Several
Black Leaf
Several
Several
Attractants, Repellents, Synergists
DEET
Piperonyl butoxide
Ethyl hexandiol
N.A.
Trimedlure
N.A.
Heliotropin acetal
Several
Several
6-12
MGK-326
Rep
Syn
Rep
Rep
N.A.
MGK-264
Tropital
Att.
Syn.
Syn.
Other Attractants, Repellents, Synergists
Total, All Products
Principal
Manufacturer
Abbott, Nutrilite
IMC
FMC, MGK
Several
Chem. Form.
Several
Several
Several
FMC
Union Carbide
MGK
Universal Oil
MGK
MGK
Production
MM Ib A.I.
1
< 1
< 1
< 1
< 1
6
2
1
1
< 1
< 1
< 1
< 1
< 1
13
Special Category
Petroleum oils including synthetic spray oils, deodorized
kerosene, and other petroleum distillates used as
diluents and carriers
a/
a/ No date available; possibly 1 billion pounds or more.
46
-------
TABLE II (Continued)
D. Fungicides
Common Name
PCP and salts
Dithio-carbamates
TCP and salts
Captan
PCNB
Dodine
Captafol
Folpet
Cu-naphtenates
Subtotal, 9 listed fungicides
>1 MM Ib production volume each
Trade Name
Several
Several
Several
Orthocide
Several
Cyprex
Difolatan
Phaltan
Several
Principal
Manufacturer
Several
Several
Dow
Stauffer
Olin
American Cyanamid
Ortho
Stauffer
Several
Production
MM Ib A.I.
461/
; 40^
20
18
3
3
2
2
2
136
Aminobutane
Benomyl
Chloroneb
DCNA
Dinocap
DMTT
Glyodin
Tetra-CP
Hg-salts
Several
Benlate
Demosan
Botran
Karathane
Dazomet, Mylone
Glyodin
Several
Several
Elanco
DuPont
DuPont
Upjohn
Rohm & Haas
Several
Union Carbide
Dow
Mallinckrodt
Subtotal, 9 listed fungicides
<1 MM Ib production volume each
All other synthetic organic fungicides
Total, all Above Products
Inorganic Sulfur and Sulfides
Inorganic Copper Salts
Total, all Fungicides
7
_J2
145
150
_2£/
297
a/ Includes use as herbicide, desiccant, molluscicide and for termite con-
trol (see Table III).
b/ Includes CDEC, Dithane M-45®, Dithane S-31®, Ferbam, Maneb, Metham, Na-
bam, Niacide®, Polyran®, Thiram, Zineb and Ziram.
£/ Published data are extremely unreliable, e.g., 45 MM Ib in Ref. 2.
47
-------
TABLE II (Concluded)
E. Rodenticides, Molluscicides, Fumigants, Soil Conditioners, etc.
Common Name
Trade Name
Principal
Manufacturer
Production
MM Ib A.I.
Rodenticides
Warfarin
Dipacinone
Norbormide
Pindone
ANTU
Na-fluoracetate
Several
Diphacin
Raticate
Pival
Several
Several
Several
Nease
Pitman-Moore
Several
Penick
Aceto
12
Molluscicides
Metaldehyde
Several
Comm. Solvents
Fumigants (Soil, Stored Product, Structural, and Household)
Methyl bromide Several
DBCP Several
Other acyclic organics
dichloro-propene- I D-D, Nemex, I
propane mixturesj Vidden D, TeloneJ
carbon disulfide
carbon tetrachloride
ethylene dichloride-
dibromide > Several
chloropicrin
formaldehyde
•and others
Dichlorobenzene Several
Napthalene Several
Inorganic fumigants Several
Several
Several
Dow, Shell
Soil Conditioners
Polyacrylonitrile
Other soil conditioners
N.A.
Several
Several
Several
Several
American Cyanamid
Total, all Rodenticides, Molluscicides, Fumigants,
Soil Conditions, etc.
a/ Excludes nonfumigant use.
b_/ Includes moth-proofing and lavatory-space deodorant use,
48
<1
22
10
75a/
10
200
-------
TABLE III
UNITED STATES USAGE OF WOOD PRESERVATIVES, 1965-69-
2/
Kind of
•Preservative
1967
1968
1969
Liquids
Creosote
Petroleum
Coal tar
Total
1,000
147,594
73,661
20.082
241,337
1,000
136,799
73,588
20.469
230,856
.1,000, :
gal.
128,226§./
68,071
19.618
215,915
Pentachlorophenol
Tanalith<§k/ (Wolman Salts®)
Chromated zinc 0'
Acid copper chromate
Osmosalts<§£.'
Chromated copper arsenate£jj/
Other
Solids
1,000
Ib
'.. f
24,814
3,922
1,664
1,405
1,419
2,330 .
1.281
1,000
Ib
26,389
2,683
1,526
1,139
1,288
3,215
1 . 554
1,000
Ib
25,542
3,067
1,384
872
1,472
4,668
1.050
Total
36,835
37,794
38,055
a/ Estimate 1 billion pounds, 1971.
b/ Mixture of Na2Cr04 (37.5%), NaF (257.), Na2HAs06 (25%) and Dimitrophenol
(12.5%).
c_/ Includes copperized.
d_/ Includes fire retardant use.
e_/ Apparently similar to Tanalith.
f_/ Includes Boliden Salts© which contain arsenic, chromium, and zinc.
49
-------
TABLE IV
UNITED STATES IMPORTS OF SYNTHETIC ORGANIC PESTICIDES. 1965-69J/
Pesticide^
Chloranll
Copper 8-quinollnolate
Dexon®
Dichlone
Oxycarboxln (Plantvax®)
Pentachloronltrobenzene
Thlrara
2,4,5-Trlchlorophenol
Bromoxynil
Chloroxuron
Dlchlobenil
2,4-D
Dinltrocresol
Dlchlorprop
Dlquat dibromlde
loxynll
Maleic hydrazlde
MCPA
MCPB
Mecoprop
Neburon
Nitrofen
Paraquat-'
Phenmedlpham (Betanol®)
Metobromuron
Preforan®
Pyrazon
2.4.5-T
Aldrin
Propoxur (Baygon®)
Bromophos
Dlcofol
Dieldrln
Llndane
Malathlon
Methyl parathlon
Oxythloqulnox (Morestan®)
Parathlon
Plperonyl butoxlde
Fenttrothlon (Sumithion®)
Zlnophos
ANTU
Pindone
Warfarin
p-Chloro-m-cresol
Hexachlorophene
1967
(lb)
130,870
47,600
14,062
36,574
0
30,000
110,538
71,060
58,000
165,380
0
2,805,354
42,952
604,160
107,670
0
0
141,736
40,318
120,406
40,000
0
1,033,525
0
110
0
111,039
25,904
212,082
33,069
0
0
0
0
0
126,765
0
20,944
11,464
4,409
31,416
2,000
0
11,308
42,519
88,184
1968
(lb)
Fungicides
103,410
7,071
31,923
172,758
0
20,000
107,001
79,261
Herbicides
40,240
145,502
0
2,473,578
55,040
535,563
374,100
3,300
0
0
39,352
156,055
64,092
22,046
1,663,683
0
24,967
0
144,472
315,556
Insecticides and Mttlcldes
0
172,777
0
0
0
0
551
0
0
0
0
0
0
Rodentleides
3,637
210
1,241
Other
72,508
0
1969
(lb)
110,109
1,000
11,243
148,079
10,250
132,400
0
0
65,280
0
34,888
0
6,400
525
744,318
0
3,307
104,107
0
312,627
60,036
0
2,945,619
48,505
49,714
82,407
103,040
45,418
0
83,100
199,956
4,564
12,885
0
466,291
0
40,265
0
0
11,022
0
5,676
0
10,420
28,347
150,321
a/ Minor items not shown.
b_/ Includes dlchlorlde and bis (methyl sulfate).
c_/ MRI estimate for 1971: 1 million pounds.
50
-------
TABLE V
UNITED STATES EXPORTS OF PESTICIDES. 1968-69J/
Volume
Export Grouping
Inorganic fungicides, tech-
Organic fungicides, tech
Fungicide formulations^/
Total
Inorganic herbicides, techc/
2,4-D and 2,4,5-T tech. acid basis!/
Other organic herbicides, tech
Herbicide formulations^/
Total
Inorganic insecticides, tech!/
DDT, tech
DDT, 20-74%, 100% basis
DDT, 75%, plus, 100% basis
Other polychlor insecticides, tech&/
Other polychlor formulations
Organic phosphorus insecticides, tech
Organic phosphorus formulations
Other organic insecticides, tech
Other organic formulations
h/
Household and industrial formulations-
Total
Organic rodenticides, tech
Disinfectants, tech
Disinfectant formulations
Dips, growth regulators
Organic fumigants
Total
Grand Total
1968
1.000 Ib
1,855.0
5,480.2
30.294.2
37,629.4
2,325.3
3,391.0
20,822.1
46.326^8
72,865.2
322,523.3
604.5
4,077.2
6,046.5
3,959.4
24J.06.J.
38.793.7
471,811.6
Fungicides
Herbicides
Insecticides
Other
1969
1.000 Ib
6,255.9
5,017.7
24.974.1
36,247.7
2,870.4
7,287.1
27,564.5
31.759.7
69,481.7
2,276.8
38,998.0
6,923.8
63,226.4
67,532.8
8,683.5
56,146.8
7,672.4
29,821.2
32,489.5
8.752.1
5,466.7
27,900.7
5,554.8
48,621.5
30,198.6
14,697.8
57,157.0
7,738.4
25,615.6
17,068.9
10.519.5
250,539.5.
396.1
3,819.7
5,956.0
5,669.0
37.274^0
53.114.8
409,383.7
a_/ Includes copper sulfate, sulfur, etc.; see next footnote.
b/ Includes conditioned sulfur dust and sulfur pastes, precipitated, colloidal, and flowers of
sulfur are not shown.
c_/ Includes sodium arsenite.
d/ Includes technical salts and esters on acid basis.
e/ Includes calcium cyanamide for weed control and defoliation.
f_/ ' Includes calcium arsenate and lead arsenate; also inorganic fumigants and rodenticides.
g_/ Includes technical BHC and paradichlorobenzene.
h_/ Includes repellents and rodenticide preparations.
51
-------
The production data shown in Tables II and III show that the pes-
ticide market is dominated by a small number of major products, while a
large number of minor products compete for a small share of the market. By
far the largest pesticidal class of ingredients used is the petroleum oils
of all types, including the synthetic and refined oils used as insecticidal
spray oils, the diluent and carrier oils used for thousands of formulations,
and the 0.5 billion pounds per year used as wood preservative. The next
largest product is the general purpose wood preservative, creosote, for
which production is about 1 billion pounds per year. However these products,
along with the 160 million pounds per year of coal tar and other products,
used as wood preservatives do. not appear to be of major concern as environ-
mental pollutants (although more study of their effects is obviously needed)
and will not be considered further here.
Based on the data in Table II the total pesticide production in
the United States is about 1.344 billion pounds per year, excluding the
petroleum and coal products. Of the synthetic organics, six products are
produced in amounts of 45 million pounds per year or more. These are: the
agricultural herbicide a'trazine; the insecticides DDT; toxaphene, carbaryl
and methyl parathion; the herbicide 2,4-D used agriculturally, on rights of
way, etc.; and the wood preservative and herbicide pentachlorophenol. (Di-
chlorobenzene also falls in this production category, but the use breakdown
between moth control and lavatory-space deodorant is uncertain.) These six
products account for over 25% of the total volume of pesticide production.
'• I '•.'•:'
Nine herbicidal products are produced in amounts, of .over 10 million
pounds per year and have a combined total production of 298 million pounds
per year. Ten insecticides are in the 10 million pounds per year class and
account for 290 million pounds per year. Five fungicides or classes of
fungicides (inorganic sulfides, pentachlorophenol and salts, trichlorophenol
and salts, the dithiocarbamate group, and captan) are over the 10 million
pounds per year mark and account for a total of 274 million pounds per year.
These 24 product groups have a combined production volume of 862 million
pounds per year or about 64% of the total for all pesticides.
The remaining 26% of production is divided between about 250 other
pesticides, of which 133 are listed in Table II. Some 65 to 75 of these are
estimated to have production volumes of over 1 million pounds per year each,
and about 60 are produced in less than 1 million pounds per year quantities
but are sufficiently important that they were included in Table II.
A further summary of the major herbicides, insecticides and fungi-
cides is given in Table IV. For the 135 specified products or groups of
products the average production volume is 7.4 million pounds per year and is
about the same for all three classes.
Further information and comment on the production and use of 22
major pesticides are given in Chapter IV.
52
-------
u>
TABLE VI
SUMMARY OF PRODUCTION VOLUMES OF SELECTED HERBICIDES. INSECTICIDES. AND FUNGICIDES
~ Number of Products by Production Volume Total No. of Production Volume (MM
Pesticide . Ranges (MM Ib) Specified
Group > 45 < 45-25 < 25-10 < 10-5 < 5-1 <1 Products
Herbicides*/ 1 4 4 11 17 22 59
Insecticides^/ 3 3 4 6 , , • 15 25 58
Fungicides-'' 02 2 0 5 9 18
Total 4 11 10 17 37 56 135
Specified Unspecified
Products Products
423 5
393 10
143 2
959 17
Ib)
All
Products
428
403
145
976
a/ Including defoliants and plant growth regulators.
b_/ Including organic, inorganic, and biological insecticides; excluding attractants, repellents, synergists; rodenticides,
molluscicides, fumigants, and soil conditioners.
c/ Considering the dithiocarbamate as a single product, and counting pentachlorophenol as primarily a. fungicide, but
excluding sulfur, inorganic Cu and other salts.
-------
B. Geographical Location of Producers and Transportation Patterns
The location of the production sites for pesticides is to a con-
siderable degree influenced by the proximity to raw materials and to major
use areas for specific products, and also by the existing plant facilities
which a company has when production of a new product is being planned. Thus,
the production sites are clustered in several centers including: the New
York-New Jersey area; the Baltimore-Wilmington area; West Virginia; the
Cleveland-Detroit area; the Chicago area; St. Louis-Kansas City area; New
Orleans-Alabama area; the Houston area; Los Angeles area; and the San
Francisco Bay area, as shown in Figure 16. The major production sites by
company are listed in Table VII. The distribution of major pesticide*
production volume is shown in Figure 17.
The transportation routes for the major pesticides show wide
variation. For DDT, for example, the only production site is in the Los
Angeles area, but the only major domestic use, at present, is in the cotton
states of the South (see Figure 6, p.23). On the other hand, toxaphene
which is used extensively also on Southern cotton is produced in Georgia
and trifluralin which is used extensively on Midwestern soybeans (see Figure
7, p. 24), is produced in Indiana. In general, products which have the longer
distribution routes probably are transported more often as active ingredients
or concentrates and formulated to more dilute levels nearer to the use areas,
but practices vary widely and many newer plants include formulation facilities,
Major pesticides refer here to the 22 pesticides selected as representatives
in Chapter IV.
54
-------
Figure 16 - Locations of Pesticide Production Plants
-------
TABLE VII
MAJOR PESTICIDE PRODUCTION SITES
Company
Abbott Laboratories
Aceto Chemical Company
Alco Chemical Corporation
Allied Chemical Corporation
American Cyanamid Company
Amchem Products, Inc.
American Potash & Chemical Company
(Subsidiary, Kerr-McGee Corporation)
Ansul Chemical Company
Arapahoe Chemicals Division, Syntex
Berkeley Chemical Department,
Millmaster Chemical Company
Buckman Labs, Inc.
Chemagro Corporation
Chemical Formulators, Inc.
Chemical Insecticide Corporation
Chevron Chemical Company, Ortho Division
Chipman Division, Rhodia, Inc.
W. A. Cleary Corporation
Commercial Solvents Corporation
Diamond Shamrock Corporation
Dow Chemical Corporation
E. I. du Pont de Nemours & Company
Production Site
North Chicago, Illinois
Flushing, New York
Whiteford, Maryland;
Hanover, Pennsylvania
Baltimore, Maryland;
Marcus Hook, Pennsylvania;
Carteret, New Jersey
Warners, New Jersey
Ambler, Pennsylvania;
Freemont, California;
St. Joseph, Missouri
Los Angeles, California;
Hamilton, Mississippi
Marionette, Wisconsin
Berkeley Heights, New Jersey
Memphis, Tennessee
Kansas City, Missouri'
NitroV' Wes't Virginia:' '
Metuchen, New Jersey1'
Perry Ohio;
Fort Madison, Iowa;
Richmond, California
Portland, Oregon
New Brunswick, New Jersey
Terre Haute, Indiana;
Agnew, California
Newark, New Jersey;
Des Moines, Iowa;
Greens Bayou, Texas;
Curtis Bay (Baltimore), Maryland
Midland, Michigan;
Freeport, Texas;
Pittsburg, California
East Chicago, Indiana;
Deepwater, New Jersey;
Linden, New Jersey;
La Porte, Texas;
Belle, South Carolina
56
-------
TABLE VII (Continued)
Eli Lilly & Company
Blanco Products Division
Fairmont Chemical Company
F.M.C. Niagara Chemical Division
GAF Corporation, Chemical Division
Geigy Agricultural Chemicals Division
of CIBA-Geigy
Glenn Chemical Company, Inc.
Gordon Corporation
Great Lakes Chemical Corporation
Gulf Chemical Division of Gulf Oil
Corporation
Guth Chemical Corporation
Hercules, Inc.
Imperial, Inc.
International Minerals & Chemical
Corporation
Mallinckrodt Chemical Works
McLaughlin Gormely & King Company
Merck & Company, Inc.
Michigan Chemicals Corporation
Mobil Chemical Company Division
Mobil Oil
Monsanto Company
Montrose Chemical Corporation
Morton Chemical Company
Motomco, Inc.
Indianapolis, Indiana;
Lafayette, Indiana
Middleport, New York;
Baltimore, Maryland
Linden, New Jersey;
Texas City, Texas
St. Gabriel, Louisiana;
Mclntosh, Alabama;
Summit, New Jersey
Chicago, Illinois
Kansas City, Missouri
El Dorado, Arkansas
Pittsburg (Jayhawk), Florida
Hillside, Illinois
Brunswick, Georgia
Shenandoah, Iowa
St. Louis, Missouri;
Jersey City, New Jersey
Minneapolis, Minnesota
Rahway, New Jersey;
Hawthorne, New Jersey
St. Louis, Michigan
Richmond, Virginia;
Mount Pleasant, Tennessee;
Charleston, South Carolina
St. Louis, Missouri;
Anniston, Alabama;
Lauget (E. St. Louis), Illinois;
, Nitro, West Virginia;
Muscatine, Iowa;
Luling, Louisiana
Torrance, California
Clark, New Jersey
57
-------
TABLE VII (Continued)
Nease Chemical
Niklor Chemical Company, Inc.
Nutrilite Products, Inc.
Nor-Am Agricultural Products, Inc.
Occidental Chemical Company
Olin Corporation, Agricultural Division
Ott Chemical Company
Penick Division, CPC International, Inc,
Pennwalt Chemicals Corporation
Pfizer, Inc.
Phelps Dodge Refining
PPG Industries
Prentiss Drug & Chemical
Reichold Chemicals, Inc.
Riverdale Chemical Company
Roberts Chemicals
Rohm & Haas Company
Shell Chemical Company
Shepard Chemical Company
Sabin Chemical, Inc.
Sanford Chemical Company
Stauffer Chemical Company
Tenneco Chemicals, Inc.
State College, Pennsylvania;
Salem, Ohio
Long Beach, Ca/lifornia
Lake View, California
Chicago, Illinois
Mclntosh, Alabama;
Rochester, New York;
Little Rock, Arkansas
Montville, New Jersey;
Lyndhurst, New Jersey;
Wyandotte, Michigan
Greensboro, North Carolina
Barberton, Ohio
Newark, New Jersey
Tuscaloosa, Alabama;
Tacoma, Washington
Chicago, Illinois
Nitro, West Virginia
Ambler, Pennsylvania;
Bristol, Pennsylvania
Martinex, California;
Norco, Louisiana;
Denver, Colorado;
Mobile, Alabama;
Deer Park, Texas;
San Ramon, California
Niagara Falls, New York
Port Neches, Texas
Perry, Ohio;
Richmond, California
Mount Pleasant, Tennessee;
Bucks, Alabama;
Henderson, Nevada;
Ardsley, New York
Elizabeth, New Jersey;
Long Beach, California
58
-------
TABLE VII (Concluded)
Thompson-Hayward Chemical Company
Troy Chemical Company
Tull Chemical Company
Union Carbide Corporation
Uniroyal Chemical Division, Uniroyal
Universal Oil Products Company
Upjohn Company
Vanderbilt Chemical Corporation
Velsicol Chemical Corporation
Vineland Chemical Company
Vulcan Materials Company Chemical
Division
Wilco Chemical Company, Inc.
Wood Ridge Chemical Corporation
Wyandotte Chemical, Division BASF
Kansas City, Kansas;
New Orleans, Louisiana;
Brea, Ohio
Newark, New Jersey
Oxford, Alabama
Institute, West Virginia;
South Charleston, West Virginia
Gastonia, North Carolina;
Geismar, Louisiana;
Naugatuck, Connecticut
Kalamazoo, Michigan;
North Haven, Connecticut
Bethel, Connecticut
Marshall, Illinios;
Bayport, Texas;
Memphis, Tennessee;
Chattanooga, Tennessee
Vineland, New Jersey
Wichita, Kansas
59
-------
Figure 17 - Production Distribution for 22 Major Pesticides
-------
LITERATURE REFERENCES
1. United States Production and Sales of Pesticides and Related Products,
1970, Preliminary, United States Tariff Commission, Washington, D.C.,
September 1971.
2. Fowler, Lee D., and Harold H. Shepard, The Pesticide Review 1970, U.S.
Department of Agriculture, Agricultural Stabilization and Conservation
Service, Washington, D.C., 1971.
3. Copeland, Jack G., Statement, "Federal Environmental Pesticide Control
Act," U.S. Congress 92nd, 1st Session, Senate Committee on Agriculture
and Forestry, Hearings before the Subcommittee on Agricultural Research
and General Legislation, U.S. Government Printing Office, Washington,
1971.
4. "Pesticide Use Reports" (Published Quarterly), Department of Agriculture,
Sacramento, California.
5. Illinois Agricultural Statistics/Pesticide Use by Illinois Farmers,
1970, Illinois Cooperative Crop Reporting Service, Illinois Department
of Agriculture and U.S. Department of Agriculture, Bulletin 71-3, 1971.
6. General Farm Use of Pesticides, 1.970, Minnesota and Four Other Great
Lakes States, Minnesota Department of Agriculture and State-Federal
Crop and.Livestock Reporting Service, 1971.
7. "Chlorinated Hydrocarbons in the Marine Environment," Report by the
Panel on Monitoring Persistent Pesticides in the Marine Environment,
Committee on Oceanography, National Academy of Sciences, Washington,
D.C., 1971.
61
-------
IV. MODERN MANUFACTURING METHODS
The number of pesticides produced in the United States is so
large that a complete study of the pollution aspects of the production
of all of them could not be undertaken under the time requirements of the
present program. Therefore, the approach adopted was to select approxi-
mately 20 or so key pesticides which would be truly representative of the
industry and to make an intensive study of the pollution aspects of their
production, transportation, formulation, and marketing. This intensive
study approach included plans to visit with knowledgeable company repre-
sentatives for each of the key pesticides and to visit the actual produc-
tion plants wherever permitted.
A. Criteria for Selection of Pesticides for Case Studies
Extensive efforts were made to select the key pesticides so that
they would be representative of the environmental pollution potential of
all pesticides in use. Our consultants Dr. L. E. Cronin and Dr. Gordon
Guyer were instrumental in this selection process. Important criteria of
production, use, and environmental properties included:
1. Production volume (current and projected).
2. Chemical class of pesticide (chlorinated hydrocarbon, organo-
phosphate, botanical, microbiological, inorganic, etc.).
3. Pesticide class (herbicide, insecticide, fungicide, etc.).
4. Use class (corn, cotton, soybeans, vegetables, public health,
right-of-way, etc.).
5. Method of application (fumigant, etc.).
6. Chemical and physical properties (including persistence and
accumulation tendencies in the environment).
7. Biological properties (including specificity and biomagnifi-
cation).
8. Nontarget toxicity (to invertebrates, birds, fish, and
mammals).
9. Concern (public or legislative and special health aspects,
e.g., mutagenic, teratogenic).
62
-------
Data for categories 1-9 have already been indicated in Tables II,
III, and VI. Toxicity data (mammalian I^Q'S) are given in Appendix A for
a number of pesticides. Further considerations and ratings for about 60
major pesticides or classes of pesticides were made with the results* in-
dicated in Table VIII.
B. Summary of Classes, Producers, Production, Formulations, and Use
Patterns for Case Study Pesticides
On the basis of the considerations in Section IV-A, 22 key pesti-
cides were selected for intensive study. A brief summary of the pesti-
cidal use class and chemical class of these 22 pesticides is given in
Table IX. A summary of the producers and production sites is given on
p. 72. Tables X, XI, and XII summarize for these 22 products estimated
1971 production volume; formulation site (at manufacturing site or away
from it); formulations; major uses; and major areas of use, broken down
by five geographical regions of the U. S., U. S. total, and export. These
22 "intensive study" products account for a combined production volume of
about 540 million pounds or about 58% of the total U. S. pesticide produc-
tion.
We estimate that a combined total of about 110 million pounds of
these products is exported. DDT has by far the highest export percentage,
i.e., about>70% of the total U. S. production. Approximately one-half of
the total U. S. production of carbaryl is also exported. Other products
of which major quantities are exported include toxaphene, methyl parathion,
and malathion. The export of 2,4-D and 2,4,5-T products for military pur-
poses has declined greatly.
Formulation practices by different manufacturers vary, depending
on marketing policies. Some companies sell primarily technical active
ingredient to formulators who formulate it, alone or with other active
ingredients, into products which are marketed under the formulator's label
and brand name. In other instances, the basic manufacturer formulates his
product(s) himself and distributes and sells it under his own label and
brand name. There are many other patterns of formulating, labeling, and
product identification and control between these two extremes.
Ratings in Table VIII are on a relative scale with each dot representing
a higher level of the property shown. A blank space does not neces-
sarily represent the lowest level, however, but may reflect a lack of
data available to the project team and consultants at the time of
making the ratings.
63
-------
TABLE VIII
PESTICIDE RATINGS
Actidione
Aldrin • |
Amiben
Acrolein (Aqualin)
Arsenic Compounds
BHC
Bidrin
Calcium Arsenate
Captan
Carbamate
Chlordane
Copper Sulfate
Cyanide
Diazinon
.j ^jj
DDT
DDVP
Delnav
Dieldrin
Disulfoton (Di-Syston) .
Endrin
SPH
3uthion (Azinphosmethyl)
I '
Volume
Present
....
Potential
...
•'
II
Chemical
and
Physical
Properties
Persistent
•«
....
Phasophile
1
..
••
••
III
Biological
Properties
Wide Spectrum
'.' r
"
...
Magnified
*
IV
Toxicity
Invert-
w
•H
CP
..
....
'
.c
to
•r-t
..
....
Mammal
•«
...
...
....
...
...
Human
- - .-
V
Concern
Recommend
...
...
I'opular
...
64
-------
TABLE VIII (Continued)
Heptachlor
Lead Arsenate
Lindane
Malathion
Methyl Bromide
Mercury Fungicides
Methyl Parathion
Mirex
Parathion .
Pentachlorophenol (PGP)
Mevinphos (Phosdrin)
Nitralin (Planavin)
Pyrethrura
Ramrod
Carbaryl (Sevin)
Sodium Arsenate
Sodium Chlorate
Sodium ELuoroacetate (1080)
Strobano
Strychnine
Demeton (Systox)
TEPP
Phorate (Thimet)
Toxaphene
I
Volume
.p
c
0)
03
<0
£
••
...
H
cd
•H
-p
s
+>
£
...
...
II
Chemical
and
Physical
Properties
$
CJ
-p
w
w
fc
QJ
&4
0>
H
X!
a
0
w
1
OM
1
,
•
in
Biolocical
Properties
e
2
+>
o
CJ
o.
CO
'o
•d
>H
s
I
Tf
>(U
'«
•iH
C
M
s
TV
• • Toxicit
+>
M
(U
§
H
I
••
.
-H
FQ
,
J3
U
•H
f
H
1
v
••
fi
a
••
....
V
Concern
s
o
0
0
K
...
h
cd
H
3
a
8.
65
-------
TABLE VIII (Concluded)
Zinc Phosphide
Zinophos
Amitrole
Atrazine
2,4-D
Dinitro Compounds
2,4,5-T
Picloram (Tordon)
Trifluralin (Treflan)
I
Volume
c
(U
W
-------
TABLE IX
USES AND CLASSES OF SELECTED PESTICIDES
Pesticidal Use Class
Chemical Class
Selected Pesticides
Alachlor (Lasso)
Aldicarb (Temik)
Aldrin-Dieldrin
Atrazine
B. thuringiensis
Captan
Carbaryl (Sevin)
Chlordane
2,4-D
DDT
Disulfoton
Malathion
Mercury Fungicides
Methyl Bromide
Methyl Parathion
Parathion
Phorate (Thimet)
Pyrethrins
2,4,5-T
Toxaphene
Trifluralin (Treflan)
1 Fungicides
F
F
1 Fumigants
(Herbicides
H
H
"
. H
Fu
1 Insecticides
I
I
I
I
I
I
I
I
I
I
I
I
H
H
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE X
SELECTED HERBICIDES. ESTIMATED PRODUCTION VOLUME,
Product
.Atrazine
2,4-D
Trifluralin
Alachlor
2,4,5-T
FORMULATION, USES. AND AREAS OF USE, 1971
Annual
Prod.
(MM Ib)
90
45
25
20
6
Plant
Site
Form.3/
100
20
90
95
0
Formulations (%)—
EC G WP Other
< ' 5 - 95
100 -
» 95 - - « 5 .
70 30
100 - -
Areas of Use
Major Uses
Corn>>Sorgham> Indus t.
Small grains, Corn,H&G
Soybeans>Cotton
Corn, Soybeans
Pasture, Brush Control
E
4
3
1
-
-
SE
8
3
5
2
1
MW
60
22
9
14
1
S
9
3
6
2
2
W
4
8
1
-
1
(MM Ib, a.i.Y-
U.S.
85
39
22
18
5
Export
5
6
3
2
1
oo
a_/ Percent of active ingredient formulated at manufacturing site.
b_/ Percent of active ingredient (a.i.) formulated as emulsifiable concentrate (EC), granular (G),
wettable powder, including dust concentrate (WP) , or into other formulations.
£/ Definition of symbols: E - Maine, New Hampshire, Vermont, Massachusetts, Rhode Island, Connecticut,
New York, New Jersey, Pennsylvania
SE - Delaware, Maryland, Virginia, West Virginia, North Carolina, South
Carolina, Georgia, Florida
MW - Ohio, Indiana, Illinois, Michigan,, Wisconsin, Minnesota, Iowa, Missouri,
North Dakota, South Dakota, Nebraska, Kansas .
S - Kentucky, Tennessee, Alabama, Mississippi, Arkansas, Louisiana,
Oklahoma, Texas
W - Montana, Idaho, Wyoming, Colorado,-New Mexico, Arizona, Utah, Nevada,
-Washington, Oregon, California, Hawaii, Alaska
-------
TABLE XI
SELECTED CHEMICAL INSECTICIDES. ESTIMATED PRODUCTION VOLUME.
Product
Toxaphene
DDT
Carbaryl
Me-parathion
ON Ma lath ion
Chlordane
Parathion
Aldrin
Disulfoton
Phorate
Aldicarb
Dieldrin
Annual
Prod.
(MM Ib)
50
45
45
45
35
25
15
10
8
8
3
< 1
Plant
Site
Form. §./
0
50
0
< 5
Negl.
5
< 5
0
60
0
0
0
FORMULATIONS
Formulations
EC G WP
95 - 5
< 5 - 95
- > 95
100 -
100
100
100
10 80
30 60
- —
10 90
- 100
80
, USEJL, AND AREAS .OF USIL, 197.1 .. . .
(70)b/
Other Maior Uses
Cotton, other
livestock
Cotton
< 5 Cotton, many
crops
Cotton, many
crops
crops,
other
other
Many crops, H&G
Many crops, PCO,
HSfi
Fruit, many o.ther
crops
10 Corn
10 Corn, cotton,
grains
Corn, cotton
- •' Cotton, sugar
small
beets
20 PCO, industrial
Areas
E SE
8
2
3 3
1 8
6 4
. A 1
1 2
. -
0.5 1
1 1
- 0.2
of Use (MM Ib, a.i.)c/
MW
5
<1 .
5
2 '
8
1 Ar(
3
1Q
4
4
0.2
S W
25 4
9 <1
8 4
20 2
3 4
ias
2 3
-
2 0.5
1- 1
2 0.6
All Areas
U.S.
42
12
23
33
25
- 23
11
10
8
8
3
0.5
Export
8
33
22
12
10
2
4
Negl
Negl
Negl
Negl
Negl
•
•
•
•
•
a/ Percent of active ingredient formulated of manufacturing site.
b/ Percent of active ingredient (a.i.) formulated as emulsifiable concentrate (EC), granular (G), wettable
powder, including dust concentrate (WP), or into other formulations.
c_/ See Table X, p. 68 for definition of symbols.
-------
TABLE XII
SELECTED BIOLOGICAL INSECTICIDES, FUMIGANTS. AND FUNGICIDES:
Product
Biology and
Botanical
Insecticides
B. thurin-
giensis
Pyrethrins
Fumigant
Methyl bromide
Fungicides
Captan
Hg- fungicides
ESTIMATED PRODUCTION VOLUME. FORMULATIONS. USES AND AREAS OF USE. 1971
Annual Plant
Pi-r>H
-------
Types of formulations also vary considerably, within the limits
set by the physical and chemical properties of the different active ingre-
dients. Granular formulations are popular for corn insecticides and at
least one corn herbicide, alachlor. For products to be sprayed, emulsi-
fiable concentrates are usually preferred over wettable powders because
of greater ease of measuring and handling and less trouble with nozzle
clogging. However, atrazine, by far the biggest of all herbicides was
until recently available only as a wettable powder. This has obviously
not prevented it from gaining its dominant position as a corn herbicide.
Apparently, pesticide users will accept certain handling inconveniences
in return for superior performance.
Most cotton insecticides are applied as sprays and consequently,
emulsifiable concentrate formulations predominate among cotton insecti-
cides.
Considering all of the "intensive study" pesticides combined,
the midwestern states, according to our estimates, account for approxi-
mately 40% of the domestic consumption of these products. Of the balance,
about 26% were used in the southern states, 15% in the southeastern states,
11% in the western states and 8% in the eastern states. This distribution
pattern reflects the extensive use of pesticides on midwestern farm crops,
especially corn and soybeans, and on cotton in the southern and south-
eastern states.
It must be emphasized that these figures represent the distribu-
tion pattern of only 22 selected pesticides. Similar information for all
pesticides might indicate a somewhat different geographical distribution,
although we believe that it would not be too drastically different. In
the past, the western states, especially California, accounted for a rela-
tively larger share of total pesticide consumption. However, the greatest
increase in pesticide use has been in herbicides, and herbicide use in turn
has increased most in the midwestern states. This explains the increase
in the midwest's share of total pesticide consumption.
C. Case Studies
Following the selection of the 22 key pesticides for intensive
study the major producers of these materials were contacted* and requests
made for an interview with individuals who would be knowledgeable about
the manufacturing processes and waste disposal practices for these pesti-
cides. A tour of the production facilities was also requested. The pro-
ducers and types of visits conducted are summarized in Table XIII.
The cooperation of the National Agricultural Chemicals Association is
appreciated.
71
-------
TABLE XIII
CASE STUDIES: SUMMARY OF PRODUCERS VISITED
Producer Visited
Monsanto Company
Union Carbide Corporation
Shell Chemical Company
Abbott Laboratories
Nutrilite Products
Geigy Agricultural Chemicals
Calhio Chemical Company
Union Carbide Corporation
Velsicol Chemical Corporation
Dow Chemical Company
Chipman Division, Rhodia, Inc.
Montrose Chemical Corporation
Chemagro Corporation
American Cyanamid Company
Mallinckrodt Chemical Works
Dow Chemical Company
Monsanto Company
Monsanto Company
American Cyanamid Company
FMC, Niagara Chemical Division
Dow Chemical Company
Thompson-Hayward Chemical
Company
Hercules, Inc.
Blanco Products Company
Pesticide
Alachlor
Aldicarb
Aldrin-dieldrin
B. thurin-
giensis
Atrazine
Captan
Carbaryl
Chlordane
2,4-D
DDT
Disulfoton
Malathion
Mercury
fungicides
Methyl bromide
Methyl parathion
Parathion
Phorate
Pyrethrins£/
2,4,5-T
Toxaphene
Trifluralin
a/ Interview at home office or elsewhere.
b_/ Plant tour provided.
£/ Information also furnished by McLaughlin Gormley King Company, Minneapolis,
Minnesota. _
Production Facilities
Muscatine, Iowa3./
Institute, West Virginia**/
\
Denver, Colorado
North Chicago, Illinois^/
Buena Park, California3./
St. Gabriel, Louisiana!/
Perry, Ohio
Institute, West Virginal/
Marshall, Illinois
Midland, Michigan
Portland, Oregon3/
Torrance, California^/
Kansas City, Missouri^/
Warner, New Jersey
St. Louis, Missouri and
Jersey City, New Jersey
Midland, Michigan
Anniston, Alabama3./
Anniston, Alabama3/
Warner, New Jersey—/
Baltimore, Maryland^./ and
Middleport, New York3/
Midland, Michigan
Kansas City, Kansas
Brunswick, Georgia3/
Indianapolis, IndianalL/
-------
The results of the key pesticide studies are tabulated in Case
Studies 1 through 22 arranged as shown in Table XIV. Each study summarizes
the process chemistry, a schematic depiction of the production and waste
disposal system, the movement of raw materials to the production site, the
disposal of by-products and waste products, the movement of technical and
formulated products from the production site, and other information per-
tinent to pollution potential. Special note is made here that the produc-
tion diagrams shown for many products were not provided by the producer:
these were prepared by the authors for descriptive purposes and may not
represent all or the exact process steps in use. Similarly, the percentage
yield of active ingredient or a complete materials balance were not re-
vealed by the producers because of proprietary considerations and the data
shown are author estimates. Unfortunately the effluent data being sub-
mitted by producers under the 1899 Refuse Disposal Act have not become
available in significant amounts in time for inclusion in the study.
TABLE XIV
ORDER OF PRESENTATION OF CASE STUDIES
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Pesticide
DDT
Aldrin
Dieldrin
Chlordane
Toxaphene
Disulfoton
Malathion
Phorate
Parathion
Methyl parathion
Carbaryl
Aldicarb
2,4-D
2,4,5-T
Atrazine
Trifluralin
Alachlor
Captan
Methyl bromide
Pyrethrin
Bacillus thuringiensis
Mercury chlorides
Class
Insecticide, chlorinated hydrocarbon
Insecticide, chlorinated hydrocarbon
Insecticide, chlorinated hydrocarbon
Insecticide, chlorinated hydrocarbon
Insecticide, chlorinated hydrocarbon
Insecticide, alkyl organophosphorous
Insecticide, alkyl organophosphorous
Insecticide, alkyl organophosphorous
Insecticide, aryl organophosphorous
Insecticide, aryl organophosphorous
Insecticide, carbamate type
Insecticide, carbamate type
Herbicide, chlorinated phenoxy
Herbicide, chlorinated phenoxy
Herbicide, triazine
Herbicide, nitroaryl
Herbicide, amide type
Fungicide, chloroalkylthio type
Fumigant, halogenated
Insecticide, botanical
Insecticide, microbiological
Fungicide, inorganic
73
-------
CASE STUDY NO. 1
Pesticide: DDT
Chemical name and formula:
91
Cl—C—Cl
ci-^ y~c~\ y~cl
l,l,l-Trichloro-2,2-bis(p-chloro-
phenyl) ethane
Chemical class: Chlorinated hydrocarbon
Pesticide class: Broad spectrum insecticide
Description: Solid; nearly insoluble in water; moderately toxic;
persistent
Producers: Montrose (Torrance, California)
Production chemistry:
* ? CC13CH(C6H4C1)2
C6H6 + C12—
74
-------
NaOH
Vent
t
H2O
Scrubber
C6H5CI
CCI3CHO
H2SO4
c
Liquid Waste
Vent and COH5CI Recycle
Reactor
(2-Stage)
I
DDT
Separator
\
Spent
Acid
L
Floor and
Surface
Drains
Vent
Labs and
"Wash-Up
DDT
Washer
i
-
1
Crystal lizer
Dryer
Flaker
I
Evaporative
and Recycle
Water Pond
Dilute
Caustic
Recycle
"Acid
Acid
Recovery
Plant
Lie
Wa
uid
Waste
Acid
Neutra-
lizer
stes
1
Formulation
Plant
to Class 1
Dump
Figure 18 - Production and Waste Schematic for DDT
-------
Production Equipment
Process continuity: semibatch Est. Annual production: 45 MM Ib/year
Equipment dedication: DDT only Plant capacity: 81 MM Ib/year
Equipment age: Not available
Formulation on site: Yes
Raw Materials
Material
1. Choral
2. CeH5Cl
3. Oleum
4. Caustic
Received From
Henderson, Nevada
Henderson, Nevada
Cpmpton or
Dominques,
California
Henderson, Nevada
Received By
Tank cars
Tank cars
Tank trucks
Storage
Steel storage tanks on
plant site
Steel storage tanks on
plant site
Steel storage tanks on
plant site
Tank trucks Steel storage tanks on
plant site
Material
1. None
2.
Reaction By-Products
Amount Produced
Form (Ib/lb A.I.)
Disposition
Material
1. Active ingre-
dient
2. Solvents
3. Na2SO.
4. Solid waste
Other Process Wastes and Losses
Amount Produced
Form (Ib/lb A.I.)
Aqueous Unknown
Aqueous 0.87
10-15 cu yd
Disposition
Class 1 dump
Holding pond, recycle
Class 1 dump
76
-------
Disposition of Technical and Formulated Products
Shipments
Technical Product
Formulated Products
Warehouse
On Site Container Transportation Formulation Container Transportation
50 Ib bags Boxcar
WP (75%
A.I.)
100-200 Ib
lined
fiber
drums and
75 Ib
boxes
Truck for export
via Los Angeles;
boxcar for other
destinations
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture
Yes
X No
Other regulations apply: The Department of Occupational Health,
Air Pollution Control District, the Water Resources Control Board (state
and regional), and the Los Angeles Sanitation Districts (city and county)
are active in pollution control.
Formulation: A 75% wettable powder DDT is formulated for WHO
and AID according to the following process.
Technical DDT
Silica
Wetting Agent
Dispersing Agent
-------
Hoods are located at points having emissions potential-arid ex- .
haust under vacuum to a baghouse. No scrubbers are used. Liquid formu-
lations are no longer being made. . •
Pollution control: The process portion of the plant has .rib
liquid waste outfall. Much of the water from the process goes to; an .open,;'
concrete-lined evaporative holding pond and is recycled. All drains and
process sewers have been isolated from the city sewer system. Only sanitary
waste and boiler blowdown water go to the city sewers. The restroom lava-
tory basins, however, discharge to the holding pond system. Water con-
sumption has been reduced from 20 million to 1.5 million gallons per month.
Water.from the recycle pond is also used for cooling water without filtra-
tion. This practice has caused no problem to date. The "recycle" water
typically contains 10 to 15 ppm DDT.
From 20,000 to 25,000 gallons per day of liquid waste are gen-
erated from the neutralization step and are removed by truck to a Class 1
dump. Some 10 to 15 cu yd/day of solid waste bags, empty containers, etc.,
are also taken to this dump by a commercial disposal service. All vents
from the second stage of the reactor are NaOH scrubbed and the liquid goes
to the recycle water pond. Equipment washdown is not a problem as this is
normally done only during shutdowns. Wash water goes to the recycle pond.
Spills and leakers have not been a major problem. One spill occurred when
a truck carrying technical material had an accident and spilled DDT. The
material was picked up along with the top 3 in. of soil and disposed of.
Prior to the modification of the waste treatment facilities DDT
losses from this plant were apparently fairly high: DDT levels of 70 ppb
were observed!' in the river below the plant and 0.5 million pounds
sediments from the river containing about 4,500 Ib of DDT have been dredged
up for treatment.—'
Quality control: Montrose maintains its own quality control lab
for routine analyses. Setting point is the major quality control used.
To date they have had no off-specification material that could not be
reworked.
Personnel safety; No unusual safety or hazard problems are
associated with DDT production. Standard personnel safety equipment are
used.
This plant does not come under the 1899 Act.
78
-------
General information: Montrose is the only DDT producer left in
the U. S. and only about 10 million pounds per year are used domestically.
Major use areas are the cotton states: Arkansas, Mississippi, Texas, and
Louisiana,, Montrose does have intrastate registration in California for
alfalfa seed, citrus, peppers, onions, and public health purposes. Major
domestic DDT formulators are, Helena Chemical and Valley Chemical
(Mississippi), Olin (Arkansas), and Micro Chemical (Louisiana).
79
-------
CASE STUDY NO. 2
Pesticide: Aldrin
Chemical name and formula:
1,2,3,4,10,10-Hexachloro-l,4,4a,
5,8,8a-h exahydro-1,4-endo-exo-
5,8-dimethanonaphthalene
Chemical class: Chlorinated hydrocarbon
Pesticide class: Broad spectrum insecticide
Description: Solid, insoluble in water, very toxic; persistent in form
of dieldrin
Producers: Shell (Rocky Mountain Arsenal, Colorado)
Production chemistry:
CaC2 + H20—>Ca(OH)2 + C2H2
C10H12
80
-------
oo
Lime
S lurry ~*"Lime P!t
t
CaC2 •* Acetylene _^
_ Generator . ^ 2
H2O — »•
B
-»• D
C
C10H12 •" Cracker -*- CsH6 ''•?
(
By-Prc
A
Bo
Fu<
f
1
>ducts
f '. '
ler
z\
C5CI6
. " /- LJ Diene , Aldrin Solvent Technical
lene — ^ ^-ynS ^ n ^ ~^r- i »• ~^ ci • ~^ A i j •
' ° Reactor Solution Stripper Aldrin
venerator
t ; 1
1 C7HB
- ; (Excess)
i '
Bottoms
,'••.
Figure 19 - Production and Waste Schematic for Aldrin
-------
Production Equipment
Process continuity: Semicontinuous Est, Annual production: 11 MM Ib/year
Equipment dedication: Aldrin Plant capacity: ~ 25 MM Ib/year
Equipment age:
Formulation on site: ~ 10%
Raw Materials
Material
1. Calcium
carbide
Received From
Received By
2. Dicyclopenta-
diene
3. Hexachloro-
cyclopenta-
diene
4. Petroleum
solvent
(for formulation)
Oregon; Midwest Rail & gondola
car (12 2-ton
containers/
car)
Rail, tank cars
Baton Rouge
Niagara Falls
Hous ton
Rail, tank cars
Rail, tanks
Reactions By-Products
Amount Produced
Storage
Tote bins
Tank cars
2.
Material
Ca(OH)2
Form
Slurry
(Ib/lb A.I.)
0.202
Disposition
Lime pit
Material
1. Active
ingredient
2. Solvents
3. Hydrocarbons
Other Process Wastes and Losses
Form
Amount Produced
(Ib/lb A.I.)
Disposition
Used for fuel
82
-------
Disposition of Technicaland Formulated Products
Shipments
Warehouse Technical Product^./ Formulated Products
On Site Container Transportation Formulation Container Transportation
X 28 Gal. Truck and rail 10% of prod- 5, 30 and Mostly trucks
fiber uct, E.G. 55 gal.
Mylar- form lined
lined drums
drums
a_/ Approximately 907o of production is shipped as technical and is nearly
all formulated to granules.
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture Yes _2L_^°
Other regulations apply;
Pollution control; No liquid waste streams contain aldrin.
Small amounts of aldrin-containing liquid wastes from spill cleanup or
floor washings would go to a 100-acre asphalt-lined evaporation basin on
the arsenal. This basin is capable of evaporating 150 gal. of water per
minute year-round and has shown no signs of leaks in its 16 years of use.
The arsenal is also diked so that all surface waters go to unlined storage
basins. During shutdown the aldrin unit would be washed with toluene and
the washings would go to dieldrin manufacture. Damaged drums containing
aldrin would be similarly cleaned, then incinerated, flattened and sold
as scrap steel. Some wipe cloths are burned, some are cleaned. Have had
no railroad accidents in shipping aldrin.
Quality control; No significant impurities or off-specification
problems with aldrin and no shelf life problems. The drums for the E.G.
receive a statistical leak inspection, which goes to 100% inspection if a
lot looks poor. Biggest problem is rub-off of part of drum label.
Personnel; Production workers are trained. Production is sea-
sonal with a shutdown usual in summer, but production workers are utilized
elsewhere. Workers get a pre-employment physical, and monthly cholin-
esterase test because of related work on organophosphate pesticides.
Workers receive clean coveralls daily, which are sent along with wipe cloths
to a commercial laundry where they are said to be handled separately.
83
-------
CASE STUDY NO'. 3
Pesticide: Dieldrin
Chemical name and formula:
l,2,3,4,10,10-Hexach.loro-6,7-
epoxy-l,4,4a,5,6,7,8,8a-
octahydro-1,4-endo-exo-5,8-
dimethanonaphthalene
Chemical class: Chlorinated hydrocarbon
Pesticide class: Broad spectrum insecticide
Description: Solid; insoluble in water; very toxic; persistent
Producers: Shell ^(Denver, Colorado). ; . i ;
• ' , i • '-U
• • q-
Production chemistry: ; ,
H0
Aldrin
Dieldrin
84
-------
oo
"2^2—^
CHoCOOH-*-
"P
Aldrin— ». Aldrin . ....
y i r i .• ^^ ' ''TCP
i i
f
Paper
Incinerator
n2->^4
er" Acid j j (Catalyst)
Oxidation D
Reactor Sc
Aqueou
Phase
eldrin Solvent
>lution Stripper
L^
s
\
V
V
-\2o
\
Extractor 1
i
Dieldrin
taste
^ater
J
' "1
Evaporation
Basin
Figure 20 --• Production and Waste Schematic for Dieldrin
-------
Production Equipment
Process continuity:
Est. Annual production: 0.5 MM Ib
Equipment dedication: 0-P prod- Plant capacity:
ucts also
Equipment age:
Formulation on site:
Material
1. Aldrin
2. Toluene
3. Acetic acid
4. H202
Raw Materials
Received From
On site
Received By
Storage
Material
1. Water
2.
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
Disposition
Evaporation basin
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3.
Form
Amount Produced
(Ib/lb A.L)
Disposition
86
-------
Disposition of Technical and Formulated Products
Shipments
Technical ProductiiL'
Formulated Products
Warehouse
On Site Container Transportation Formulation Container Transportation
Some
(drums )
30 Gal.
drums
Rail and truck
(in less than
full lots)
None
a/ Mostly used for termite control now.
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture
Yes X No
Pollution control: Liquid wastes go to evaporation basin (see
aldrin, case study 2). A small amount of solid waste, including filter
paper, is burned in a smokeless-type incinerator. Equipment cleanup with
toluene, which is apparently saved. See aldrin for further remarks.
87
-------
CASE STUDY NO. 4
Pesticide: Chlordane '
Chemical name and formula:
Mixture of octachloro-4,7-methanotetra- •'
hydroindane and related compounds
Chemical class: Chlorinated hydrocarbon
Pesticide class: Broad spectrum insecticide
Description: Solid, insoluble in water; moderately toxic
Producers: Velsicol (Marshall, Illinois)
Production chemistry: The process reactions are approximately as follows;
1 ... . - . _ ,."!,«•-' '"•!>, '-} • '
Naptha - • - 1 - '• — — » "Cyclopentadiene
C12 + NaOH (aq.) - ; - — *. NaCIO (aq.) :
NaCIO (aq.)"+ C5Hg- - ^ - »• C$&16 +-NaCl (alk. soln)
C5C16 + C5H6 - ->Chlordene (C10H6C16)
Chlordene + C12 - ^ Tech. chlordane
v related epds.)
-------
oo
vO
Naphtha
Vapor Phase
Cracker
80-90 %
Resin Manufacture
Condenser
• Vent
Diels-Alder
Reaction
70-85°C
—^ Chlordene
S02CL2 i S02a9?
Generator} (Excess)
Chlorinator
Waste Water Scrub Solids
(NaCI + NaOH)-Water
I
Deep
Well
Disposal
T
Clay Pit
•
*-*"
Make-Up Vacuum
Vent
Chlordane Mixture,
"SO2CI2?, SO2?
SO-
I
Technical
Chlordane
Figure 21 - Production and Waste -Schematic for Chlordane
-------
Production Equipment
Process continuity: Continuous Est. annual production: 25 MM Ib/year
Equipment dedication:
Equipment age:
Plant capacity:
Formulation on site: No
Raw Materials
Material
1. Naphtha'
2. Chlorine
3. Caustic
Received From
Woodriver, Illinois
Memphis, Tennessee
Received By
Pipeline
Tank Cars
Tanks
Storage
Material
1.
2.
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
Disposition
Material
1. Active ingre-
dient
2. Solvents
3. All waste
liquids
4. Filter solids
Other Process Wastes and Losses
Amount Produced
Form (Ib/lb A.I.)
Disposition
Deep well
Clay pit
90
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product Formulated Products
On-Site Container Transportation Formulation Container Transportation
Small amt. 40-50% None
tanks Rail and track
40-50%,
30-gal.
drums, Truck and rail
5-gal.
drums
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture Yes X No
Pollution control; The spent hypochlorite wastewater has
about 2% NaOH and 400 ppm C5Clg. The chlordane production and handling
area is diked and all run-off and process wastes go to deep well disposal
on the plant site.
The well is state approved and has been in use for 6 years. It
goes 2,600 ft deep to a Dolomite (Vugular) layer which is very porous and
the discharge does not spread much—perhaps 5 acres in 6 years. The strata
already has salt in it. The shaft has three casing. A tube liner contain-
ing water at high pressure goes to 2,300 ft and the top 600 ft is further
sealed to prevent surface water contamination. Velsicol has a permit for
a second well which will go to 6,000 ft, to be completed in December 1971.
It will also handle wastes from the resin part of the plant (these contain
fluorides) which are presently being discharged. Those wastes have to be
monitored for chlordane, for dissolved solids, BOD, etc. Velsicol monitors
chlordane, but also has an outside lab check occasionally and the state also
checks sometimes—levels are probably below 1-5 ppb, level which would be
toxic to fish (LD^Q = 1 ppb for chlordane; 25-30 ppb for heptachlor).
Five companies in Illinois use deep-well disposal. Cost is $40-90/ft.
Chlorine from the Cl2 tanks is forced out under pressure—no
losses—meets Chlorine Institute Specifications. Velsicol is installing
automatic shutoffs.
The tank cars are leased, used for chlordane only. Occasionally
some are not needed and are returned to railroad company following cleanup
with detergent—the wash goes to deep-well disposal. The tank trucks are
received clean and dry from the trucking company--make a one-way trip and
91
-------
then are cleaned by the trucker before being sent to the next job. The
trucks are self draining and the trucker may use a-bucket to catch drips,
but he probably cleans the truck with detergent, steam and air and dumps the
washings in the sewer. , < .
Drums are lined, open top: ; filling—no .ventilation problems-^
no controls. Have had drum punctures, rail accidents, but no full truck
spills: biggest spill in the last couple of years was three or four drums.
Drum (disposal) is the formulators1 problem. Recommended cleanup is
kerosene wash and detergent wash but they may throw washings on the ground.
Chlordane is very stable and does not degrade in detergent.
The half-life in soil is about 2 years (although it does not migrate or
biomagnify). The technical material is fairly viscous.
Emergency procedure—send technical assistance as soon as word
of spill is received. Recommend clay absorption or rag wipe-up of spill
with burial of material at least 12 in. below ground level. Do not rec-
ommend absorption on sawdust and burning.
Quality control; Velsicol uses glc to monitor product and
to get what they call "fingerprint" chlordane which apparently contains
7-8% heptachlor. Product color can be a bigger problem than composition.
Any off-specification materials are easily blended off. Analytical sam-
ples are drummed and sold. Drums are inspected for water or liner tears.
Have had little if any rejects from formulators—one claim about water
content.
Safety and personnel health; Operating personnel are union;
new operators come from other parts of the plant by making a bid for an
opening in the chlordane unit. (No one has ever bid out of chlordane).
New operators get a 15-30 day training period under a chief operator.
A study of 15 employees who had been handling chlordane for a
long time found no detrimental health effects: Ind. Med. & Surg., 33 (10),
726-7 (1964). There has been no authenticated loss of life from chlordane,
see: "Monograph on Chlordane Toxicological and Pharmacological Properties,"
Dr. L. Ingle (1965). Workers around the chlorination units have hand, eye,
foot protection and standby (Scott) respiratory equipment.
Fires—have plant fire squad; have had no warehouse fires or
major plant explosions.
92
-------
General: Most of the Chlordane is sold to independent femulators,
with only a few tank car customers. Ve'lsicol has started formulating only
last year and has this done by contractors in Des Moines, Iowa and Napoleon,
Ohio. Products are Belt-(clay powder pellets for use on corn)- and Gold
Crest-(a 72% solution, 8 Ib/gal in petroleum distillate - 10% inert - for
use with fertilizer). These are sold through independent stores.
93
-------
CASE STUDY NO. 5
Pesticide: Toxaphene
Chemical name and formula:
6(C1)
Mixed isomers of chlorinated camphene
(67-69% chlorine)
Chemical class: Chlorinated hydrocarbon
Pesticide class: Broad spectrum insecticide
Description: Waxy solid, insoluble in water; moderately toxic; low
persistence compared to DDT
Producers: Hercules (Brunswick, Georgia); Sonford Chemical; Strobane-T
produced by Tenneco is similar
Production chemistry:
a-Pinene
Camphene
Cl
- CH2C1
_CH3
CHo
Cl-
UV or cat,
C10H10C18 + 6 HC1
Toxaphene (mixed isomers
and related compounds
67-69% Cl)
94
-------
Ui
Southern
Pine Stumps
100 Other Products
Chlorine
Solvent?'
Wastes—^. Bio-Treatment Plant
Mixed
Xylenes
NaOH-
Alkali as
Needed
Chlorinator
f
HCI
1
Waste
S ^ 1 | 1 1 •
^
1^1 Toxaohene _
Solution
|
L
Other
Wastes
1 Pond
Filter
1 «
Cake
Wash
\
-»•
Stripper
[
"*" 1
—
L
Discharge
to Creek
Dust
Formulation
— Baghouse
Solid
Waste
T
Atmosphere
90 % Toxaphene
•Toxaphene—^-Solution
^ CL:
^Shipments
Figure 22 - Production and Waste Schematic for Toxaphene
-------
Production Equipment
Process continuity:
Equipment dedication:
Equipment age: From 20 years to
brand new
1948 plant
Est. annual production: 45 MM Ib/year
Plant capacity:
Formulation on-site: Most is diluted
Raw Materials
Material
1. Camphene
2. C12
3. Solvent
4. Clay
5. NaOH
Received From
On site from
ot Pinene ,
Six local (Georgia)
sources
(Georgia) ,
(Georgia)
Received By
Tank cars
Tank cars
Bulk by rail
Tank car
Tank truck
Storage
Material
1. HC1
2.
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
0.53
Disposition
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Camphene pro-
duction
4. Waste from
scrubbers
Form
Liquid
Liquid
Amount Produced
(Ib/lb A.I.)
Disposition
Holding ponds system;
discharge
Biowaste treatment
Holding pond to creek
96
-------
Disposition of Technical and Formulated Products
Shipments
Technical Product
Formulated Products
Warehouse
Elsewhere Container Transportation ' Formulation Container Transportation
% Small 'Exported via
amt., East cost
250-gal
galvan-
ized drums
% Most, -90% Tanks',
concentrate;; 55 Gal,
10% xylene SO^lb,
bags
pellet-
ized
= Rail and truck
Exports
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes
No
Pollution control; All liquid effluent from the camphene produc-
tion step goes to the plant biowaste treatment system. All liquid wastes
from the toxaphene unit go to a large holding pond system. This is a
new pond system which is about 657« complete; and should be finished in
April 1972. The production area is diked so that all liquids go to the
holding pond.
Process vents are water, caustic, or lye-scrubbed before venting
to the atmosphere. The waste from these scrubbers also goes to the holding
pond. The effluent from the holding pond goes to a creek, which goes into
the ocean. An "insignificant" amount of toxaphene will be released when
this system is put into operation. They have no major problems with leakers
or spills. Baghouses are used in the dust concentrate unit, which is lo-
cated in the toxaphene production area. Dust from the collection system
is recycled. There are no scheduled maintenance shutdowns of the complete
toxaphene unit. Short shutdowns are made when needed.
The tank cars whether owned by the company or by the railroad
are dedicated to toxaphene and are cleaned yearly, with the washings going
to the toxaphene recycle system. Tank trucks are customer or truck line
owned and are cleaned by them.
Quality control: Technical toxaphene contains 20-30 compounds
according to gas chromatographic analysis. Quality control is accomplished
by both chlorine content analysis and bioassay. Both must be considered as
chlorine content alone does not insure efficacy. There are no impurities
that are a particular problem. Off-specification material can generally
be reworked with no trouble. Shelf life is excellent.
97
-------
Personnel and safety; Hercules has rigorous safety standards
because of their history in explosives work. They maintain a fire truck
and crew on-site. Production workers receive annual checkups and have
had an excellent health record with no correlations of death or illness
with toxaphene handling.
General; Hercules maintains over 100 aluminum bulk storage
tanks at formulator-customer locations. The 90% concentrate is trans-
ferred from tanks into these and the formulator draws it out as needed,
so that no used drums are generated, and personnel risks are minimized.
Hercules operates their own emergency aid program to handle
spills, although they also belong to the NACA and MCA teams.
Hercules has prepared a 2,500 page report on toxaphene for the
Pesticides Regulation Division, Agricultural Research Division (i.e.,
Federal Register, Vol. 35, No. 148, 31 July 1970).
98
-------
CASE STUDY NO.. 6
Pesticide: Disulfoton (Di-Syston®)
Chemical name and formula:
CH3CH2(
S
P-S-CH2-CH2-S-CH2-CH3
0-0-Diethyl-S-[2-@thylthio)-
ethyl]phosphorodithioate
Chemical class: Organophosphate
Pesticide class: Systemic insecticide
Description: Liquid of low volatility; insoluble in water; highly toxic;
nonpersistent
Producers: Chemagro (Kansas City, Missouri)
Production chemistry:
P2S5 + 4C2H5OH + 2NaOH To uene> 2 (C2H50)2P(S)SNa + H2S + 2H20
"Diethyl Salt" (DES)
PC13 + 3HCC2H4-S-C2H5 - >3C1C2H4-S-C2H5 + P(OH)3
"Thio Alcohol" "Chloro Thio Alcohol" (CTA)
(C2H50)2P(S)SNa + C1C2H4-S-C2H5 - >(C2H50)2P(S)-S-C2H4-S-C2H5 + NaCl
Disulfoton
99
-------
STEAM
WATER »
o
o
ORGANIC
TO BURIAL
(Adapted from a drawing provided by Chemagro Corporation)
WASTEWATER TO
TREATMENT PLANT
Figure 23 - Production and Waste Schematic for Disulfoton
-------
Production Equipment
Process continuity: Semicontinuous Est. Annual Production: 10 MM Ib/year
Equipment dedication: One product Plant capacity:
Equipment age: ~ 15 years
Formulation on site: Yes
Raw Materials
Material
1. P2S5
2. Ethanol
3. NaOH
4. Ethyl mer-
capto
ethyl
alcohol
5. PC13
6. Toluene
solvent
7. Sodium Kypo-
chlorite
Received From
Received By
Rail in 5,000 Ib
tote bins
4,000-5,000 gal.
tank trucks
Kansas City, Missouri
8-10,000 gal.
tank cars
4,000-gal. tank
cars
Chicago or Houston 8-10,000 gal.
tank cars
Storage
Material
1. H2S
2. P(OH)3
3. NaCl
Reaction By-Products
Amount Produced
Form . (Ib/lb A.I.)
0.06
0.075
0.214
. . Disposition
Scrubber and flare
Wastewater treat-
ment
Wastewater
Material
1. Active ingre-
dient
2. Solvent
3. Other
Other Process Wastes and Losses
Form
Amount Produced
(Ib/lb A.Ii)
101
Disposition
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse
Technical Product
. Formulated Products
On Site Container Transportation Formulation Container Transportation
X (drum) 40%, 55
gal.
drums
Mostly truck
(some piggy-
back)
6 Ib/gal
E.G.
(xylene)
70%, De-
odorized
Granular
1,30,55-
gal.
drums
55-Gal.
drums
55-Gal.
steel
drums
As per technical
As per technical
As per technical
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes
No
Pollution'control: A new $1.9 million wastewater treatment
plant came on stream in June. Caustic conditions (lime) removes some of
OPs during retention time of 36 hr. Adjust pH and use polyelectrolyte
floculent. Power plant water and sanitary wastes also handled and added.
Final effluent is discharged to Blue River—probably has no more than ppm
range of any one pesticide now.
Solid waste from treatment plant goes to commercial landfill.
Chemagro is planning a biological treatment backup system—possible con-
struction 1973-4. .
Process filter cake of diatomaceous earth is decontaminated (No
blow; toluene flush (recycle); steam; N2 blow) then buried. The solids
formulation line is well covered by a dust collection system which has a
baghouse backed up by a newly installed Venturi-type wet scrubber (alkaline)
Formulation equipment cleaned by solvent flush (which is used in next batch)
and then by steam and water. Problems: trace emissions of odorants (more
in production than in formulation), and disposal of containers. (Est. 2-40
oz liquid left/drum.) I^S flare and particulates emission from fuel com-
bustion appear to be biggest pollution sources.
Quality control; Di-Syston checked for purity—sometimes must
retreat to remove water or unreacted CTA. Impurities may result from poor
analysis on intermediate, poor phase separation or equipment failure. Have
never had a phytotoxic batch of Di-Syston and no reject batches which could
102
-------
not be reworked or blended off. In one incident disposal of a technical
ingredient was necessary: a batch of coumaphos had become contaminated
with DDT by an outside formulator and had to be returned and disposed.
Incoming drums are spot checked for defects and filled drums are inverted
to check for leaks before shipment.
Shelf-life is no problem with Di-Syston—have had no recalls to
date. Analytical samples of all products are held in a warehouse several
years—will probably recycle eventually.
Personnel health; Workers wear control clothing, boots, gloves,
glasses, aprons at times. Have cholinesterase test schedule—every two
weeks for production workers and every week for fortnulators. In addition
to the Di-Syston. (class B poison) the CTA intermediate is very irritating
to skin and eyes. H~S is toxic. The Filter Cake cleanup (probably once
a day) requires extra care—full face mask and respiratory equipment.
Have had no fatalities or major injuries, fires or explosions at Chemagro
and no small fires with Di-Syston.
103
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CASE STUDY NO. 7
Pesticide: Ma lath ion
Chemical name and formula:
H 8
P-S-C-C-0-CH2CH3
HoC-C-0-CHoCHo
i in ^ f.
0
0-0-Dimethylphosphorodithioate of
diethyl mercaptosuccinate
Chemical class: Organophosphate
Pesticide class: Nonsystemic insecticide and acaricide
Description: Liquid of low volatility; slightly soluble in water; low
toxic ity; nonper sis tent
Producers: American Cyanamid (Warners, New Jersey)
r I
i
Production chemistry:
§
P2S5 + 4MeOH - >2(MeO)2PSH + H2S
TT C C S
(MeO)2PSH + HC-COOEt -^-^ - '—^ (MeO)2PSCHCOOE^
HC-COOEt CH2COOEt
104
-------
P2S5 — •*
CH3OH — »•
Toluene; — ^
t
Dithio
Unit
/ ' •
NaOH (as needed) -
Diethylmaleater-
i
i_
to. fCHiO'\tp(s
*
1
rianr
)SH Vent
HCondenserl
-* Biathlon _ Reco- H
-*• Unit 7 .
i
r*r*i ie*i t* •
Caustic
f
\
Disti
1
Filter
Cake
\ •
, Landf
lotion
H2O
i
»• Wash -
1
Acid
Waste
Water
Air?
1
^ Drier -
1
Overhead!
Collector
^Technical
Malathion
• • ••,-*•
ill 1
^ Barqe
Wastes to Sea
Figure 24 - Production and Waste Schematic for Malathion
-------
Production Equipment
Process continuity: Batch
Est. annual production: 20-25 MM Ib/year
Equipment dedication: Other OPs Plant capacity:
also
Equipment age: Est. 15-20 years Formulation on site: Very little
Raw Materials
Material
1. P2S5
2. MeOH
3. Diethyl
maleate
4. Toluene
5. Caustic
Received From
Three local sources
Linden, New Jersey
Local
Received By
Truck, in tote
bins
Rail, tank cars
Pipeline
Storage
Tote bins
Bulk
Bulk
Material
. H2S
2.
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
0.098
Disposition
Recovered as 1^804 in new
plant with good controls
Other Process Wastes and Losses
Material
Form
1. Active ingre- Aqueous
dient
2. Solvents Gaseous
toluene
3.^Liquid Wastes
and spills
Amount Produced
(Ib/lb A.I.)
Unknown
Unknown
Disposition
Barge to deep sea
Atmosphere
To holding pond eventually
barged to the sea
106
-------
Disposition of Technical and Formulated Products
Shipments
Technical Product
Formulated Products
Warehouse
Elsewhere Container Transportation Formulation Container Transportation
X (10-12
loca-
tions)
10-12%,
tanks,
5,30,55-
gal.
lined
drums
Rail and truck < 5%, pro-
duction,
dust and
powder
Drums
Mostly export
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture _ Yes ' X NO
Other regulations 'apply; Federal government regulations apply
to sea disposal.
Pollution control; The only by-product of malathion is
which is recovered as HoSO^ in a new sulfur recovery unit. Emissions
from this recovery unit meet New Jersey requirements of < 5.5 Ib NO per
ton H2S04 and < 6.5 Ib S02 per ton H2S04. Some toluene is lost from the
malathion distillation process, but emission factors are not known.
The acid production center, which was rebuilt 2 years ago and is
used to produce both malathion and phorate, is generally considered to be
the most hazardous area of the plant. This unit is completely diked, has
separate fire walls, C02 blanket system, and no_ floor drains.
Wash water from the washing process as well as other liquid
waste (spills, etc.) go to a holding pond and is eventually barged to
sea (150-200 miles out). Cleanup of equipment is limited to once or
twice a year when changing products. Waste from this operation is barged
to sea. "Extensive" precautions are taken against cross-contamination at
this time, and to date they have had no problems. They have been barging
their waste to sea for about 4 years.
The only solid wastes generated are filter cartridges. These
are decontaminated with NaOH, and are buried with lye in a land fill (on
site?). Dust in the formulation area is collected in a baghouse and
recycled.
107
-------
Containers are statistically spot checked before use. Defective
lots of containers are rejected. Containers are not pressure checked.
The storage of empty containers before they are used is very
important in preventing leakers. Very few complaints about leaks have
been received. They try to use the same carriers all the time (rail,
truck etc.), and this seems to help. However, LTL shipping has the
potential for causing problems because of mixing shipments.
Quality control; AOAC methods are used on raw materials and
GLC methods are used on products. No critical impurities are a problem
and any off-specification, batches can be blended off or easily reworked.
Shelf-life of malathion is good, over 2 years. Return of purchased
product is not accepted unless special arrangements have been made.
Safety and personnel; Fire and safety practices are standard.
The plant has its own fire department which is supplemented by the local
fire department. The Po^5 ventin8 system is equipped with a CC^ extinguish-
ment system. The plant area is not systematically diked to catch fire-
water run off. Some of the bulk storage areas are diked. American
Cyanamid has its own 24 hr/day emergency service for malathion and phorate.
The phone number is on all containers as well as malathion bulk storage
tanks.
General information; The original plant was constructed during
World War I.
The distribution of technical material to formulators in the
U. S., as percentages of sales, are: West (15%); Midwest (20/0; N.E.
(25%); S.E. (20%); and Great Plains (15%). Exports of the technical mate-
rial go out of New York primarily and are in 55-gal. drums.
108
-------
CASE STUDY NO. 8
Pesticide: Phorate (Thimet
Chemical name and formula:
CH3CH20N
CH3CH20
;p-S-CH2-S-CH2-CH3
0,0-Diethyl S-(ethylthio)-methyl phosphorodithioate
Chemical class: Organophosphate
Pesticide class: Systemic insecticide
Description: Liquid of low volatility; insoluble in water; highly toxic;
~' nonpersistent
Producers: American Cyanimid (Warners, New Jersey)
Production chemistry:
4EtOH
->2(EtO)2PSH + H2S
(EtO)2PSH + H2C=0-
(EtO)2PS-CH2OH
(EtO)2P-S-CH2OH + EtSH
S
(EtO)2P-SCH2SEt
109
-------
H2S-*-To H2SO4 Plant
(C2H50)2P(S)SH
CH2O-
Vent
•(Containing
EtSH)
Flared
to Atmosphere
Condensation
Unit
Wash,
Steam
Strip,
Filter
TJ
Solid Liquid
Wastes Wastes
I I
Landfill Barge
to Sea
Phorate
Figure 25 - Production and Waste Schematic for Phorate
-------
Production Equipment
Process continuity: Batch
Est. annual production: 8 MM Ib/year
Equipment dedication: Part used Plant capacity:
for other
OP's
Equipment age:
Formulation on site: Very little
Raw Materials
Material
1. P2S5
2. Ethanol
3. Ethyl
mercaptan
4. Formalde-
hyde
Received From
Three local
sources
Local services
Received By
Truck
Tank trucks
Storage
Tote bins
Material
H2S
2.
Reaction By-Products
Form
Amount Produced
(Ib/lb A.I.)
0.12
Disposition
Sulfur recovery
to H2SO^
Burned in a flare
Other Process Wastes and Losses
Material
1. Active Ingre-
dient
2. Solvents:
toluene
3. Other: Liquid
wastes and
spills
Form
Aqueous
Gaseous
Amount Produced
(Ib/lb A.I.)
Unknown
Unknown
111
Disposition
Barge to deep sea
Atmosphere
To holding pond
eventually
barged to the
sea
-------
Disposition of Technical and Formulated Products
Warehouse Shipments
On- Else- Technical Product Formulated Products
Site where Container Transportation Formulation Container Transportation
X X 55-gal. Truck and rail Small amount 1-gal. metal
Drums in full loads to E.C. cans (4/carton)
only (6 lb/
gal) 5'8al- cans
(palletized
and strapped)
By contract formulators:
50-lb bags
10-lb bags (6/carton)
15-lb bags (4/carton)
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture Yes X No
Pollution control: The major by-product is I^S which is recovered
(see malathion). Some ethyl mercaptan is burned and discharged as S02 to the
atmosphere. Other wastes are handled as those for malathion. Equipment is
generally cleaned up once per year at the end of the 6 months or so produc-
tion run and wastes barged to sea.
Quality control: Mostly GLC methods of analysis. Have recalled
a few batches from the contract formulator for reworking. Shelf-life is
good—at least a year.
Formulation: Nearly all the phorate goes directly in full car or
truck lots to contract formulators where it is formulated to 10-15% granules.
American Cyanamid inspects the formulator's facilities at least once a year
and requires, in its contract, certification that the formulator will use
approved drum handling methods; drums are washed out with caustic-detergent
solution, sent to incinerator-type reconditioners, and are not reused for
food products. Formulated products are sold in American Cyanamid containers
to dealers, co-ops and farmers—perhaps 1,000 outlets in all. Containers
are special heat sealed 50-lb bags which have three layers—paper, aluminum
and polyethylene.
General: Phorate has agricultural use labels only. Major use areas
are: Midwest-Great Plains (60%); West Coast (15%); S.E. (10%); and N.E. (10%);
very little export. See also Malathion.
112
-------
CASE STUDY NOS. 9 AND 10
Pesticide: Parathion and methyl parathion
Chemical name • and formula:
RO. S .
\ ii //
^P-O-V
0,0-Diethyl 0-p-nitrophenyl phosphorothioate
and
0,0-Dimethyl 0-p-nitrophenyl phosphorothioate
Chemical class: Organophosphate
Pesticide class: Broad-spectrum nonsystemic insecticide
Description: Parathion: liquid of low volatility; insoluble in water;
very toxic; nonpersistent.
Methyl parathion: low melting solid (m.p. 36.5°C, low
solubility in water; very toxic nonpersistent
• . >
Producers: Monsanto (Anniston, Alabama), American Potash, Stauffer, Shell
Production chemistry:
1
P2S5+ 4ROH - >2(RO)2 pSH + H2S
S
(R0)2 PSH + C12 - >(RO)2PC1 + HC1 + S
ONa
S /^ S / - v
il i/~\\ • Arpfonp 'I //^~\\
(R0)2 P-C1 + K)| > (RO)2P-0-
-------
RON'
SO2
t
Incinerator
Dialkyl
Ester
CI2-
Chlorinator
NaOC6H4NO2-
Acetone
Na2CO3-
Partial
Recovery
Parathion
Figure 26 - Production and Waste Schematic for Parathion and Methyl Parathion
(Monsanto)
114
-------
Production Equipment (Monsanto)
Process continuity: Batch Est. annual production: Ethyl 8 MM and
methyl 20 MM
Equipment dedication: Me and Et Ib/year
parathion Plant capacity: 55 MM Ib/year
Equipment age: 12 years
Formulation on site: < 5% of product
Raw Materials
1.
2.
3.
4.
5.
6.
Material
P2S5
C12
ROH
NaOCgH4N02
Acetone
Soda ash
Received
From
On-site
Louisiana
Received
By
Tote bins
Rail, tanks
Storage
Tote bins
Tank cars
Remarks
Vented to pro-
duction system
Louisiana Rail, tanks
On-site
Southwest
East;
Rail , tanks
Rail, tanks
Tank
Bulk
middlewest
For waste
disposal
Reaction By-Products
Amount Produced
1.
2.
3.
4.
Material
H2S
HC1
S
NaCL
Form (Ib'/lb -A.I.)
Gas
Gas
Other
0.12 calcd.
0.12 calcd.
0.11 calcd.
0.20 calcd.
Disposition
Flared
Most re-
cycled
Incinerate
Biol. waste
treatment
Remarks
S02 air pollutant
Some to liquid
waste
S02, some H3P04?
Discharged to
city sewer
Process Wastes and Losses
Amount Produced
Material
Form (Ib/lb A.I.)
Disposition
Remarks
Active Ingre- Aqueous
dient
Solvents
Otherf Organo- Gas liquid
phosphates
p-nitrophenol
Liquid waste
treatment
Burned
Liquid waste
treatment
Liquid waste
treatment
< 1 ppm to city
sewer
115
-------
Disposition of Technical and'Formulated Products
Shipments
Technical Product
Formulated Products
Warehouse
On-Site Container Transportation Formulation Container Transportation
X
Mostly
55-gal.,
lined
drums,
some
smaller
90% by
truck
10% by
rail -
< 5% of 5,30-gal,
production drums
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture
X Yes
No
Pollution control: Liquid waste, including by-product HCl-NaCl,
go to biological treatment facilities, and then into the Anniston sewer
system. City specs are for < 1 ppm parathion. They have had no problem
complying on all effluent components. By-product H2S is burned in a flare,
and by-product S is burned. Waste solvent is also burned. No solid wastes
are produced except sludge from the biological oxidation system, which
is "recycled and discharged at a slow rate into the sewer."
Spills within the plant are washed down, and go into the waste
treatment system. Spills outside are handled by Monsanto personnel. The
frequency of outside spills has been about 8 to 10 per year, including
customer problems. Soda ash breaks down the parathions rather quickly,
and is used for decontamination.
Equipment clean-up is required only 1 or 2 times per year and
presents no major problem.
Quality control: G. C. methods are used. They have had no
particular problem with product quality.
Distribution: Most of the production is shipped to warehouses
around the country--Monsanto and about 20 carefully selected public
warehouses. Monsanto provides technical and safety service to the formulators,
about 90% of whom are in the South. Most of the parathions are femulated
as liquids with aromatic solvents. Drums used for the technical material are
reused for the formulated products and the formulators try to recycle drums
from their customers.
116
-------
Safety and personnel; Because of the high toxicity of these
compounds extensive precautions are taken.dJ Personnel safety record is said
to be good. Workers are provided with eye protection, gloves, aprons, dis-
posable overshoes, etc., but not with work clothing. The plant, which was
built in 1959, is said to have many safety shutdown features. The only
incidents appear to have been small solvent fires.
General: Up to 25-30% of Monsanto1s production is exported,
using Gulf ports. Other major producers of the parathions are Stauffer in
Tennessee (capacity of about 30 million pounds per year) and Bayer in
Germany.
Monsanto1s production is somewhat seasonal, but product shipments
are more so. Some of the formulators store between seasons.
117
-------
CASE STUDY NO. 11
Pesticide: Carbaryl
Chemical name and formula:
H
0—C-N-CH,
i n
0
1-Naphthyl N-methylcarbamate
Chemical class: Alkyl carbamate
Pesticide class: Insecticide
Description: Solid; solubility in water: 99 ppm; moderately toxic;
nonpersistent
Producers: Union Carbide (Institute, West Virginia)
Production chemistry:
Naphthalene
Tetralin
1-Tetralol
1-Tetralone
H,
-C(0)NHCH,
0-C(0)C1
,CH3NH2
NaOH
COC12
NaOH
1-Naphthyl-
chloroformate
CH3NCO
1-Naphthol
(Alternate Route)
118
-------
CI2.
Naphthalene
_L
Tetralin
Unit
H2
NaOH-
CH3NH2-
»-COCI2.
Vent
02
_L
Tetralol
Unit
Vent
_L
Condenser
_*~H2O.
Flare
/ Naphthol
Unit
Chloroformate
Unit
NaCI
Carbaryl
Unit
:u
NaCI
Heavy Residue^, .
_ ' -»• Incinerator
From Process
Solvent is Used for
- Some Steps
Packaging
j
Product
Secondary
Waste
Treatment
Plant
Figure 27 - Production and Waste Schematic for Carbaryl
-------
Production Equipment
Process continuity:
Combination
batch con-
tinuous
process
Est. annual production: 18 MM Ib/year
Equipment dedication:
Equipment age:
Plant capacity: 50 MM Ib/year
Formulation on site: no
Material
1. Naphthalene
2. H2
3. C12
4. 02
5. Phosgene
6. CH3OH
7. NaOH (50%)
Material
1.
2.
Raw Materials
Received From
Received By
Linde (local)
On site
Tank cars .
Barges
, Reaction By-Products;.,
Form
Amount Produced
(Ib/lb A.I.)
Storage
Dedicated tank cars and Bulk tank
barges ~ 90%
Pipeline
Tank cars, barges Bulk
50-90%
Other Process Wastes and Losses
Bulk.
Bulk.
Disposition
Material
1. Active ingre-
dient
2. Solvents
3. Other
Form
Amount Produced
(Ib/lb A.I.)
Disposition
120
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse
On-Site
~ 50% be-
fore
export
Formulated Products
Technical Product
Container Transportation Formulation Container Transportation
All, 50-lb Mostly rail;
bags of some truck
99% AI and piggy-
(pallet- back (full
ized) lots only)
By Contract Formulators
Most to WP; 2-lb bags
(25/baler bag), 5-
Ib bags (10/bailer
bag)
Some to liquid; 5-gal.
plastic drum (40/
pallet),
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes
No
Pollution control; About 2 Ib of chemicals (omitting NaOH and
are required to produce 1 Ib of carbaryl. By-product wastes are
liquid streams, vents and some heavy residues. All process water goes into
the plant 'secondary waste treatment''systems. All toxic vents are flared or
go to NaOH scrubbers. One nontoxic vent goes to a condenser and then is
vented to the atmosphere. St^ndard^hpQd .'.systems with recycle of recovered
material are used in the packaging process.
No solid waste, as such, is generated by Carbaryl production.
There is a heavy residue from the process that is burned in an incinerator.
There is one major shutdown per year in the carbaryl unit during
the slack season. There are numerous maintenance cleanups of a smaller
scale. Washings from these cleanups go into the process waste stream.
Leaks have not been a major problem. Experience with leakers
in the 5-gal. plastic drums has been less than 0.1%.
Quality control: Quality control is maintained by using their
own analytical methods. There are no critical impurities as such, and any
off-specification material can be reworked. Shelf-life is not a problem.
Returns have been because of physical inadequacy (lumps, etc.), not AI
content. This material can be reworked by the formulator.
121
-------
Formulation: The technical material goes to about six contract
formulators and about 20 customer formulators in the U. S. The contract
formulators are under UC control (quality control, production; they pack-
age under UC's label).
Safety and personnel; Standard industrial safety equipment is
used. All personnel at the plant have escape masks. Work clothes are
provided some of the workers, presumably those vho work in the most hazard-
ous operations. Work clothes from the insecticide units are bagged and
washed separately from the rest of the plant clothes. Cholinesterase
tests are routinely run on personnel working in the carbaryl unit.
The Institute plant is the regional coordinator for the NACA spill
team. They also have a "HELP program" for all chemicals that they produce.
The 1972 label will include instructions to burn, not reuse empty bags
and plastic containers.
General information; About 50% of the production is exported as
technical material primarily through East Coast ports. About 80% of the
exported material is shipped in seatainers for convenience and safety.
Some formulated material is also exported. The South is the biggest use
area; a fairly large quantity goes to the West.
122
-------
CASE STUDY NO. 12
Pesticide: Aldicarb
Chemical name and formula:
CH3 0
CH3-S-C-C=N-0-C-N-CH3
H
CHv
2-Methyl-2-(methylthio)propionaldehyde 0-(methylcarbamoyl)oxime
Chemical class: Alkyl carbamate
Pesticide class: Insecticide
Description: Liquid of low volatility; extremely toxic; nonpersistent
Producers: Union Carbide (Institute, West Virginia)
/
Production chemistry:
4HC1 >2NaCl + 2H20 +
[C1C(CH3)2CH2NO]2 —
2-Chloro-2-
methyl-1-nitroso-
propane dimer
CHoNCO
CH3SC(CH3)2CH=NOH ^ > CH3SC(CH3)2CH=NO-C(0)-NHCH3
2-Methyl-2(methyl- Aldicarb
thio)-propional-
dehyde oxime
123
-------
C4H8
1
NaNO
HCI (aq)-
t
NaCI
NaOH-
NaSCH3
*
Flare
Solvent Vent
Dimer
Reaction
Oxime
Reatibn
Aldicarb
Reaction
Aldicarb
50% Solution
•Shipment
*
NaCI Vent
Atmosphere
Liquid
Wastes
<
V *
l_
LL
Scrubber
.*
"1 •
Sump
*
fc
Secondary Waste
Treatment Plant
Figure 28 - Production and Waste Schematic for Aldicarb
-------
Production Equipment
Process continuity: Semi-batch Est. annual production: 1-3 MM Ib/year
Equipment dedication:
Equipment age: 15 years
Plant capacity:
Formulation on site: No
Raw Materials
Material
(CH3)C=CH2
2 .
3. CH3SNa
4. HC1
5. CH3NCO
6. Misc. solvents
Received From
East Coast
East Coast
East Coast
Received By
Tank cars
Tank cars
(in solution)
Tank cars
Tank cars
Material
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
1.
2.
Other Process Wastes and Losses
1.
2.
3.
Material
Active ingre-
dient
Solvents
Other effluent
streams
Form
Amount Produced
(Ib/lb A.I.)
Storage
Disposition
Disposition
Incinerated
or treated
125
-------
Disposition of Technical and Formulated Products
Shipments
Technical Product
Formulated Products
Warehouse
On-Site Container Transportation Formulation Container Transportation
None All by Truck
specially
modified
tanks
10% Granules 25-Ib
bag
(2/carton)
Truck and rail
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture
X Yes
No
Pollution control: All effluent streams from the unit are either
incinerated or treated. No solid waste, as such, is generated from aldicarb
production. NaCl goes to the liquid waste system. Organic losses are low,
about 10 Ib per 100 Ib Aldicarb, exclusive of solvent loss. Overall, 1 to
2 Ib of waste are generated per pound of product. It is anticipated that
solvent losses will be significantly improved if a new plant is constructed.
Potentially toxic liquid streams are detoxified (with caustic)
before they are sent to the plant waste treatment system. Other potentially
toxic effluents are flared. Spills and leakers are handled per "Handling
and Safety Guide for Temik 10G."
One reactor in the process is vented to a NaOH scrubber; this
waste then goes to the plant waste treatment system. For equipment cleanup
steam washout is used in the aldicarb unit for decontamination.
The aldicarb area of the production facilities are diked so that
all drainage goes to a caustic sump and then into the plant's secondary waste
treatment plant .•
The solvent from the technical material is destroyed by flaring
at the formulation site.
Formulation: All aldicarb is formulated at one facility several
hundred miles from the production site.
The technical material is formulated to a 10% granule on corn cobs
(Temik 10G). The formulation goes into DoT 2D bags, which are packaged four
to a 12B carton with liner and top and bottom pads. They are currently
126
-------
changing to a two-to-the-carton 25-lb bag. They have had no major problems
with packaging. The formulated product is shipped out by both truck and rail
shipment.
They have had to repack 3 million pounds of formulation because of
bag problems; no spills, however, were involved. Only one layer of packaging
failed.
Quality control: Quality control at the AI plant is rather stan-
dard. There are no critical impurities of consequence. Quality control at
the formulation plant, however, is more difficult than that for Sevin formu-
lation. In some case, off-spec material at the formulation plant must be
destroyed.
Safety and personnel: Aldicarb is extremely toxic and atropine is
the only antidote. UC does not know of any other industrial chemical process
that required comparable safety precautions.
Safety precautions in the production area are highly refined.
Wherever there is a possibility of contamination, air suits are worn, e.g.,
maintenance, decontamination operations. Suits are not required during rou-
tine operation. Glove-cabinets are provided at sampling points for toxic
streams. ChE's are routinely checked for production personnel.
Safety equipment and procedures at the formulation plant are ex-
tensive and are based on care, isolation and diking. The entire formulation
plant, which is located in an isolated area, is diked. Workers are supplied
with disposable paper overcoverings with taped wrists and legs, boots, and
various respiratory devices. Workers in the bagging area wear air suits.
They have had some minor problems as the result of operator error, but no
serious accidents.
Union Carbide has never had an emergency to date with Aldicarb
production or transportation. Temik 10G has been involved in three incidents
that UC was aware of:
1. A warehouse fire involving about 100 cases. Water from the
fire was diked, UC supervised the cleanup.
2. A small fire set by vandals.
3. A tornado involving about 100 cases in which a warehouse was
completely destroyed. It is assumed that the AI in Temik 10G would be
destroyed in a fire, because of the corncob rather than clay base.
General information: Union Carbide is the only known producer
of Aldicarb. Major uses are on cotton, sugar beets, primarily in the
South and West. About 507o of production is exported.
127
-------
CASE STUDY NO. 13
Pesticide: 2,4-D
Chemical name and formula:
Cl
Cl
fl
•0-C1L -C-OH
2,4-Dichlorophenoxyacetic acid
(usually as amine salts and esters)
Chemical class: Chlorinated phenoxy
Pesticide class: Herbicide
Description: Solid; salts are water-soluble, acid and esters nearly
insoluble; moderately toxic; nonpersistent
Producers: Dow (Midland, Michigan); Chipman (Portland, Oregon)
Production chemistry:
o
Dichloro-
phenol
C1CH2COOH
Chloroacetic
acid
0-CH2-COONa
Cl
CQ
H+
2,4-D Sodium
salt
OCHoCOOH
Esters
2,4-D
128
-------
C6H6-
•C6H5CI-
•CI2
-NaOH-
CH3COOH
(CH3CO)20
-2,6-C6H3CI2OH, etc.
.2,4-C6H3CI2OH
t
To Pentachlorophenol
-CICH2COOH-i
•GICH2COONa
Acid-
-NaCI-*i-
Still
Bottoms
Excess
C6H3CI2OH
Discharge
Figure 29 - Production and Waste Schematic for 2,4-D (Dow Chemical)
-------
Producer: Dow Chemical
Production Equipment
Process continuity: Semicontinuous Est. annual production: 35-40 MM Ib/year
Equipment dedication: Plant capacity: 45-50 MM Ib/year
Equipment age:
Formulation on site: yes
Raw Materials
Material
1. NaCl
2. Benzene
3. Acetic
acid
4. Acetic
anhy-
dride
Material
1. HC1, NaCl
2. 2,6-D
3.
Received From
Salt brine wells
Bay City, Michigan
South
South
Received By
Underground
pipeline
Rail, aluminum
tanks
Probably rail,
in tanks
Reaction By-Products
Amount Produced
Form (Ib/lb A.I.)
< 0.01
Storage
Disposition
Recycle
Convert to (
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Filter cakes
Form
Amount Produced
(Ib/lb A.I.)
< 2 Ib/day
Disposition
Lost through air and
shoes, etc.
Incinerator
130
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product^/
Formulated Products
On-Site Container Transportation Formulation Container Transportation
50% tank
cars,
drums,
bags
Rail
Liquids
Dry
Drums and
cans
50 Ib bags
a/ Includes acid, esters and salts (see text).
Pollution ControlRegulation
1899 Refuse Disposal Act applies to this manufacture X Yes
No
Pollution control; Dow (Midland) is on a very small river and
"had to face pollution and housekeeping problems much earlier than others."
Have extensive wastewater treatment facilities and huge incinerator equipped
with wet scrubber (for chlorinated tars especially). Wastewaters with
special contaminants (especially from the tank car wash shed) go through
special treatments such as a biologically active trickling filter before
going to the general biological treatment plant. Dichlorophenol imparts
a taste to water at 0.0005 ppm and kills fish at 2 ppm. A 1968 spill
of dichlorophenol plus some 2,4-D caused a fish kill and have since diked
around production/storage areas to prevent recurrence. In emergency, a
"shot" (holding) pond is automatically switched in.
For 2,4-D and 2,4,5-T manufacture nearly all the by-product chlor-
ide is recycled (charcoal recovery system) to electrolysis cells. By-
product 2,6-D is difficult to degrade biologically and would interfere in
waste treatment plant; therefore, it is removed (distillation or otherwise)
and converted to pentachlorophenol which has value. (Dow says that a small
producer could not afford to do this and also that the 2,6-D may run as
high as 12% of product with poor technology.) Other by-products are con-
verted by bleach-oxidation to C02, HC1, and removed.
Filter cakes, still bottoms, etc., from 2,4-D and 2,4,5-T pro-
duction are accumulated and incinerated (1000°C) during the nongrowing
season--especially not during April or May.
131
-------
Dryers are equipped with dust collection. Complete recycle is
used. Dow furnishes workers outer clothing, which is washed in in-house
laundry with wash water going to waste disposal. Wipe cloths, etc., would
also go to laundry or incinerator. Total loss of 2,4-D through air and
shoes, etc., is now less than 2 Ib/day, although it had, previously been .
as high as 150 Ib/day.
Drums used in shipments are one-way; any returns would be incin-
erated. Tank cars are owned by Dow and are used mostly for herbicides
during rush season, but may be -used for other Dow chemicals at other times.
All are cleaned as needed in a special tank washing shed with detergent
and high pressure (see above) .
Formulation and packaging; Dow sells 40-60 formulations in addi-
tion to technical. The product mix is approximately as follows:
2,4-D Acid, wet
5oJ
Esters
> Amines
Bu | -Sales
\sS*
i-Pr Y— ^Formulations
i-Octj
Many v. > Sales
T*
Formulations
Sales
Sales
Acid, dry
Formulations
Perhaps 50% of total production is shipped in tank cars (mostly
8,000 gal., some 4, 000 gal.) and the remainder in bags and drums. Con-
tainers for esters and amines range from tank cars to 5 gal. cans. Formu-
lated products usually go to smaller containers and dry products to 50-lb
bags. Over 250,000 5-gal. cans are packaged per year.
Quality control: Use VPC/ Computer . Any of f-specif icatipn mate-
rial would be treated as required: upgraded, blended, degraded, etc. The
tetrachloro dioxin which is a problem in 2,4,5-T production is not a .by-
product in 2,4-D production.
Safety and personnel ; Fire and occupational safety practices
appear to be standard for a large chemical company.
General information; Dow is the major producer (90%) of 2,4-D
left since Diamond, Hercules and Monsanto have stopped. Capacity is 45-50
million pounds per year mixed 2,4-D derivatives. Most of the 2,4-D sales
are in the grain states. Sales are made primarily through other companies
such as AmChem, American Oil, Guth and Farmland Industries. Dow is on
the NACA Safety Team, gets approximately one call per week and has com-
piled a "bible" of information on handling pesticides of all types.
132
-------
Process continuity:
Equipment dedication:
Equipment age: 1956
Producer: Chipman
Production Equipment
Est. annual production: 3-5 MM Ib/year
Plant capacity:
Formulation on site:
Raw Materials
Material
Received From
Received By
1. Cl£ Produced on site
2. Others probably the same as for Dow
3. :
Storage;
Material
1. Chlorides
2.
Reaction By-Products
Amount Produced
Form (Ib/lb A.I.)
Disposition
Discharge
see text
Material
1. Active ingre-
dient
2. Solvents
3. Other
Other Process Wastes and Losses
Form
Amount Produced
(Ib/lb A.I.)
Disposition
See text
133
-------
Disposition of Technical and Formulated Products
Shipments ;
Warehouse Technical Product , Formulated Products
On-Site Container Transportation Formulation Container Transportation
Some See text
Pollution Control Regulation
/
1899 Refuse Disposal Act applies to this manufacture X Yes No
Pollution control; Over $1 million have been spent for pollu-
tion control facilities at this production plant. The wastewater treat-
ment facilities are centered in a continuous flow charcoal absorption
plant which is said to reduce phenolics below the 1.0 mg/liter level.
(See Figure 30.) Pollution problems from pesticide production is said to
be limited to occasional phenolic odor complaints. No area vegetative
damage from 2,4-D and no corrosion damage or odor complaints from chlorine
has occurred. No landfill of solid wastes is allowed in Oregon. Trans-
portation problems have been apparently few: one incident of leakage by
a defective tank car several years ago. Filled drums receive spot check
of closures and check in storage. Drum leakers are said to result from
rough handling, not defects. Chipman has their own fire department and
works with local department. Diking, etc., in the plant area is said to
meet insurance requirements. No emergency holding pond appears to exist.
Clothing of production personnel probably go to a commercial laundry.
Quality control; No reject batches are made. They have had
minimum cross contamination problems. No problem with dioxins.
Distribution; Chipman does not retail 2,4-D. About 50% of
production is sold as acid, with formulation done at Portland and outside.
Amine salts and the octyl and butyl esters are formulated in Portland, .
in Chipman facilities in North Kansas City and St. Paul, and by outside
formulators. The 2,4-D products are shipped in tanks (rail and truck)
down to 1-gal. cans.
134
-------
10
Ui
LADSOI
RBER
ADSORBER
tf
NEUTRALIZATION
1
T
Treated
>
effluent
REGENERATED-
CARBON TANK
*-&
Figure 30 - Charcoal Absorption/Filtration Plant for Treating Phenolic WastesfL
4/
-------
CASE STUDY NO. 14
Pesticide: 2,4,5-T
Chemical name and formula:
Cl
-OH
Cl'
2,4,5-Trichlorophenoxyacetic acid
(Also used as amine or sodium salt and as esters.)
Chemical class: Chlorinated phenoxy
Pesticide class: Herbicide (brush) and growth regulator
Description: Solid; salts are water soluble, acid esters insoluble;
moderately toxic; nonpersistent
Producers: Dow (Midland, Michigan)
Thompson-Hayward (Kansas City, Kansas)
Production chemistry:
OH
Cl
NaOH ^
+ ClCH2COOH
Cl
0-CH2COONa
Cl
'Cl
Trichlorophenol chloro-
acetic acid
Cl
2,4,5-T, sodium
salt
OCH2COOH
2,4,5-T
Amine salts
136
-------
Recycle^-
HCI
TCB
Unit
C6H2CI4 -^
NaCI
TCP
Unit
ROH
NaOH'
CICH2COOH-
•Solvent, By-Products-
.C6H2CI3OH
^•To Recycle,
Recovery
- or Waste
Neutralizer
Neutralizer
Condensation
Reactor
Acid-
Recycles- NaClr"
I
2,4,5-T
Recovery
f
Product
Wastes to
Treatment
Figure 31 - Production and Waste Schematic for 2,4,5-T
(Dow--see Case Study 13 for details)
-------
Producer: Dow
Production Equipment
Process continuity: Semicontinuous Est. annual production: 3-5 MM Ib/year
Equipment dedication: Plant capacity: 10 MM Ib/year
Equipment age:
Material
1. Chorobenzene
2. Chlorine
3. Chloroacetic
acid
Material
1. HC1, NaCl
2.
Formulation on site:
Raw Materials
Received From
On-site
On-site
On-site
Received By
Material
1. Active ingre-
dient
2. Solvents and
by-products
3. Other: filter
cakes, still
bottoms incin-
erated
Reaction By-Products
Form
Amount Produced
(Ib/lb A.I.)
Other Process Wastes and Losses
Form
Amount Produced
(Ib/lb A.I.)
Storage
Disposition
Recycle to Cl2
unit
Disposition
Recycle, recovery
or waste treat-
ment
138
-------
Disposition of Technical and Formulated Products
Warehouse Shipments
On- Else- Technical Product Formulated Products
Site Where Container Transportation Formulation Container Transportation
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes No
Pollution control: See 2,4-D Case History Study No. 13 for details
of Dow's waste treatment facilities. The trichlorophenol plant is new and
maintains very careful temperature control during the hydrolysis of tetra-
chloro benzene to avoid the formation of dioxins which can cause chloracne
in humans. No chloracne cases have occurred with workers in this plant.
General: Most of the 2,4,5-T is converted to the amine or esters
and little is sold as acid. Most of the 2,4,5-T products go to the pasture
lands of Texas, etc. Some of the trichlorophenol is sold for direct pesti-
cidal use and some for other uses.
139
-------
Producer: Thompson^Hayward
Thompson-Hayward produces only the isooctylester of 2,4,5-T and
does not isolate the acid in its process.
Production Equipment
Process continuity:
Equipment dedication: One product
Equipment age: 10 years
Material
1.
2.
3.
4.
C1CH2COOH
NaOH
Isooctyl
alcohol
Material
1. Salt
2.
Est. annual production: 2.5-4 MM Ib/year
ester
Plant capacity: ~ 5 MM Ib/year (est.)
Formulation on site: Yes
Raw Materials
Received From
Michigan
Various sources
Various sources
Various sources
Reaction By-Products
Received By
Form
Amount Produced
(Ib/lb A.I.)
0.2 Ib/lb ester
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Other mixed
phenolic wastes
4. Solid wastes
Form
Liquid
Amount Produced
(Ib/lb A.I.)
50-75 Ib/month
Storage
Disposition
Oxidation pond,
then discharge
Disposition
Sewer
Commercial landfill
Landfill
140
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product. -_ Formulated Products
On-site Container Transportation Formulation Container Transportation
X Very Isooctyl -55-gal. Mostly trucks,
little ester in drums some rail to
xylene- 30-gal. West Coast
type drums
solvent 5-gal.
drums
1-gal.
can (all
lined)
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes No
During production most items are recycled; some of the alcohol
goes to the steam condenser and then to the sewer. The biggest problem is
disposal of salt. Their liquid waste treatment system is in the process of
modification. An "oxidation pond" presently catches all process, service and
surface waters, i.e., it receives some pesticides, detergents, spill residues,
etc. Periodically the pond level is partially lowered by pumping water over
the levee into the Kaw River. In a new system (under construction, ** $100,000)
the clean-water streams (boilers, etc.) are being separated from waste streams
and will go directly to the river. The waste streams will go to the oxidation
pond, then to a chemical treatment basin (acid or caustic) and then via city
sewer to the river. During equipment cleanup solvent is recycled to the next
batch. They usually use the same process and formulation equipment for one
product. If the product is changed they would preclean with solvent which
would be recycled; then steam clean with condensate going to the sewer; clean
with caustic which detoxifies 2,4-D and rinse. .Solid wastes go to a landfill;
purge of 2,4,5-T units give 50-75 Ib/month of mixed phenolic wastes which go
to a commercial landfill. They have had little problem from air pollution,
but some phenolics are troublesome because of odor (detectable at 0.005 ppm).
They are collected by wet scrubber and discharged; also use wet scrubbers if
they make the amine salts.
Accidents-_-a truck once dropped a trailer and broke containers.
Cleanup consisted of absorption with clay and burial in landfill. Mixed lots
of shipments on trucks are problems if breakage occurs.
Quality control: Use gas chromatography, but do not have much
fluctuation. Dioxin impurity of 0.5 ppm in finished product. (T-H process
gives only one significant dioxin impurity). In general, little trouble with
141
-------
with off-spec 2,4,5-T. A problem batch would be blended off. They keep
herbicides well separated from insecticides in warehousing to avoid cross-
contamination by the volatile esters.
General: Most of the 2,4,5-T goes to brushy regions of the south-
west, rangeland and also to south and southeast.
142
-------
CASE STUDY NO. 15
Pesticide: Atrazine
Chemical name and formula:
Cl
CHoCH,-N
NHCH
CH3
2-Chloro-4-ethylamino-6-iso-
propylamino-s-triazine
Chemical class: Triazine
Pesticide class: Selective herbicide
Description: Solid; nearly insoluble in water; low toxicity; nonpersistent
Producers: Geigy (St. Gabriel, Louisiana)
Production chemistry:
Cl
3HCN + 3C1,
Cl
Cl
A
CC1
(CH3)2CHNH2
Cyanuric
chloride
Cl
5HC1 or +
RNH3C1
•NHCH(CH3)2
Atrazine
143
-------
CI2.
HCN-
NaOH-
HCI,HCN
I
Scrubber
and Filter.,
t ,
\
\
Deep Well
Disposal
CCL
I
Amination
Unit
(CH3)2CHNH2 ™
J 2 z or Solvents
* L
Atrazine-
(Alternate)
Formulation
Baghouse
I
Discharge
to River
Packaging
I
Product
Sic i • • i
1 ^ ^ L|quid
f
\
Wastes
s
Scrubber
t
i
Ve
Figure 32 - Production and Waste Schematic for Atrazine
-------
Production Equipment
Process continuity: Continuous Est. annual production: 100 MM Ib/year
Equipment dedication: Mostly Plant capacity: 100-150 MM Ib/year
atrazine,
some other
triazines
Equipment age: 1970
Formulation on site: Yes
Raw Materials
Material
1. HCN
2. "Appropri-
ate" amines
3. C12
4. NaOH
Received From
Memphis, Tennessee
Taft, Louisiana
Adjacent plant
Received By
Tank cars
Tank cars
Pipeline
Storage
Tank
Tank
Not stored
Material
1. HC1
2.
Material
1. Active ingre-
dient
2. Solvents
3. Solid waste
4. Liquid
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
0.333
Other Process Wastes and Losses
Form
Amount Produced
(Ib/lb A.I.)
Disposition
Scrubber, then
deep well or
river
Disposition
Landfill
River
145
-------
Disposition of Technical and Formulated Products
Warehouse
Shipments
Technical Product
Formulated Products
On- Else-
Site Where Container Transportation Formulation Container Transportation
None Public
ware-
hous-
ing
Rail
% W.P. (80%
A.I.)
Liquid
(4 lb/
gal.)
5-lb bags
(multi-
walled)
(10 per
case)
1,5 gal.
plast'ic
Rail
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes
No
Pollution control; About 1 lb of effluent is generated per pound
of atrazine produced—mostly NaCl. Liquid wastes from the cyanuric chloride
production unit ordinarily go to a 6000 ft deep well disposal, after re-
ceiving a preliminary polishing (pH adjustment and filtration). The larger
amount of liquid wastes from the remainder of the plant are discharged to
the river. Sanitary wastes from the plant are chlorinated before they are
discharged. The BOD of the waste going to the river is 500 Ib/day at
the 100 million pound per year production rate.
Solid waste is primarily bag wrappers, car lining material, etc.
This waste is disposed of by a commercial operator by landfill not located
on the plant site. The formulation and packaging areas are controlled by
baghouses and wet scrubbers and atmospheric monitors are used. Losses are
said to be substantially < 1%.
Breakage and leakers have not been a major problem. Returns have
been < 1%. Overall repackaging is < 2%. Industrial average is said to
be 4-5% (for wettable powders?).
Package disposal is a problem.
happens to the atrazine is not known.
They can be burned, but what
Within the next 2 years, an additional investment equal to 10%
of the new plant's cost will be made for spill protection and the treat-
ment of organic waste. Fifty percent of the next 5 years capital budget
will be for environmental control.
146
-------
They may have to consider chlorine recovery instead of deep well
in the future, although Louisiana encourages the use of deep wells for
waste disposal, and 20 wells within 4 miles of the atrazine plant have
operated for over 10 years without major difficulty.
Quality control; Product quality is maintained by "more than
50" on-stream control devices. To date the new plant has never produced
off-specification material. Because of the sophisticated control equip-
ment, product yield has been much higher than that of the old plant. Off-
specificatiori material could be recycled to be reworked.
»
Safety; Safety at the St. Gabriel plant is standard for toxic
chemical production (HCN handling facilities). Standard emergency equip-
ment is available. Work clothes are provided.
General information; The new plant at St. Gabriel replaces a
previous Geigy atrazine plant built in 1959 at Mclntosh, Alabama, which
was a batch or semibatch operation. The new plant was designed primarily
for atrazine (although other triazines can be produced in the same equip-
ment) and production, formulation, and packaging are done in one continuous
operation.
Some atrazine is exported; 2 million pounds was exported last
year. Apparently atrazine is also produced by Geigy overseas.
The major uses for atrazine is corn; some is used on sorghum;
very little is used by industry (< 10%).
147
-------
CASE STUDY NO. 16
Pesticide: Trifluralin
Chemical name and formula:
N(C3H7)2
NC-2
-
CF3
-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine
Chemical class: Nitroaromatic
Pesticide class: Selective herbicide ,
Description: Low melting solid of low volatility and water-solubility;
very low toxicity; nonpersistent
Producers: Eli Lilly and Company (Lafayette, Indiana)
Production chemistry:
HNC-3/H2S04
CF3-C6H4-C1 —-—:t> CF3 -
NHPr2/Na2C03>
C J. •- ••»-... —— ,
N(C3H7)2 + NaCl
N00
148
-------
i
^ Mononitrator -^Q Storage j Acid
HN03- | Rec°
Sold
NH(C3H7);
verX H20 Na2
S t 11
H*,^O i Olni im r ^ PtT>tt 1 1 , .1 ,i - ^ Ft Ifnr «««r^fc» H inifrn ^fe AminfltlOn
i A in CHCI3 Keucloi
T (CH
NOX \T
i ^
Scrubber
i
Waste
Water
^x i
Cj3/J Filter
*
Decanter
^
„ , ^ Vacuum
Vac f
Exhaust Trifluralin (e:
»
C03
Salt
-^ Water
Waste
. Aromatic
Naptha
c.)
Figure 33 - Production and Waste Schematic for Trifluralin
-------
Production Equipment
Process continuity: Continuous Est. annual production: 10-20 MM Ib/year
Equipment dedication:
Equipment age: < 15 years
Plant capacity:
Formulation on site: Yes
Raw Materials
Material
1. PCBT
2. Diisopropyl-
amine
3. Nitric acid
4. Sulfuric acid
5. 20% Oleum
6. Sodium carbanate
Received From
Buffalo, Chicago
Various suppliers
Received By
Tank cars
Tank cars
Tank cars
Tank cars
Tank cars
100-Ib bags
Storage
Material
NaCl
2.
Reaction By-Products
Form
Aqueous
Amount Produced
(Ib/lb A.I.)
0.17
Other Process Wastes and Losses
Disposition
Waste treat-
ment and dis-
charge
Material
1. Active ingre-
dient
2. Solvents
3. Liquid waste
Form
Amount Produced
(Ib/lb A.I.)
Disposition
Waste treat-
ment and dis-
charge
150
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product Formulated Products
Elsewhere Container Transportation Formulation Container Transportation
Owned or Small per- Liquid 5-gal.
leased centage (4 lb/gal.) lined
ware- - in aromatic cans
houses naphtha metal
quarts
By contract
formulators
granules '
(2.5% A.I.
or clay)
: (< 1% of
sales)
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes No
Pollution control: ' NaCl and process water to waste disposal;
NOX to scrubber; H2S04 upgraded and sold; no solid wastes' from treflan.
The biological waste disposal plant services all of Lafayette
facility, but treflan unit effluent constitues a significant (20-40% ?)
part of total. Plant is $8-10 M investment with operating costs of ~ $2
M/year. It uses neutralization, settling, aeration and biological. Plant
is state approved (the Indiana Stream Pollution Board is very strict). The
discharge is cleaner than river water and contains no treflan. Lilly has
had no fish kills. The fate of the fluoride in degradation of treflan was
unknown. (A new Lilly plant at Clinton handles each waste stream at its
source in-plant.)
Leakers--only a few problems. They use corrugated layers between
cans and strapped pallets for shipment. Treflan has bright yellow color which
makes leaks obvious.
Most of the trifluralin produced is formulated directly at
Lafayette as liquids. Liquid formulation and filling equipment used only for
trifluralin. The contract formulators of the small amount of granules have no
dust problem.
151
-------
Quality control: Have own specifications and assay on raw materials,
use G.C. in process and on final product, approximately no off-specification
batches and few impurity problems. They make statistical check of incoming
cans before filling. No shelf-life problems; probably > 5 years.
Safety and personnel health: Personnel do not need protective
clothing for working with trifluralin. Nitration and dinitro units.are
watched carefully-have had no explosions.
General: About 1070 of production is sent as technical to overseas
Lilly subsidiaries and a small amount (« 5%) is sold to the home and garden
market. Most of sales are to dealers, but some goes directly to farmers.
Use pattern is ~ 60% on soybeans; ~ 30% on cotton; and ~ 10% all other.
152
-------
CASE STUDY NO. 17
Pesticide: Alachlor
Chemical name and formula:
2CH3
N
£~f2
0 Cl
2-Chloro-2',6'-diethyl-N-
(methoxymethyl)acetanilide
Chemical class: Acetanilide
Pesticide class: Selective herbicide
Description: Low melting (40°C) solid; solubility in water, 140 ppm;
moderately low toxicity; skin irritant; nonpersistent
Producers: Monsanto (Muscatine, Iowa)
Production chemistry:
C2H5.
o
CoH
2n5
H2CO
Solvent
Diethylaniline
C1CH2COC1 C2H5.
NH-,
CH0OH
NH4C1 +
u
s/
6
Alachlor
153
-------
(H2CO)2
Depolymerizer
NH3
DEA
Aromatic
Solvent
Alachlor »
Solvent
NH4CI j
Fuel
Discharge
to River
Liquid
Formulation
Granule
Formulation
'— Baghouse
Figure 34 - Production and Waste Schematic for Alachlor
-------
Production Equipment
Process continuity: Batch
Est. annual production: 20 MM Ib/year
Equipment dedication: Only this Plant capacity:
product?
Equipment age:
Formulation on site: Yes
Raw Materials
Material
1. 2,6-Diethyl
aniline
2. C1CH2COC1
3. Paraformal-
dehyde
4. Methanol
5. Ammonia
6. Aromatic sol-
vents
7. Clay
Material
. NH4C1
Received From
Southeast
Northeast
Texas
Texas
Produced on site
St. Louis
Southeast
Received By
Tank cars
Tank truck
Hopper cars
Tank cars, some tank
trucks
Tank cars
Rail
Storage
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
0.19
Disposition
Discharged to river
2.
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3.
Form
Amount Produced
(Ib/lb A.I.)
Disposition
Burned for fuel
155
-------
Disposition of Technical and Formulated Products
Warehouse
Shipments
On
Else-
Technical Product
Formulated Products
Site where Container Transportation Formulation Container Transportation
Most For
distri-
bution
(com-
pany-
owned,
con-
trolled)
5%
50-60%,
E.G. (10%
A.I.)
35-45%
Granules
5-Gal.
cans
(lined)
5-lb bags
Truck > rail
Truck > rail
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes
No
Pollution control; Process water is discharged to the Mississippi
River after mechanical treatment only. Alachlor losses are about 300 lb/
day. They are considering the recovery of by-product NH^Cl. The process
has no solid products and ;gives (no of f, gases. Production equipment re-,
quires cleanup only two or three times per year and "presents no problem."
The formulation equipment is used for some other products. Packaging.area -
has automatic bagging and filling equipment and is said to be very clean.
The production and warehouse areas are not.diked. Leaking containers have
not been a serious problem: « 1% on bags; < 0.5% on cans. Used drums are
a very small problem at Muscaline and would go to a landfill on site. Wipe
cloths, etc., are probably burned.
Quality control: Quality control is maintained by G.C. analysis
of products before they are packaged. Rework of off-specification batches
is no particular problem; Shelf-life is at least 2 or 4 years.
Safety and personnel; "Much emphasis is placed on housekeeping
and personnel safety." Work clothes are not provided. Selection of public
warehouses for product storage based on having automatic sprinkler system.
General; Monsanto markets through distributors such as co-ops,
etc., and alachlor may be available on as many as 15,000 shelves. A small
percentage of the production is exported..
156
-------
CASE STUDY NO. 18
Pesticide: Captan
Chemical name and formula:
C Cl
V-S-C-C1
/ ri
C C1
o
N-trichloromethylthio-4-cyclohexene 1,2-dicarboximide
Chemical class: Chlorinated organo-sulfur compound
Pesticide class: Fungicide
Description: Solid; nearly insoluble in water; very low toxicity; non-
persistent
Producers: Calhio Chemical (a Stauffer-Chevron subsidiary, Perry, Ohio)
Production chemistry:
CH=CH2 CH-CO HC' "^CR-CO l,NaOH
+ NH3 > I | >NH 2,CC13SC1
CH=CH2 CH-CO HC CH-CO
^CH2X
Butadiene Maleic Tetrahydrophthalimide
anhydride /^2
HC NCH-CO
|| | > NSCC13 + NaCl
HC CH-CO
Captan
I,
CS2 + 3C12 ^-> CC13SC1 + SC12
Perchloromethyl mercaptan
157
-------
Vent
Vent
Vent
Ln
oo
1 1
1
* *
Scrubber
|
Duraaiene ^
1
Scrubber
f 1
H~° ' , -
i
1
* f
Scrubber
t
» FlnLnr
I
Scrubber
f 1
T
,
I
i 1 t
Scrubber
f
PMM
Storage
THPI
i i i i •
Vent Vent
(Adapted from drawings supplied by Calhio Chemical) .
I
Wa
* Liq
/Line
f Hoi
\Pon
1
Disc
to Ri
,
03
,
* Captan _ , „ ,
. . V — ^Captan ^ Package
1 1 1
1 — ' r— - • i
Baghouse Ship
i
Vent
ste
uid
k
ding)
d 7
Under ^ Deep Well
Construction Disposal
narge
ver
I
ment
Figure 35 - Production and Waste Schematic for Captan
-------
Production Equipment
Process continuity:
Est. annual production: 18 MM Ib/year
Equipment dedication: Also used Plant capacity:
for Folpet
Equipment Age: 1954
Formulation on-site: No
Raw Materials
Material
Received From
Received By
Storage
1.
2.
3.
CS2
Cl,
4. NH3
5. CaC03
6. Maleic
anhydride
7. Butadiene
8. NaOH
Delaware
Michigan
Louisiana
West Virginia,
Kentucky
Missouri,
Pennsylvania,
New Jersey
Texas
Tank cars
Drums
Tank cars
Tank cars
Truck loads
Tank cars
Tank cars
Tank cars
Drums
Used directly
from tanks
Used directly
from tanks
Bulk
1.
2.
Reaction By-Products
Material
Form
Amount Produced
(Ib/lb A.I.)
Disposition
159
-------
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Liquid
4. Solid paper
5. Metal
6. Chemical
Form
Patriculates
Amount Produced
(Ib/lb A.I.)
~ 4 Ib/day
10 tons/year
10 tons/year
25 tons/year
1,200 Ib/year
1 Disposition
Asphalt lined
settling pond;
discharge
Local collector
Local scrap
dealers
Buried oh plant
property
Disposition of Technical and Formulated Products
Shipments
Warehouse
On-site
Formulated Products
Technical Product
Container Transportation Formulation Container Transportation
50-lb bags ~ 98% in boxcars;
2% in trucks
3-day
capacity (92% A.I.
only for 87» CaC03)
bags (some (55/pallet)
outdoor
bulk bins)
See text
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture . X Yes
No
Pollution control: All liquid effluents from the production facility
(including 70-80 gpm dilute saline from the captan unit and that from the
scrubbers) go to an asphalt-lined settling pond; retention time is about 6 or
7 days. The effluent from the holding pond (averaging 75 to 80 gpm) goes
to a river that feeds into Lake Erie. This effluent is monitored weekly.
Captan levels in the discharge are said to be nil. This system has been in
operation since the 1950*s and no sludge has been removed to date. Depth
ranges from 3-1/2 to 4-1/2 ft. Sanitary waste goes to a septic tank.
Calhio is currently testing a new deep well (6,000 ft deep) to be
used for liquid wastes. Over 1 million gallons of clean water are being
pumped down the well before waste injection can be initiated. This will be
160
-------
the only well in this part of the state; five or six wells are located in
the western part of Ohio. Surface facilities for the well have not been
designed yet, pending results from the current tests. The well should be
in operation by next summer. Capital investment at this plant for environ-
mental protection, including the new deep well, is between $1-2 million,
Solid waste disposal includes; Solid chemical waste--!,200 lb/
year (from spills, contaminated waste from floors, etc.) which are buried
on plant property; trash paper—cardboard—(10 tons/year), moved out by
local collector; metal scrap--(25 tons/year), sold to local scrap dealers.
Air pollution controls include:
Baghouse stacks - 8,000 cfm
i Particulates - captan
3.43 Ib/day (0.048 grains/ft3
Filter hood exhaust - 6,500 cfm
Steam
Particulates (captan and water—quantities unknown—less than
above)
Packer baghouse stack - 3,500 cfm
Particulates—quantities unknown—less than above
Product change over is about once per year. Clean up is required
of the imide and captan processes only. "All" the material from the clean
up of these units is salvaged: dust is returned to the broken bag handling
system; lumps are slurried and refiltered; and water from the clean up goes
into the waste system.
Quality control; Each 10,000 to 12,000 lb of captan are desig-
nated as a batch for quality control purposes. .A small sample is taken from
each 50-lb bag to make up one composite sample for each batch. A titration
method is used for AI analysis. They have no particular problems with off-
specification materials as it can be reworked without major difficulty. .
Shelf-life of the formulated material is not a problem. The
function of the CaC03 in the technical material is to control the pH for
better stability.
Safety: Standard safety equipment is used in the plant. All
personnel are issued protective masks. Safety standards appropriate for
Cl2 handling are used.
161
-------
No fires were known that involved captan.
General: Calhio is a jointly-owned subsidiary of Stauffer Chemical
Company and Chevron Chemical Company. The technical captan is not an item of
commerce; it is shipped only to Stauffer and Chevron, with the exception of
an occasional carload shipment to Canada. Captan is formulated by Chevron
and Stauffer at 7-10 locations: usually two in New Jersey, two in the
Midwest, three or four on the West Coast, and one in Florida (very small
quantity only).
Captan is also produced in France in "their" plant and in Israel
(Makhteshim?).
Deciduous fruit is the largest use, although there is some use
on citrus and seed treatment.
162
-------
CASE STUDY NO. 19
Pesticide: Methyl Bromide
Chemical name and formula:
CH3Br
Bromomethane
Chemical class: Halocarbon
Pesticide class: Fumigant
Description: Liquified gas (BP 3.6°C); very toxic; probably not
persistent in sunlight
Producers: Dow (Midland, Michigan); Michigan Chemical; American Potash;
Great Lake Chemical; Vulcan
Production chemistry:
6 CHsOH + 3Br2 + S > 6CH3Br + H2S04 + 2H20
163
-------
Br2
' CH3OH
S.
L
Reactor
System
/ NaOH
Fractionation
System
Scrubber
1
Waste
Treatment
Plant
Discharge
to River
CH3Br
H2SO4 — ^ Recovery
Dryer
/ O * 1 *
Packaging
Shipment
Figure 36 - Production and Waste Schematic for Methyl Bromide (Dow Chemical)
-------
Production Equipment
Process continuity:
Equipment dedication:
Equipment age:
Est. annual production: 13 MM Ib/year
Plant capacity:
Formulation on site: Not formulated
Raw Materials
Material
1. Methanol
2. Bromine
3. Sulfur
Received From
DuPont
From chlorine
production units
Various sources
Received By
Tank cars or trucks
Storage
Material
H2S04
2.
Reaction By-Products
Form
Amount Produced
(Ib/lb A.I.)
0.183
Disposition
Recovered
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Other
Form
Amount Produced
' (Ib/lb A.I.)
Disposition
165
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product Formulated Products
On-Site Container Transportation Formulation Container Transportation
X 1-lb cans
10,50,100,
150 Ib
cylin-
ders
1,500 Ib
pigs
13,000 Ib
cylin- Export
ders
tank cars
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes No
Pollution control; Methyl bromide is a colorless, odorless,
poisonous gas which requires handling in a closed refrigerated system.
By-product l^SO^ is recovered; some sold to fertilizer producers; some used
to make bromates for photographic purposes. Dow gets ^90% recovery of
Q^Br on first pass (have some recycle streams). A possible by-product is
(CHo^O and some of competitors produce considerable. The CH-jBr system is
vented through a caustic scrubber and the product is dried with silica gel.
Dow has had almost no accidents with MeBr. Have had almost no
leaks on cans or small cylinders; filled cans are checked in a water bath
and with halogen leak detector. Dow makes a 9 for 1 offer if a customer
gets a leaker. Have recently put in an 18 month shelf-life limitation on
cans to guard against corrosion from outside in during storage under poor
conditions. Dow uses a shielded type of valve on "pigs" which is drop-
proof. Have had minor leaks from sticking valves on tank cars but have
handled easily. Biggest problem is the costly reconditioning given to
all returned cylinders. Nearly all (90%) of these are Dow-owned and are
returnable. Chlorpicrin, a lacrymator, is added to some of the MeBr as
a warning agent. See 2,4-D, case study number 13, for further details of
Dow's liquid waste disposal system.
166
-------
Dow produces 50-60% of the CH-Br in the U. S. with the remainder
divided between Great Lakes, Michigan Chemical (St. Louis), Vulcan (Newark),
and American Potash (Los Angeles). Some foreign producers also. Probably
the largest part of Cl^Br volume goes to commercial applicators, although
some goes to packagers (to whom Dow furnishes technical assistance such
as on caustic scrubbers). Major shipment areas are:
1. Southeast (North Carolina, etc.) - tobacco, etc. Biggest
use probably
2. California - Truck farming
3. Kansas City/Midwest - Grain fumigant
The cost of putting CH-Br in 1-lb cans is high: (40-50% of
price) but Dow fills over 5 million cans per year.
167
-------
CASE STUDY NO. 20
Pesticide: Pyrethrins
Chemical name and formula:
CHo CHo
CH3
Several insecticidal components present
in the flowers of Pyre thrum cineraefolium
Chemical class: Botanical product
Pesticide class: Insecticide
Description: Solid or liquid mixture; low toxicity; nonpersistent
Producers: FMC-Niagara (Baltimore, Maryland and Middleport, New York) ;
Mclaughlin Gormley King; Penick
Production chemistry:
Extraction Process
Extract Extract
Chrysanthemum Solvent W/CH3OH W/CgHj^ Pyrethrum
flowers - » Crude Extract - > - > concentrate
168
-------
(Adapted from drawings furnished by FMC Corporation)
Many extraction, washing and recycle steps omitted for simplicity.
Figure 37 - Pyrethrum Refinery and Waste Schematic (FMC Corp.)
169
-------
Producer: FMC Corporation
Production Equipment
Process continuity: Batch
Est. annual production: 130,000 Ib/year
(1007, basis)
Equipment dedication: Pyrethrins Plant capacity: 150,000 Ib/year (est.)
only
Equipment age: Est. 30 years avg. Formulation on site: At Middleport,
New York site
Raw Materials
Material
Received From
Received By
Storage
1. Crude pyrethrin Africa
2. Kerosene (de- New Jersey
odorized)
3. Lexane New Jersey
4. Methanol New Jersey
Drum air freight
Tank trucks
Tank trucks
Tank trucks
Drums
Tanks
Tanks
Tanks
Reaction By-Products
Material
Form
Amount Produced
(Ib/lb A.I.)
Disposition
1. Wax
2. Resin
3.
Solid
Solid
Drummed and stored
Drummed and stored
Other Process Wastes and Losses
Material
Form
Amount Produced
(Ib/lb A.I.)
Disposition
1. Active ingre-
dient
2. Solvents
3. Filter cakes
4. Resin and wax
residues
5. Atmospheric
losses
Virtually none--too expensive
Very small
Recycled
On site landfill
Drummed and stored
Vent
170
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Products/
Formulated Products
On-Site Container Transportation Formulation Container Transportation
Available ~ 100%;
but do 30-gal.
not use drums
Truck to
Middleport
Small amt. 55-gal. Direct to cus-
12% concen- drums tomer
trate
Rest at Middleport, New York
a/ "20%" concentrate.
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes No
Pollution control; The emphasis on control is to avoid any losses
of the active ingredient because of its high price ($52.50/lb, 100%). Ex-
tensive recycling is done to minimize losses. Leaks from pump packing, etc.
are absorbed on filter aid and recycled. Floor drains in the production
area are normally closed to prevent washdown of any spills, and all process
drains in the production area are connected to a separation pit. This pit
also provided a holding capacity in the event of a large spill. The filter
cake is washed, the washings are recycled, and the spent filter material is
disposed in an on-site landfill. The bottoms from the MeOH distillation
go to a holding drum where the organic layer is separated and recycled.
The water fraction is discharged to the sewers and eventually to one of
three outfalls. The COD of this water is about 2,000 ppm. The water stream
will go into the city sewer system in 1973.
Resin and wax residues from the refining process are currently
being drummed and stored: this material will be sold if a market can be
developed. Empty crude extract drums are used to store the resin and wax
residue. Any excess drums are rinsed with solvent (with washings used in
formulation) and then sold to a drum reconditioner. There is some loss of
solvents to the atmosphere, but this is thought to be quite small.
The pyrethrin is shipped out of the Baltimore plant in 200 Ib net
30-gal. lined drums at a "20%" (21-24%) concentration in deodorized kero-
sene. Mixing with the synergist, piperonyl butoxide is not done at the
Baltimore plant; pyrethrin is shipped to Middleport separately from
other toxic materials.
171
-------
Formulation; Two separate, parallel formulation lines are
operated at Middleport: one for residual pesticides and one for non-
residual (pyrethrin) pesticides. AI storage is also isolated. The
"toxic" formulation area is kept under negative pressure to prevent pos-
sible contamination of the pyrethrin area. Floor drains are plugged to
avoid any loss of pyrethrin and all of the drums coming into the formu-
lation plant are reused for formulated product.
Most of formulated products go directly to the buyer, but some
are warehoused briefly in 11 different locations. Buyers are usually
intermediate handlers and formulators or packagers, e.g., aerosol.
Quality control; AOAC methods are used for official purposes,
although methods (LGC) are used for internal control. Many physical
properties are also seen on the products. Although there are no critical
impurities, Fe contamination is a concern. Off-specification material
can be reworked with no major problems. No shelf-life problems. Cleanup
of equipment is limited to a once a year shutdown for maintenance. The
production equipment is used exclusively for pyrethrin production.
General information: The pyrethrin used by FMC is imported as
crude extract from the Kenya Marketing Board. One domestic producer,
however, does import and sell some flowers.
Generally increased use of pyrethrins is expected. About 40% of
current production goes for aerosol use but Niagara does not package
aerosols or have retail sales; the remainder goes for a multitude of uses.
Pyrethrins, the most expensive pesticide, has been registered in combina-
tion with almost all other pesticides. Animal husbandry applications
(horse rub) is becoming a significant market.
172
-------
Producer: Mclaughlin Gormley King
Production Equipment
Process continuity:
Est. annual production:
Equipment dedication: Plant capacity:
Equipment-age: Est 30 years avg. Formulation on site:
110,000 Ib/year
(100% basis)
Raw Materials
Material
1. Kerosene (de-
odorized)
2. All other
3.
Received From
Received By
Rail (tanks)
Storage
Enclosed tank yard
or underground
tanks
Material
1.
2.
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
Disposition
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Liquid wastes
from surface
washdown
4. Solid wastes
5. Atmospheric
losses
Form
Amount Produced
(Ib/lb A.I.)
Nil
Disposition
Recycled
Municipal sewer system
Contract hauler (to
state-controlled
disposal)
Vent
173
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product Formulated Products
On-Site Container Transportation Formulation Container Transportation
X Steel Truck . , Steel Truck
drums drums
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture Yes X No
174
-------
CASE STUDY NO. 21
Pesticide: Bacillus thuringiensis
Chemical name and formula:
^3% Viable spores of B.t. in organic media
Chemical class: Microbiological product
Pesticide class: Selective insecticide, lepidoptera
Description: Dust; nontoxic to mammals; nonpersistent
Producers: Abbott (North Chicago, Illinois); Nutrilite (Lake View,
California)
Production chemistry:
Fermentation Process
Solid Containing
Nutrient Sterilize Innoculate> Ferment> Separate.^ Dry> ^3% B.t.
Mixture
175
-------
Water-
Soybean Meal
Corn Steep Liquor
Minerals, etc.
or
Wheat 'Bran
Casein.
Molasses
Vitamins, -etc..
Innoculant-
B.T.
Incinerate
T Alternate
•^•Vent
Excess
A.?r Air
Baghouse or
Absolute Filter
-»•
-^
f T
Fermentation
Tank
1
Centrifuge
Spray
Dryer
-^ Product
T
Liquid
Waste
1
Alternate
Sterilize
with Heat
\
Evapo
Pond
i
Waste
Treatment
Plant
T
Discharge
to Lake
Figure 38 - Production and Waste Schematic for Bacillus thuringiensis
-------
Producer: Abbott Laboratories
Production Equipment
Process continuity: Batch
Est. annual production:
0.9 million
Ib/year
Equipment dedication:
Equipment age: > 3 years
Plant capacity:
Formulation on site:
Raw Materials
Material
Received From
Received By
Storage
1. Soybean
meal
2. Corn steep
liquor
3. Mineral
(NaCl etc.)
Rail
Material
Form
Reaction By-Products
Amount Produced
(Ib/lb A.I.)
Disposition
1. Liquid'waste
from
centrifuge
2.
Other Process Wastes and Losses
Material
Form
Amount Produced
(Ib/lb A.I.)
1. Active ingre-
dient
2. Solvents
3. Other Liquid
wastes Aqueous
177
Disposition
Heat sterilized, then
to biological waste
treatment plant and
discharge.
-------
Disposition of Technical and Formulated Products^
Warehouse Shipments
On Else- Technical Product Formulated Products
Site where Container^ Transportation Formulation Container Transportation
Very Mostly 25-lb Trucks None
little in fiber (full loads)
publicly drums
owned 2-lb
ware- paper
houses bags
(121
car-
ton)
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture X Yes No
Production; Fermentation process uses nutrient mixture; soy bean
meal (received by rail), corn steep liquor, minerals (NaCl, etc) and about
75% H20 in tanks of 10,000-35,000 gal. The liquid mix is sterilized and the
sterile liquid is then innoculated (5 gal/10,000 gal). The fermentation is
"submersed" and proceeds aerobically (air is bubbled through) for 2-3 days
during which temperature, pH, light and stirring are regulated. Monitor
turbidity by visual observation through portholes. The product, a white
milky suspension is drained from the tank and centrifuged. The ^.t,
spray dried and the powder is milled and packaged.
Abbott ships in truck load quantities. Use five publicly owned ,
warehouses at present but will use ^20 Abbott-owned ones. Some JB._t. is
reshipped from warehouse by truck to distributors. Some distributors re-
formulate to dusts, etc.
Pollution control; Raw materials received by rail are unloaded in
shed equipped with dust collection equipment. Materials are loaded into
fermentation tanks through portholes—no dust problems. Excess air during
fermentation goes to an incinerator. Wastewater from the centrifuge is
heat sterilized (not required, but good ethical drug practice and good waste
control) to kill residual B..J:.. and then sent to the state approved waste
treatment plant which treats all Abbott wastes and discharges into Lake
Michigan. The centrifuge .and spray dryer are contained so that no B_._t.
escapes into the air. The milling and packaging area is enclosed and main-
tained under "negative" pressure via vacuum take-off through absolute filter:
178
-------
collected dust is recycled. Filled bags are sealed and vacuum cleaned before
coming out of enclosure. Abbott maintains petri dish cultures throughout
the plant to monitor for airborne biological effluent.
Quality control; A contaminated fermentation batch would soon
show up, be sterilized and disposed—no salvage. No reject batches have
been made.
The product contains about 3.2% j^._t_. It is given spore count and
biological activity assay (min. is 16,000 internat. units/mg) and also
checked for impurities, given mouse test, etc.
The B..J^. as produced is a unit containing a protein crystal and
a spore, both of which contribute to efficacy. Shelf-life is no problem;
have stored samples 3 years at 120°F.
General; Abbott sells to distributors such as Niagara and have
perhaps 500 outlets. Abbott may also sell directly to very large growers
such as Campbells, Birdseye, Libby, etc. Major markets are: in truck-
gardening areas in Illinois-Wisconsin; New Jersey; California; and Florida.
Have registration on a number of cole crops (cabbage, lettuce,
etc.) and will soon add melons, grapes, ornamental trees, tobacco, etc.
Application rate is 0.5-1.0 Ib/acre, and most B..J:.. is applied by commercial
applicators.
The B.._t. is foufl'd Widely in fixture and rio tolerance is required
on presently registered crops, it is" nontoxic to mammals, but is toxic
to most Lepidoptera larvae, apparently because the high pH (approximately
9) in their gut activates the infection.
Abbott has had no personnel health probelms from B^. production.
Studies of possible B_.J^. mutations are underway, but no indication of trouble.
Ultraviolet light destroys B_._t.—keeps it to low level in nature.
179
-------
Producer: Nutrilite
Production Equipment
Process continuity:
Equipment dedication:
Equipment age:
Est. annual production: 0.5 MM
Ib/year
Plant capacity:
Formulation on site:
Raw Materials
Material
Received From
Received By
Storage
1. Wheat bran
2. Casein
3. Sugar
4. Vitamins
Midwest
Locally and
New Zealand,
Argentina
West Coast
Rail
Tank trucks
Tank truck
Drums
Material
Reaction By-Products
Form
Amount Produced
(Ib/lb A.I.)
Disposition
1.
2.
Other Process Wastes and Losses
Material
1. Active ingre-
dient
2. Solvents
3. Other: liquid
wastes
Form
Amount Produced
(Ib/lb A.I.)
Disposition
Evaporative
Pond
180
-------
Disposition of Technical and Formulated Products
Shipments
Warehouse Technical Product Formulated Products
On-Site Container Transportation Formulation Container Transportation
25-lb Truck
lined
fiber-
board . • .
containers
Pollution Control Regulation
1899 Refuse Disposal Act applies to this manufacture Yes X No
Production; Nutrilite produces B_.^. as a wettable powder in
5,000-lb batches. All of the product is shipped to a single formulator/
distributor, Thompson-Hayward who apparently formulates in Los Angleles,
Fresno, New Orleans. Dusts: 1.5% and 2.5% on clay and'bait 3% on corn
meal.
Pollution control; Wastewater is nontoxic and is sent to settling
pond where it evaporates. -.The .grinding operation is controlled by cyclone/
baghouse. No odor problems during manufacture.
Quality control; Raw materials are food grade. They analyze
for heavy metals (emission spectroscopy) and insecticides such as DDT
and PCB's (G.C.) as these are deadly to growth. Cannot really monitor
a batch as it is growing, as spore count takes 4 days and bioassay 2 weeks,
but do use turbidity as a check. Each batch has to be tested for safety
(mouse test, Botulinus, etc.)--no failures—and for effectiveness. Shelf-
life is good unless temperature gets high; ex. 200-°F for 2 weeks--may keep
for 5 years at 125°F. Must make sure that spores are not exposed to water
which generates bacterium.
181
-------
CASE STUDY NO. 22
Pesticide: Mercury compounds
Chemical name and formula:
Mercury Chlorides
(Mixture of HgCl2 + Hg2Cl2)
Chemical class: Heavy metal
Pesticide class: Fungicide
Description:
Producers:
Solids; variable water solubility; most are very toxic;
persistent
Production Chemistry:
Hg + HN03
Hg + C12
Hg2Cl2
Mercurous chloride
Hg(N03)2
Ho SO/.
NaCl
HgS04 - > HgCl2
Mercuric chloride
182
-------
CI2
Hg
HNO-
oo
-
Mercurous *»Ha rlo
Reactor
NO, H2S04 HCI
f 1 1
„ 1
Mercuric D
*• Reactor *-Hg(NO3)2 +- m
f
i
i
i
!
^__l_l _C
*~l
1 ^_
Residue
i
1 1
.Shipped to
Hg Recovery
Firm
isplace- _^ Displace- ^PacHn- i
ent ment ^
t t *
HNO3 H2SO4 Air
1
1 ' j
Recovery p»- Filter No. 2
Unit
i
Filter ~" *
/ N ^
' ^ ^
\
Liquid Waste
(< 0.5 ppm Hg)
I
Discharge
to Sewer
•Products
•Atmosphere
Figure 39 - Production and Waste Schematic for Mercury Chloride
-------
Production Equipment
Process continuity: Batch
Est. annual production: 50,000 Ib/year
Equipment dedication: Separate Plant capacity: 50,.000 Ib/year
equipment
for each
process
Equipment age:
Formulation on-site:
Raw Materials
1.
2.
3.
4.
5.
Material
Hg°
C12
HN03
H2S04
NaCl
Received From
Most overseas
Received By Storage
76-lb flasks Flasks
250-lb cylinders Flasks
Tank truck Tanks
Tank truck Tanks
Tank truck Tanks
1.
2.
Material
Reaction By-Products
•Form
Amount Produced
r(lb/lb A.I.)
Other Process Wastes and Losses
Disposition
Material
1. Active ingre-
dient
2. Solvents
3. All wash water
and waste
Form
Amount Produced
(Ib/lb A.I.)
Disposition
To mercury
recovery
system
184
-------
Disposition of Technical and Formulated Products
Warehouse
On- Else-
Shipments
Technical Product
Formulated Products
Site Where Container Transportation Formulation Container Transportation
St.
If
10-gal. Piggy-back,
Piggy-back
Louis needed
Jersey
City
and
Los
Angeles
fiber
drums
pak exclusive use
trucks, rail
Pollution Control Regulation
1899 Refuse Disposal.act applies to this manufacture X Yes
No
Formulation process: The mercury compounds are shipped to
St. Louis for formulation. The formulation process is rather typical. The
active ingredient is normally milled by itself before being added to the other
ingredients. The process for the mercury chloride formulations is depicted
in the following diagram.
ACTIVE INGREDIENT
CLAY-
>l
MI]
\
[MD
\
IT]
4
rrm 1.
ll!iKJ
f
•s^
^
PACKAGING
(Normally in two
size containers)
A
VENT TO
ATMOSPHERE
WETTING AGENT
DYE, ETC.
WASTE TO SEWER
All five mercury formulations are made in the same equipment.
185
-------
Pollution control in manufacture; All wash water and wastes from
the active ingredient manufacturing plant go to a mercury recovery system
where it is precipitated with I^S. The mother liquor from this recovery
contains about 100 to 500 ppb of Hg, and is discharged to the sewer (part
of the New Jersey Sewer Authority). Concentration of mercury in the actual
outfall is <100 ppb. This effluent contains only a small quantity of mer-
cury. All residue from the acid redigestion operation are drummed and
shipped to a mercury recovery company in Houston, Texas, although analysis
of the residue indicates that it contains no mercury.
The only solids generated from these processes are from the de-
contamination of process equipment. This material is drummed up with the
other waste material sent to Houston for mercury recovery.
The finished material is filled in hooded filling tables. The
hoods exhaust to two filter systems. The first filter elements are peri-
odically removed and processed through the acid-digester mercury recovery
system. Filter elements from the second system go into the drummed material
sent to Houston for mercury recovery.
All work clothes are given a preliminary wash on site before
being sent out for final washing. Water from this preliminary wash goes
to the mercury recovery system.
They have had no odor complaints.
Pollution control in formulation; The sewers in the plant area
are sumped (collected) and all washings are caught in floor trenches leading
to the sump. The washings are periodically pumped into a. special tank and
treated with sodium hydroxide to precipitate the mercury. This material is
then filtered into a second tank with the collected liquors being reused for
wash down during the product run. Solids collected from the recovery opera-
tion are packed in drums and shipped to the active ingredient production
plant to recover the available mercury. At the end of a production run or
if the volume becomes too great; treated, filter liquors are released to
the sewer.
Rags, liners from raw material drums, and other material that
might come in contact with active ingredients are returned to the active
ingredient production plant for mercury recovery and disposal. Uniform
contamination has not been a problem in this operation but in the event it
happened, company policy is to prewash any contaminated uniform prior to its
being returned to the vendor for standard cleaning procedures.
Effluents from the hoods in the fermentation plant are vented to
the atmosphere.
186
-------
Quality control; Quality control is maintained by Hg analysis and
specific impurities: sulfide, sulfate content, other heavy metals. As these
are batch processed, rework of off-specification materials is not a major
problem.
General; Some of this material is exported, apparently not a major
part of the production. Shipments would go out of the new York port. Major
shutdowns are unusual. The last one was about 2 years ago, to repair a
chlorine burner. About once a week, however, something requires a minor re-
pair.
Safety: Workers are checked by weekly blood and urine analysis.
187
-------
D. Summary of Pollution Aspects Based on Case Studies
The case studies developed a considerable amount of information
on the practices of the pesticide manufacturers which is related to the
overall pollution potential. Because of the diversity of processes used
for the different pesticides, and the different pollution control practices
employed, comparison is difficult; but several aspects are worthy of dis-
cussion.
1. Raw materials; The raw materials used for the synthesis of
many pesticides are hazardous materials and some pollution potential is
inherent in the transportation and handling of materials of this nature.
Some of these materials are flammable, some are corrosive and poisonous,
and some may be exceptionally toxic to fish if spilled into waters. How-
ever, the transportation of these materials are subject to close govern-
mental regulation and the handling practices of the pesticide manufacturers
are as good as or better than those of industry in general.
The raw material which is common to the most pesticides is ele-
mental chlorine which is used directly on-site in the production of chlor-
dane, toxaphene, 2,4-D, 2,4,5-T, atrazine, captan, carbaryl and mercuric
chloride, and is used to prepare raw materials brought in for the production
of DDT, Aldrin-Dieldrin and perhaps also trifluralin and alachlor. The
production of this chlorine formerly involved extensive use of the mercury
cells which led to the well-publicized mercury losses. Now, however, these
cells are being better controlled and are being gradually displaced by the
mercury-free diaphragm cells. Dow Chemical's Midland facility, which uses
the diaphragm cell and Chipman appear to be the only facilities among those
studied here which use on-site chlorine generation. Most of the producers
of the other products mentioned receive C^ in tank car quantities by rail
with the exception of Geigy's new St. Gabriel plant which receives Clo by
pipeline.
Other materials of unusually hazardous nature which are trans-
ported by rail, barge or truck include hydrogen cyanide (of which over
10 million pounds are required for atrazine), carbon disulfide, various
amines, and the concentrated acids and caustic. The P2S5 used in all the
organophosphorus pesticides, the C5C16 used for aldrin, and numerous
other materials also pose some hazard. Time did not permit an in-depth
study of actual vs. potential pollution caused by the transport of all
these materials, but overall the record appears to be relatively good.
The raw materials may be stored on-site in bulk storage facili-
ties, but in many cases are drawn directly from the shipping container
(e.g., tank car or tote bin) and used in the production processes. The
handling of materials such as chlorine are apparently in conformity with
188
-------
good industrial practice codes such as those of the Chlorine Institute.
Instances of accidental spills of raw materials were mentioned which re-
quired special cleanup and disposal procedures, e.g., a phenol spill by
a tank truck operator during transfer to company storage facilities. In
many cases scrubbers or dust collection equipment are used in the raw
material unloading^areas.
2. Production processes: The manufacturing processes for pesti-
cides vary considerably from product to product, but two characteristics
are generally present which may differentiate the pesticide industry from
many if not all of the large industries which are of environmental pollu-
tion concern: (a) the ingredients handled or produced have unusually high
toxicity to some animals (e.g., man or fish) or plant-life; and the pro-
duction processes normally require only low or moderate temperatures, com-
pared, for example, to industries producing ore- or rock-derived products.
Because of the toxicity of the materials handled, production facilities
were designed to include a great many safety features to minimize occupa-
tional hazards. Because of the moderate temperature, air pollution control
of good efficiency could be largely adapted from existing technology. Water
pollution control, as will be discussed in a subsequent section, poses a
much more difficult problem than air pollution in the pesticide industry.
The production plants for the 22 key pesticides studied range
from capacities of 1 million pounds per year or less to about 100 million
--pounds per year and the plant equipment ranges from 1 year old to over 20
years old and in at least two cases the plant buildings are over 50 years
old. In general, the more toxic materials such as the organophosphorus
and carbamate insecticides and some of the herbicides which have undergone
rapid growth recently (such as atrazine) are produced in newer plants,
while many of the older chlorinated hydrocarbons and other products are
produced in somewhat older equipment. However, almost none of the plants
have been designed since the advent of the recent increased consciousness ,
of environmental concern, and most of the companies interviewed have re-
cently completed, are building, or are designing new pollution control
equipment to bring their plants into conformity with local standards.
The production equipment is used in almost every case either for
only one product or for two very similar products, i.e., two products of
the same chemical family and with similar pesticidal applications. Cleanup
of equipment is therefore minimized and is small compared to that required
in a formulation plant where many products are processed through the same
equipment. In cases where solvent cleanup of process equipment is required,
the used solvent is generally reused as a matter of economics by recycle to
the process, or it may be used in formulation, or combusted for fuel pur-
poses.
189
-------
Most of the companies interviewed have farily extensive contin-
gency plans. Many of them maintain a company fire department and others
state that they work closely with local fire departments, but this cooper-
ation could probably be improved in nearly all cases.
Good practice dictates that production facilities be diked and
that runoff from malfunction, spills, fire extinguishment, etc., can be
contained in a holding pond or pit until treated, so that over-loading of
the conventional waste treatment plant is avoided. In many, but not all
plants, this procedure is in effect and in some cases is said to serve as
a safety for recovery of valuable product.
All the manufacturers of the 22-key pesticides have on-site
quality control laboratory facilities and frequently monitor the raw
materials and reaction intermediates as well as the final product. In
almost no case, it would seem, is a production run of such poor quality
or so far "off-specification" that it cannot be used—either blended off
with a higher quality batch or reworked to remove objectionable impurities.
The efficiency of the synthesis reactions as commercially con-
ducted is generally regarded or proprietary information. Similarly, the
efficiencies of recovery of products, by-products and unreacted starting
materials are not available. Unfortunately, even data on the quantities
of these materials being discharged or disposed by those manufacturers
who must file under the Refuse Disposal Act of 1899 became available during
this study on only a few plants. These data indicate, however, that dis-
charges of active ingredients range from undectable or but a few pounds
per day to nearly 1,000 Ib/day. (At the lower levels the difference be-
comes a problem of analytical sensitivity, of course, since a level of
only 1 ppm in the discharge from a large plant may mean several pounds per
day.) The efficiency of recovery in the past has often depended on the
price of the product balanced against the difficulty of recovery, and
hence, a widely and easily produced material like DDT was discharged in
sizable quantities. The present trend is toward better recovery and water
economy in order to minimize treatment or disposal costs.
3. Storage, handling and shipping; The use of most pesticidal
products is seasonal with the major application occurring during the spring
or summer season. Therefore, production and formulation also tend to be
seasonal in order to avoid building up undesirably large inventories.
Among the manufacturers of the key pesticides studied, several noted that
their production peaked in late winter or early spring; and some stated
that they did not produce during the summer months. On the other hand,
most companies do produce the year around and also may formulate on site
so that extensive storage facilities are required. A brief summary of the
formulation and warehousing practices of the producers of key pesticides is
given in Table XV. Production site storage in bulk or tank car quantities
is sometimes practiced, but long-term storage appears to be more often in
drums.
190
-------
TABLE XV
SUMMARY OF FORMULATION AND WAREHOUSING ACTIVITIES
BY KEY PESTICIDE PRODUCERS
Product
Formulation at (Technical or Formulated)
Product Production Site3/ Warehoused On-SiteV
Montrose
Shell
Velsicol
Hercules
Chemagro
American Cyanamid
Monsanto
Union Carbide
Dow
Chipman
Dow
Thompson -Hayward
Geigy
Lilly
Monsanto
Calhio
Dow
FMC
Abbott
Nutrilite
Mallinckrodt
DDT
Aldrin
Dieldrin
Chlordane
Toxaphene
Disulfonton
Malathion
Phorate
Parathions
Carbaryl
Aldicarb
2,4-D
2,4-D
2,4,5-T
2,4,5-T
Atrazine
Trifluralin
Alachlor
Captan
Some
~107o
No
No£/
Only a dust
concentrate
Yes
~17o
No£./
<57»
No£/
Nol/
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No£/
Methyl Bromide No
Pyrethrins
Bacillus t.
Bacillus t.
HgClo -HgoCl'
Nol/
No
No
> No£/
Yes
Some
Some
Small, tank car amounts
Ye si/
Drum only
No
Yes
Yes
Some
No
Yes
Some
Yes
Yes
No
Nol/
Yes
Very little
Yes
Negligible
No
No
Yes
a/ Formulation is by customer where not otherwise indicated.
b/ Warehoused by customer or in public warehouse where not otherwise indicated.
c_/ Portion formulated at contractor facilities.
d_/ Company warehouses or bulk storage at other locations.
e_/ Formulation at company facilities at another location.
191
-------
Good storage practices dictate that different pesticides be
stored separately, or at least in well-marked locations within a ware-
house. In cases where a company handles more than one pesticide at a
given location, special care is usually.taken to keep herbicides well
segregated from fungicides and insecticides, but pesticides which are
similar chemically and in activity, may be produced in the same equipment
and stored in the same area.
The storage facilities of the major producers appear to be gen-
erally well regulated to prevent accidental losses of pesticides during
handling and storage and well equipped with fire protection. These fac-
ilities, however, are not as frequently diked as are the production areas.
Similarly, most companies appear to specify such fire protection equipment
as automatic sprinklers when they use public'warehouses, but few of these
are diked. Thus, warehouse fires which require use of large amounts of
water are a serious potential source of pesticide pollution. The further
the warehouse is from the control of the primary producer, the greater
the potential in an estimated majority of cases.
The mode of transportation of pesticides away from the produc-
tion sites to the customer, distant storage facility or formulator varies
widely because of the variations in location of production sites and use
areas. The products are shipped by various combinations of rail.and truck,
depending on the nature of the material, packaging practices and the market-
ing structure. Shipping containers range in size from gallon cans and small
bags to 6,000-gal. tanks. A general outline of the packaging and trans-
portation practices is given in Table XVI. The Department of Transporta-
tion regulates transportation of pesticides by rail and motor carrier.
The packaging and transportation practices generate different
pollution potentials for different products. Most of the highly toxic
organophosphates such as disulfoton and the parathions are never shipped
in tanks--only drums. (A part of the less toxic malathion is shipped in
tanks.) Similarly, the toxic carbamates are shipped as 50-lb bags, in
the case of carbaryl, and in two specially modified tank trucks (which
are nearly "roll-proof") in the case of the extremely toxic aldicarb.
The shipment of liquid pesticides (and particularly toxic organophosphates)
in drums reduces the potential for a large spill of hazardous material,
but the handling and disposal of the emptied drums are a serious problem.
On the other hand, most of the toxaphene is shipped in tank cars and trucks
and transferred directly into company-owned bulk storage tanks at the
formulators1 location and no used drums are generated in this step.
192
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TABLE XVI
SUMMARY OF PACKAGING AND TRANSPORTATION PRACTICES
FOR KEY PESTICIDES
Pesticide
Transportation Mode
• Packaging
DDT
Aldrin-dieldrin
Chlordane
Toxaphene
Disulfoton
Malathion
Phorate
Parathions
Carbaryl
Aldicarb
2,4-D (Dow)
2,4^D (Chipman)
2,4,5-T
Atrazine
Trifluralin
Alachlor
Captan
Methyl bromide
Pyrethrin
Bacillus t_._
HgCl2-Hg2Cl2
Boxcars > Trucks
Truck and rail
Rail and truck
Rail and truck
Truck » rail
Truck and rail > sea train
Truck and rail
Truck » rail
Rail > piggyback or truck
Truck !
Rail (and trucks?)
Rail and truck
Rail and truck
Rail
Rail and truck
Truck > rail
Rail
Rail and truck?
Rail or truck
Trucks
Piggyback truck/rail
Bags > fiber drums
Fiber drums
Drums > tank cars and
trucks
Tank cars and trucks >
drums and bags
Drums
Drums > tank cars and ,
trucks
Drums
Drums
Bags
Special tank truck
Tank cars = bags and
drums
Tank cars and trucks,
drums, cans
Mostly drums
Bags > plastic cans
Cans
Cans and bags
Bags
Cans and cylinders (10-
13,000 Ib)
Drums
Drums and bags
Drums
A significant difference in pollution potential exists between
transport in tank cars and tank trucks. Tank cars are either company-
owned or leased by the company from the railroad, and are used over and
over for the same or a similar product. If the tank car requires cleaning
between shipments or before return to the railroad (as during the slack
season), cleanup is done at the production site and wastes go to the com-
pany's detoxification or disposal system. Tank trucks on the other hand
normally are received from the trucking firm in a clean and dry condition,
are filled, then transported to the destination and unloaded by the trucker,
who then has the responsibility for cleanup before the truck goes to another
193
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customer. The trucking firm, however, normally does not have the detoxi-
fication and decontamination equipment nor the technical expertise avail-
able at the manufacturer: washings are probably most often disposed in
the most convenient manner.
Pesticides which are packaged in cans, drums and bags are very
often shipped from the manufacturers only in truckload or carload lots.
In many cases, however, as the distribution system fans out, consignment
becomes less than carload or truckload lots and the pesticides become part
of mixed lot shipments. In such cases the manufacturer loses some control
over the product and it may be shipped together with flammable solvents
or other material which might increase the pollution potential.
In summary, the storage handling and shipping practices of the
manufacturer are generally well regulated and supervised, but accidents
can occur.
4. By-products and wastes; Virtually every pesticide produc-
tion process produces aqueous or gaseous streams and frequently solid
wastes which contain unreacted ingredients, unrecovered products and
solvents, and unavoidable or undesired by-products. Extensive efforts
are usually made to minimize by-products and to recover, recycle, or
otherwise prevent these process losses from occurring. For each pro-
.cess, however, a balance point is eventually reached between the expense
of recovery and the value of the recovered product. In the past, the
economic considerations were frequently dominant and process losses were
included as unavoidable costs. Under the recent emphasis on environmental
contamination further efforts have been made to recover many previously
lost materials--even when economics indicated that it was more expensive
to do so--and most pesticide manufacturers have invested in or are in the
process of building extensive waste treatment facilities wherein those
wastes which cannot be recovered are degraded to acceptable levels or
disposed by state approved methods. A summary of the principal waste
generated and the disposal method employed by the producers of the key
pesticides is shown in Table XVII.
While most of the companies interviewed indicated that they are
presently in conformity with local standards, a quantitative picture of
the overall pollution potential could not be developed during this program.
Under the 1899 Refuse Act Permit program, those companies which discharge
to navigable waters have been filing discharge data with the Corps of
Engineers, but unfortunately, these data started to become available only
very late in our study (Part B of the applications was due in October).
These data indicated that in several instances, sizable amounts of un-
reacted raw materials or unrecovered active ingredients are discharged
(see Appendix C), but these materials are generally not the persistent
pesticides.
194
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TABLE XVII
SUMMARY OF MANUFACTURING WASTES AND DISPOSAL
Pesticide
Liquid Wastes
Source
Solid or Other Wastes
Source Di
DDT
Aldrin
Dieldrin
Chlordane
Toxaphene
Disulfonton
Malathion
Phorate
Parachlons
Carbaryl
Aldicarb
2.A-D (Dow)
2,4-D (Chipman)
2,4,5-T (Dow)
2,4,5-T (Thompnon
Hayward)
Atrazine
Trlfluralin
Alachlor
Captan
Methyl Bromide
Pyrethrin
Bacillus £.
(Abbott!
Bacillus t_.
(Nutrilite)
HgCl2-Hg2Cl2
Processing solutions
Floor washings, etc.
Process solutions
Process solutions
Pinene-Camphene plant
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
As per 2,4-D
Process solutions
Process solutions
Process solutions
Process solutions
Process solutions
Aqueous still bottoms
Process solutions
Process solutions
Process solution
Evaporative basin
Evaporation basin
Evaporation basin
Deep well
Bio-treatment plant
Neutralize, hold, discharge
Secondary treatment plant
Barge to deep sea
Barge to deep sea
Waste treatment plant
Secondary waste treatment
Neutralize, secondary waste
treatment
Trickling filter; biological
waste treatment plant
Charcoal absorption/
filtration treatment
Oxidation pond, discharge
Most to river; some to
deep veil
Biological waste treatment
Discharge
Hold, discharge
Sewer
Sterilized; biological
waste treatment
Evaporation pond
Hg-recovery;
discharge to sewer
Reactor solutions
Lime slurry
Filter solids
Filter solids
Filter solids
Filter solids, etc.
H2S
Filter solids
Filter solids
Mercaptan losses
H2S; S
H2> COC12, amine
Heavy residues
Process vents
Filter solids and
still bottoms
Solids
NOX
Solvent
Gas streams
Gaseous wastes
Process solids
Filter solids
Process air
Filter solids
NOx, H2S
County Dump
Lime pit
Incinerate
Clay pit
Solid waste
Commercial landfill
Flare
Landfill (with lye)
Landfill
Flare
Flare; incinerate
Flare
Incinerate
Flare
Incinerate, Scrub
Landfill
Scrubber
Fuel
Scrub, vent
Scrub, waste treatment
plant
Storage
Landfill
Incinerate or filter
Hg recovery
Recovery
195
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The producers of the persistent chlorinated hydrocarbons use:
an evaporative basin, in part* for DDT; an evaporative basin for dieldrin;
and deep well disposal for chlordane. Therefore, these plants have no
discharges subject to the 1899 Act. . The evaporative basins require a
word of further comment: evaporative and wind blown losses from these
facilities require evaluation and the long-term future of the basin should
be considered, e.g., what happens if the production site is closed 25 years
from now and converted to other (even residential) uses?
Deep well disposal is also used by several pesticide producers
in states where that practice is permitted. Sea disposal is.also prac-
ticed by a number of producers in the eastern seaboard area and one re-
port states that 329,000 tons of pesticide wastes were disposed at sea
in 1968,^-' but the amount of active ingredients of any kind were not
specified.
The air pollution aspects of pesticide production are essentially
without quantitative data. The only air pollution data which we have seen
on pesticides are for ambient air samples: i.e., almost no emissions data
on specific pesticides from a given plant have been published. These data
are much needed.
V __
A number of minor sources of pesticide losses were noted during
the interviews. One of which has received the attention of a few companies
is the small amounts which collect on workers clothing, wipe cloths, etc.
Good data 'on losses on shoes, etc., are simply unavailable, although one
company noted that they had reduced miscellaneous losses from 150 to 2 lb/
day by increased vigilance to small details. Some companies furnish all
production workers with clothing which is then collected and washed or
prewashed in a company run laundry from which the wastewater goes to de-
toxification treatment. On the other hand, some pesticide producers utilize
commercial laundries which may wash the company's materials separately from
all others, but do not use any special detoxification treatment. The use
of disposable clothing and cloths also requires attention to see that these
materials are incinerated rather than go to a landfill if the contaminant
is a persistent pesticide.
Another potential pollution source is contaminated solvents which
might be sent to a solvent reclamation service. None of the major manu-
facturers appear to do this, but smaller producers or formulators may (par-
ticularly with solvents used for cleanup purposes). The pesticide content
of the solvents may be concentrated in still bottoms or on filter media
which are not detoxified.
* DDT - containing liquids do go to an approved county Class 1 dump.
196
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5. Cleanup and decontamination of equipment: Equipment cleanup
is an integral part of pesticide manufacture. This operation is both time
consuming and expensive, and therefore, is kept -to an absolute minimum.
Equipment cleanup is generally required for one of two reasons: (1) for
equipment maintenance, or (2) for quality control purposes.
Repair and preventive maintenance of production equipment is a
continuing process. This is due not only to the types of equipment used,
but also to the age of the production facility (new to over 20 years old) ._'
Corporate philosophy on maintenance varies from scheduled shutdowns of the
complete production unit to only unscheduled shutdowns of specific items of
equipment for needed repair. Generally, continuous processes require a '
scheduled shutdown whereas batch operation can be maintained on a less rigid
schedule. In either case, the equipment must be emptied of toxic material be-
fore it can be opened for inspection or repair.
Quality control necessitates the cleanup of production equipment
when the same facility is used for production of different active ingredients.
This is frequently the case when two or more pesticides can be manufactured
by the same process. Parathion and methyl parathion, for example, are made
in the same production unit by using essentially the same process and the
appropriate alcohol. —' Extensive cleanup between different process runs is
necessary to prevent possible cross-contamination. Production scheduling
that minimizes the number of product changes is used to reduce this type of
cleanup as much as possible. Product change-over usually involves cleanup
of only that portion of the process that would contain potential contaminants.
Conversion from the production of Captan to Folpet, as an example, requires
the cleanup of only one of the three unit processes involved.£/
Cleanout procedures generally involve flushing the production
system with a solvent. In some cases, steam also is used.—' Wastes from
these cleaning operations normally go into the plant's process-waste system.
The pollution potential associated with equipment decontamination
and cleanup is not particularly significant. First of all, only a small
quantity of active material is involved in this operation, much less .than
1% of the equipment capacity. Of more importance is the fact that wastes
generated by equipment cleanup in almost all cases go into the plant waste
systems. Thus, the pollution that could result from discharge of these wastes
is primarily dependent on the efficiency of the waste handling system.
6. Safety practices: Safety practices in the pesticide production
industry are designed for both the protection of the workers and the con-
tainment of highly toxic or dangerous chemicals. The degree and sophistica-
tion to which safety measures are used are primarily dependent .on the hazard
involved.
197
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Three types of pesticides require special environmental control:
(a) the organophosphates, because of their anticholinesterase activity;
(b) the chlorinated hydrocarbons, because of their stability; and (c) the
carbamates which also have anticholinesterase activity. Effects from
these, as well as other toxic pesticides, may be produced by swallowing
breathing, or absorption through the skin.12' Personnel protection mea-
sures and devices are designed to prevent these three types of contamina-
tion.
Coveralls, boots, gloves, goggles, and a variety of respiratory
devices are used to protect production workers. In addition, exhaust
ventilation systems are used where there is a potential for atmospheric
vapor, spray, or dust containing active ingredients, for a hazardous raw
material or intermediate. These devices seem to protect personnel from
respiratory and dermal routes of intoxication.
Protection against ingestion of toxics is a matter of personal
hygiene which is largely the responsibility of the individual worker.
Hands and face should be thoroughly washed before eating, drinking, or
smoking. Tobacco, food, beverages, or gum should not be brought into
the pesticide production area. These guidelines help prevent poisoning
resulting from ingestion.
Figures 40 and 41 illustrate the range of toxicities encountered
and the variations in the sophistication of safety practices that might be
expected. The facility for manufacturing-aldicarb, one of the most toxic
pesticides made in the United States, utilizes highly refined precautions,
including air suits for maintenance and decontamination, and glove-cabinets
at toxic sample points. Respirators are issued to all personnel who come
on the plant site. Less toxic pesticides, such as carbaryl, only require
the use of standard personnel safety equipment.
The containment practices and equipment used are also commensurate
with the hazard involved. Fire, explosion, and toxicity risks are considered
Control devices commonly used for containment include diking the production
area, vacuum operation of process vessels, and caustic scrubbing of process
vents.
Medical facilities are a part of the overall safety program found
at pesticide plants. Both preventive medicine and first aid services are
provided. Typical medical services include a periodic physical examination,
first aid for minor cuts or burns, and periodic cholinesterase tests for
employees potentially exposed to anticholinesterase pesticides (organo-
phosphates and carbamates)
198
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The potential for environmental damage resulting from inadequate
safety equipment and procedures apparently exist for some facilities that
are not adequately prepared to handle emergency situations. Contingency
plans specifically designed to handle fires, explosions, or vandalism in-
volving pesticide production plants are not universally available.
199
-------
O
O
aldicarb
tepp
phorate
demeton
parathion
mevinphos
endrin
carbophenothion
azinphosmethyl
methyl parathion
Bidrin®
endosulfan
phosphamidon
ethion
aldrin
dieldrin
diazinon
toxaphene
DDT
dimethoate
chlordane
naled
carbdryl
trichlorfon
dicofol
malathion
chlorobenzilate
Aramite
tetradifon
10 ' 0 100 200 300 400 500 600 700 800 900 1000 2000
LDcn in Rats, mg/kg
Figure 40 - Acute Oral Toxicityl£/
5000
-------
tepp
phorate
mevinphos
aldicarb*
parathion
demeton
endrin
carbophenothion
dieldrin
ethion
methyl parathion
endosulfan
aldrin
phosphamidon
. azinphosmethyl
Bidrin®
methyl demeton
dimethoate
diazinon
chlordane
toxaphene
Undone
dicofol
naled
trichlorfon
DDT
carbaryl
malathion
tetradifon*
* rabbits
•••BBS
mmmmat
jam
mEmOm
— r-
=\
—
=
mmmmmm
•^v-
s\.
•
•B
am
mam
earn
^mm
mmmm
maaat
eons
KMB
1
mamm
ammo*
tmtmm
•
•
on
0 5 10 "10 100 200 300 400 500 600 700 800 900 1000 Above Above Above
LD50 in Rats, mgAg 200° 400° 1000°
Figure 41 - Acute Dermal Toxicity!£/
-------
LITERATURE REFERENCES
1. Schmidt, T. T., R. W. Risebrough and F. Gress, Bull. Environ. Contain
Toxicol., 6, 235 (1971).
2. Air/Water Pollution Report, p. 285, July 12, 1971.
3. Greek, B. F. and F. E. Rosenberger "Design and Construction of a
Phosphate Insecticides Plant," Ind. and Eng. Chem.. 51, 104 (1959).
4. Henshaw, Tom B., "Absorption/Filteration Plant Cuts Phenols from
Effluent," Chem. Eng., 7£, (12) pp. 47-49, May 31, 1971.
5. Breidenbach, A. W., "Application of Solid Waste Research to Pesticide
Disposal," presented at The National Working Conference on Pesticide
Disposal at National Agricultural Library, Beltsville, Maryland,
June 30 and July 1, 1970, U. S. Department of Agriculture, Washington,
D. C., September 1970.
6. Personal communication, Mr. Jack G. Copeland, Hercules, Inc., November
19, 1970.
7. Personal communication, Mr. Joe W. Gillespie, Monsanto Company, October
11, 1971.
8. Personal communication, Mr. Don Gohlson, Cook Chemical Company, November
9, 1971.
9. Personal communication, Mr. J. H. Bees, Union Carbide Corporation,
November 3, 1971.
10. Safe Use of Pesticides. The American Public Health Association, Inc.
New York (1967).
202
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V. FORMULATION OF PESTICIDES
The general nature of the art of formulating active chemical
compounds into finished, ready-to-use pesticides has been described on
pages 33-36. In this section the various aspects and practices of the pesti-
cide formulation industry which relate to potential environmental pollution
are discussed. Interviews and plant-site visits were conducted during the
course of this study with the femulators, packagers, and distributors
listed in Table XVIII, in addition to several manufacturer-formulators al-
ready listed in Section IV, in order to gain an understanding of the in-
dustry as it exists today.
TABLE XVIII
SUMMARY OF FORMULATORS. PACKAGERS, AND DISTRIBUTORS VISITED
Arlington Blending and
Packaging Company
Chapman Chemical Company
Chase Chemical
Coahoma Chemical Company
Cook Chemical Company
E-Z Flow Chemical
FMC-Niagara
Helena Chemical Company
Michliri Chemical
Corporation
Pulvair Corporation
Riverside Industries
Thompson-Hayward
Valley Chemical Company
Wilbur-Ellis Company
Wilbur-Ellis Company
Formulation
Formulation
Aerosol Packaging
Formulation
Aerosol Packaging
Formulation and
Distribution
Formulation
Formulation
Formulation and
Distribution
Formulation
Formulation
Formulation
Formulation
Formulation
Formulation and
Distribution
Arlington, Tennessee3-'
Memphis, Tennessee3-'
Chicago, Illinois^./
Clarksdale, Mississippi—'
Baton Rouge, Louisiana3.'
Lansing, Michigan3'
Fresno, California
West Helena, Arkansas
Detroit, Michigan^./
Memphis, Tennessee^.'
Marks, Mississippi3/
Fresno, California
Greenville, Mississippi
Los Angeles, California
Fresno, California
a/ Office visit only.
203
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A. Formulation Facilities
Although virtually all pesticides are formulated before they are
used, formulating is not necessarily done at the site of- active ingredient
manufacture, or by the active ingredient manufacturer. Thus, formulation
facilities must be evaluated in light of both ownership and location patterns.
1. Producer-formulator; The producer-formulator, or integrated
producer, not only manufactures the basic active ingredient but also formu-
lates it in his own facilities into a marketable product. Such formulation
facilities may be located at the site of active ingredient production or in
major use areas. (See Table VII and Figures 5-10.) '
Generally, this type of facility is used for the production of only
a few formulations. Safety and operating standards are in keeping with the
corporate philosophy.
2. Independent formulators; The independent formulation operation
involves the processing of active ingredients into formulated pesticides under
one of several business arrangements.
One common practice is the contract formulation of proprietary
pesticides for the active ingredient manufacturer. In this type of operation,
formulation technology, the active ingredient, and operating assistance are
provided by the basic manufacturer. The formulated product is marketed under
the basic manufacturer's label. Frequently, an independent formulator will
have contracts of this type with several active ingredient manufacturers.
Many independent formulators package and sell pesticides under their
own label. These operations, however, generally limit their marketing to the
use area in which they are located.
Another category of formulation facilities combines these two opera-
tions by producing formulated pesticides under their own label as well as pro-
prietary formulations for active ingredient manufacture.
Farm cooperatives are an important class of independent formulators
because they handle a significant part of the pesticides used for agricultural
purposes. In 1962-1963, for example, farmers purchased about 19% of their
pesticides through cooperatives. — ' A major portion of these pesticides was
formulated by the cooperatives in their own formulation facilities.
The independent formulators, as most formulation facilities, are
generally located within the use area that they service. As has been shown
in the section on geographical locations of producers (page 54), active in-
gredient producers are frequently located at sites remote from major use areas,
and therefore, from many formulators of their active ingredient.
204
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3. Small packagers: There are some packagers in the United States
for whom pesticide formulation is a minor part of their operation. These
packagers frequently process a wide mixture of materials that include paint,
perfume, pesticides, and other specialty items.
This type of operation, however, is the least significant in terms
of quantity of pesticide formulated. These formulators generally service a
small geographical area in which they are located.
4. Aerosol packagers; Aerosol packaging is a unique segment of
the pesticide industry. About 100 million aerosol pesticide containers are
packaged per year.—' It has been estimated that over 90% of these containers
are filled by six companies.£'
The formulation of aerosols is essentially a mixing process. In
some cases, the aerosol femulator is supplied with a concentrate containing
all ingredients of the aerosol except solvent and propellant. The only opera-
tions required in this case are dilution of the concentrate with the appro-
priate solvent and filling.
Many of the facilities that fill pesticide aerosols also fill other
product lines, such as paint, varnishes, disinfectants, air fresheners, and
specialty items. The major fillers of pesticide aerosols, however, generally
have filling facilities used exclusively for pesticides. The names and loca-
tions of the major pesticide aerosol filling plants are shown in Table XIX
and Figure 42. Pesticides account for about 87« of the aerosol containers
packaged in the United States as shown in Figure 43. ft/
B. Pollution Potential in Pesticide Formulation
The preceding sections on major pesticide formulations (page 33)
and types of formulation facilities illustrate the diversity of operations
involved in this industry. The pollution potential that results from pesti-
cide formulation can be best evaluated by considering the basic elements
required for all formulation activities.
1. Raw materials; Three basic raw materials are required for
pesticide formulation: (1) the active ingredient; (2) other chemicals that
make up the formulated products (solvents, inert carriers, dyes, etc.); and
(3) containers.
The active ingredients are received in containers ranging in size
from 5 gal. up to tank cars and tank trucks. Generally, the active ingredient
shipping container is used as the storage vessel, and the active ingredient
goes directly from the storage container into the formulation process equipment.
205
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TABLE XIX
AEROSOL PESTICIDE FILLING PLANTS
Major Filling Facilities
S. C. Johnson and Son, Inc.
Boyle-Midway
ATI (Aerosol Techniques, Inc.)
Con-Wood Corporation (Hot Shot)
Ban-Stalfort
Chase
ATI (Aerosol Techniques, Inc.)
Peterson-Puritan
Cook Chemical
Aerosols, Inc.
Racine, Wisconsin
Cranford, New Jersey
Los Angeles, Danville, Illinois;
Milford, Connecticut
Memphis, Tennessee
Philadelphia, Pennsylvania
Chicago, Illinois
Boston, Massachusetts
Danville, Illinois; Rhode Island
Baton Rouge, Louisiana
Neodesha, Kansas
Other Filling Facilities
Purex Corporation
E. A. Thompson
Parrott Chemical Company
Sprayway
Tripple-X
Boyer Chemical Company
Tripple-X
Camie Company
Midwest Consultants
Orb Industries, Inc.
Delta Chemical Corporation
Lakewood, California
San Francisco, California
Stamford, Connecticut
Chicago, Illinois
Chicago, Illinois
Evanston, Illinois
Mundelein, Illinois
St. Louis, Missouri
St. Louis, Missouri
Media, Pennsylvania
Memphis, Tennessee
206
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tv>
O
-j
• Major Plants
O Other Plants
Figure 42 - Pesticide Aerosol Filling Plants
-------
MILLIONS
OF UNITS
TOTAL -2,462.3
i.4
31
. I
?.8
>.o
.0
J.O
•
«« —
«« —
cc
HC
PEF
FOOD
INSECT SPRAYS
MISCELLANEOUS
HOUSEHOLD PRODUCTS
PERSONAL PRODUCTS
Source: Working Group on Pesticides, Proceedings of the National Working
Conference on Pesticide Disposal (July 1, 1970).
Figure 43 - 1969 United States Aerosol Container Production
208
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Other chemicals are received by virtually all available means and
in all sizes of containers. Wherever economically feasible, large volume
chemicals, such as solvents, are received in bulk. Bulk chemicals are
either stored as received, e.g., in tank cars, or they are transferred into
bulk storage tanks.
The empty containers are received from local sources whenever pos-
sible. Paper, plastic, and small (less than 5 gal.) metal containers are
normally stored in a warehouse before being used. Many of the 55-gal. drums,
however, are stored outdoors until needed.
Spot or statistical sampling of empty containers is done in most
cases. This technique has generally been successful in detecting lots of
defective containers. The inspection of all containers before filling,
however, is not commonly practiced.
The greatest pollution potential associated with raw materials is
the chance of spilling the active ingredient before it 'is introduced into
the formulation process. The active ingredient receiving, unloading, and
storage areas observed for nonbulk shipments were generally not adequately
diked or otherwise equipped to deal with spills.-il£' Bulk shipment and
storage areas, however, are normally better equipped to deal with a spill.
Potential for environmental contamination exists from the cleanout of some
bulk containers used for shipping active ingredient. Rail cars are generally
in dedicated service (used only for shipment of a given active ingredient),
and are periodically cleaned at the active ingredient manufacturing plant.
Tank trucks, however, are generally not used exclusively for a specific
active ingredient, and must, therefore, be cleaned after each use. This
cleaning is the truckers responsibility, and is done at his or at other
commercial truck washing stations. In some cases, effluent from these
washing facilities is discharged into sewer systems or held in evaporation
ponds without being treated.£/
2. Formulation process; Pesticide formulation processes are pri-
marily batch mixing operations. The desired active ingredient, the appropri-
ate carrier or solvent, and the necessary additives are blended and milled'in
the ratios needed to give the desired active ingredient concentration and
physical properties in the finished product.
An example of a liquid formulation plant is given in Figure 44.
The active ingredient is proportioned into a mixing tank with the correct
amounts of solvent, such as xylene and emulsifying agent, and blended.
Both weight and volume measurements are used to achieve the desired pro-
portions.
209
-------
ACTIVE INGREDIENT
EMULSIFIERS, ETC,
MIXING TANK
SOLVENT STORAGE
MIXING BLADE
HOLD TANK
TO PACKAGING
Source: Toxaphene Bulletin 621, Synthetics Department,
Hercules, Inc., Wilmington, Delaware
Figure 44 - Liquid Formulation Process
210
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The finished batch is normally stored in either the mixing tank
or a hold tank until the material can be analyzed to ensure that it meets
specifications.
Dust and powder formulations require mixing and milling operations
(see Figure 45). The inert carrier material commonly comes in 50-Ib bags.
These bags are broken open into a pit which feeds a conveyor to a weigh
hopper. This hopper feeds into a mixer or blender where the inert is sprayed
with a solution of the active ingredient. This mixture is then milled to
achieve the desired pesticide size before being filled into containers.
The potential exists for loss of active material to the environ-
ment during the formulation process. Open mixing tanks are used in several
liquid formulation lines. At most sites visited, however, lids and vent-
scrubber systems are used on mixing tanks to minimize losses to the atmo-
sphere. Rupture of formulation equipment or piping could cause a spill of
large columns of technical grade active ingredient or formulated material.
Many of the formulation plants visited did not have adequate facilities for
dealing with this kind of event.
Quality control techniques for formulation plants are generally
limited to the analysis of finished formulation for active ingredient con-
tent, for specific impurities and for chemical properties. These tests re-
quire a very small quantity of material. Many of the methods used for
active ingredient analysis are destructive methods, i.e., they deactivate the
active ingredients. Sample material in excess of that actually used for
analytical tests is normally recycled into the formulation process. Waste
generated by the quality control analysis is normally disposed of in the
formulation plant waste systems. Thus, the quality control activities found
at the pesticide formulation facilities generally do not represent a pol-
lution potential.
3. Packaging; The finished formulations are normally packaged
in facilities adjacent to the formulation lines. Frequently, the formula-
tion step and filling step are one integrated operation.
Formulated pesticides are filled into an array of containers, in-
cluding glass bottles, paper bags, metal cans and drums, cartons, and fiber-
board drums, and in a few cases in bulk containers.
Table XX shows the results of a recent survey on these types of
containers used for pesticide formulations.
211
-------
INERT MATERIAL
IN BAGS
BAG BREAKING
PIT
BAG BREAKING
PIT
AFTER MIXER
BAG MACHINES
ACTIVE INGREDIENT
SOLUTION
SPRAY NOZZLE
PREMIXER
SEPARATOR
BAG MACHINES
Source: Toxaphene Bulletin 620, Synthetics Department,
Hercules Inc., Wilmington, Delaware
Figure 45 - Dust Formulation Process
MILL
CYCLONE
AFTER MIXER
212
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TABLE XX
HOW PESTICIDES ARE MOVING TO MARKETJ2/
Package/Container Size Percentage
Wettable Powders
1 Ib 3
2.5 Ib 2
3 Ib 8
4 Ib 37
5 Ib 35
10 Ib 3
24 Ib 2
50 Ib 10
Emulsifiable Concentrates
1 gal. 26
5 gal. 44
30 gal. 15
55 gal. 15
Granules
4 Ib 4
5 Ib 8
10 Ib 10
20 Ib 4
25 Ib 4
50 Ib 66
80 Ib 4
Smaller packages are normally shipped in a master container. Four
1-gal. containers or four 5-lb cans, for example, are frequently packaged
in a cardboard case. Small bags are often packaged in a multiwalled baler
bag for shipment. The use of master containers permits palletizing shipments
and handling with automated equipment. There is also less danger of damage
to the actual pesticide container.IP.'
The points at which the potential exists for pesticide emissions
in the packaging operation are the package filling stations and from leaking
containers. Filling stations are normally fitted with hoods and a vent sys-
tem to remove any spilled material. Leaking containers discovered in the
packaging area can be readily emptied back into the filling line. Leaking
containers discovered in the packaging plant, however, are rather unusual.
The packaging operation, therefore, has only a low potential for pollution.
213
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4. Storage and shipping; Most of the formulated goods are stored
for at least a short period at the formulation site. This storage facility
may serve as only a staging area for shipping to remote warehouses, or it
may be the principal warehouse itself.
The on-site storage facility is most frequently located on the
same plant site, and often in the same building or a building adjacent to
the formulation plant. Where a number of different products are formulated,
the finished goods are segregated, with herbicides generally isolated from
other types of products.JJL/
Both public and private warehouses are used to store formulated
pesticides. Selection of a warehouse to be used differs from company to
company, but generally whether or not the facility is heated and equipped
with a sprinkler system are considered.—'
Both truck and rail shipments are used for formulated pesticides,
with trucks being used more frequently for local delivery. Less than car
or truck load shipments are normally not made from the initial warehouse in
the distribution system. Mixed shipments, however, are apparently common
after the first one or two phases of shipping.
Leakers during transportation are an ever present problem and
potential source of pollution. Frequency of leaking containers is generally
much less than 1%.—' Leaks are most often caused by rough handling during
loading and shipping rather than by defective containers..i-t'
The potential exists for the release of significant quantities of
pesticides to the atmosphere as the result of either a warehouse fire or
accidental spillage or leakage during shipment. The National Agricultural
Chemicals Association (NACA) has established a nationwide Pesticide Safety
Team Network to deal with accidents involving Class B poison pesticides.
This cooperative program provides the personnel, equipment, and expertise
necessary for efficient clean-up and decontamination. Ten members provide
this service on a 24-hr a day basis: Chevron, Shell, Stauffer, Chemagro,
Diamond Shamrock, Velsicol, Niagara, Union Carbide, Monsanto, and Dow.
Many of the major companies, including many of those who cooperate with the
NACA team, independently provide the same type of assistance for accidents
involving any of their products.12,15,16/
Procedures have been developed for dealing with spills or warehouse
fires that help minimize possible pollution hazards and exposure of personnel
to toxic vapors.—' (See Appendix B, page 239). Rapid implementation of these
procedures will mitigate the effects of a spill or fire to a large extent.
214
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5. Equipment clean-up: Frequently, the same equipment is used
to produce; a number of pesticide formulations containing different active
ingredients, solvents, etc. Great care must be taken not to contaminate
one formulation with traces of another pesticide. Contaminants could
adulterate or dilute the following batch, leave an illegal residue on crops
to which the formulations were applied, or cause chemical degradation of the
active ingredient. Prevention of such "cross-contamination" during formula-
tion requires extensive clean-up of the facility between the formulation of
different active ingredients. Guidelines for equipment have been developed
by the NACA subcommittee on Cross-Contamination to aid formulators.18/
Liquid formulation process equipment are generally rinsed with the
solvent used in the previous formulation. The number of rinses as well as
the quantity of solvent required depends on the specific equipment. Gener-
ally, however, from one to five rinses with 20 to 50 gal. of solvent are
sufficient to decontaminate most types of equipment. Line strainers, fil-
.ters, and other points in the system where residues could accumulate must
be cleaned. In many cases, the solvent used for rinsing can be saved and
used the next time the same product is formulated.
Dry formulation plants generally require flushing with a dry
inert material before producing a different product. In many cases, it
is possible to save this inert material for use in later production.
-If liquid spraying was used on the previous product, a solvent
must be used to flush the spray system.
In many cases, it is necessary to disassemble some items of
equipment and use mechanical cleaning equipment. Steam and hot water washes
are also used.
The material used to clean the equipment is generally handled in
one or two ways. It can be temporarily packaged and stored until it can be
used the next time the same product is formulated, or it can be treated
as a liquid or solid waste, and treated accordingly as discussed in the
following section. The pollution potential that exists from equipment
clean-up is dependent on the adequacy of the formulation plant's liquid and
solid waste treatment system. Material that is packaged and held until it
can be used does not represent a significant pollution hazard.
6. Wastes and by-products: By-product and waste production
from pesticide formulation facilities is less of a problem than for active
ingredient manufacture. There are no major by-products as such, and wastes
are primarily limited to empty containers, wrappers, and small volumes of
liquid and solid material.
215
-------
These wastes are treated by almost all of the available means,
including incineration, landfill, evaporation, special waste treatment
systems, deep wells, and discharge into municipal sewer systems.
The formulation facilities best equipped to handle their wastes
are generally those located at the site of active ingredient manufacture.
Such a location can recycle waste streams from the formulation activity to
either the production facility for recovery or to the production facility's
waste treatment system.
Landfill is the method most frequently observed for the disposal
of solid wastes. This is normally done by a contract service that picks
up the waste at the formulation plant. The ultimate destination of the
solid waste is not always known by the pesticide formulator.
Liquid wastes can be effectively handled in some parts of the
country by evaporation ponds. > —' Ponds of this type have been used
for several years without having to remove accumulated sludge.—' Atmos-
pheric emissions of active ingredients from this type of system, however,
have apparently not been determined.
The problem of how to adequately handle liquid wastes has re-
sulted in a concentrated effort to minimize liquid waste production. Wash-
downs of equipment and facilities are kept to an absolute minimum. In-
dustrial vacuum cleaners are used to clean up solid material, adsorbents
for liquids. Production runs are scheduled to minimize the number of
equipment clean-ups necessary. Many formulation facilities have removed
or plugged all floor drains.
Discharge data on pesticide formulation facilities were generally
not available. However, it appears that there is potential for significant
discharge of pesticidal material from some formulation plants.
7. Surplus pesticides: The term surplus pesticides, as is used
in this study, encompasses three situations where formulated material is
not marketable: (1) formulated material left at the end of the season—
truly surplus pesticides; (2) off-specification material; and (3) formula-
tions that can no longer be legally sold—recalled material.
The least troublesome category is that material left over after
the growing or use seasons. In most cases, pesticide formulations are
stable for extended periods when stored under the proper conditions. Con-
sequently, material left over after the use period is simply stored until
needed.
216
-------
Off-specification batches of material are a fact of life in
pesticide formulation as they are for all types of manufacturers. Formu-
lations generally fail to meet specifications for one of two reasons;
(1) the wrong concentration of active ingredient; or (2) inadequate physi-
cal properties.
Material that is off-specification for .these reasons can generally
be reworked or blended off without major difficulty. Reference to only one
occasion was found where a batch of off-specification material had to be
destroyed, and this was because of cross-contamination with DDT.—' Recent
effort by the NACAl^' as well as individual formulators has helped to
virtually eliminate cross-contamination as a major problem.
Recalled material has been a serious problem for some formula-
tors.^' The 15 April 1970 suspension of several registrations for liquid
2,4,5-T formulations is a classic example. This announcement resulted in
an attempt by over 100 formulators to recall 6,000,000 containers of over
300 products from more than 200,000 retail outlets. The most difficult
problem in dealing with recalled material, however, was how to adequately
dispose of it after it has been collected. One company was reported to
have accumulated 44,000 gal. of a 1% 2,4,5-T formulation. This volume of
unwanted pesticidal material certainly has potential for environmental
damage.
8. Empty containers; Empty active ingredient containers are
a problem. Pesticide formulators generally solve this problem in one of
two ways; (1) reuse of the containers; or (2) burial.
Many fomulators reuse incoming active ingredient containers
(primarily 55-gal. drums) for formulations that contain the same active
ingredient. This practice not only eliminates his immediate problem of
container disposal, but also reduces the overall number of empty con-
tainers to be dealt with. Formulators who service a local market are also
able to recycle drums and use them in the same service for three to six
cycles.—'
Many 55-gal. drums can be reconditioned and reused for other
purposes. The reconditioning procedure normally includes preliminary
decontamination, firing to about 1200°C, reshaping, sand-blasting and
repainting.
Nonreusable containers are most frequently disposed of by land-
fill. Thus, after being crushed, these empty containers become part of
the solid waste from the formulation plant.
217
-------
The potential exists for environmental damage from empty active
ingredient containers if they are not properly disposed of. One major
active ingredient manufacturer requires as a part of his contract with
the formulator that a certificate of disposal for all containers be sub-
mitted.iz' Only disposal methods approved by the basic manufacturer are
accepted.
9. Safety practices; Two general categories of safety equip-
ment and practice are found in industry: (1) those designed specifically
for personnel protection, and (2) control devices used to contain and con-
trol potentially toxic or polluting substances.
Personnel safety standards observed in pesticide formulation
plants are less stringent than those found in active ingredient plants.
Standard industrial safety equipment, including rubber gloves, aprons,
and various types of respiratory devices are generally available. Use
of these items, however, is apparently not always enforced.
Control devices used include baghouses, vent systems, and
scrubbers. Generally, more sophisticated and efficient devices are used
whenever highly toxic pesticides are formulated.
Perhaps the greatest pollution potential associated with the
safety aspects of pesticide formulation is the lack of adequate contingency
plans for handling fires or explosions. Detailed procedures for handling
pesticide warehouse fires have been outlined— and are generally appli-
cable to formulation plants. Preexisting plans to implement these pro-
cedures, however, are apparently uncommon among pesticide formulators.
218
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LITERATURE REFERENCES
1. Eichers, Theodore R., Liquid Pesticides: Formulation and Distribution
by Two Southern Cooperatives. U. S. Department of Agriculture,
Washington, D. C., 1965.
2. Personal communication from Mr. Don Gohlson.
3. Personal communication from Dr. J. B. Moore.
4. Day, Hurbert M., "Report of Review Committee of Chemical Specialties
Manufacturers Association," presented at the National Working
Conference on Pesticide Disposal, Beltsville, Maryland, 30 June
find 1 July 1970.
5. Personal communication from Mr. Phil Henery.
6. Anon., "Mercury Containing Pesticides Licensed in 1967," Environment.
Vol. 11, No. 4, pp. 6-7, May 1969.
7. Raw, G. R., Ed., CIPAC Handbook. Vol I: Analysis of Technical and
Formulated Pesticides, National Agricultural Chemists Association,
Washington, D. C., 1970.
8. Dawson, G. W., A. J. Shuckrow, and W. H. Swift, Control of Spillage
of Hazardous Polluting Substances, Department of the Interior,
Washington, D. C., 1970.
9. Personal communication from Transamerica Trucking Company.
10. Anon., "What Pesticide Formulators Say About Packaging." Farm Chemicals
pp. 62-68, September 1968.
11. Personal communication from Mr. Willis H. Hart.
12. Personal communication from Mr. Joe W. Gillespie.
13. Personal communication from Mr. Bud Schroeder.
14. Personal communication from Mr. Tom J. White.
15. Personal communication from Mr. James H. Vines.
16. Personal communication from Mr. J. H. Bees.
219
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17. Cenner, James T., "Report of the National Agricultural Chemical
Association," presented at the National Working Conference on
Pesticide Disposal, Beltsville, Maryland, 30 June and 1 July 1970.
18. Prevention of Cross-Contamination of Pesticide Chemicals, National
Agricultural Chemicals Association, Washington, D. C«, 1965.
19. Personal communication from Mr. Max Sobelman.
20. Personal communication from Mr. E. A. Gilbert.
21. Personal communication from Mr. Darol Lloyd.
22. Hill, Ralph M.,"Recall and Disposal," presented at the National
Working Conference on Pesticide Disposal, Beltsville, Maryland,
30 June and 1 July 1970.
220
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VI-. MARKETING OF PESTICIDES,
The marketing of pesticides constitutes a number of activities
which, in total, compose a large segment of commerce. As .used herein, marketing
will be-used to cover the movement of finished pesticidal goods from the
manufacturer, formulator or packager into the hands of the actual consumer.
Separate activities include transportation; warehousing,' redistribution and
storage or shelving at the point of purchase. The evaluation of the pol-
lution potential associated with pesticide marketing activities is made
extremely difficult by the multiplicity of pathways utilized in getting the
manufactured active ingredient to the consumer... '••.••,-
•I o /
The nearly 100 domestic manufacturers^^' of pesticides and related
products utilize widely' varying systems for distributing or selling their
products — some may sell directly to the consumer while most work through
various chemical companies, formulators, packagers, distributors, brokers or
retailers. A considerable amount of the manufactured pesticides moves
through the hands of possibly as many as 500 independent formulators and an
unknown number of packagers including over 20 aerosol packagers. Many of
these forinulators and packagers have their own label registrations, market
their own products, and are frequently listed as manufacturers: e.g.,
mailing lists^./ indicate 68 DDT manufacturers and distributors, 68 weed-
killer manufacturers, 647 insecticide manufacturers, 639 disinfectant
manufacturers, 5,545 manufacturers of agricultural chemicals, and 9,632 chemical
manufacturers of all kinds (although only about 600 producers of synthetic
organics of all kinds were listed by the tariff commission—')- On the other
hand, many of the manufacturers and formulators do not market directly to
the consumer at all. The movement of pesticides from producer to consumer
can be summarized by the seven routes shown below:
Movement of Pesticides From Manufacture to Consumer
1. Manufacturer Direct
2. Distributor to Dealers
3. Area or Regional Distributors--to distributors to dealers
4. Manufacturer's Agents
5. National Distributors
6. Co-Manufacturers
7. Formulator--Distributors
The total number of outlets varies widely for different pesticides,
depending on their properties, application patterns, and company marketing
programs, ranging from hundreds of thousands of outlets for pyrethrum-containing
products to very few for the extremely toxic sodium fluoroacetate, which
221
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is used only by certain professional applicators. The number of outlets
is not available for each pesticide (or for almost any pesticide), but
estimates have been made according to the type of business involved relying
on mailing list information!' as shown in Table XXI.
Some overlap occurs between some categories, but one can conser-
vatively estimate that the United States has 30,000 locations handling lawn
and garden, home (excluding aerosols), industrial and structural pesticides,
i.e., excluding large-scale agricultural or land management usages. The
number of outlets for agricultural pesticides is smaller, but one herbicidal
product (alachlor, which is used primarily on midwestern corn and soybeans)
was estimated^/ to be available on "about 15,000 shelves." Agricultural
pesticides in general probably fall in the range of 100 to 20,000 outlets
each. Good data on the pesticide losses during the various marketing
activities are nonexistent. As a minor task of this program, different
methods of estimating losses were made, based on the data in Table XXI, the
literature, and an informal survey of local pesticide handlers.
Losses would occur during transporation, from the formulator to
the wholesaler or retailer, in handling and warehousing, and at the place of
sale to the consumer, or point of export. The total amount of pesticides
of all kinds produced and sold in the United States averages about 1 billion
pounds per year. An estimate of 0.1% loss from all sources during marketing
would mean losses of 1 million pounds per year. This estimate is probably
too large, but may serve as an upper limit. An estimate of 0.01% may be
realistic and would mean 100,000-lb loss.* The actual number may be less
significant than the methods used to handle the losses — for example, effective
detoxification is probably not practiced for spills at these points as they
would be in the plant of the experienced manufacturer or formulator. In
addition, technically untrained drivers, warehousemen, stock boys or janitors
may be exposed to hazardous spills.
The home and garden market for pesticides is a sizable segment
of the industry--perhaps as large as 20% of the total. Over 100 chemicals
are said—' to be used in this market and are marketed as many hundreds of
finished products. Major pesticides by use category are shown in Table XXII.
These products are normally marketed in small containers as shown£' in
Table XXIII. The total number of containers is uncertain, but about
100 million units of pesticides in aerosol containers are sold annually,
most of which goes to the home and garden market. The aerosols are the
largest single type of container and one might assume that the total number
of containers is in the range of 200-500 million.
The loss at the marketing level would actually include much formulated or
diluted product whereas the 1 billion pounds production figure refers
largely to the technical (concentrated) product.
222
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TABLE XXI
MARKETING OUTLETS TO THE CONSUMER FOR PESTICIDES
Halor Agricultural Outlets
Manufacturers 40 (estimate)
Formulators 300 (estimate)
Distributors, Independent 100 (estimate)-'
Farm Cooperatives 3,640 of the 8,090 Co-Ops are said to handle
agricultural chemicals^'
Feed and Grain 27,904 (10,108 grain elevators are also
listed)
Fertilizer Retailers 8,905
Specialized Outlets
Structural Pest Control 23 members of United Pesticides Formulation
and Distributors Association sell to structural
pest control operators-
Turf Pest Control 110 distributors sell primarily to professional
golf course applicators
Household Pest Control 540 members of the Chemical Specialties
Manufacturers Association are engaged in
production and marketing of chemicals for
household use
Others Mot available ,
Home and Garden Market
' Gardener's Supplies 7,919 firms
Two Categories of Firms Which Frequently Handle a Wide Range of Pesticides
j . •
Hardware Retailers 28,297
i • *
Department Stores 1,500 of the 11,580 department stores are
estimated to have garden centers—'
Six Categories Which Handle Smaller Amounts or Selected Lines of Pesticides
Lumber and Wood Builders Supplies 20,602 retailers
Drug Stores 48,869 total (11,200 rated at $50,000
per year)
Discount Stores 4,888 retailers
Industrial Supplies 7,500 wholesalers
Janitor Supplies 5,000 dealers
Nurseries 1,000 estimated large mail order firms of the
31,885 total
Three Categories Which Primarily Serve the Home-Use Market, Particularly Aerosols
Grocery Stores 75,000 supermarkets of the 220,000 retail grocers
Variety Stores 22,708 retailers
Sporting Goods Stores 13,000
Other Categories Which May Carry Pesticide Lines
Chemical Exporters 513
a/ Based on distributors and'dealcrs listed under agricultural chemicals by Ref. 7.
W '!.« national Pest Control Association has over 1,220 member companies engaged primarily in structural
pest control and is said to account for about 507. of that industry's business.
£/ Montgomery Ward has about 580 and Sears has nearly 400 retail stores In the United States.
223
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TABLE XXII
MAJOR PESTICIDES SOLD IN THE GARDEN AND HOME MARKET^/
Insecticides
Aspon
Allethrin
Aramite
Aldrin
BHC
Chlordane
Ciodrin
Diazinon
Dibrom
Disyston
DDT
Dieldrin
Dimethoate
Dimetilon
DDVP
Ethion
Guthion '
Heptachlor
Kelthane
Kepone
Lethane
Lindane
Lead Arsenate
Malathion
Meta-Systox
Metaldehyde
Methoxychlor
Naptha
Nictone
Sulfate
Oils
Pyrethrum
Para Dinitrobenzene
Piperonyl Butoxide
Rotenone
Ronnel
Sevin
Sulfur
Tedion
Toxaphene
TDE
Trithion
Rodenticides
Cumarin
Diphacin
Warfarin
Herbicides
Amiben
Amitrol
Ammonium Sulfamate
Benefin
Bensulide
Cacodylic Acid
CIPC
Dalopon
Daethai
Dicamba
Dichlobenil
Diphenamid
DSMA
Endothall
EPTC
MCPP.
Metham
Paraquat
POP
Sesone
Siduron
Silvex
Trifluralin
Terbutol
TCA
2,4-D .
2,4-DB
2,4,5-T
Pramitol
Erbon
DAMA
AMA
224
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TABLE XXIII
TYPES OF CONTAINERS USED FOR GARDEN AND HOME PESTICIDES-'
8/
Constructions
Paper Plastic
Sites Bags Bags Glass
4 oz X
8 oz X
Pint X
Quart X
Gallon X
Over gallon
1/2 Ib X X
1 Ib X X
1-5 Ib X X
5 Ib and over X X
Other - Cardboard— /
Plastic Carton & Can
X
X
X
X
X
X
X
X
X
Nonpressurized
Metal
X
X
X
X
X
X
Aerosol—
X
X
. X
a/ Odor barriers may be part of bag, carton, and can construction. These barriers are generally various
plastic laminations or foil.
]>/ Aerosols vary more in size than other containers and may be sold in odd ounce sizes such as 22 oz.
-------
The lawn and garden portion of the total home and garden market
is somewhat narrower in the number of pesticides involved and probably much
narrower in terms of the number of outlets. About a dozen local retail and
wholesale lawn and garden centers were surveyed. They said that they
experience breakage or spillage of one or two containers each per year, but
in some cases part of the contents can be salvaged. We estimate an average
loss of about 5-10 Ib/year/center. If we assume there are 10,000 major
lawn and garden centers, then the total estimated loss is about 75,000 Ib/year.
The remainder of the home and garden market would in general
utilize smaller containers and based on the estimate for lawn and garden
we would estimate the total home and garden loss during marketing as less
than 100,000 Ib/year of formulated products. These contain generally much
lower than average amounts of active ingredient—perhaps 10-20%.
The agricultural market is by far the largest segment of the
pesticide industry with perhaps 500 pesticidal chemicals and 50,000 formu-
lations marketed. The container size averages larger than those in the
home and garden market as does also the content of active ingredient.
Estimates of the number of units (containers) of pesticides sold to farmers
for uses on crops, livestock, etc., range from 91—' to 134 million^' for
1966. The average container was estimated to contain about 8 Ib total of
which about half was active ingredient. The distribution according to
container size and use is shown in Table XXIV.
Evaluation of the losses of pesticides during marketing to
agricultural uses is hindered by a good estimate of the number of outlets.
The 3,640 farm cooperatives in the United States which handle agricultural
chemicals account for a large share of pesticide sales: 32% for the Co-Ops
vs. about 15% for the lawn and garden centers. (Some of the Co-Ops also
formulate, but this activity is not included here.) Neglecting for the
present that the Co-Ops handle larger-size containers on the average than
the lawn and garden centers, and assuming that losses are proportional to
the amount sold, one would estimate losses of about 160,000 Ib/year. How-
ever, if losses at the Co-Op average 20-25 Ib/year, then a total loss of about
80,000 Ib/year occurs.
The total loss for all agricultural outlets may run as high as
200,000 Ib/year during marketing activities.
Another sizable segment of the pesticide industry is the structural
use and the professional applicator. No estimates have been found for the
number of containers or average container size for these general areas.
The number of containers used is probably smaller than either of the two
previous categories considered—perhaps 5-10 million—but the average size
and content of active ingredient is probably larger—possibly 10 Ib and
65%. Losses during marketing are probably very small because of the more
direct-order nature of the business.
226
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TABLE XXIV
NUMBER AND TYPES OF CONTAINERS FOR AGRICULTURAL AND RELATED PESTICIDE USE-
9/
N3
•vj
(Million Containers)
Crop
Size of 2/
Container-
Dry containers:—
Less than 3
3 to 6
7 to 10
11 to 20
21 and over
Total dry containers
Liquid containers:—'
1 pint
1 quart
1 gallon
5 gallons
30 gallons
55 gallons
Total liquid
containers
Total containers •
Unit
Pounds
Pounds
Pounds
Pounds
Pounds
Number
Pints
Quarts
Gallons
Gallons
Gallons
Gallons
Number
Number
Herbicides
0.1
2.7
1.0
0.4
1.6
5.8
20.1
1.5
0.1
0.2
0.1
0.1
22.1
27.9
Insecticides
1.1
21.0
2.1
0.5
4.8
29.5
2.8
13.3
0.1
0.1
16.3
45.8
Other Crop
Pesticides
0.1
1.3
-
-
0.1
1.5
0.4
1.5
0.2
0.3
0.1
0.1
2.6
4.1
All Crop
Pesticides
1.3
25.0
3.1
0.9
6.5
36.8
23.3
16.3
0.4
0.6
0.2
0.2
41.0
77.8
Livestock
1.3
1.1
1.1
-
3.5
0.4
1.8
1.6
0.4
4.2
7.7
Noncrop
Stored
Crops
0.1
0.2
6.7
0.1
1.1
0.1
0.1
0.2
1.3
Seedbeds and
Transplants
0.1
0.2
0.7
0.1
1.1
-
0.1
0.1
0.2
1.3
Total
1.5
1.5
2.5
0.2
5.7
0.5
2.0
1.7
0.4
4.6
10.3
Rodent Control
Note: Total pesticides containers: 91.1 million.
-------
Contacts with local firms regarding pesticide losses in trans-
portation and warehouse handling indicate that' records are not kept, although
Hazardous Materials Incident Reports are filed as required by the Department
of Transportation. Losses may total twice that in the lawn and garden
centers or 150,000 Ib/year. The total for the three phases of marketing would
then be on the order of 450,000 Ib/year or 0.04% of the pesticides produced.
Discussions with local pesticide handlers regarding clean-up procedures in
event of spills or breakage indicate that much of this estimated 300,000 Ib
would be washed into city sewers, disposed of with other solid wastes or
perhaps thrown on the ground.
228
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LITERATURE REFERENCES
1. "Pesticides and Related Products, 1970," United States Tariff Commission,
Washington, September 1971.
2. Neumeyer, J., D. Gibbons, and H. Trask, "Pesticides," Part I and II,
Chemical Week, pp. 38-68, 12 April, and pp. 38-68, 26 April 1969.
3. 1971-1972 Hofheimer Catalog of United States and Canadian Mailing Lists,
Fritz S. Hofheimer, Inc., New York.
4. "Synthetic Organic Chemicals 1969," United States Tariff Commission,
Washington, 1971.
5. Personal Communication, Mr. Joseph Gillispie, Monsanto Company,
11 October 1971.
6. Personal Communication, Dr. Bernard Sanders, Farmland Industries,
September 1971.
7. Farm Chemicals Handbook-1971, Meister Publishing Company, Willoughby,
Ohio.
8. Day, H. M., "Report of Study Committee-Chemical Specialties Manufacturers
Assocations," presented at The National Working Conference of
Pesticide Disposal National Agricultural Library, Beltsville, Maryland,
30 June - 1 July 1970.
9. Davis, V. W., "Farmer's Use of Pesticides and Pesticide Containers,"
presented at The National Working Conference on Pesticide Disposal
National Agricultural Library, Beltsville, Maryland, 30 June - 1 July 1970.
10. Jansen, L. L., "Estimates of Container Numbers by Size, Type and
Formulation Involved," presented at The National Working Conference
on Pesticide Disposal National Agricultural Library, Beltsville,
Maryland, 30 June - 1 July 1970.
229
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VII. CONCLUSIONS AND RECOMMENDATIONS
The use of pesticides plays an important role in the health and
economy of the United States, but this use is also a cause of much concern
over the contamination of the environment and the unbalancing of delicate
ecosystems. The industrial and commercial enterprise, which exists to make
these pesticides available to the consumer,comprises a large network of
activities including synthesis, testing, production, formulation, packaging,
transportation, warehousing, and marketing at many levels. Accompanying
these activities are numerous points at which pesticides' and related hazardous
materials can be discharged, emitted, disposed, spilled or otherwise released
to endanger man and the local or global environment. The evaluation of the
pollution potential of these sources is hindered in many areas by the un-
availability of good information. In this study we have attempted to evalu-
ate this potential and have reached a number of conclusions:
1. The unavailability of data on how much of each pesticide is
produced or even which ones are produced in the largest quantities is a
serious handicap. This information is in the hands of the United States
Tariff Commission, but is not disclosed in a meaningful manner because of
confidential nature of production data. We recommend that disclosure of
production data for pesticides and all hazardous materials be made mandatory
so that the public can use these data to evaluate environmental danger.
2. The major pesticide producers have, on the whole, extensive
wastewater treatment facilities. Many of these are new or newly-modified and
many are under construction or in design, but some still have little or no
effective treatment procedures at some facilities. The disposal of liquid
wastes from pesticide manufacture varies widely with different companies,
different products, and different geographical locations. Methods being used
include: many varieties of neutralization, oxidation, settling, and holding
ponds and also secondary and biological waste treatment plants (all of which
are followed by discharge to a stream or lake); evaporation basins (which
have no outfall); deep well disposal; deep ocean disposal; and incineration.
Unfortunately, data on the discharge of effluents to navigable waters is only
beginning to become available under the "1899 Refuse Act," for disposal of
materials into navigable waters. Pesticide producers were scheduled to sub-
mit discharge data to the Corp of Engineers at a time when this study was
nearing completion and very little data became available in time to be evalu-
ated. Preliminary review, however, indicates that production processes as
presently employed for several product lines do lead to sizable losses of
active ingredients, toxic raw materials, by-products, etc., and that these are
often not detoxified by the waste treatment facilities. On the other hand,
this study has found that the major persistent chlorinated hydrocarbon
insecticides are now produced in facilities which do not discharge liquid
wastes to a river, i.e., they are using evaporative basins, deep well, etc.
230
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3. The production processes have numerous potential sources of
pollution in addition to the primary liquid waste streams, including air
emissions, solid wastes, and miscellaneous liquid wastes. The major producers
appear to be cognizant of these sources and exercise controls to satisfy local
requirements. In a number of cases solid or liquid wastes containing active
ingredients go to approved landfills or other burial sites without detoxifi-
cation, e.g., a liquid waste which apparently contains DDT goes to an ap-
proved Class 1 dump in California. At a few facilities high efficiency in-
cinerators are used to dispose of such wastes and we recommend this practice.
Data on air emissions of pesticides are not yet available from
production plants and are much in need. The major producers have expended
much effort to install baghouses, scrubbers, and other air pollution controls;
but data on loss of active ingredients through these devices are needed.
4. Some of the biggest sources of pollution from the major manu-
facturers are not from the active ingredient (i.e., the pesticide) but from
unrecovered by-products such as l^S which may be flared to SC^: e.g., a
plant which produces 10 million pounds per year of most thioorganophosphates
could emit over 2 million pounds of SC^ which would compare with that emitted
from a small electric power plant. In addition, and depending on the fuel
used for process heat and the air pollution controls installed, such a plant
might well produce 5 to 10 million pounds per year of particulate pollutants
(fly ash, etc.). By comparison, the amount of active ingredient discharged
through the waste treatment plant would probably be less than 10,000 Ib/year.
5. Numerous examples were noted wherein companies have recently
modified their production and waste disposal facilities to decrease the
amounts of wastes generated or lost; e.g., improved recycle; recovery and
decontamination of by-products; use of lined settling basins to avoid seepage,
etc.
Most of the production equipment is dedicated to one product or
to two very similar products so that cleaning wastes are minimal.
A host of smaller potential pollution sources were noted, some of
which have received attention by some producers, but not by others, e.g.;
carry-out of pesticides on shoes and clothes are prevented by sending company-
provided work-wear along with wipe cloths, etc., to special laundries, fol-
lowed by recycle or detoxification of the wash liquid; wash basin or lavatory
wash water is sent to the waste treatment plant rather than discharged with
sanitary wastes; and the proper disposal of "bottoms" from solvent recovery
operations.
6. The formulation of pesticides is probably a larger source of
environmental pollution than is the initial production. The formulation is
231
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done in some cases by the manufacturer at the production site, but in most
cases it is not. A host of formulators process hundreds of pesticides into
thousands of finished products. By the nature of this arrangement many of
the formulators have relatively small facilities and many of the formula-
tion runs are relatively short. The combined result is that formulators
with few exceptions have less extensive waste treatment facilities than do
the manufacturer, but they generate considerably more wastes from equipment
clean-up. However, the majority of the forulators probably send liquid
wastes to municipal sewer systems so that no data are becoming available
on the amounts discharged. These smaller businesses are also more apt to
send pesticide-containing solvents to commercial solvent reclamation services
(where the fate of the pesticide is uncertain) than is the manufacturer.
7. The transportation of pesticides, as with many other products,
causes increased chances of accidental breakage, spills and losses. The
potential for environmental damage is higher in the case of concentrated
active ingredient than it is with more dilute formulated products, but the
frequency of accidental occurrences varies widely with packaging and shipping
practices. Overall, the pesticide industry has had relatively few major
spills, but the potential remains inherent in the transportation of hazardous
materials.
Of smaller scope, but of importance we believe, is the increased
pollution potential of tank trucks over railroad tank, cars in regard to
clean-out procedures; cars are frequently dedicated, require only occasional
clean-out, and this is done at the manufacturer's site with wastes going to
treatment; the trucks are most often leased one-way and are cleaned by the
operator at a point remote from detoxification facilities.
Another important pollution point related to the need to transport
pesticides is the inability to empty the standard 5- and 55-gal metal drums
completely. These drums may often be reused for formulated products, etc.,
and losses at the manufacturer/formulator/packager level are not nearly so
large as those at the consumer level; but new designs are needed which permit
complete drainage.
8. The warehousing and marketing of pesticides are a smaller
source of pollution, but losses in this area are frequently disposed to the
nearest sewer or trash can.
9. Overall the environmental impacts from pesticide manufacturing/
formulating/packaging/marketing activities appear to be small compared to
those resulting from consumer use of these products, but those negative im-
pacts of the former activities have zero benefit/cost ratios and should be
minimized.
. 232
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APPENDIX A
TOXICITY DATA ON SELECTED PESTICIDESit!/
233
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I Herbicides and growth regulants
Oral LD5Q- Dermal LD .-
mg/kg mg/kg
Acrolein 42-46 562 Rb '
Allidochlor (CDAA,
Randox®) 700 360
Ametryne (Gesapax®) 1110-2980
Amiben (Chloramben®) 3500-5620 3136 Rb
Aminotriazole (Amitrole®) 1100-2500 >10,000
Ammonium sulphamate
(Ammate®) 3900-4400
Arsenites, Na/K 70 150
Asulam >5000
Atratone 1465-2400
Atrazine (Gesaprim®) 2000
Avadex® (Di-allate) 393-1000 2000-2500 Rb
Avadex BW® (Tri-allate) 800-1810
Azak® (Terbutol) >34,600 >10,250
Balan® (Benefin,
Quilan®) >10,000
Banvel-D® (Dicamba) 1100 >1000
Banvel-I® (Tricamba) 300-450 >1000
Barban (Carbyne®) 600 . . >1600
Benazolin >3000
Benefin (Balan®,
Quilan®) . >10,000
Bensulide (Betasan®) 770-1910 2000->9400 Rb
Benzthiazuron (Gatnon®) 1280 >500
Betanal® (Phenmedipham) >2000 >500
Betasan® (Bensulide) 770-1910 2000->9400 Rb
BIPC (Chlorbufam) 2500
"Borates 2000-5330
Bromacil (Hyvar-X®) 5200
Bromoxynil 190-260
Cacodylic acid 1350-3200
Carbyne® (Barban) 600 >1600
Casoron® (Dichlobenil) 2700-6000 1350 Rb
CDAA (Allidochlor,
Randox®) 700 360
CDEC (Sulfallate,
Vegadex®) 850
Chlorthal-methyl (DCPA,
Dacthal®) >3000 >10,000 Rb
Chloramben (Amiben) 3500-5620 3136 Rb
Chloranocryl (Dicryl,
DCM) 3160 >3160 Rb
Chlorates, Na/K 1200-7000
Chlorazine 1950
Chlorbromuron 4287
Chlorbufam (BIPC) 2500
Chlorfenac (Fenac®) 1780-3000 >1360 Rb
Oral LD,.3-/ Dermal LD,,.-/
Chlormequat chloride
(ccc)
Chloroxuron (Tenoran®)
Chlorpropham (CIPC,
Chloro-IPC)
Chlorthiamid (Prefix®)
CIPC (Chlorpropham,
Chloro-IPC)
CMPP (Mecoprop,
Isocornox®)
CMU (Monuron)
Clobber® (Cypromid)
Cotoran® (Fluometuron)
Cycluron (OMU)
Cypromid (Clobber®)
2,4-D
Dacthal® (Chlorthal-
methyl, DCPA)
Dalapon-Na
Daxtron® (Pyriclor)
Dazomet (DMTT®,
Mylone®)
2,4-DB
DCM (Chloranocryl,
Dicryl)
DCPA (Chor thai-methyl,
Dacthal®)
DCU (Dichloral urea)
DBF
2,4-DEP
2,4-DES-Na (Sesone,
Disul)
Desmetryne (Semeron®)
Di-allate (Avadex®)
Dicamba (Banvel-D®)
Dichlobenil (Casoron®)
Dichlone (Phygon®)
Dichloral urea (DCU)
Dichlorprop (2,4-DP)
Dicryl (Chloranocryl,
DCM)
Dimexan
Dinitrocresol (DNOC)
Dinoseb (DNBP)
Dinoterb-acetate
Diphenamid
Diphenatrile
Diquat dibromide
(Reglone®)
!_/ Jones, K. H. et al., "Acute Toxicity Data for Pesticides (1968)",
World Review of Pesticides (Autumn, 1968).
2/ Neumeyer, John, et al., "CW Report Pesticides", Parts I and II.
Chemical Week (April 12 and 26, 1969).
3_/ LDe/j in rats except where noted for rabbits (Rb).
mg/kg
50~
670
3700
3800-8000
757
3800-8000
700-1500
3600-3700
215-900
8900
1500-2600
215-900
400-500
>3000
4000-9300
80-130
320-1000
700
3160
>3000
6800
325
850
ng/kg
50
232-440 Rb
>10,000 Rb
1000
>2500 Rb
3038 Rb
>10,000 Rb
3038 Rb
1500
>10,000 Rb
>2000
>1000 Rb
800
>3160 Rb
>10,000 Rb
700-1400
1630-2375
393-1000
1100
2700-6000
1300-2250
6800
800
3160
>1000
2000-2500 Rb
>1000
1350 Rb
1400
3160 Rb
240-340
25-40
50
62
700-1050
3500
400-440
200-600
80-200
>2000 Rb
>500 Rb
234
-------
Disul (2,4-DES-Na,
Sesone)
Diuron (Karmex®)
DMPA (Zytron®)
(DMTT®, Dazomnt,
Mylone®)
DNBP (Dinoseb)
DNOC (Dinitrocresol)
2,4-DP (Dichlorprop)
DSMA
Endothal
EPTC (Eptara®)
Erbon
EXD (Herbisan®)
Fenac® (Chlorfenac)
Fenoprop (Sllvex®,
2,4,5-TP)
Fenuron
Fluoraeturon (Cotoran®)
G 36393 (Methoprotryne,
Gesaran®)
Gatnon® (Benzthiazuron)
Gesagard® (Prometryne)
Gesapax® (Ametryne)
Gesaprim® (Atrazine)
Gesaram® (Methoprotryne,
G 36393)
Gesatop® (Simazine)
Glytac®
Gramoxone® (Paraquat
diclorlde)
Herban® (Noruron,
Norea)
Herbisan® (EXD)
Hydram® (Molinate,
Ordram®)
Hyvar® (Isocil)
Hyvar-X® (Bromacil)
loxynil
I PC (Propham)
Isocil (Hyvar®)
Isocornox® (Mecoprop,
CMPP)
Karroex® (Diuron)
Lenacil (Venzar®)
Linuron
Maleic hydrazide
MCPA
MCPB
Mecoprop (CMPP,
Isocornox®)
Medinoterb-acetate
Merphos
Metabromuron (Patoran®)
Metham-Na (Vapam®)
Methiuron (Thiuron)
Methoprotryne (G 36393,
Gesaran®)
Molinate (Hydram®,
Ordram®)
Monalide
Monochloracetates
Oral LD
mg/kg
700-1400
3400-3700
270
320-1000
50
25-40
800
1800-2800
80
1600-3160
1120
603
1780-3000
650-1070
6400-7500
8900
>5000
1280
2500
1100-2980
2000
>5000
5000
7000
112-200
1476-4000
603
501-720
3400
5200
100-305
1000-9000
3400
700-1500
3400-3700
>11,000
1500-4000
3800-6800
800
680
700-1500
42
1270
2000-3000
820
2200
>5000
501-720
>4000
300-400
Dermal LD
mg/kg
-
ural
= Dermal LD
mg/kg
>1000 Rb
80-200
200-600
1400
750
1460-10,000 Rb
>3160 Rb
>10,000 Rb
>150
>500
>1000
>150
236-500 Rb
>2000 Rb
>4000 Rb
>1000
1000
>10,200 Rb
800 Rb
>150
>2000 Rb
Monolinuron
Monuron (CMU)
Morfaraquat Dichloride
(PP 745®)
Mylone® (Dazomet,
DMTT®)
Naptalam (NPA)
Neburon
Nitralin
Nitrofen
Norea (Noruron,
Herban®)
Noruron (Norea,
Herban®)
NPA (Naptalam)
OMU (Cycluron)
Ordram® (Molinate,
Hydram®)
Paraquat dicloride
(Gramoxone®)
Patoran® (Metabromuron)
PCP (Pentachlorphenol)
Pebulate (PEBC, Tillam®)
Pentachlorphenol (PCP)
Pentanochlor (Solan)
Phenmedipham (Betanal®)
Phygon® (Dichlone)
Picloram (Tordon®)
Planavin®
PP 745® (Morfamquat
dichloride)
Prefix® (Chlorthiamid)
Prometon (Prometone)
Prometryne (Gesagard®)
Propachlor (Ramrod®)
Propanil (Stam F-34®,
Surcopur®)
Propazine
Propham (IPC)
Pyrazon (Pyramin®)
Pyriclor (Daxtron®)
Quilan® (Benefin, Balan®)
Ramrod® (Propachlor)
Randox® (Allidochlor,
CDAA)
Reglone® (Diquat
dibromide)
Semeron® (Desmetryne)
Sesone (2,4-DES-Na,
Disul)
Siduron
Silvex® (Fenoprop,
2,4,5-TP)
Simazine (Gesatop®)
Simetryne
Sinbar® (Terbacil)
Sirmate®
Solan (Pentanochlor)
Stam F-34® (Propanil,
Surcopur®)
Sulfallate (CDEC,
Vegadex®)
1800-2250
3600-3700
368-800
320-1000
1770-8500
>11,000
>2000
3050
1476-4000
1476-4000
1770-8500
1500-2600
501-720
112-200
2000-3000
280
1020-1120
280
10,000
>2000
1300-2250
8200
>5000
368-800
757
1750-3000
2500
1200
1300-1384
>5000
1000-9000
3300-4200
80-130
>10,000
1200
700
400-440
1630-2375
700-1400
>7500
650-1070
5000
1830
>7500
1870-2140
10,000
1300-1384
850
mg/kg
>2500 Rb
>1000 Rb
>2000 Rb
236-500 Rb
>10,200 Rb
105-350
>3000 Rb
105-350
>10,000 Rb
>500
>4000 Rb
>2000
1000
>1000
380 Rb
>2000
380 Rb
360
>500 Rb
>1000
570-2500 Rb
>10,000 Rb
235
-------
Oral LDj
mg/kg
-
Surcopur® (Propanil,
Stara F-34®)
Sutan®
Swep
2,4,5-T
2,3,6-TBA
Tenoran® (Chloroxuron)
Terbacil (Sinbar®)
Terbutol (Azak®)
Thiuron (Methiuron)
Tillam® (Pebulate,
PEBC)
Tordon® (Picloram)
2,4,5-TD (Fenoprop,
Sllvex®)
Tri-allate (Avadex BW®)
Tribonate®
Tricamba (Banvel-T®)
Trichloroacetates
Trietazine
Trifluralin
Vapam® (Methara-Na)
Vegadex® (Sulfallate,
CDEC)
Venzar® (Lenacil)
Vernolate (Vernara®)
Zytron® (DMPA)
1300-1384
4000
552
300-800
1500
3700
>7500
>34,600
2200
1020-1120
8200
650-1070
800-1810
108
300-450
3200-6000
1750-3800
5000-10,000
820
850
>11,000
1780
270
Dermal LD i
mg/kg.50
II Insecticides and acaricides
other than organophosphates
Aldicarb (Temik)
Aldrin
Allethrin
Amlnocarb (Metacil®)
Animert® (Tetrasul)
Aramlte®
Arprocarb (Baygon®)
Binapacryl (Moroclde®)
Bromodan®
Carbaryl (Sevin®)
Chlorbenside
(Chlorparacide®)
Chlordane
Chlordecone (Kepone®)
Chlorfenson
Chlorobenzilate
Chloropropylate
Chlorparacide®
(Chlorbenside)
Chlorphenaraide
DDD (IDE)
DDT
Derris
Dicofol (Kelthane®)
Dieldrin
Dilan®
Dimetan®
Dimethrln
DimetlIan®
.93 •
40-60
680-1000
30
6800->14,700
4000-6000
83-175
58-225
12,900
400
2000-10,000
283
114-140
2000
700-3200
>5000
2000-10,000
340
400-3400
300-500
1500
575->2000
40
475-4000
140-150
>15,000
25-50
>2000 Rb
2480 Rb
>1000
>10,000 Rb
>10,250
>3000 Rb
>4000 Rb
>1000
>200 Rb
800 Rb
>9000 Rb
5
>200
11,200 Rb
>1000
1350 Rb
>500
>1600
>2000
>5000
>150
>5000 Rb
2500
1000-1230
>100
6000
600-700
Dimlte®
Dlnobuton
Dithioquinox
(Quinomethionate,
Mores tan®, Forstan®)
Endosulfan (Thiodan®)
Endrin
Eradex® (Thioquinox)
Fenazaflor (Lovozal®)
Fluoroacetamide
Forstan®
(Quinomethionate,
Dithioquinox,
Mores tan®)
gamma-BHC (Lindane)
Genite®
Heptachlor
Isobenzan (Telodrin®)
Isodrin
Isolan
Kelthane® (Dicofol)
Kepone® (Chlordecone)
Lead arsenate
Lethane®
Lindane (gamma-BHC)
Lovozal® (Fenazaflor)
Matacil® (Aminocarb)
Methiocarb (Mesurol®) '
Methoxychlor
Mi rex
Mobam®
Morestan® (Forstan®,
Dithioquinox®,
Quinomethionate )•
Morocide® (Binapacryl)
Neotran®
Nicotine
o-Dichlorobenzene
Penphene® (Tetrachloro-
thiophene, TD 183®)
Perthane®
Pyethrins
Pyrolan®
Quinomethionate
(Dithioquinox,
Morestan®, Forstan®)
Rotenone
Ryania
Sevin® (Carbaryl)
Strobane®
Sulphenone®
(TD 183®, Tetrachlor-
thiophene, Penphene®)
TDE (DDD)
Tedion® (Tetradifon)
Telodrin® (Isobenzan)
Temik®-
Tetrachlorothiophene
(Penphene®, TD 183)
Tetradifon (Tedion®)
Tetrasul (Animert®)
Thanite®
Oral LD -1
i, 50
mg/kg
500
140-460
1100-3000
35
3-6
1800-3400
240 ,
15
Dermal LD
mg/kg
1100-3000
58-225
5800
70
500
70->80
8170-9340
570
50-90
1100-3000
25-132
750-1200
400
200-250
1400-3650
70->80
400-3400
5000-14,700
5-10
0-6
i2500-5000
>1000
74-130
60-120
>3000
>1000
80
1100-3000
200
1400-1900
40
5-10
7-17
12
575->2000
114-140
10-100
90-300
200
240
30
100-135
5000-7000
600-740
>234
>1000
500-1000
200-250
5-30
23-35
35-60
1000-1230
>2000
>2400
125-250 Rb
500-1000
>1000
6000->6000
>2000
>6000 Rb
>1000
1350 Rb
>1000 Rb
140
256 Rb
>1350->5400
>1000
>940 Rb
>4000 Rb
>500
>5000 Rb
>1000 Rb
256 Rb
>5000 Rb
>10,000 Rb
5-30
\ 2/5
70->80 256 Rb
5000-14,700 >10,000 Rb
6800->14,700
1600 6000 Rb
236
-------
Oral LD
MR/kg
50
Dermal L
mg/kg
Oral LD
mg/kg
0~ Dermal LD50~
Thiodan® (Endosulfan)
Thiequinox (Eradex®)
Toxaphene
Tranld®
35
1800-3400
283
17
15-63
74-130
>3000
>1000
200-400 Rb
1500-2500
Zectran15
III Qrganophosphorus insecticides
Abate® 1000-4000 1370-4000
Amidothion (Thiocron®) 600-660
Aspon® 1295
Azinphos-ethyl (Ethyl,
Guthion®) 9 280
Azinphos-methyl
(Guthion®) 7-13 280
Baytex® (Fenthion) 200 1300
Bidrin® 22-45 225 Rb
Birlane®
(Chlorfenvinphos) 10-155 108
Brotnophos 3750-5180 >1000 Rb
Butonate 1050 >2000
Carbophenothlon
(Trithion®) 7-30 800
Chlorfenvinphos
(Birlane®) 10-155 108
Chlorthion® 625-1500 1500-4500
Cidial® 200-300 700->1400
Ciodrin® 125 385 Rb
Co-Ral® (Coumaphos) 13-180 860
Coroxon 10
Coumaphos (Co-Ral®) 13-180 860
Coumithoate (Dition®) 67 >200
Cygon® (Dimethoate) 200-300 700-1150
DDVP (Dichlorvos) 25-30 75-900
Delnav® (Dioxathion) 20-40 350
Demeton (Systox®) 3-5 200
Demeton-methyl
(Metasystox®) 50-75 300-450
Demeton-S-nethyl
(Meta-iso-Systox®) 40 85
Diazinon 300-600 500->1200
Dibrom® (Naled) 430 800-1100
Dicapthon 330-475 800-1250
Dichlofenthion
(Nemacide®) 250
Dichlorvos (DDVP) 25-30 75-900
Dimefox (Terra-Sytam®,
Hanane®) 2 2-10
Dimethoate (Rogor®,
Cygon®) 200-300 700-1150
Dioxathion (Delnav®) 20-40 350
Dipterex® (Trichlorphon) 650 >2800
Disulfoton (Dlsyston®) 4 50
Dition® (Coumithoate 67 >200
Dowco 109® (Ruelene®) 460-1000 4000 Rb
Dow ET-14®
(Fenchlorphos) 1000-3000 >5000
Dow ET-15® 710 >1000
Duraban® 135-163 2000 Rb
Dyfonate®
Ekatin® (Thiometon)
Endothion
EPN
Ethion
Ethoate-methyl
(Fitios B-77®)
Ethyl guthion®
(Azinphos-ethyl)
Etrolene® (Fenchlorphos)
FAC 20® (Prothoate)
Fenchlorphos (Ronnel,
Etrolene^, Dow ET-14®)
Fenitrothion (Sumithion®)
Fenthion (Baytex®,
Lebaycide®)
Fitios B-77® (Ethoate-
methyl)
Folimat®
Forraothion
Guthion® (Azinphos-
methyl)
Haloxon
Hanane® (Dimefox)
Imidan® (Prolate®)
Kilval® (Vamidothion)
Lebaycide® (Fenthion)
Malathion
Mercarbam
Menazon
Meta-iso-Systox®
(Demeton-S-methyl)
Metasystox® (Demeton-
methyl)
Metasystox R®
(Oxyderaeton-methyl) x
Methidathion
(Supracide®)
Methyl Trithion®
Mevinphos (Phosdrin®)
Mocap®
Morphothion
Naled (Divrom®)
Nemacide®
(Dichlofenthion)
Oxydemeton-methyl
(Metasystox®)
Parathion
Parathi on-methyl
Phenkapton
Phenkaptone®
Phorate (Thimet®)
Phosalone (Zolone®)
Phosdrin® (Mevinphos)
Phosphamidon
Potasan®
Prolate® (Imidan®)
Prothoate (FAC 20®)
Pyrazothion
Rogor® (Dimethoate,
Cygon®)
4-17
100
23
8-17
13-34
125
1000-3000
14-25
1000-3000
250-673
200
125
50
400
7-13
900-2000
2
113-230
64-100
200
1400-1900
15
1200-1600
40
50-75
57
147
>200
130
25-230
1600
2000
280
>5000
100-200
>5000
1500->3000
1300
2000
700
400-1680
280
>6000
2-10
>3160 Rb
1160 Rb
1300
>4000
380
>500
85
300-450
100
20-48
98-200
3-5
61
200
430
25-400
190-215
90
26-46 Rb
283
800-1100
250
57
3-6
12-16
50
2-3
120-170
3-5
15
19-40
113-230
14-25
36
200-300
100
4-200
67
>1000
70-300
390
90
125
300 Rb
>3160 Rb
100-200
700-1150
237
-------
Oral LD
nig /kg
- Dermal
Ronnel (Fenchlorphos)
Ruelene® (Dowco 109®)
Schradan
Sulfotep
Sumlthion® (Fenitrothion)
Supracide® (Methidathion)
Systox® (Demeton)
TEPP
Terra-Sytara® (Dimefox)
Thimet® (Phorate)
Thiocron® (Amidothion)
Thiometon (Ekatin®)
Thionazin (Zinophos®)
Trlamide
Triaraiphos (Wepsyn®)
Trichlorphon (Dipterex®)
Trithion® (Carbo-
phenothion)
Vamidothion (Kilval®)
Wepsyn® (Triamiphos)
Zinophos® (Thlonazin)
Zolone® (Phosalone)
IV Fungicides
Allisan® (Dicloran)
Binapacryl (Morocide®)
Botran® (Dicloran)
Captafol (Difolatan®)
Captan (Orthocide®)
Chloranil
Copper salts
Daconil®
Dazomet (Mylone®,
DMTT®)
DCMOD (Plantvax®)
Dehydroacetic acid (DHA)
Dichlofluanid (Elvaron®)
Dichlone (Phygon®)
Dichloran (Allisan®,
Botran®)
Difolatan® (Captafol)
Dinitrotrichlorobenzene
Dinocap (Karathane®)
Dithianon
Dithiocarbamates
(Maneb, Zineb, etc.)
Dithioquinox
(Quinomethionate)
(DMTT®, Dazomet)
Dodine (Melprex®)
Dyrene®
Elvaron® (Dichlofluanid)
Ethylnercuric salts
Fentin salts (Triphenyl
tin salts)
Folpet (Phaltan®)
1000-3000
460-1000
5
1-5
250-673
20-48
3-5
0-5
2
2-3
600-660
100
9-16
20
10-20
650
>5000
4000 Rh
50-100
20 Rb
1500->3000
25-400
200
20
2-10
70-300
>200
8-15
1500-3000 Rb
>2800
7-30
64-100
10-20
9-16
120-170
320-1000
2000
500-1000
500-1000
1300-2250
1500-4040
4200-6200
500
2000
1000-1015
1000-8000
1100-3000
320-1000
566
2700
500-1000
30
800
1160 Rb
1500-3000 Rb
8-15
390
1500-4040
58-225
1500-4040
4200-6200
8400
4000
700-1000
>1 0,000
1350 Rb
>800 Rb
>1000
238
>1000 Rb
>1000
>800 Rb
>9400 Rb
>1000
>1000
>1000 Rb
>1500 Rb
>1000
200
450
Forstan^ (Quino-
methionate)
Furidazole (Voronit®)
Glyodin
Karathane® (Dinocap)
Maneb: see dithiocarba-
mates
Melprex® (Dodine)
Metham-Na (Vapam®)
Morestan® (Quino-
methionate)
Morocide® (Binapacryl)
Mylone® (Dazomet)
Olin 1763®
Orthocide® (Captan)
PCNB (Quintozane)
Pentachlorophenol (PCP)
Phaltan® (Folpet)
Phenylmercuric salts
Phygon® (Dichlone)
Plantvax® (DCMOD)
Quinomethionate
(Dithioquinox,
Morestan®, Forstan®)
Quintozene (Terrachlor®,
PCNB)
Sulphur
Terrachlor® (Quintozene,
PCNB)
Thiram (TMTD®)
Triphenyl tin salts
(Fentin salts)
Vapam® (Metham-Na)
Voronit® (Furidazole)
Zineb: see dithiocarba-
mates
Oral LD
mR/k;'.
1100-3000
1100
6800
2000
566
820
1100-3000
58-225
320-1000
>10,000
8400
1650-12,000
280
>10,000
60
1300-2250
2000
1100-3000
1650-12,000
non-toxic
1650-12,000
375-1000
23S
820
1100
Dermal
IHR/KR
^
>1000
>1000
>9400 Rb
>1500 Rb
800 Rb
>1000
1350 Rb
>1000 Rb
105-350
>1000
450
800 Rb
>1000
000
238
-------
APPENDIX B
EMERGENCY PROCEDURES IN EVENT OF FIRE
IN A WAREHOUSE CONTAINING PESTICIDES^7
239
-------
A. In the event of fire, the following agencies should be notified and
the noted information supplied;
1. The Fire Department
a. Advise of hazards from vapor, smoke and contact through
contaminated run-off water on actual contact upon entry
into burned out area.
b. Notify of any explosive nature of solvents or other
materials if stored.
2. Notify the Police Department
a. Block off area from all unauthorized persons.
b. Advise of necessity for evacuation of neighboring
businesses or residential areas of persons in the event
smoke or vapors drift into their area.
c. Advise of danger of contact with run-off water and ask
help to prevent persons from contact.
d. In certain areas where active civil defense organizations
are found, police may call on them for assistance.
3. In the event rail cars containing pesticides or solvents are
in danger of exposure, railroad personnel should be notified
and an effort made to switch the cars out.
4. Public health and pollution control agencies (city, county
and state) should be advised of types and quantities of
pesticides on hand at time of fire and of disposal and
decontamination plans.
5. Notify municipal waste treatment personnel if sewers are in
the area. Advise of materials possibly going to sewer either
directly or in run-off water so they may check for quantity
which can be handled in plant and if necessary shutoff sewer
lines if overloaded.
B. Examine area for broken water lines and if there is a possibility of
contamination through back-up, shutoff if possible or be sure enough
pressure is maintained to prevent back-up.
_!/ Conner, James T., "Report of the National Agricultural Chemicals
Association," presented at the National Working Conference on Pesticide
Disposal, Beltsville, Maryland (30 June and 1 July 1970).
240
-------
C. Check flow of run-off water and make provisions to divert or dam up
if flow constitutes undue hazard of exposure or pollution.
D. Check for possible exposure of food products to smoke or vapor. If
so, advise public health officials.
E. Call the "Pesticide Safety Team Network" (513-961-4300) for all possible
aid and assistance in decontamination and disposal.
F. Provide for the protection of personnel involved in the clean-up and
decontamination of the area.
1. Advise physician having a laboratory of possible types of
exposure.
2. In the event of involvement of organic phosphate compounds,
arrange for blood tests for cholinesterase level for reference
on all personnel at the site and anyone off-site who may be
exposed. Arrange for periodic (at least weekly) retest.
3. Provide necessary rubber boots, rubber or plastic gloves,
rubber or plastic aprons or clothing and/or disposable
clothing, suitable respirators or masks.
4. Make arrangements for a supervised emergency showering and
personnel hygiene program for showers and clothing changes
prior to eating, smoking, drinking coffee or changing
clothes prior to leaving the area.
i
Make preparations for disposal by burial of both contaminated building
contents and building debris.
1. Contaminated building contents
a. Locate an area where quantities of material either
pesticides or other items contaminated may be buried
without danger of contaminating ground water or where
surface water will not be contaminated.
b. Arrange for test drilling to a depth of approximately
7 ft and have soil tested by a consulting.engineer
or soil conservation agency for porosity.
c. If soil porosity is high or if in doubt, place 4 to
6 in. of powdered attapulgus-type clay as a lining in
the burial trench or pit.
241
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d. Material must be transported to burial site in closed
containers to avoid contamination enroute and preferably
buried in these containers at the site.
e. A cover of 2 to 3 in. of lime and a minimum of 18 in.
of dirt cover must be placed and compacted over each
load immediately after being placed in the pit or trench.
f. Each load deposited and covered should be supervised by
a responsible company employee or a public health official.
g. After disposal is completed, the area should be marked
and properly recorded on a plat of the area.
2. Contaminated building debris
a. Building ashes, wood, brick, stone, etc., may be disposed
of by using ordinary sanitary land fill techniques.
b. Debris must be transported in covered trucks to prevent
contamination during transport if burial on site not
possible.
c. All debris must be covered with a minimum of 6 in. of
dirt each day.
d. Area selected must be such that ground or surface water
will not be contaminated.
3. A check with local authorities must be made for regulations
governing this type of disposal. All governing regulations
must be followed and the procedures above are intended to
augment and not supersede these regulations.
H. Area decontamination
1. A check of the recommendations for decontamination of the
area after debris removal with a representative of the
"Pesticide Safety Team Network" must be made.
2. A check must be made with the supplier regarding the
decontamination recommendations.
3. In lieu of a firm recommendation, the contaminated area may
be tested for contamination and grossly contaminated areas
wet down with a 1% solution of bleach or if concrete scrubbed
down with a 17o bleach solution and rechecked for contamination.
This procedure is repeated until contamination is at a low
level.
I. Arrangements should be made to provide around-the-clock watchman service'
to prevent sightseers and scavengers from exposure until disposal and
decontamination is complete.
242
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APPENDIX C
PRELIMINARY DISCHARGE DATA SUBMITTED BY PESTICIDE PRODUCERS
UNDER THE 1899 REFUSE ACT
243
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Under the "1899 Refuse Act Permit Program," industries are re-
quired to obtain permits to make discharges into navigable waters or their
tributaries. Companies have recently been required, under the new enforce-
ment of this act, to submit applications describing the nature of their dis-
charges. The applications, which are submitted to the Corps of Engineers
and are to be reviewed by the Environmental Protection Agency, were to be
made in two parts: Part A was required of all companies having discharges
and describes facilities and the general nature of the discharge and was
due in July 1971; Part B was required of companies in a critical industry
classification, including pesticide producers and describes the quantitative
nature of the discharge (including levels and amounts of specific pesticides)
and was due in October 1971.
While many pesticide producers use other means of wastewater
disposal, most are believed to come under the 1899 Act. Unfortunately,
most of the data which will be contained in the Part B's of the applications
did not become available in time to be included in this study. Copies of
applications from only six companies were obtained. A small part of the
pertinent data contained therein are shown in Table C-I.
244
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TABLE C-I
PRELIMINARY DISCHARGE DATA SUBMITTED BY PESTICIDE PRODUCERS
UNDER THE 1899 REFUSE DISPOSAL ACT
Company and
•Plant Location
Chemagro Corp . ,
Kansas City,
Missouri
Ciba-Geigy,
St. Gabriel,
Louisiana
^^
^Pramond
Shamrock, Deer
Park, Texas
Du Pont,
La Porte,
Texas
Monsanto,
Muscatine,
Iowa
Shell Chemical
Company ,
Mobile,
Alabama
Active Ingredient
and Related
Products
Monitor
Guthion
Dasanit
Coumaphos
Systox
Meta-Systox
Dyrene
Fenthion
Di-Syston
Atrazine "|
Propazine >
Simazine J
Dacthal
MSMA
DSMA
Diuron
Monuron
Linuron
Thiuram
Alachlor
Machete
Propachlor
Methylchloroacetate
Gardona
Vapona
Dibrom
Landrin
Temik
Loss ( Total Discharge
(Ib/day) (MM gal/day) pH
, ' D
7 - 0.32 8
-
3
5
-
-
-
19
P
2,300 5.5 11.5
0.334 6.9
350 9.5 5.5-9.0
310
390
9
90 12.35 4.1
30
360
612
Max 0.02 0.175 12
Max 1.0
Max 1.0
Max 1.5
Max 1.0
Remarks
Dashes indicate
not being pro-
duced at time o
analysis
Projected for full
capacity operation
245
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APPENDIX D
LIST OF INDIVIDUAL CONTRIBUTORS TO THIS STUDY
The assistance of the following individuals who generously con-
tributed their time and information to this study is greatfully acknowledged.
-------
Dr. Ralph F. Anderson
International Minerals and
Chemical Corporation
Mr. R. W. Arns
Chevron Chemical Company
Ortho Division
Mr. D. B. Barlow
Chevron Chemical Company
Ortho Division
Mr. Charles Barnett
Shell Chemical Company
Mr. Carl A. Bauer
Valley Chemical Company
Mr. William E. Baum
Abbott Laboratories
Mr. H. A. Beckman
Chevron Chemical Company
Mr. J. H. Bees
Union Carbide Corporation
Mr. Bill Bell
Arlington Blending and
Packaging Company
Mr. Edsel H. Blair
Dow Chemical Corporation
Mr. Charlie Blue
Helena Chemical Company
Mr. Parke C. Brinkley
National Agricultural
Chemists Association
Mr. William Brothers
Helena Chemical Corporation
Mr. George E. Brown
Mallinckrodt Chemical Works
Mr. Jack Buan
Abbott Laboratories
Mr. Henry (Hank) F. Clancy
American Cyanamid Company
Dr. E. L. Clark
Chipman Division
Rhodia, Inc.
Mr. Charles J. Coken
Chemagro Corporation
Mr. R. A. "Rip" Collins
Hercules, Inc.
Mr. Jack:G. Cop'eland
Hercules, Inc.
Mr. D. 'Dick DeLine
'Dow' Chemical Corporation
Mr. Charles L. Dunn
Hercules, Inc.
Mr. M. A. Eggleton
Mallinckrodt Chemical Works
Mr. Tom Engerson
FMC, Niagara Chemical Division
Mr. John Ferguson
Geigy Agricultural Chemicals
Division of Ciba-Geigy
Dr. W. Brooks Fortune
Blanco Products Division of
Eli Lilly and Company
Dr. Frank Fronec
E-Z Flow Chemicals, Division of
Kirsto Company
247
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Mr. E. A. Gilbert
FMC, Niagara Chemicals Division
Mr. Joe W. Gillespie
Monsanto Company
Mr. H. M. Godson.
Calhio Chemical, Inc.
Mr. Don Gohlson
Cook Chemical Company
Mr. Harvey Gresheim
Coahoma Chemical Company
Mr. William H. Gurnee, Jr.
Ciba-Geigy Corporation
Mr. Bob Hamman
Geigy Agricultural Products
Division of Ciba-Geigy
Mr. Willis H. Hart \
Thompson-Hayward Chemical Company
Dr. Friedrich Hellrung
Chemagro Corporation
Mr. George G. Hinkson
FMC-Niagara Chemical Division
Mr. Loren J. How
Agricultural Division
Stauffer Chemical Company
Dr. Herbert E. Johnson
Union Carbide Corporation
Mr. John L. Kallok
Montrose Chemical Corporation
Mr. D. J. Keating
Stauffer Chemical Corporation
Mr. Douglas Kelly
Riverside Industries, Inc.
Dr. Edward M. Kiggins
Abbott Laboratories
Mr. Peter J. Klaphaak
Union Carbide Corporation
Mr. J. Harvey Knaus
Shell Chemical Company
Mr. T. J. Koffolt
Union Carbide Corporation
Mr. Joe Langer
Chase Chemical Company
Mr. Dick Leonard
Hercules, Inc.
Mr. Donald Lloyd
Wilbur-Ellis Corporation
Mr. Bruce MacDonald
Pulvair Corporation
Mr. Paul Manfredi
Wilbur-Ellis Corporation
Mr. Bob Mathews
Velsicol Chemical Corporation
Mr. Russell W. McCalley
0. M. Scott Corporation
Mr. D. B. McClellan
McLaughlin Gormley and King Company
Mr. A. M. McVie
Blanco Products Division
Eli Lilly and Company
Dr. J. B. Moore
McLaughlin Gormley and King Company
Mr. Robert E. Naegele
Dow Chemical Corporation
Mr. Leonard W. Nelson
Velsicol Chemical Corporation
248
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Mr. Bill Niggle
Chemagro Corporation
Mr. Jan Platou
The Sulphur Institute
Mr. Gene Renolds
FMC, Niagara Chemical Company
Mr. W. B. Roebird
Monsanto Company
Mr. Frank Saviez
Wilbur-Ellis Company
Mr. Bud Schroeder
Thompson-Hayward Chemical Company
Dr. Warren C. Shaw
U.S. Department of Agriculture
Mr. Max Sobelman
Montrose Chemical Corporation
Mr. Ed Spring
Gordon Corporation
Mr. John Stevens
Monsanto Company
Dr. Warren T. Trask
Mallinckrodt Chemical Works
Mr. John H. Vines
Chemagro Corporation
Mr. Edward B. Westall
Nutralite Products, Inc.
Mr. Tom J. White
American Cyanamid Company
Mr. Norman Zausmer
Michlin Chemical Corporation
OAQ
OU.S. GOVERNMENT PRINTING OFFICE: 1972 722-061A17 1-3 f.*+7
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