EPA-600 2-78-004d
March 1978
Environmental Protection Technology Series
SOURCE ASSESSMENT:
PESTICIDE MANUFACTURING AIR EMISSIONS-
OVERVIEW AND PRIORITIZATION
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development. U.S Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This document is available to the public through the National Technical Intoima-
tion Service. Springfield. Virginia 22161.
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EPA-600/2~78-004d
March 1978
SOURCE ASSESSMENT:
PESTICIDE MANUFACTURING AIR EMISSIONS
OVERVIEW AND PRIORITIZATION
by
S. R. Archer, U. R. McCurley, and 6. D. Rawlings
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
Contract No. 68-02-1874
ROAP No. 21AXM-071
Program Element No. 1AB015
EPA Task Officer: David K. Oestreich
Office of Energy, Minerals, and Industry
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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PREFACE
The Industrial Environmental Research Laboratory (IERL) of the
U.S. Environmental Protection Agency (EPA) has the responsibility
for insuring that pollution control technology is available for
stationary sources to meet the requirements of the Clean Air
Act, the Federal Water Pollution Control Act and solid waste
legislation. If control technology is unavailable, inadequate,
or uneconomical, then financial support is provided for the
development of the needed control techniques for industrial and
extractive process industries. The Chemical Processes Branch of
the Industrial Processes Division of the IERL has the responsi-
bility for investing tax dollars in programs to develop control
technology for a large number of operations (greater than 500)
in the chemical industries.
Monsanto Research Corporation (MRC) has contracted with EPA to
investigate the environmental impact of various industries which
represent sources of pollution in accordance with EPA's respon-
sibility as outlined above. Dr. Robert C. Binning serves as MRC
Program Manager in this overall program entitled "Source Assess-
ment," which includes the investigation of sources in each of
four categories: combustion, organic materials, inorganic mate-
rials, and open sources. Dr. Dale A. Denny of the Industrial
Processes Division at Research Triangle Park serves as EPA
Project Officer. Reports prepared in this program are of three
types: Source Assessment Documents, State-of-the-Art Reports,
and Special Project Reports.
Source Assessment Documents contain data on emissions from
specific industries. Such data are gathered from the literature,
government agencies and cooperating companies. Sampling and
analysis are also performed by the contractor when the available
information does not adequately characterize the source emissions.
These documents contain all of the information necessary for
IERL to decide whether a need exists to develop additional con-
trol technology for specific industries.
State-of-the-Art Reports include data on emissions from specific
industries which are also gathered from the literature, govern-
ment agencies and cooperating companies. However, no extensive
sampling is conducted by the contractor for such industries.
Results from such studies are published as State-of-the-Art
Reports for potential utility by the government, industry, and
others having specific needs and interests.
iii
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Special projects provide specific information or services which
are applicable to a number of source types or have special util-
ity to EPA but are not part of a particular source assessment
study. This special project report, "Source Assessment: Pesti-
cide Manufacturing Air Emissions - Overview and Prioritization,"
was prepared to provide a general summary of pesticide manufac-
turing, and to furnish information on individual pesticide source
types. Mr. David K. Oestreich of IERL-RTP served as EPA Task
Officer.
IV
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ABSTRACT
This report provides an overview of the pesticide manufacturing
industry and a prioritization listing of 80 major pesticides
based upon their potential environmental burden from an air
pollution standpoint. Production of synthetic organic pesticides
is estimated to have been 6.4 x 105 metric tons in 1974. Thirty-
seven major synthetic organic pesticides, those with annual
production greater than or equal to 4,540 metric tons, accounted
for 74% of the market. The raw material most commonly used in
pesticide manufacturing is elemental chlorine, but other raw
materials include hydrogen cyanide, carbon disulfide, phosgene,
phosphorus pentasulfide, hexachlorocyclopentadiene, various
amines, and concentrated acids and caustics.
Air pollution aspects of the pesticide manufacturing industry are
essentially without quantitative data. For some plants, the
pollution caused by loss of active ingredient is less significant
than that caused by unreacted byproducts. Evaporation from
holding ponds and evaporation lagoons may also be an emission
source, although few quantitative data are available. Emissions,
including particulates, gases, and vapors from the manufacturing
process, emanate from various pieces of equipment (for example,
reactors, driers, and condensers) and enter the atmosphere as
both the active ingredient and as raw materials, intermediates,
and byproducts. Air emission control devices include baghouses,
cyclone separators, electrostatic precipitators, incinerators,
and gas scrubbing units. Based on an estimated 1% annual growth
rate, total synthetic organic pesticide production in 1985 will
be approximately 8.06 x 105 metric tons.
Toxaphene ranked highest among the 80 pesticides prioritized.
The listing points out the potential environmental burden due to
evaporation from holding ponds and evaporation lagoons, and due
to sulfur dioxide emissions from flaring and incinerating sulfur
containing compounds.
This report was submitted in partial fulfillment of Contract No.
68-02-1874 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. The study described
in this report covers the period July 1976 to January 1978.
v
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CONTENTS
Preface iii
Abstract v
Figures ix
Tables xi
Abbreviations and Symbols xiii
1. Introduction 1
2. Summary 2
3. Pesticide Production 6
Production statistics 6
Producers 11
Production process 13
4. Industry Segmentation 15
Simple and aromatic chlorinated hydrocarbon
pesticides 16
Organophosphate pesticides 17
Carbamate pesticides 29
Triazine pesticides 33
Anilide pesticides 35
Organoarsenic and organometallic pesticides ... 37
Other nitrogenous pesticides 38
Diene-based chlorinated pesticides 39
Urea and uracil pesticides 43
Nitrated hydrocarbon pesticides 45
Microbial and naturally-occurring pesticides. . . 47
Other pesticides 49
5. Air Emissions Characterization and Pollution Control
Technology 52
Emissions 52
Emissions control 54
Selected pesticides 54
6. Pesticide Prioritization 75
Prioritization model 75
Prioritization by air emissions 77
Mass of emissions 81
Data sources, quality, and methodology 109
7. Growth and Nature of the Industry Ill
Government regulation Ill
Alternatives to pesticide chemicals 114
Future production 117
VII
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CONTENTS (continued)
References 121
Appendices
A. Prediction of Pesticide and Ammonia Emissions from
Holding Ponds and Evaporation Lagoons 123
B. Emission Factors used in Prioritization 134
Glossary 136
Conversion Factors and Metric Prefixes 138
Vlll
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FIGURES
Number
1 Schematic representation of pesticide manu-
facturing plant emissions 3
2 Pesticide production plant locations, by
state, in 1976 11
3 Synthesis of some chlorinated hydrocarbons and
related pesticides 18
4 Chemical reactions for organophosphate pesti-
cides from phosphorus pentasulfide 24
5 Chemical reactions for organophosphate pesti-
cides from phosphorus triclorosulfide .... 25
6 Chemical reactions for organophosphate pesti-
cides from other phosphorus compounds .... 26
7 Typical chemical reactions to produce carbamate
pesticides 31
8 Synthesis of triazine pesticides 34
9 Chemical reactions for production of anilide
pesticides 36
10 Chemical reactions to produce organoarsenic and
organometallic pesticides 38
11 Chemical reactions and structures for imides,
amides and other nitrogenous pesticides ... 40
12 Synthesis of the diene group of chlorinated
insecticides—from hexachlorocyclopentadiene. 42
13 Chemical reactions to form urea and uracil
pesticides 44
14 Chemical reactions to produce the nitrated
hydrocarbon pesticides 48
15 Chemical reactions and structures of other
pesticides 51
16 Production and waste handling schematic for
toxaphene 56
17 Production and waste handling schematic for
methyl parathion 58
IX
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FIGURES (continued)
Number Pac
18 Parathion residue and off-gas incinerator ... 60
19 Production and waste schematic for carbaryl . . 61
20 Production and waste schematic for atrazine . . 62
21 Production and waste schematic for alachlor . . 64
22 Production and waste handling schematic for
MSMA 64
23 Production and waste schematic for captan ... 67
24 Production and waste schematic for chlordane. . 69
25 Production and waste schematic for bromacil . . 70
26 Production and waste handling schematic for
trifluralin 71
27 Production and waste schematic for bacillus
thuringiensis 73
28 Production and waste schematic for methyl
bromide 74
29 U.S. estimated average annual growth of
synthetic organic pesticides 119
x
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TABLES
Number Pa.9e
1 Pesticide Classes by Purpose 6
2 U.S. Production of Synthetic Organic Pesticides,
by Usage Category, in 1974 9
3 U.S. Production of Synthetic Organic Pesticides,
by Chemical Groups, in 1974 9
4 Estimated U.S. Production of Major Individual
Synthetic Organic Pesticides, by Category,
in 1974 10
5 Selected Pesticide Plant Locations and
Capacities in 1972 12
6 Pesticide Manufacturers Producing a Large Number
of Active Ingredients at a Single Location . . 12
7 Input Materials for Chlorinated Hydrocarbon
Pesticides 19
8 Chemical Structure of Acyclic Organophosphate
Pesticides 20
9 Chemical Structure of Cyclic Organophosphate
Pesticides 21
10 Input Materials for Organophosphate Pesticides . 27
11 Structure of Carbamate and Thiocarbamate
Pesticides 30
12 Input Materials for Carbamate Pesticides .... 32
13 Input Materials for Triazine Pesticides 35
14 Input Materials for Four Anilide Pesticides. . . 37
15 Input Materials for Arsenical and Metallic
Pesticides 39
16 Input Materials for Other Nitrogenous Pesticides 41
17 Input Materials for Diene-based Pesticides ... 43
18 Urea Pesticides Structure 45
19 Input Materials for Urea and Uracil Pesticides . 46
20 Input Materials for Nitrated Hydrocarbon
Pesticides 47
xi
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TABLES (continued)
Number Page
21 Input Materials for Three Other Organic
Pesticides 50
22 Summary of Principal Air Emissions 53
23 Summary of Air Emission Control Devices for Five
Major Pesticides 55
24 Air Contaminant Emissions, Sources, and Rates
from Methyl Parathion Manufacture and Waste
Treatment 59
25 Air Contaminant Emissions, Sources, and Rates
from Trifluralin Manufacture 72
26 Industrial Chemicals, Useful as Pesticides,
Excluded from the Pesticide Prioritization . . 78
27 Prioritization of Pesticide Chemical Manufac-
turing Sources with Respect to Source Type . . 79
28 State-by-State Listing of Criteria Pollutant
Emissions from Prioritized Pesticide Chemical
Manufacturing Sources 84
29 National Listing of Criteria Emissions from
Prioritized Pesticide Chemical Manufacturing
Sources 1°4
30 Proposed Substitute Insecticides 113
31 Integrated Pest Management Options 115
XI1
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ABBREVIATIONS AND SYMBOLS
A — surface area
C. — concentration of pesticide "i" at time t
C. — initial concentration of pesticide "i"
10
C — saturation concentration of pesticide "i"
is
G! — total ammoniacal nitrogen at time tj
C2 -- total ammoniacal nitrogen at time t2
e — 2.72
E — water evaporation rate
F — hazard factor
F. — environmental hazard potential factor of the ith
1 material
F — ratio of undissociated ammonia to the total ammoniacal
r • nitrogen in solution
G — weight of body of water
h — stack height
I — impact factor
x
K — operational desorption coefficient
K — number of sources emitting materials associated with
x source type x
m — mass of ammonia desorbing from pond or lagoon
A
m. — mass of material "i" evaporating from pond or lagoon
M — molecular weight of water
w
M. — molecular weight of "i"
N — number of materials emitted by each source
p — vapor pressure of pure solid or liquid "i"
p. — population density in the region associated with the
J jth source
p — vapor pressure of water
w
Q — emission rate
S. — corresponding standard for the ith material (used only
i for criteria emissions, otherwise set equal to one)
xii
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t — averaging time
Si
ABBREVIATIONS AND SYMBOLS (continued)
t — time
aver<
"tin hydraulic retention time
HR
TKN — total Kjeldahl nitrogen
TLV — threshold limit value
t — instantaneous averaging time
o
u — wind speed
UL — uncertainty level
V — volume of water body
0 — temperature
IT ~ 3.14
X1•. — ambient concentration of the ith material in the
x^ region associated with the jth source
x". . — calculated time-averaged maximum ground level concen-
13 tration of the ith material emitted by the jth source
X — instantaneous (i.e., 3-min average) maximum ground
max level concentration
T7 — maximum time-averaged ground level concentration
Amax
xiv
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SECTION 1
INTRODUCTION
Pesticide chemical manufacturing results in air emissions, but
too few quantitative data are available to determine whether
sufficient pollution control technology is available. Due to
this lack of emissions data, an industry overview and emissions
source prioritization model was necessary to furnish information
regarding major pesticide chemicals. This report provides an
industry overview and prioritization of mass emissions from pes-
ticide chemical manufacturing in order to permit selection of
specific pollution sources for detailed assessment.
Contained in the industry overview is a description of the scope
of the pesticide manufacturing industry in terms of process
operations, raw materials, final products, and production trends
The industry is then divided into 12 segments for air emissions
evaluation and source prioritization. Quantitative emissions
data are presented where available. Estimates of emission
species and emission factors are determined from raw materials
used, process chemistry, and unit operations where quantitative
emissions data are unavailable.
Environmental impact factors are determined from the emissions
data for 80 pesticide chemical manufacturing source types.
These source types are then rank ordered, by pesticide chemical,
with regard to their commonly described potential hazard to the
environment from an air pollution standpoint.
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SECTION 2
SUMMARY
A pesticide is defined as 1) any substance or mixture of sub-
stances intended for preventing, destroying, repelling, or miti-
gating any pest, or 2) any substance intended for use as a plant
regulator, defoliant, or desiccant. The pesticide manufacturing
industry with its associated sources of emissions is represented
schematically in Figure 1. Production of synthetic organic pes-
ticides is estimated to have been 6.4 x 105 metric tons in 1974.
The pesticide manufacturing industry is dominated by a small
number of major products, while a large number of minor products
compete for a small share of the market. Thirty-seven major
synthetic organic pesticides, those with annual production
greater than or equal to 4,540 metric tons, accounted for 74% of
the market in 1974. The remaining 26% of production was divided
among about 300 other pesticides.
In 1976, there were 139 pesticide manufacturing plants (excluding
industrial chemicals with minor pesticide uses, which are pri-
marily products of other industries) distributed throughout 34
states in the United States. These plants generally employ unit
operations and equipment similar to those used by the chemical
processing industry (reaction kettles, driers, filters, etc.).
The raw material common to the most pesticides is elemental
chlorine, which is used directly on site in the production of
chlordane, toxaphene, 2,4-D, 2,4,5-T, atrazine, captan, carbaryl,
and mercuric chloride. Chlorine is also used to prepare raw
materials brought in for production of DDT, aldrin, and perhaps
trifluralin and alachlor. Raw materials of an unusually hazard-
ous nature include hydrogen cyanide, carbon disulfide, various
amines, and concentrated acids and caustics. The phosphorus
pentasulfide (P2S5) used in manufacturing organophosphorus
pesticides, the hexachlorocyclopentadiene (C5C16) used for cyclo-
diene pesticides, the phosgene used to make carbaryl, and numer-
ous other raw materials, as well as solvents such as xylene,
toluene, and similar materials, present potential health hazards.
Air pollution aspects of the pesticide manufacturing industry
are essentially without quantitative data. For some plants, the
pollution caused by loss of active ingredient is less significant
than that caused by unreacted byproducts such as hydrogen sul-
fide (H2S), which is flared to form sulfur dioxide (S02), or
particulates resulting from fuel combustion. A plant producing
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EVAPORATION
CHEMICAL
TREATMENT
CONTRACT
SLUDGE
DISPOSAL
INCINERATION
LANDFILL
OCEAN DISPOSAL
1
SOLID
AIR EMISSIONS
t
AIR EMISSIONS
CONTROL DEVICE
EVAPORATION
' / PESTICIDE \ ' imiiTn'«Mn WASTEWAItK
WASTF / \ LIQUID AND TREATMENT
w«3lt iMAMiirArTtiDTMr" 1 ,-«,.. T™., _ '"h.."-' —
EMISSIONS V n,.,T / EMISSIONS _. AND/OR..
i
\ ' """ / tV«fUKMUUI\
\^^X r- POND -i
| POND LINING 1
-
LEAKAGE
GROUND GROUND
CONTAMINATION CONTAMINATION
1
RUNOFF RUNOFF
LEACHING LEACHING
EVAPORATION EVAPORATION
BIODEGRADATION BIODEGRADATION
DISCHARGE TO
MUNICIPAL
WASTEWATER
PLANT
(OPTIONAL)
ENVIRONMENT
Figure 1. Schematic representation of pesticide manufacturing plant emissions.
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4.54 x 103 metric tons per year of most thioorganophosphate pes-
ticides, for example, could emit over 907 metric tons per year
of SO2- Such a plant might also produce 2.27 x 103 metric tons
to 4.54 x 103 metric tons per year of particulate pollutants,
depending upon the fuel used for process heat and the air pollu-
tion controls installed.
Evaporation from holding ponds or evaporation lagoons may also
be an emission source, although few quantitative data are avail-
able. Equations are presented which were used to predict the
evaporation rates of several pesticides and develop evaporation
emission factors for additional input into the prioritization
model. These equations indicate that up to 5.6 kg/day of aldrin
could be emitted from an evaporation lagoon having a surface
area equal to 4.05 x 105 m2 if aldrin were still manufactured.
Emissions, including particulates, gases, and vapors from the
manufacturing process, emanate from various pieces of equipment
(for example, reactors, driers, and condensers) and enter the
atmosphere both as the active ingredient and as raw materials,
intermediates, and byproducts. Air emission control devices
used in the pesticide manufacturing industry include baghouses,
cyclone separators, electrostatic precipitators, incinerators,
and gas scrubbing units.
Major pesticide chemicals were rank ordered or prioritized based
on their air pollution potential by computing a relative envi-
ronmental impact factor. A prioritization was conducted because
a realistic assessment of the environmental significance of air
emissions from pesticide manufacturing plants is inconceivable
due to the limited quantitative emissions data available. The
prioritization model is simply one tool used to aid decision
making regarding further characterization of the pesticide manu-
facturing industry. The pesticide ranking should by no means be
considered rigid, but it should highlight areas for future
consideration.
The prioritization list of 80 pesticides highlights two facts:
1) little information is available concerning the environmental
burden due to potential evaporation emissions from holding ponds
and evaporation lagoons, and 2) sulfur dioxide emissions may be
substantial for some pesticides, resulting from flaring H2S and
mercaptans and the incineration of sulfur-containing compounds.
Four of the nine pesticides receiving the highest prioritization
impact factors are potentially emitted to the atmosphere from
holding ponds or lagoons. Eight pesticides appear in the upper
20% of the prioritization list due primarily to the potentially
high emission of SO2, resulting from flaring H2S and mercaptans
and the incineration of sulfur-containing compounds.
Due to increasingly stringent regulations, rising costs, insect
resistance to pesticide chemicals, and greatly increased reliance
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on herbicides for cultivation, changes are occurring in pest
control strategies; however, chemical pesticides should continue
to play a significant role in pest management. Pesticide produc-
tion beyond the next few years is difficult to estimate because
of diverse changes in government regulations, the influence of
research on new products and on application rates of products,
and a variety of economic factors. Production of synthetic
organic pesticides is estimated to increase by an average of 1%
annually until 1985 with average annual herbicide growth of
approximately 2%, average annual insecticide growth unchanged
from the present level, and average annual fungicide growth of
approximately 1.8%. At this predicted growth rate, total syn-
thetic organic pesticide production in 1985 will be 8.06 x 105
metric tons.
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SECTION 3
PESTICIDE PRODUCTION
PRODUCTION STATISTICS
Pesticides have become an important factor in the United States
economy because they are used to increase the production of food
and fiber and to control organisms that destroy useful materials
or threaten public health. A pesticide is defined as 1) any
substance or mixture of substances intended for preventing,
destroying, repelling, or mitigating any pest, or 2) any sub-
stance intended for use as a plant regulator, defoliant, or
desiccant (1). Pesticides are usually classified by the kind of
pest they control, purpose of application, or mode of action on
a certain pest as listed in Table 1 (2).
TABLE 1. PESTICIDE CLASSES BY PURPOSE (2)
Algicides Herbicides Pheromones
Bacteriostats Insecticides (attractants)
Defoliants Larvacides Repellants
Desiccants Miticides Rodenticides
Fumigants (acaricides) Sterilants
Fungicides Molluscicides Synergists
Growth regulants--
insect and plant
The major pesticide classes in Table 1, based on the largest
annual productions, are herbicides, insecticides, and fungicides,
Herbicides are used for preventing or inhibiting the growth of
(l) Pesticides and Pesticide Containers. Federal Register,
39(85):15236, 1974.
(2) Kelso, G. L., R. R. Wilkinson, and T. L. Ferguson. The
Pollution Potential in Pesticide Manufacturing—1976 (Draft
Final Report). Contract 68-02-1324, Task 43, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, April 16, 1976. 236 pp.
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plants or plant parts, or for killing or destroying them (3).
Insecticides constitute a class of pesticide that prevents or
inhibits the establishment, reproduction, development, growth or
presence of any member of the class Insecta or other allied classes
in the phylum Arthropoda-considered to be pests (3). Fungicides
are used on farm crops, preferably as protective rather than cura-
tive treatment, being applied to the surface of the plant in water
suspensions or dusts before attack of a fungus (4) .
The 1974 production of all synthetic organic pesticides is esti-
mated to have been 6.4 x 105 metric tons3 (2). The 1974 produc-
tion estimates were used as prioritization input, rather than
more recent statistics, because these 1974 data are the only
comprehensive data base for all pesticide categories as well as
for individual pesticides. In order to provide a general over-
view of the industry, however, more recent production statistics
are presented.
The 1975 production for all synthetic organic pesticides was 7.3
x 105 metric tons. Herbicides dominated the 1975 market, account-
ing for more than 48% of the total. Herbicide production in 1975
totaled 3.5 x 105 metric tons, a 30.4% increase over the previous
year. Insecticide production in 1975 increased only 2.4%, reaching
3.0 x 105 metric tons or over 41% of the total synthetic organic
pesticide production for that year. Production of fungicides in
1975, which accounted for less than 10% of the total, decreased
4.5% from the previous year to 7.1 x 101* metric tons (5).
Available statistics indicate that inorganic pesticides consti-
tute only about 10% of the total U.S. pesticide production (5).
Fungicides account for 55% of the inorganic pesticide business,
herbicides for 38%, and insecticides for 7% (5). A total of 79
inorganic and metallic-organic pesticides were in use in 1973.
Of these compounds, 28 were mercury based, 17 arsenic based, 11
copper based, 6 other metal based, and the remainder other in-
organic compounds (6).
al metric ton equals 106 grams; conversion factors and metric sys
tern prefixes are presented at the end of this report (p. 138) .
(3) Ouellette, R. P., and J. A. King. Chemical Week Pesticides
Register. McGraw-Hill Book Company, New York, New York,
1977. 346 pp.
(4) 1976 Farm Chemicals Handbook. Meister Publishing Co.,
Willoughby, Ohio, 1976. 577 pp.
(5) Ouellette, R. P., and J. A. King. Pesticides '76. Chemical
Week, 118(25) :27-38, 1976.
(6) Patterson, J. W. State-of-the-Art for the Inorganic
Chemicals Industry: Inorganic Pesticides. EPA-600/2-74-
009a, U.S. Environmental Protection Agency, Washington,
D.C., March 1975. 39 pp.
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Copper sulfate, zinc sulfate, sodium chlorate and sulfur are
among the leading inorganic pesticides, but these compounds are
primarily products of other industries and have other uses in
addition to being pesticides. Sodium chlorate, for example, is
used in the metallurgical, textile, dye, and pulp and paper
industries, and as an agricultural herbicide, but the actual
percentage of production used as a pesticide is not known.
Inorganic pesticides were not included in the prioritization
with the exception of arsenates, for which reasonably accurate
estimates of pesticide use could be made. Also, the inclusion
of inorganic arsenicals in the prioritization shows that their
small production is a principal factor for their low ranking.
The pesticide 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. Thirty-seven major synthetic organic
pesticides, those with production greater than or equal to 4,540
metric tons, accounted for 74% of the market in 1974. The
remaining 26% of production was divided among about 300 other
pesticides. A total of 140 to 150 synthetic organic pesticides
are estimated to have had production greater than 454 metric
tons in 1974 (2) .
Actual production figures for specific pesticide compounds are
usually not available unless there are three or more producers
(none of which are excessively dominant over the others), be-
cause these data are considered proprietary by the companies and
are accepted in confidence by the U.S. Tariff Commission. As a
result of this reporting procedure, U.S. production data are not
available on many pesticides, including the most widely used
insecticide (toxaphene) and the largest selling herbicide
{atrazine). Combined toxaphene and atrazine production accounts
for an estimated 15% of all synthetic organic pesticide produc-
tion in the United States (2).
U.S. production of synthetic organic pesticides in 1974 has been
reported, by category, as shown in Table 2 (2). These basic
data are utilized to develop production estimates for use in
this study. Production estimates presented in Table 3 are
believed to be accurate within ±10%. These estimates are based
on the data in Table 2 as well as current knowledge regarding
various segments of the pesticide industry gathered in part from
confidential sources (2).
Table 4 presents estimated 1974 production of individual pesti-
cides within each category (2).
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TABLE 2. U.S. PRODUCTION OF SYNTHETIC ORGANIC PESTICIDES,
BY USAGE CATEGORY, IN 1974 (2)
Pesticide usage categories
1974 Production,a
103 metric tons
Fungicides:
Pentachlorophenol and sodium salts 23.8
Naphthenic acid, copper salt 0.9
Other cyclic fungicides 31.8
Dithiocarbamic acid salts 16.1
Other acyclic fungicides 1.3
Total fungicides 73.8
Herbicides and plant hormones:
Maleic hydrazide 2.6
2,4-D acid,b dimethylamine salt 6.6
Other cyclic compounds 212.0
All acyclic compounds 52.8
Total herbicides and plant hormones 274.0
Insecticides, rodenticides, soil conditioners
and fumigants:
Aldrin-toxaphene group 64.3
Methyl parathion 23.3
Other cyclic organophosphorus insecticides 25.6
Methoxychlor 1 •5
Other cyclic insecticides and rodenticides 72.8
Methyl bromide 13.8
Acyclic organophosphorus insecticides 35.7
Chloropicr in 2.2
Other acyclic insecticides, rodenticides, soil
conditioners, and fumigants 55.8
Total 294.9
Total synthetic organic pesticide
production, 1974 642.7
3Data may not add to totals due to independent rounding.
2,4-Dichlorophenoxyacetic acid.
TABLE 3. U.S. PRODUCTION OF SYNTHETIC ORGANIC
PESTICIDES, BY CHEMICAL GROUPS, IN 1974
(2)
Chemical group
Chlorinated hydrocarbons
Organophosphorus compounds
Carbamates
Triazines
Anilides
Other nitrogenous compounds
Organoarsenicals and
organometallics
Diene-based compounds
Ureas and uracils
Nitrated hydrocarbons
All others
TOTAL
Estimated 1974
production,3
10 3 metric tons
208.6
90.7
68.0
68.0
49.9
31.7
24.9
18.1
18.1
18.1
46.3
642.6
Estimated
percentage
of total
production
(rounded)
33
14
\ 10
v 10
8
5
4
3
3
3
7
100
aData may not add to totals due to independent rounding.
-------
TABLE 4. ESTIMATED U.S. PRODUCTION OF MAJOR INDIVIDUAL SYNTHETIC
ORGANIC PESTICIDES, BY CATEGORY, IN 1974 (2)
Chemical group
Chlorinated hydrocarbons
Organophoaphates
Carbamatee
Triazines
Anilides
Organoarsenicals and organometallics
Other nitrogenous compounds
Diene-based
Nitrated hydrocarbons
All others
Total all synthetic organic pesticides
Pesticide
Toxaphene
DDT"
2,4-D acid, eaters, salts
PCP and sodium salts
Trichlorophenols
Dichloroprene
Chloramben
DBCP'
Sodium TCA
All others
Methyl parathion
Malathion
Parathion
Diasinon
Disulfoton
Phorate
Monocrotophos
Fensul f othion
Merphos
All others
Carbaryl
Maneb
Metalkamata
Carbofuran
Butylate
zineh
EPIC'
Nabam
Vernolate
Aldicarb
All others
Atrazine
Simazine
Propazine
All others
Propachlor
Alachlor
Propanil
Butaohlor
MSMA?
DSMA"
Cacodylic acid
Copper naphthenates
All others
Captan
Hethyonyl
CDAAl
Haleic hydrazide
Benomyl
Nitralin
Picloran
Captafol
Folpet
All others
Chlordane
Aldrin
Endrin
Heptachlor
Endosulfan
All others
Brofflacil
Diuron
Fluometuron
Linuron
Terbacil
All others
Trifluralin
Chloropicrin
Dinoseb
Benefin
All others
Methyl bromide
Miscellaneous
10' metric tons
49.9
27.2
24.9
23.6
11.3
11.3
10.0
9.1
6.8
34.5
2S6.S
23.1
13.6
1.1
5.4
4.5
4.5
3.2
2.7
2.3
23.6
90.7
26.3
5.4
4.5
4.5
3.6
3.2
2.7
2.3
2.3
2.3
10.9
6"575
49.9
6.8
4.5
6.8
eTTff
20.4
18.1
6.8
4.5
4TT5
15.9
4.5
1.4
0.9
2.3
24.9
9.1
4.5
3.2
2.7
1.8
1.4
1.4
1.4
1.4
5.0
3T7T
6.8
4.5
1.4
1.4
1.4
2.7
~I8TT
5.4
4.5
2.3
1.4
1.4
3.2
18.1
11.3
2.3
1.4
1.4
1.8
1371
14.1
32.2
JS73
642.6
Approximate percentage
of group production
24
13
12
11
6
6
5
4
3
16
150
25
15
9
6
5
5
4
3
2
26
100
39
8
7
7
5
5
4
3
3
3
16
100
73
10
7
10
IM
41
36
14
9
loo"
64
18
5
3
10
loo"
29
14
10
9
6
4
4
4
4
16
100
38
25
7
7
7
16
I7JO
30
25
13
7
7
18
loo
63
13
7
7
10
Io"6"
30
70
100
*Data Buy not add to totals due to independent rounding.
"oichlorodiphenyltrichloroe thane.
c Pentachlorophenol.
dAlso known as dibromochloropropane, the cheaical name
is l,2-dibroso-3-chloropropan» (principal constituent).
BTrichloroacetic acid.
's-Ethyl n,n-dipropylthiocarbamate.
^Monosodiun methanearsonate.
"oisodium methanearaonate.
'N,!I-diallyl -2-chloroaceteamide.
10
-------
PRODUCERS
In 1976, there were 139 pesticide manufacturing plants in the
United States (excluding those that produce industrial chemicals
with pesticide utility, which are mainly products of other
industries), as shown in Figure 2 (2). These plants are dis-
tributed throughout 34 states, but major pesticide production
plants, those with capacities over 2.27 x 103 metric tons, are
located in 25 states. Table 5 (7) lists the 20 pesticide
producing plants with the largest capacities. Many plants are
located near the coast in close proximity to refineries that
supply petroleum and chlor-alkali feedstocks. Approximately 25%
of all the pesticide manufacturing plants are located in New
Jersey and California, with 17% located in New Jersey alone.
Pesticide plants vary in size from less than 2.27 x I0k kg/yr up
to 9.07 x 10"4 metric tons/yr (7).
Approximately 60 plants produce only one active ingredient, and
86 plants (62% of the total) produce two or less. In contrast,
however, several plants produce a large number of active ingre-
dients, as shown in Table 6 (2, 7) .
Figure 2. Pesticide production plant locations,
by state, in 1976 (2) .
(7) Parsons, T. B. (ed.), and F. I. Honea. Industrial Process
Profiles for Environmental Use: Chapter 8, Pesticides In-
dustry. EPA-600/2-77-023h (PB 266 225), U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
January 1977. 240 pp.
11
-------
TABLE 5. SELECTED PESTICIDE PLANT LOCATIONS
AND CAPACITIES IN 1972 (7)
Company
Ciba-Geigy Corporation
Tenneco Chemical, Inc.
Monsanto Chemicals
Dow Chemical Company
Hercules, Inc.
Union Carbide
Corporation
E. I. du Pont de
Nemours and Company
Eli Lilly and Company
Velsicol
American Cyanamid
Stauffer Chemical
Company
Ansul Company
Diamond Shamrock
Chemical Company
Calhio Chemical
Rohm and Haas Company
Shell Company
Company*
Major pesticide
Atrazine
Diazinon
Toxaphene
Alachlor
Maneb (dithio-
carbamates)
Pentachlorophenol
Methyl parathion
and parathion
2,4-D
Pentachlorophenol
Dichlorobenzene
Methyl bromide
Toxaphene
Carbaryl
Uracils (Bromacil)
Ureas (Diuron)
Trif luralin
Chlordane
Organophosphates
Malathion
Parathion and
methyl parathion
MS MA
MS MA
Captan
Dithiocarbamates
Aldrin
Plant location
Mclntosh, AL
St. Gabriel, LA
Fords, NJ
Muscatine, IA
Sauget, IL
Anniston, AL
Midland, MI
Brunswick, GA
Institute, WV
LaPort, TX
Lafayette, IN
Marshall, IL
Bayport, TX
Warners, NJ
Mount Pleasant, TN
Marinette, WI
Green Bayou, TX
Perry, OH
Philadelphia, PA
Denver , CO
Estimated plant
capacity,
10 3 metric tons
90.7
6.8
56.7
13.6
6.8 to 9.1
11.8
22.7
20.4 to 22.7
8.2
7.3
6.8
22.7 to 34.0
29.5
9.1
13.6
15.9
13.6
15.9
13.6
11.3
9.1
11.3
9.1 to 11.3
9.1
aAldrin and dieldrin are no longer manufactured.
TABLE 6. PESTICIDE MANUFACTURERS PRODUCING A LARGE NUMBER
OF ACTIVE INGREDIENTS AT A SINGLE LOCATION (2, 7)
Company
Location
Number of
active ingredients
produced
Dow
Rorer-Amchem
Mobay
Ciby-Geigy
Transvaal
Blue Spruce
Rorer-Amchem
Riverdale
McLaughlin Gormely King
Rorer-Amchem
FMC
Midland, MI
Ambler, PA
Kansas City, MO
St. Gabriel, LA
Jacksonville, AR
Edison, NJ
Fremont, CA
Chicago Heights, IL
Minneapolis, MN
St. Joseph, MO
Middleport, NY
28
22
21
16
16
13
10
10
10
10
10
12
-------
The data in Tables 5 and 6 must be qualified to the extent
that the plants either manufacture a given pesticide or have
the capacity to manufacture a given pesticide. Pesticide
producers generally do not simultaneously manufacture their
entire product line but do have facilities for production of
various pesticides without extensive plant modification.
PRODUCTION PROCESS
Technology for the production of pesticides varies considerably
depending on the properties of the compounds. Generally, how-
ever, the pesticide industry employs unit operations and equip-
ment similar to those used by the chemical processing industry
(reaction kettles, driers, filters, etc.) (8). Two character-
istics of the pesticide manufacturing industry differentiate it
from many, if not all, of the large industries of environmental
concern: 1) raw materials, byproducts, and products may be
highly toxic to certain plants and animals (including man); and
2) the production processes normally require only low to moderate
temperatures (2).
The raw materials required for pesticide production include many
petroleum-based hydrocarbon chemicals from the petroleum and
chemical industries, and some chlorine and sodium hydroxide from
the chlor-alkali industry. Large amounts of sulfuric acid and
nitric acid from the inorganic chemical industry are also used.
Gases including chlorine, phosgene, and ammonia are used in the
production of some pesticides, and'these gases can be extremely
toxic if released to the atmosphere. Atmospheric emissions of
heavy metals, arsenic, cyanide, and phosphate raw materials, as
well as partially chlorinated hydrocarbons, may also present a
potential health hazard (7).
The raw material common to the most pesticides, elemental chlo-
rine, is used directly on site in the production of chlordane,
toxaphene, 2,4-D, 2,4,5-T, atrazine, captan, carbaryl, and mer-
curic chloride. Chlorine is also used to prepare raw materials
brought in for the production of DDT, aldrin, and perhaps
trifluralin and alachlor. Production of chlorine previously in-
volved extensive use of mercury cells, leading to mercury
losses, but these cells are being better controlled and are
being displaced by mercury-free diaphragm cells. Unusually
hazardous raw materials include hydrogen cyanide (of which over
4.54 x 103 metric tons are required annually for atrazine pro-
duction), carbon disulfide, various amines, and concentrated
(8) Air Pollution Engineering Manual, Second Edition.
J. A. Danielson, ed. Publication No. AP-40, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, May 1973. 987 pp.
13
-------
acids and caustic. The P2S5 used in manufacturing organophos-
phorus pesticides, the C5Cl6 used for cyclodiene pesticides, the
phosgene used to make carbaryl, and numerous other raw materials,
as well as solvents, such as xylene, toluene, and similar materi-
als, present potential health hazards (2).
Actual pesticide production processes require only low or mod-
erate temperatures. Normally, these temperatures range from
approximately 0°C to 200°C (personal communication with G. A.
Richardson, Monsanto Research Corporation, 17 October 1977).
The production of DDT, for example, is exothermic; the reactants
are initially cooled to a temperature of 0°C to 30°C, and the
cooling is continued to maintain the reaction temperature in
this range (9). The batch preparation of DDT may be carried out
at atmospheric pressure in a closed reaction vessel equipped
with an agitator and a jacket, internal cooling coils, or an ex-
ternal heat exchanger circuit (9).
Plant equipment is generally newer for the more toxic materials
such as the organophosphorus and carbamate insecticides which
have undergone rapid growth in recent years. Many of the older
chlorinated hydrocarbons and other products are manufactured in
somewhat older equipment, up to and over 50 years old. The
majority of basic facilities and equipment now in use for pesti-
cide manufacture was designed and built prior to the present age
of intense concern about the environment, and many manufacturers
seem to be building or designing new pollution control equipment
to bring their plants into conformity with local standards.
Equipment is usually isolated from other company activities, and
it is dedicated to one pesticide or to two pesticides in the
same chemical family with similar pesticidal applications.
Cleanup of equipment is therefore minimized, and the associated
pollution potential is not particularly significant. Only a
small quantity of active ingredient (usually much less than 1%
of equipment capacity) is involved in this operation, and the
wastes generated are usually recycled, discharged to the plant
waste treatment system, or combusted as fuel (2).
Information regarding the energy requirements for the pesticide
industry is generally not available since many of the production
processes are proprietary. The feedstock raw materials such as
chlorine and sodium hydroxide may require large amounts of
energy if electrodialysis of a brine solution is used, but most
of these feedstocks are actually products of the chlor-alkali,
petroleum, and chemical industries. The final pesticide re-
actions themselves require relatively low amounts of energy for
heating and maintaining reaction temperatures, for some reflux
and stripping operations, and for pumping fluids (7).
(9) Sittig, M. Agricultural Chemicals Manufacture - 1971. Noyes
Data Corporation, Park Ridge, New Jersey, 1971. 264 pp.
14
-------
SECTION 4
INDUSTRY SEGMENTATION
A variety of manufacturing processes are utilized in the pesti-
cide industry due to the large number of chemical compounds used
as pesticides. The Federal Register has published a comprehen-
sive list of 1,605 pesticide active ingredients for reregistra-
tion (10). Over 300 pesticide products are in current production
and use, and over 500 pesticide products have been identified
(2, 7). The pesticide industry is therefore difficult to cate-
gorize in terms of processes and operations. In this respect,
it is not like other portions of the chemical industry. The
bromine industry, for example, is concentrated in Arkansas and
Michigan and is dominated by six producers and essentially one
process. Similarly, the vinyl chloride industry is composed of
11 companies located at 15 sites and utilizing 4 different
manufacturing processes. It is possible to describe the vinyl
chloride manufacturing operation in terms of a representative
facility having measured and/or estimated emission rates. The
chemistry of the emitted pollutants from a vinyl chloride plant
is well known, and emission standards in terms of threshold
limit values (TLV®) have been established for these pollutants.
The pesticide industry cannot be similarly categorized, nor have
emission standards been established for many pollutants from
this industry (2).
In order to present a clearer picture of the process relation-
ships in the pesticide industry, the pesticides have been sep-
arated, based on similarities in chemical structures and synthe-
sis reactions, into 12 industrial segments (7). Based on produc-
tion estimates from Table 4 the following segments are arranged
in decreasing order:
simple and aromatic chlorinated hydrocarbon pesticides
organophosphate pesticides
carbamate pesticides
triazine pesticides
anilide pesticides
organoarsenic and organometallic pesticides
other nitrogenous pesticides
(10) Pesticide Programs: Data Requirements to Support Registra-
tion of Pesticide Active Ingredients and Preliminary Sched-
ule for Call-Ins. Federal Register, 41 (32):7218-7376, 1976
15
-------
• diene-based chlorinated pesticides
• urea and uracil pesticides
• nitrated hydrocarbon pesticides
• microbial and naturally-occurring pesticides
• other pesticides
Many of the production processes in the industry are considered
proprietary, and detailed operational data and process descrip-
tions are of limited availability. In addition, some pesticides
may be produced by as many as eight different processes, none
specifically identified with a particular producer or plant (7).
Due to the limited availability of detailed data and the variety
of potential production processes, the following descriptions of
the 12 industrial sements are somewhat generalized.
SIMPLE AND AROMATIC CHLORINATED HYDROCARBON PESTICIDES
The simple and aromatic chlorinated hydrocarbon pesticides in-
clude about 90 pesticides which may be separated into three
groups: 1) simple chlorinated hydrocarbons, 2) DDT-family of
chlorinated hydrocarbons, and 3) aromatic-chlorinated hydrocar-
bons. Pesticides having phenol as a base ("phenoxie" pesticides)
are included as aromatic-chlorinated hydrocarbons. The general
structure of aromatic-chlorinated hydrocarbons is (7):
where at least one R group is chlorine, as summarized in the
following tabulation (7).
Aromatic pesticide Rj R2 RS R4 R5 . Re
Phenoxie pesticides
2,4-D -OCH2COOH -Cl -H -Cl -H -H
2,4-DBa -OCH2CH2COOH -Cl -H -Cl -H -H
MCPA° -OCH2COOH -CH3 -H -Cl -H -H
MCPBC ' -CH2CH2COOH -CH3 -H -Cl -H -H
2,4,5-Td -OCH2COOH -Cl -H -Cl -Cl -H
Silvex -OCH(CH3)COOH -Cl -H -Cl -Cl -H
Bromoxynil -CN -H -Br -OH -Br -H
PCP -OH -Cl -Cl -Cl -Cl -Cl
2,4,5-Trichlorophenol -OH -Cl -H -Cl -Cl -H
a4-Chloro-2-oxobenzothiazolin-3-ylacetic acid (benazolin).
b[(4-Chloro-o-tolyl)oxy]acetic acid.
C4-[(4-Chloro-o-tolyl)oxy]butyric acid.
d (2,4,5-Trichlorophenoxy)acetic acid.
16
-------
Aromatic pesticide
(continued) RI R2 RS Ri» RS RB
Others
PCNBe -NO2 -Cl -Cl -Cl -Cl -Cl
2,3,6-TBAf -COOH -Cl -H -Cl -H -Cl
Chloramben -COOH -H -Cl -H -NH2 -Cl
Dichlorobenzene -Cl -H -H -Cl -H -H
Hexachlorobenzene -Cl -Cl -Cl -Cl -Cl -Cl
Dicamba -COOH -OCH3 -Cl -H -H -Cl
ePentachloronitrobenzene.
Trichlorobenzoic acid.
The estimated annual production of chlorinated hydrocarbon pesti-
cides in 1974 was 208.6 x 103 metric tons. Toxaphene, the most
extensively used insecticide in the United States, accounted for
24% of this total. DDT production, accounting for 13% of the
total, was estimated as 27.2 x 103 metric tons in 1974. Phenoxie
pesticides are used as herbicides, and 2>4-D acid, esters, and
salts accounted for 24.9 x 103 metric tons in 1974 (2). A
number of chlorinated hydrocarbon pesticides, such as DDT and
2,4,5-T have been banned from U.S. distribution, have had U.S.
registrations canceled, or are under review due to their poten-
tial carcinogenicity. Twenty-four substitute pesticides have
been nominated to replace DDT as discussed in Section 7. Several
uses of the herbicide 2,4,5-T have been restricted, and eight
herbicides (bromacil, MSMA/DSMA, cacodylic acid, dinoseb,
dicamba, monuron, simazine, and trifluralin) have been nominated
as replacements (5). Methyl bromide is included in this industry
segment based on similarities with chlorinated hydrocarbon
pesticides.
Chemical reactions involved in the synthesis of various chlorin-
ated hydrocarbon pesticides are presented in Figure 3. Table 7
shows the raw materials used in production of several chlorinated
hydrocarbon pesticides.
ORGANOPHOSPHATE PESTICIDES
Organophosphate pesticides, most of which are insecticides, are
hydrocarbon compounds containing one or more phosphorus atoms.
The organophosphates may be separated into three main groups:
1) those derived from phosphorus pentasulfide (P2S5), 2) those
derived from thiophosphoryl chloride (PSC13), and 3) those
derived^from phosphorus trichloride (PC13). The typical struc-
ture of'acyclic organophosphorus pesticides (those derived from
P2S5 or PSC13) and a tabular presentation of several pesticides
are shown in Table 8; Table 9 presents the typical structure
and several examples of cyclic Organophosphate pesticides (those
derived from PC13) (7).
17
-------
METHOXYCHUJR
DOT
00
2.4,5-IRICHLOROPHeNOl.
OH
PCP
2,4-DB
CHjO
C'o
METHYL BROMIDE
Figure 3. Synthesis of some chlorinated hydrocarbons and related pesticides (7)
-------
TABLE 7. INPUT MATERIALS FOR CHLORINATED
HYDROCARBON PESTICIDES (7)
Pesticide
Input materials
Toxaphene
Strobane
Bandane
Ethylene dichloride
Hexachloracetone
Chloroacetic acid
TCA
Dalapon
PCNB
Dacthal (DCPA)
Dicamba
2,3,6-TBA
Chloramben
Methoxychlor
DDDa
DDT
2,4,5-Trichlorophenol
PCP
2,4-D
2,4-DB
Dichlorobenzene
Hexachlorophene
2,4,5-T
Silvex
Hexachlorobenzene
Benzene hexachloride
MCPA
MCPB .
Bromoxynil
Dichloropropene
Methyl bromide0
Chlorine, a-pinene
Chlorine, mixed terpenes
Chlorine, bicyclopentadiene
Chlorine, ethylene
Chlorine, acetone
Chlorine, acetic acid
acetic acid (3 moles)
propionic acid
nitrobenzene
CgH^ (COC1)2, CH3ONa
benzene, methanol, CO2,
toluene ,
(CH 3
ethanol,
Chlorine,
Chlorine,
Chlorine,
Chlorine,
Chlorine,
Chlorine,
Chlorine,
Chlorine,
Chlorine,
Chlorine, ethanol,
Phenol, chlorine
Phenol, chlorine
2,4-Dichlorophenol,
2,4-Dichlorophenol,
Chlorine, benzene
2,4,5-Trichlorophenol, CH2O
2,4,5-Trichlorophenol, NaOH, C1CH2COOH
2,4,5-Trichlorophenol, NaOH, C1(CH2)2COOH
Chlorine, benzene, catalyst
Chlorine, benzene, UV light source
4-Chloro-o-cresol, sodium monochloroacetate
4-Chloro-ci-cresol, butyrolactone
4-Hydroxybenzaldehyde, bromine, (NH2OH)
l,3-Dichloro-2-propanol, POC13
Methyl alcohol, bromine, and sulfur
(Alternate: methyl alcohol and hydro-
bromic acid)
oxygen
benzoic acid, ammonia
ethanol, anisole
chlorobenzene
chlorobenzene
C1CH2COOH, NaOH
butyrolacetone
2,2-Bis(p-chlorophenyl)-l,l-dichloroethane (common name - TDE).
Bromoxynil is classified as a phenoxie but is brominated instead of
chlorinated.
"Methyl bromide is included in this industry segment based on
similarities with chlorinated hydrocarbon pesticides.
19
-------
TABLE 8. CHEMICAL STRUCTURE OF ACYCLIC
ORGANOPHOSPHATE PESTICIDES (7)
Monophosphorus :
(Systox)
Demeton (mixture) :
Dichlorvos
Dicrotophos
Dimethoate
Disulfoton
Malathion
Mevinphos
Monitor
Monocrotophos
Naled
Oxydemeton-methyl
(m-systox)
Phorate (Thimet)
Phosphamidon
Trichlorfon
Diphosphorus :
Aspon
Ethion
TEPP3
B Me
II
II
(A)2-P-C-D Et
A B
j_^. EtO S
" *" EtO O
MeO 0
MeO O
MeO S
EtO S
MeO S
MeO 0
Meo and MeS O
MeO 0
MeO 0
MeO S
MeO 0
EtO S
MeO 0
MeO 0
F H
yd
II
(E)2-P-G-P-(I)2
_E F
C3H70 S
EtO S
EtO O
« methyl
= ethyl
C D
0 CH2CH2SC2H5
S CH2CH2SC2H5
O CH = CC12
0 C(CH3) = CHCON(CH3)2
S CH2CONHCH3
S CH2CH2SC2Hs
S CHCOOC2H5
CH2COOC2H5
O C(CH3) = CHCON(CH3)2
NH2
0 C(CH3) = CHCONHCH3
O CHBrCBrCl2
O CH2CH2SC2H5
S CH2CH2SC2H5
S CH2SC2H5
0 C(CH3) = CC1CON(C2H5)2
CH(OH)CC13
G H
0 S
SCH2S S
0 0
I
C3H70
EtO
EtO
Tetraethyl pyrophosphate.
20
-------
The development of organophosphorus insecticides was an out-
growth of World War II research on organophosphorus compounds
used as nerve gas. Tetraethyl pyrophosphate (TEPP) was the first
commercial insecticide of this industry segment, followed by
parathion and methyl parathion in the late 1940"s. Methyl
parathion, an acyclic organophosphate, is currently the nation's
most widely used organophosphorus insecticide with an estimated
annual production of 23.1 x 103 metric tons (2).
More than 100,000 organophosphorus compounds have been screened
as possible insecticides (11). Among the most widely used
today, besides methyl parathion and parathion, are malathion,
diazinon, disulfoton, chlorpyriphos, phorate, fonofos, azinophos-
methyl (Guthion), dimethoate, monocrotophos, and methidathion.
The organophosphorus insecticides kill insects by inactivating
cholinesterase and acetylcholinesterase, which are found in
nerve cells and the brain and play a vital role in nerve action.
These compounds break down more rapidly to form innocuous sub-
stances in plants, animals, and the soil than do the chlorinated
hydrocarbon pesticides. Organophosphorus insecticides do not
accumulate in animals to produce harmful effects. Therefore,
some can be used to protect crops shortly before harvest without
leaving potentially harmful residues. The organophosphorus
insecticides are usually active against a narrower range of
insects than are the organochlorines. They are, however, more
expensive than organochlorines and, since they degrade more
rapidly, they generally must be applied more often to crops.
Because they are usually more toxic to humans, they must be
handled with greater care (11).
A number of organophosphates, such as phorate, disulfoton,
dimethoate, monocrotophos, dicrotophos, demeton, and mevinphos,
act as systemic insecticides, meaning that when sprayed on
plants they do not remain on the surface but are rapidly trans-
located to many parts of it. Thus, plants do not have to be re-
sprayed frequently to protect areas of new growth, and less of
the insecticide is lost to rain or spray irrigation. However,
when systemic compounds are applied to food crops, care must be
taken so that excessive residues are not present in edible parts
of the plant when harvested (11).
Chemical reactions and their relationships for key pesticides in
the three main organophosphate groups are presented in Figures
4, 5, and 6. The input materials used in the manufacture of
these pesticides are shown in Table 10.
(11) Sanders, H. J. New Weapons Against Insects. Chemical and
Engineering News, 53 (30):18-31, 1975.
23
-------
I
( CH30)2P - SCHCOOC2H5
CH2COOC2Hs
MALATHION
S
(CH3O)2P - SCH2 - N
N
AZINPHOS-METHYL (GUTHION)
(CH3O)2P-SCH2
-H
PHOSMET (PROLATE)
S H
» Cl - CH2 - C - NHCHa
(CH30)P-SNo i<
O
II
(CH3O)2P - SCH2C - NHCH3
DIMETHOATE
S S
I I
(C2HsO)2P - SCH2S - P(OC2Hs)
ETHION
V u r^\ o CU'NOOH " ciCjH.scoHs i
(C2H50)2P - SH -^~U (C2H50)2P - SNa Z 4 " . (C2H5O)2P - SC2CH4SC2H3
DISULFOTON
s
(C2H50)2P-SCH2SC2H5
PHORATE
(C2H5O)2P-SNo
(C2H50)2P-SCH2-N
AZINPHOS ETHYL
S
(C2H50)2P-
CARBOPHENOTHION
Figure 4. Chemical reactions for organophosphate pesticides
from phosphorus pentasulfide (7) .
24
-------
(CH30)jP -
- SCHjCHjSCiHj OXYDEMETON (META SYSTOXI
- '(OCH3)2 ABATE
(CH^H-V^jUo " P'OC2H5)2
METHYL PARATHION
DICAPTHON
FAMOPHOS
DEMETON (SYSTOX)
TEPP
DURSBAN(CHLORPYIFOSJ
COUMAPHOS
DIAZINON
PARATHION
S - CH3 FENSULFOTHION
(C3H70)2P-CI
» (C3H70)2 - P - O - P(C3H70)2 AS PON
Figure 5.
Chemical reactions for organophosphate pesticides
from phosphorus trichlorosulf ide (7) .
25
-------
9 ChCCHO 9
(CH3O)2PH » (CH3O)2 P - CH(OH)CCI3
TRICHLORFON
-CI.-H
(CH30)3P
TRIMETHYL
PHOSPHITE
(CH30)2 P - OCH = CCI2
DICHLORVOS
N.N-DIMETHYLMETHYL-2-
CHLOROACETOACETAMINE
o
*
NALED
9
(CH3O)2P -
9
= CHCN(CH3)2
o o
CH3C - CCI2 - C - N(C2H5)2
O ' O
SCI3 +CH3C - CH2 - CN(C2H5)2
DICROTOPHOS
9 9
(CH3O)2P - OC(CH3) = CHCNHCH3
MONOCROTOPHOS
O
(CH3O)2P OC(CH3) =CHCOOCH3 (CIS AND TRANS MIXTURE)
MEVINPHOS(PHOSDRIN)
O O
(CH30)2P - OC(CH3) - CCICN(C2H5)2
PHOSPHAMIDON
Cl
2NaOCH3
.Cl
Cl-
-OP.
cr
2,4,5-TRICHLOROPHENYL
'DICHLOROPHOSPHATE
Figure 6.
C| OCH3
RONNEL
Chemical reactions for organophosphate pesticides from
other phosphorus compounds (7).
-------
TABLE 10. INPUT MATERIALS FOR ORGANOPHOSPHATE PESTICIDES
Pesticide
Input materials
Acyclic:
Aspon
DEFa
Demeton
Dichlorvos
Dicrotophos
Dimethoate
Disulfoton
Ethion
Malathion
Merphos
Mevinphos
Monitor
Monocrotophos
Naled
Methyl demeton
(oxydemeton)
Phorate
TEPP
Pho sphamidon
Trichlorfon
o-o-Di-n-propyl phosphorochloridothioate, water,
pyridine and sodium carbonate
Butyl mercaptan and phosphorus oxychloride
o-o-Diethyl phosphorochloridothioate and
2-hydroxethyl ethyl sulfide
Trimethyl phosphite and chloral (Alternate:
triclorfon)
Trimethyl phosphite and N,N-dimethyl methyl-2-
chloroacetoacetamide
Sodium dimethylphosphorodithioate and N-methyl-
a-chloroacetamide
Sodium diethylphosphorodithioate and B-chloro-
ethyl thioethyl ether
o-o-Diethyl phosphorodithioic acid and dibromo-
methane
o-o-Dimethyl phosphorodithioic acid and diethyl
maleate
Butyl mercaptan and phosphorus trichloride
(Alternate: dibutyldisulfide and phosphorus)
Trimethyl phosphate and methyl-2-cniorocicetu-
acetate
o-o-Dimethylphosphoroamidothioate
Trimethyl phosphite and N-methyl methyl-2-
chloro-acetoacetamine
Dichlorvos and bromine
Dimethyl phosphorochloridothioate and 2-hydroxy-
ethyl ethyl sulfide
o-o-Diethyl phosphorodithioic acid, formaldehyde
and ethyl mercaptan
Diethyl phosphorochloridothioate and water
(with pyridine and sodium carbanate)
Trimethyl phosphite, sulfurylchloride and
acetoacetic acid diethylamide
Dimethyl phosphite and chloral
(continued)
27
-------
TABLE 10 (continued).
Pesticide
Input materials
Cyclic:
Abate
Dimethyl phosphorochloridothionate and bis-
(P-hydroxyphenyl) sulfide
Azinphos-methyl (Guthion)
Carbophenothion
Dursban (clopyrifos)
Crotoxyphos
Coumaphos
Crufomate
Diazinon
Dioxathion
Dyfonate (fonophos)
Dasanit (fensulfothion)
Fenthion
Methyl parathion
Parathion
Phosmet (Imidan)
Fenchlorophos (Ronnel)
Dicupthon
Famophos
o-o-Dimethyl phosphorodithioic acid and
N-chloromethylbenzazimide
o-o-Diethyl phosphorodithioic acid and
N-chloromethylbenzazimide
Sodium diethylphosphorodithioate and 4-chloro-
phenyl chloromethyl sulfide
Diethy1 phosphorochloridothioate and 3,5,6-
trichloro-2-pyridinol
Diethyl phosphorochloridothionate and 3-chloro-
4-methyl-7-hydroxycoumarin
4-t-Butyl-2-chlorophenol, phosphonyl chloride,
methanol, methylamine
Diethyl phosphorochloridothionate and
2-isopropyl-4-methyl-6-hydroxyprimidine
o-o-Diethyl phosphorodithioic acid and 2,3-
dichloro-p-dioxane
No data
Diethyl phosphorochloridothioate and 4-methyl-
thio-1-hydroxybenzene
Dimethyl phosphorochloridothionate and
4-methyl-thio-m-cresol
Dimethyl phosphorochloridothioate and sodium
4-nitrophenate
Diethyl phosphorochloridothioate and sodium
4-nitrophenate
Sodium dimethylphosphorodithioate phthalimide,
formaldehyde and chlorine
2,4,5-Trichlorophany1 phosphorochloridothioate
sodium and methanol
Dimethyl phosphorochloridothionate and sodium
2-chloro-4-nitrophenate
o-o-Dimethyl phosphorochloridothioate, N,N-
dimethyl-1-phenol-sulfonomide, sodium hy-
droxide and water
S,S,S-Tributylphosphorotrithioate.
28
-------
CARBAMATE PESTICIDES
Carbamate pesticides have the characteristic carbamate carbon-
nitrogen (-N-C-) structure. There are more than 50 of these,
which may be separated into three groups: 1) carbamate pesti-
cides, 2) thiocarbamate pesticides, and 3) dithiocarbamate acid
salt pesticides.
The structure of the major carbamate and thiocarbamate pesticides
is:
R20
as summarized in Table 11
Rj-N-C-Rg
(7) .
The dithiocarbamate acid salts have the characteristic carbamate
structure with two sulfur atoms added3:
R2S
The structures of dithiocarbamate acid salt pesticides are
summarized below.
Ri
-CH3
-CH3
R2
-C2H5
-CH3
-CH3
R3
-CH2CC1=CH2
-K
=Mn
C2Hi+
CH3
;C2Ht+
'CH3
:C2H|+
•C?Ku
-H
-CH3
-H
-H
-H
-H
-NHn
= V3
-Mn
-Na
-Na
= Zn
Pesticide
CDEC
Dimethyl dithiocarbamic acid, K salt
Dimethyl dithiocarbamic acid, Mn salt
Ethylene bis(dithiocarbamic acid),
ammonia salt
Ferbam
Maneb
Metham-sodium
Nabam
Zineb
The first commercial carbamate insecticide to be used on a large
scale in the United States was carbaryl, introduced by Union
Carbide in 1958 (11). Accounting for approximately 38% of this
group's annual production, carbaryl is used widely today to con-
trol insects on cotton, vegetables, fruits, rice, sugarcane and
ornamental plants.
For maneb, nabam, and zineb the structure is better represented
as:
CH2-NH-CS-S\
I R
CH2-NH-CS-S/
where R indicates the corresponding metals.
2-Chloroallyl-N,N-diethyldithiocarbamate (Vegadex®).
29
-------
TABLE 11. STRUCTURE OF CARBAMATE AND THIOCARBAMATE PESTICIDES (7)
Pesticide
Aldicarb
R20
. 1 II
Ri-N-C-R3
RI R2 R3a
-CH3 -H -ON=CH-(CH3)2SCCH3
Barban
Butylate
Carbaryl
Carbofuran
-H
-CH2CH(CH3)2 -CH2CH(CH3)2
-CH 3 -H
-OCH2C=CCH2C1
-CH3
-H
Chloropropham
Cycloate
Di-allate
EPTC
Metalkamate
Molina te
Pebulate
Propham
Tri-allate
Vernolate
V^/tl
-o
-CH(CH3)2
-C3H7
_b
-H
-CH{CH3)2
-C3H7
_b
< 1 ) — hexamethy 1 — ( 2 ) c
-»C,H,
-©
-CH(CH3)2
-nC3H7
-C2HS
-H
-CH(CH3}2
-nC3H7
-OCH(CH3) 2
-SC2H5
-SCH2CC1=CHC1
-SC2H5
_b
-SC2H5
-SC3H7
-CH(CH3) 2
-SCH2CC1=CC12
-SC3H7
aPesticides with S in the R3 group are thiocarbaiuates.
Mixture of m-(Ethylpropyl)phenyl methylcarbamate and
m-(l-methylbutyl)phenyl methylcarbamate in an approximate
ratio of 3:1.
CA clearer representation for the structure of molinate is as
follows:
30
-------
Thousands of carbamates have been tested over the years for
insecticidal activity. Among the most widely used insecticides
of this type, besides carbaryl, are carbofuran, methomyl,
aldicarb, propoxur, and metalkamate. Generally, the advantages
of these pesticides over the organophosphorus pesticides are
their effectiveness against insects resistant to organophos-
phorus compounds and their frequently greater safety in handling
(11).
Like the organophosphorus compounds, the carbamates kill insects
by acting as cholinesterase and acetylcholinesterase inhibitors.
Like various organophosphorus compounds, some carbamates also
act systemically. Among these are Isolan, carbofuran, aldicarb,
and methomyl (11).
Chemical reactions for production of pesticides in the carbamate
family are indicated in Figure 7 (7). This figure presents five
different classes of reactions utilized in the manufacture of
carbamate pesticides. Table 12 lists 23 carbamates and the raw
materials for the production of each compound (7).
CARBAMATE PESTICIDES (AMINE REACTION);,
R2
I
R, - N - H
O
II
+ CI - C - R3
AMINE FORMATE
(OR PHOSGENE)
R2 O
r it
Rl - N - C - R3 +
CARBAMATE PESTICIDE
OR INTERMEDIATE
CARBAMYL CHLORIDE
THIOCARBAMATE PESTICIDES:,
R9 O
r n
R, -N-C-CI
INTERMEDIATE
CARBAMYL CHLORIDE1
R2 O
R4SH •• Ri-|s|-C-S-R4
MERCAPTAN, THIOCARBAMATE
ORTHIOL PESTICIDE'
CARBAMATE PESTICIDES (CYANATE REACTION)::
R! - NCO
CYANATE
R5OH •
ALCOHOL:
H O
i II
R)-N-C-ORs
CARBAMATE PESTICIDE
DITHIOCARBAMIC-ACID SALTS:
CS2 + R) - NH +
AMINE HYDROiCIDE
ORNH3'
DITHIOCARBAMIC-ACID SALTS (REPLACEMENT):
HCI
(O
HCI
(2)
R2 S
r n
(R,-N-C-S)R3
•CARBAMICACID
SSALT PESTICIDES
. . (3)
H20 (4)
CARBAM1C ACID SALT
PESTICIDE:(»1)
R4CI -
(SALTCIjOR!
SULFATE)
R2 S
• (R1-N-C-S)!tR4 + R3CI .
CARBAMIC ACID SALT SALT (Cl
PESTICIDE <»2) OR SULFATE)
(5)
Figure 7. Typical chemical reactions to produce
carbamate pesticides (7).
31
-------
TABLE 12. INPUT MATERIALS FOR CARBAMATE PESTICIDES (7)
Pesticide
Input materials
Carbaraates and thio-:
Aldicarb
Barban
Butylate
Carbaryl
Carbofuran
Chloroprophan
Cycloate
Di-allate
EPTC
Molinate
Pebulate
Propham
Tri-allate
Vernolate
Dithiocarbamates:
CDEC
DimethyIdithiocarbamic
acid, K salt
Dimethyldithiocarbamic
acid, Mn salt
Ethylene-bis(dithio-
carbamic acid), di-
amroonium salt ferban
Ferban
Metham
Nabam
Maneb
Zineb
Dimethylethylene, sodium nitrate, HCl, methyl-
thiosodium and methylisocyanate
4»-Chlorc—2-butynol and 3-chlorophenylisocyanate
(Alternate: 4-chloro-2-butynol, 3-chloroaniline)
Diiasobutylamine, phosgene and ethyl mercaptan
1-Napthyl-chloroformate, methylamine and sodium
hydroxide
2,3-Dihydro-2,2-dimethyl-7-benzofuranol and methyl
isocyanate
m-Chloroaniline and isopropyl chloroformate
N-ethylcyclohexylamine and ethylchlorothioformate
Diisopropylamine, phosgene and 2,3-dichloro-
propenyl-1-thiol
Di-n-propylamine, phosgene and ethyl mercaptan
(Alternate: di-n-propylamine arid ethylchloro-
thioformate)
Hexamethyleneimine and ethylchlorothioformate
Ethyl-n-butylamine, phosgene and n-propyl mercaptan
(Alternate: ethyl-rt-butylamine and n-propyl-
chlorothioformate)
Aniline and isopropyl chloroformate
•Diisopropylamine, phosgene and 2,3,3-trichloro-
phenyl-1-thiol
Di-n-propylamine, phosgene and n-propyl mercaptan
Diethylamine, carbon disulfide, sodium hydroxide
and 2,3-dichloropropene
Dimethylamine, carbon disulfide and potassium
hydroxide
K salt (above) or Na salt and manganese sulfate
(or chloride)
Ethylenediamine, carbon disulfide and ammonia
Dimethylamine, carbon disulfide, sodium hydroxide
and iron salt (chloride or sulfate)
Methylamine, carbon disulfide and sodium hydroxide
Ethylenediamine, carbon disulfide and sodium
hydroxide
Nabam and manganese salt (chloride or sulfate)
Nabam and zinc salt (chloride or sulfate)
32
-------
TRIAZINE PESTICIDES
The general structure of triazine pesticides is (7):
X
where A and B are normally amine groups and X is a less basic
group, as shown below.
B
Ametryne®
Atratone
Atrazine
Bladex®
Chlorazine
Cyprazine
Dyrene®
Igran SOW® (terbutryn)
MPMTC
Prometone
Prometryne
Propazine
Simazine
Triatazine
EtNH-a
EtNH-
EtNH-
EtNH-
Et2N-
CH2CH2CHN-
EtNH-
CH30(CH2) 3NH-
i-PrNH-
i-PrNH-
i-PrNH-
EtNH-
EtNH-
i-PrNH-b
i-PrNH-
i-PrNH-
(CH3)2C(CN)NH-
Et2N-
(CH3)2CHNH
Cl-
(CH3)3CNH-
CH3O(CH2)3NH-
i-PrNH-
i-PrNH
i-PrNH-
EtNH-
EtNH-
-SCH3
-OCH3
-Cl
-Cl
-Cl
-Cl
-Cl
-SCH3
-SCH3
-OCH3
-SCH3
-Cl
-Cl
-Cl
Derivatives of s-triazine form an important class of herbicides.
The 1974 estimated U.S. annual production was 68.0 x 103 metric
tons. Atrazine, the largest selling herbicide in the U.S. today,
accounted for 74% of the production of all triazine pesticides
(2).
Cyanuric chloride is reacted with appropriate amino hydrocarbons
to yield different triazine pesticides as indicated in Figure 8.
Table 13 lists raw materials for triazine pesticide manufacture
(7).
Et is used as an abbreviation for an ethyl subgroup.
b.
i-Pr is used as an abbreviation for an isopropyl subgroup.
'2,4-Bis[(3-methoxy propyl)amino]-6-(methylthio)-s-triazine.
33
-------
OYRENE
SIMAZINE
NH-CH(CH3)2
(CH3)2CHNH' ^N' "NHCH(CH3)2
PROPAZINE
CH3OH
N:
Cl SCH3
CH3SH ^ Nx-^N
C2H5NH^ ^N"^NHC(CH3)3 C2H5NH^tr^NHC (CH3) 3
TERBUTRYNE
OCH3
(CH3 ) 2CHNiT TJ^ ^NHCH (CH3 )
PROMETON
N ^NHCH(CH3)2
PROMETRYNE
Figure 8. Synthesis of triazine pesticides (7).
34
-------
TABLE 13. INPUT MATERIALS FOR TRIAZINE PESTICIDES (7)
Pesticide
Input materials (1 mole/mole base)
Ametryne®
Atrazone
Atrazine
Bladex®
Chlorazine
Cyprazine
Dyrene®
Igran 80V*S> (terbutryn)
MPMT
Prometone
Prometryne
Propazine
Simazine
(CH3)CHNH2
(CH3)2C(CN)NH2
Atrazine, methyl mercaptan
Atrazine, methyl alcohol
Cyanuric chloride, ethylamine
Ethylamine, cyanuric chloride .-..^^.^
Cyanuric chloride, (C2H5)2NH, CIC6Hi4NH2
Cyanuric chloride, CH2CH2CHNH
o-Chloroaniline, cyanuric chloride
Cyanuric chloride, ethylamine, (CH3)3CNH2, methyl
mercaptan
Cyanuric chloride, CH3O(CH2)3NH2 (2 moles)
Propazire, methyl mercaptan
Propazine, methyl alcohol
Cyanuric chloride, (CH3)2CHNH (2 moles)
Cyanuric chloride, ethylamine (2 moles)
ANILIDE PESTICIDES
Anilide pesticides are a small group of important herbicides
which includes propachlor, alachlor, propanil, and butachlor as
the major pesticides. These pesticides are derived from aniline
and possess the following general structure (7):
Pesticide
Alachlor
Butachlor
Propachlor
Propanil
CH3OCH2
CitH9OCH2
(CH3)2CH
H
CH2C1
CH2C1
CH2C1
C2H5
C2H5
H
H
C2H5
C2H5
H
H
H
H
H
Cl
H
H
H
Cl
Total estimated 1974 production for this group was 49.9 x 103
metric tons. Propachlor (20.4 x 103 metric tons) and alachlor
(18.1 x 103 metric tons) accounted for over three-fourths of the
group's 1974 production (2). Figure 9 presents synthesis
reactions for four anilide pesticides, and Table 14 lists input
materials for their manufacture (7).
35
-------
oo
CTi
NH2
"DIETHYLONILINE
NH2
ANILINE
H2CO (
SOLVENT ~
HjCO
cr»i WCMT
CH2
N
V
N
o
5 CICH^OCI
CICH2COCI
NH2
<-,
CH3CH2COOH
SOCI2
CATALYST
3,4-DICHLOROANILINE
O
i
- C2H5
"Cl
Cl
PROPANIL
ALACHLOR
9
j:4H9OH
NH3
BUTAtHLOR
CH3CHOCH3v
CH3CHOHCH3
NHjl '
'N
PROPACHLOR
NH4CI
+ NH4CI
+ NM4CI
Figure 9. Chemical reactions for production of anilide pesticides (7).
-------
TABLE 14. INPUT MATERIALS FOR FOUR ANILIDE PESTICIDES (7)
Pesticide Input materials
Alachlor Diethylaniline, p-formaldehyde, chloroacetyl
chloride, anhydrous ammonia, methanol
Butachlor Diethylaniline, p-formaldehyde, chloroacetyl
chloride, anhydrous ammonia, butanol
Propachlor Aniline, p-formaldehyde, chloroacetyl chloride,
anhydrous ammonia, isopropanol
Propanil 3,4-Dichloroaniline, propionic acid, thionyl
chloride
ORGANOARSENIC AND ORGANOMETALLIC PESTICIDES
The organoarsenical and organometallic pesticides are a small
group of about 15 pesticides. The organoarsenical pesticides
are herbicides, and* the organometallic pesticides are pre-
dominantly mercury and copper fungicides.
The organoarsenic pesticides are all derived from sodium
arsenite. DSMA, the derivative, is also the intermediate chem-
ical for producing MSMA, methane arsenic acid and cacodylic acid
as indicated in Figure 10 (7) . The structure of the organo-
arsenic pesticides is (7):
CH3As <
R2
Pesticide RI &2
DSMA -ONa -ONa
MSMA -ONa -OH
MAAa -OH -OH
Cacodylic acid -CH3 -OH
The two main organomercuric pesticides are formed with benzene
from mercuric acetate and mercuric oleate to form PMA and phenyl
mercuric oleate. The major organocopper pesticide is formed by
reacting naphthenic acids with soluble copper salts to form
copper naphthenates .
The 1974 estimated production of organoarsenic and organo-
metallic pesticides totaled 24.9 x 10 3 metric tons. MSMA and
DSMA combined for over 81% of this group's 1974 production.
Copper naphthenates were the leading organometallic pesticides
Methanearsonic acid.
37
-------
ARSENICALS:!
3N«OH
CH^iO(ONa), H2SO4
55MA 2H -
Sl» "^
O |ls>
CH3A$O
I
K>
O
\
Is)
Q
O
z
CH.CI
MSMA
NoSO4
NoSO4
METHANEARSONIC ACIC
+ NaCI
.MERCURIC:!
0-C-CH
(PHENYLMERCURIC ACETATO
-C-C7H,
rQ\__ H9-O-C-C7HM-CH
-------
TABLE 15. INPUT MATERIALS FOR ARSENICAL
AND METALLIC PESTICIDES (7)
Pesticide Input materials
Organoarsenical:
DSMA Arsenic trioxide, sodium hydroxide, methyl
chloride
MSMA DSMA (or materials) and sulfuric acid
Methyl arsenic acid DSMA (or materials) and sulfuric acid
Cacodylic acid DSMA (or materials), sulfur dioxide, sodium
hydroxide, and hydrochloric acid
Organometallics:
PMA Mercuric acetate and benzene
Phenyl mercuric oleate Mercuric oleate and benzene
Copper naphthenates Copper salts and naphthenic acids
_
Phenylmercuric acetate.
The estimated production of other nitrogenous pesticides in 1974
was 31.7 x 103 metric tons. The imide fungicides had the largest
1974 production with captan at 9.1 x 10 3 metric tons. Methomyl,
an insecticide, was next 4.5 x 103 metric tons, followed by CDAA,
a preemergence herbicide at 3.2 x 103 metric tons (2).
The' structures of and chemical reactions used to produce many of
these compounds are shown in Figure 11. The imide pesticides
(captafol, captan and folpet) have a similar reaction of a sul-
phenyl chloride with an imide and NaOH. Many other nitrogenous
pesticides also have a similar reaction between a chloride and
an amine or other nitrogenous compound. No information is
available for the reactions that produce methomyl and benomyl,
which are both classified as amate pesticides (7) .
Raw materials utilized in the manufacture of 15 pesticides in
this group are presented in Table 16 (7).
DIENE-BASED CHLORINATED PESTICIDES
Diene-based chlorinated pesticides are derived from hexachloro-
cyclopentadiene. This group includes the following 13 pesti-
cides: aldrin, dieldrin, heptachlor, chlordane, isodrin, endrin,
endosulfan, isobenzan (telodrin), alodan, bromodan, kepone,
mirex, and pentac. Toxaphene has a similar chemical structure
and is sometimes grouped together with the dienes as the aldrin-
toxaphene group (7) .
39
-------
CHLORIDE
COMPOUND
»*OM • CMCljCCIjSCI
N,OM • CCIjVCi
NITROGEN
COMPOUND
Q£
o
CM,£I{ - Cl
C4HfOC HjCH jOC M,c MTCI
CMjCHjOCCI
NITROGENOUS
PESTICIDE
. SCCI ,C HCIj
CAPTAFOl
CAPTAN
. HNICH^M CKj)? •
• »NN»MNCN i • C|jHjJ-N-C-NMj.CMjCOOH «f*C(
HYDROCARBON
COMPOUND
1. M,$0,
O
• Ci - C -
PODINE
PICHLORAM
MALE1C HYDRAZIDE
NAPTHAIAM
: - c . N(c«ih
DIPHENAMID
«KM}SO4
• HjSOi • MjO
• N^l • MjO
CMJ -i-C'N-O-C-N- CMj
METHOMYl
d CONHCMjCHjCMjCH)
BENOMYl
-NTCH,CHiCH,),
NITRALIN
Figure 11.
Chemical reactions and structures for imides,
amides and other nitrogenous pesticides (7) .
40
-------
TABLE 16. INPUT MATERIALS FOR OTHER NITROGENOUS PESTICIDES (7)
Pesticide
Input materials
Captafol
Captan
Folpet
CDAA
Diphenamid
Deet
Naphthalam
Methomyl
Benomyl
Le thane 384
Methyl isothio-
cyanate
Nitralin
Maleic hydrazide
Dodine
Pichloram
Sodium hydroxide, 1,1,2,2-tetrachloroethylsulphenyl
chloride and tetrahydrophthalimide
Sodium hydroxide, trichloromethylsulphenyl chloride
and tetrahydrophthalimide
Sodium hydroxide, trichloromethylsulphenyl chloride
and phthalimide
Chloroacetyl chloride and diallyamine
Sodium hydroxide, dimethylcurbamyl chloride and
diphenylmethane
m-Toluyl chloride and diethylamine
Phthalic acid and 1-naphthylamine
(Data not available)
(Data not available)
Butyl "carbitol" chloride and sodium thiocyanate
Ethyl chlorocarbamate and N-methyldithiocarbamate
4-Chloro-3-nitrophenyl methylsulfone
Maleic anhydride and dihydrazine sulfate
Dodecyl chloride, sodium cyanide, ammonia and
acetic acid
Chlorine, a-picoline, sulfuric acid and ammonia
The structure of many diene pesticides is of the form (7):
where the Cl denotes a saturated chlorinated loop and A and B
are side chains. A and B are quite often linked together to
form another loop, as indicated for some diene pesticides in
Figure 12, which summarizes reaction sequences for diene
insecticides.
Estimated 1974 production of diene group pesticides include
chlordane (6.8 x 103 metric tons), aldrin (4.5 x 103 metric
tons), and endrin (1.4 x 103 metric tons) (2). The production
trend is downwards since aldrin and dieldrin have been banned by
the U.S. Environmental Protection Agency (EPA) because of high
toxicity and low degradable, long-term persistence. Some uses of
heptachlor have also been canceled, and chlordane is being re-
viewed. Mirex, which received widespread use for fire ants, is
also restricted by the EPA.
41
-------
ISOOKIN
ENDIIN
NJ
tNOOSULfAN
EPOXIOATION
H202 OR PEK ACIDS
AICI3. Si
IAHTH IN CCI< O« Ct>Ht
CMIOHOANE \O« S02CI2 » lENZOYt
nDOXIOE IN C6H4 \ ALDSIN
M Cl
HEXACHLOKOCYCLOfENTADIENE
WCYCtortNTA
DIENE
PfNTAC
• Ptrchlorfnatcd King
MIRIX
KEPONE
Figure 12. Synthesis of the diene group of chlorinated insecticides—
from hexachlorocyclopentadiene (12).
-------
Figure 12 indicates the synthesis reaction of the 13 pesticides
in the diene group, and Table 17 lists the raw materials used in
their production (7, 12).
TABLE 17. INPUT MATERIALS FOR DIENE-BASED PESTICIDES (7)
Pesticide
Input materials
Aldrin
Dieldrin
Chlordane
Heptachlor
Isodrin
Endrin
Endosulfan
Isobenzan (telodrin)
Alodan
Bromodan
Kepone
Mirex
Pentac
Hexachlorocyclopentadiene; bicyclo-(2.2.1)-2,5
heptadiene
Aldrin; H2O2; acetic acid
Hexachlorocyclopentadiene; cyclopentadiene; C12
Hexachlorocyclopentadiene; cyclopentadiene; A1C13
or SC>2Cl2 + benzoyl peroxide in benzene
Hexachlorocyclopentadiene; vinyl chloride (or
acetylene); cyclopentadiene
Isodrin (or ingredients); H2O2; acetic acid
Hexachlorocyclopentadiene; cis-2-butane-l,4-diol;
thionyl chloride
Hexachlorocyclopentadiene (2 moles); 2,5-dihydro-
furan; Cl2
Hexachlorocyclopentadiene; CH-CH2C1
CH-CH2C1
Hexachlorocyclopentadiene; CH2 = CHCH2Br
Hexachlorocyclopentadiene; SO3/- H20
Hexachlorocyclopentadiene; A1C13
Hexachlorocyclopentadiene; H2 or Cu
UREA AND URACIL PESTICIDES
Urea and uracil pesticides are commonly used as herbicides.
These pesticides can be synthesized from urea as a common base,
but they are more frequently synthesized from an isocyanate
compound. Phosgene is used in the synthesis of most urea and
uracil pesticides as indicated in the synthesis reactions pre-
sented in Figure 13 (7).
Most urea pesticides have the common chemical structure of (7):
Ri. - HO
(12) Lawless, E. W., R. von Rumker, and T. L. Ferguson. Pesti-
cide Study Series - 5: The Pollution Potential in Pesti-
cide Manufacturing (PB 213 782). U.S. Environmental
Protection Agency, Cincinnati, Ohio, June 1972. 249 pp.
43
-------
H O
-N - C - N(CH3)2
coo
4 -(4-CHLOROPHENOXY) ANILINE
CKO)-O-N = C « O
H
TERBACIL
Figure 13. Chemical reactions to form urea and uracil pesticides.
with the R groups indicated in Table 18 for each pesticide.
Other urea pesticides (noruron, isonoruron, cycluron and norea)
have a similar structure with a replacement for the phenoxy ring
44
-------
The uracils have a common structure of the form (7)
sea
where R is "-Br" for bromacil and "-C1" for terbacil.
TABLE 18. UREA PESTICIDES STRUCTURE (7)
H 0 .R3
II /
N-C-N
R2
Pesticide:
Chloroxuron
Diuron
Fluometuron
Linuron
Monuron
Monuron-TCA
Siduron
Other urea pesticides:
-4-chlorophenoxy -H
-Cl
-H
-Cl
-Cl
-COOC13
-H
-Cl
-CF3
-Cl
-H
-H
-H
-CH3 -CH3
-CH3 -CH3
-CH3 -CH3
-OCH3 -CH3
-CH3 -CH3
-CH3 -CH3
-H -2-methycyclohexane
Fenuron
Neburon
Buturon
Monolinuron
Metabromuron
Chlorobromuron
Metoxuron
-H
-Cl
-Cl
-Cl
-Br
-Br
-OCH
-H
-Cl
-H
-H
-H
-Cl
-Cl
-CH3
-CH3
-CH3
-OCH 3
-OCH 3
-OCH 3
-CH3
-CH3
-n-butyl
-l-butyn-3-yl
-CH3
-CH3
-CH3
-CH3
The production of urea and uracil pesticides in 1974 was esti-
mated as 18.1 x 103 metric tons. Bromacil, a uracil pesticide,
had an estimated 1974 production of 5.4 x 103 metric tons. The
urea pesticide with the largest production in 1974 was diuron at
4.5 x 103 metric tons (2). Table 19 lists input materials .used
to produce seven urea pesticides and two uracil pesticides (7).
NITRATED HYDROCARBON PESTICIDES
Nitrated hydrocarbon pesticides include several compounds con-
taining one or two of the characteristic nitro(-N02) groups in
their chemical structure. Four major pesticides in this group
are dinitroaromatics (trifluralin, benefin, dinoseb, and DNOC)
45
-------
TABLE 19. INPUT MATERIALS FOR UREA AND
URACIL PESTICIDES (7)
Pesticide
Input materials
Ureas:
Diuron
Linuron
Fluometuron
Siduron
Chloroxuron
Monuron
Monuron-TCA
Uracils:
Bromacil
Terbacil
3,4-Dichloroaniline, phosgene and dimethyl-
amine (Alternate: 3,4-dichloroaniline,
urea and dimethylamine)
3,4-Dichloroaniline, phosgene and
0,N-dimethyl hydroxylamine
3-Trifluoromethyl aniline, phosgene and
dimethylamine
Aniline, phosgene and 2-methylcyclohexylamine
4-(4-Chlorophenoxy) aniline, phosgene and di-
methylamine
p-Chloroaniline, phosgene and dimethylamine
(Alternate: p-chloroaniline, urea and di-
methylamine )
Monuron and trichloroacetic acid
sec-Butylamine, phosgene, ammonia, ethylaceto-
acetate and bromine
see-Butylamine, phosgene, ammonia, ethylaceto-
acetate and chlorine
and one is a chlorinated nitrohydrocarbon (chloropicrin) (7).
Other pesticides in this group include Basalin®, isopropalin,
oryzalin, butralin, dinitramine, Prowl® and Dinocap®.
The general structure of the four nitroaromatic pesticides is (7)
with the individual "R" groups indicated below.
The formula for chloropicrin is CC13NO2.
46
-------
Pesticide R± R2 R3 R^ R5 Rg
Dinoseb -OH -CH(CH3)CH2CH3 -H -N02 -H -NO2
DNOC3 -OH -CH3 -H -N02 -H -NO2
Trifluralin -N(CH2CH2CH2) -NO2 -H -CF3 -H -NO2
Benefin -CH3CH2NCH2CH2CH2CH3 -NO2 -H -CF3 -H -NO2
Estimated 1974 production of the nitrated hydrocarbon pesticides
was 18.1 x 103 metric tons. The dinitroaromatic pesticides are
herbicides, and chloropicrin is an insecticide. Trifluralin
dominated the production in this group with approximately
11.3 x 103 metric tons in 1974 (2).
Table 20 lists raw materials used in the production of nitrated
hydrocarbon pesticides (7). The chemical reactions for the pro-
duction of dinitroaromatic and other nitrated hydrocarbon pesti-
cides are indicated in Figure 14.
TABLE 20. INPUT MATERIALS FOR NITRATED
HYDROCARBON PESTICIDES (7)
Pesticide Input materials
Trifluralin HNO3/H2SOtf, chloro-4-trifluoromethylbenzene and
dipropylamine
Benefin HNO3/H2SOi+, chloro-4-trif luoromethylbenzene and
butylethylamine
Dinoseb HN03/H2SO[+, o-sec-butylphenol
DNOC3 o-Cresol, H2SO4 and HNO^/H2SO^
Chloropicrin Nitromethane, chlorine and sodium hydroxide
34,6-Dinitro-o-cresol.
MICROBIAL AND NATURALLY-OCCURRING PESTICIDES (7)
Two types of microorganisms pathogenic to insects have been
developed and are in limited commercial use on several crops
today, i.e.; preparations of Bacillus species, and nuclear poly-
hedrosis viruses.
Several commercial products based upon Bacillus thuringiensis
are currently available on the U.S. market. These products are
exempted from the requirement of a tolerance and are registered
47
-------
CH3CHJCH2 -
CI2
CH3NO2
CCI3 NO2 CHLOROPICRIN
Figure 14.
Chemical reactions to produce the nitrated
hydrocarbon pesticides (7).
for the control of Jepidopterous insects on a considerable num-
ber of crops. The main deterrent to their use is that growers
are familiar with the chemical insecticides and their more rapid
mode of action, and chemical insecticides are often less expen-
sive per unit control Preparations based on Bacillus popilliae
and several other Bacillus species are under commercial develop-
ment, but have not yet reached the volume of use of Bacillus
thuringiensis.
Several nuclear polyhedrosis virus preparations are available in
the United States for control of cotton bollworms, but these
products are not widely used at this time. Problems concerning
48
-------
their large-scale production, formulation, storage stability,
application timing and methods, stability after application, and
safety precautions remain to be resolved. Development work is
in process on a number of other insect viruses.
Microbial pathogens useful for the nonchemical control of weeds
or plant diseases have not been commercially developed to this
date.
Natural-occurring pesticides include the pyrethrins, obtusaquin-
one, and rotenone. The»pyrethrins are derived from the chrys-
anthemum flower, obtusaquinone is an orange pigment of a tropical
tree, and rotenone is derived from cube, which is a tropical
plant. Pyrethrin pesticides have also been synthesized, and
some of these offer promise as insect-specific insecticides.
The processes for production of the microbial and natural-occur-
ring pesticides are at present considerably different from the
chemical reactions for other pesticides. The microbial pesti-
cides are developed from cultures in fermented solutions as
expressed by the following procedure for Bacillus thuringiensis:
Product
Nutrient solid
mixture Sterilize^ Innoculate Ferment^ Separate^ Dry^ con-
taining
^3% B.t.
The pyrethrins are extracted from chrysanthemum flowers as
follows:
Chrysanthemum Extract Extract
flowers Crude with with Pyrethrin
(Pyrethrum Solvent Extract CH^OH_ .J^eHiit...^ concentrate
ainerae folium)
The most popular microbial pesticide is Bacillus thuvingiensis
with an estimated production of 450 metric tons in 1972.a The
total production of microbial and natural-occurring pesticides
was about 900 metric tons in 1972. The use of these pesticides
is expected to increase significantly in the next decade as new
and more effective derivatives are formed and as some of the
more toxic and persistent chemical pesticides are forced out by
environmental restrictions.
OTHER PESTICIDES
Organic pesticides which are not easily classified in other
industry segments include endothall, bensulide, EXD (Herbisan®),
Ordam®, acephate, Thanite®, thiabenazole, Terrazole®, diquat,
paraquat, and dodine. Other organic pesticides may have been
omitted because they are produced only in small quantities.
Large-production pesticides, such as elemental sulfur, sodium
49
-------
chlorate, and the organotin compounds were excluded because these
materials are products of other industries and are predominantly
used for other purposes (7). Creosote has also been excluded
since it is a product from coking operations at foundries.
Table 21 lists the raw materials used as input for the production
of endothall, bensulide, and EXD. Structures and chemical
reactions representing synthesis of these compounds are shown in
Figure 15 (7).
TABLE 21. INPUT MATERIALS FOR THREE OTHER
ORGANIC PESTICIDES (7)
Pesticide Input materials
Endothall Furan and maleic anhydride (plus reducing or
oxidizing agent)
Bensulide N-(3-chloroethyl)benzene sulfonamide and
potassium diisopropyl dithiophosphate
EXD9 Ethyl alcohol, carbon disulfide, sodium
hydroxide and an oxidizer (HC1 or ^SO^)
dDiethyl dithiobis(thionoformate) (Herbisan®).
50
-------
1. ENDOTHALL:
2. BENSULIDE:
3. EXD:
\c
C— ONo
C-ONo
° ENDOTHALL- Na
NaC,
BENSULIDE
NaOH 5
+ CS2 - »• C2H5OC-S-Na + H2O
SODIUMETHYLXANTHATE
| OXIDIZED (HCI?)
C2H5O-C-S-S-C-OC2H5 + (NoCI?)
EXD (HERBISAN®)
Figure 15.
Chemical reactions and structures
of other pesticides (7) .
51
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SECTION 5
AIR EMISSIONS CHARACTERIZATION AND POLLUTION CONTROL TECHNOLOGY
EMISSIONS
There are essentially no quantitative data covering air pollution
aspects of the pesticide manufacturing industry. In many cases,
the pollution caused by loss of active ingredient is less signifi-
cant than that caused by unrecovered byproducts such as H2S,
which is flared to form SO2, or particulates resulting from fuel
combustion. A plant producing 4.54 x 103 metric tons/yr of most
thioorganophosphate pesticides, for example, could emit over 900
metric tons of SO2 annually, which would be comparable to the
amount emitted from a small electric power plant (2). Such a
plant might also produce 2.27 x 103 metric tons/yr to 4.54 x 103
metric tons/yr of particulate pollutants (flyash, etc.), depend-
ing upon the fuel used for process heat and the air pollution
controls installed (2). Table 22 (2, 13) summarizes principal
information regarding emission species, emission factors, and
emission rates for seven major pesticides.
Although few quantitative data are available concerning it,
evaporation from holding ponds or evaporation lagoons may also be
a potential emission source. Liquid wastes from pesticide manu-
facturing plants often go to a holding pond before treatment or
to an evaporation basin for ultimate disposal. Aldrin, for
example, was discharged to a 4.05 x 105-m2 asphalt-lined evapora-
tion basin capable of evaporating 0.57 m3 of water/min (12).
Aldrin could have been transferred directly from the lagoon to
the atmosphere despite the characteristic low vapor pressure and
low solubility. Appendix A presents equations that were used to
predict the evaporation rate of several pesticides and develop
evaporation emission factors for additional input to the priori-
tization model. These equations estimate that up to 5.6 kg/day
of aldrin could be emitted from the evaporation basin if aldrin
was still manufactured.
(13) Ifeadi, C. N. Screening Study to Development Background
Information and Determine the Significance of Air Contami-
nant Emissions from Pesticide Plants. EPA-540/9-75-026,
Washington, D.C., March 1975. 85 pp.
52
-------
TABLE 22. SUMMARY OF PRINCIPAL AIR EMISSIONS (2, 13)
u;
Quantity of
pollutant emitted
Pesticide manufactured
Methyl parathion
MSMA
Trifluralin
Pentachlorophenol
Captan
DDT
Toxaphene
Type of pollutant
Sulfur dioxide (gas)
Arsenic trioxide
(particulate)
Nitrate (particulate)
Sulfate (particulate)
Chloride (particulate)
Sulfur dioxide (gas)
Sulfur trioxide (gas)
Hydrogen fluoride (gas)
Hydrogen chloride
(vapor)
Nitrogen oxide (gas)
Pentachloropheno 1
(particulate)
Sodium pentachlorophenol
(particulate)
Phenol (vapor)
Captan (particulate)
DDT (particulate)
Hydrogen chloride
(vapor)
kg pollutant/
kg active ingredient
0.41
3 x ID"11
3.2 x ID'4?
3.2 x 10-4*
3.2 x 10-43
9.5 x 10-4?
3.2 x ID'49
3.2 x 10-*?
3.2 x ID'33
9.5 x 10"4
5.5 x'10-4
2.2 x 10"3
1.0 x 10~3
6.6 x 10-5°
3.3 x 10-4d
(0.53)6
kg pollutant/unit time
703.7 kg/hr
2.92 x 10" 8 kg/hr
4.54 x 10~ J kg/hr
4.54 x 10- l kg/hr
4.54 x 10- l kg/hr
1.36 kg/hr
4.54 x 10- x kg/hr
4.54 x 10" 1 kg/hr
4.54 kg/hr
1.36 kg/hr
K
u
k
u
"h
V
1.82 kg/day
1.14 kg/hr
(1,974.9 kg/hr) 6
Calculated based on a production rate of 1.13 x 104 metric tons/yr, 330 days/yr, and 24 hr/day.
b
Blanks indicate data not available.
Calculated based on a production rate of 9.07 x 103 metric tons/yr, 330 days/yr.
Calculated based on a production rate of 2.72 x 104 metric tons/yr, 330 days/yr, and 24 hr/day.
Q
Data given in Reference 13; however, it is believed that this emission is absorbed in a wet scrubber
thus reducing emissions by greater than 99%.
-------
EMISSIONS CONTROL
Air emissions from the pesticide industry are generally analogous
to emissions from conventional chemical manufacture. Emissions
from the manufacturing process, including particulates, gases,
and vapors, emanate from various pieces of equipment (for example,
reactors, driers, and condensers) and enter the atmosphere as raw
materials, intermediates, byproducts, and the active ingredient
itself. Several air emission control devices are available, such
as baghouses, filters, cyclone separators, electrostatic precip-
itators, incinerators, and gas scrubbing units for purposes of
trapping, separating, washing, and otherwise collecting gases
and particulates (2).
The most popular and practically applicable technique used in
controlling emissions from the manufacture of pesticides3 in-
volves wet scrubbing with water. A smaller percentage of plants
employ alkali absorption and adsorption processes and baghouses.
Wet scrubbing, absorption, and adsorption processes are used
mainly for controlling gases and vapors, controlling particu-
lates to a lesser extent. Baghouses are used primarily for
controlling particulate emissions. A summary of air emission
control devices, emission species controlled, and control effi-
ciency is presented in Table 23 for five major pesticides (13).
SELECTED PESTICIDES
In order to present a general overview concerning atmospheric
emissions and air pollution control technology found in the
pesticide manufacturing industry, 12 pesticides, corresponding
to major products in each of the 12 industry segments, are dis-
cussed in the following sections. Information presented, when
available, includes emission species, sources and rates; process
description; and emissions control technology for the following
pesticides:
toxaphene - chlorinated hydrocarbon
methyl parathion - organophosphate
carbaryl - carbamate
atrazine - triazine
alachlor - anilide
MSMA ' - organoarsenic
captan - other nitrogenous
chlordane - diene-based
bromacil - uracil
trifluralin - nitrated hydrocarbon
Bad, llus
thuringiensis - microbial
methyl bromide - other
aBased on a study of methyl parathion, toxaphene, MSMA, tri-
fluralin, pentachlorophenol, and p-dichlorobenzene.
54
-------
TABLE 23. SUMMARY OF AIR EMISSION CONTROL DEVICES FOR FIVE MAJOR PESTICIDES (13]
Pesticide
Control device
Emissions controlled
Reported
efficiency,
Ln
ui
Methyl parathion
P
Toxaphene
MSMAd'C
Trifluralinf
Pentachlorophenol"
Incinerator
Water scrubber
Brink® mist eliminator
Alkali and water scrubber
Stripping
Limestone adsorption
Baghouse
Baghouse
Water scrubber
Acidifier vent scrubbers
1- and 2-Stage venturi scrubber
and Tri-mer wet scrubber
Packed and venturi scrubber
Baghouse
Mechanical seals
Hydrogen sulfide, sulfur, mercaptan
Phosphorus pentoxide, hydrogen chloride
Phosphorus pentoxide (for visibility)
Solvent vapor, hydrogen chloride, chlorine
Solvent vapor, hydrogen chloride, chlorine
Solvent vapor, hydrogen chloride, chlorine
Toxaphene
Arsenic trioxide
Arsenic trioxide
Chlorine, phenol, acids
Pentachlorophenol
(For pentachlorophenol reactor)
95
99.9
100
90
90 to 100
95 to 99
Information reported by Monsanto.
Blanks indicate data not available.
LInformation reported by Hercules.
Information reported by Diamond Shamrock.
Information reported by Ansul.
Information reported by Eli Lilly.
Information reported by Reichhold.
-------
Toxaphene
Toxaphene is an important chlorinated hydrocarbon insecticide
containing 67% to 69% chlorine. Toxaphene production involves
two main steps: the production of camphene in a reactor from
a-pinene, and the reaction of chlorine gas with camphene in a
solvent solution at the chlorinator. The raw materials involved
in the manufacture of toxaphene are a-pinene, chlorine, solvent,
and compounds used'in effluent treatment operations (13).
The production and waste handling schematic used by one manu-
facturer is presented in Figure 16 (13). The gaseous emissions
from the chlorinator (chlorine gas, hydrochloric acid, and
solvent vapors) are passed through condensers, caustic scrub-
bers, and a neutralization tower containing limestone, while the
solution containing toxaphene is filtered, stripped, and formu-
lated into marketable forms.
s
PII
H20— -
LIME— -
NaOH—
LIME-_^
STONE
SURFACE
WATERS
OUTHERN
« STUMPS
<1% MAIN PLANT
L~ » Q PINENE WASTE STREAM
I )
I
CAMPHENE
I , ,
CHLORINE GHLORINATOR -^S H FIL™ |— STRIPPER
^ntvFNT i » iUUJ ' 1U™ 1 I
HCIGAS— J Cf
I |
ABSORBER
*
SCRUBBERS
12)
1
NEUTRALIZER
|
PRIMARY
WASTE
TREATMENT
PLANT
1
DISCHARGE TO
TIDAL CREEK
RECOVERED
MURIATIC ACID
TO SOLID
MIXED
XYLENES
L,
- 90% TOXAPHENE
TOXAPHENE —SOLUTION
SHIPMENTS
ATMOSPHERE
Figure 16.
Production and waste handling schematic
for toxaphene (13) .
Emission sources from the manufacture of toxaphene include the
reactor and the chlorinator. No information is available re-
garding emissions from a-pinene production. The main emission
from the reactor is chlorine gas; emissions from the chlorinator
contain quantities of chlorine gas, hydrochloric acid, and sol-
vent vapor. Uncontrolled hydrogen chloride emissions have been
56
-------
estimated to be 0.53 kg/kg active ingredient (13). However,
these emissions are known to be controlled by absorption using
a wet scrubber (14). Assuming a control efficiency of 99.5%, the
estimated hydrogen chloride emission factor from this source
would be 2.65 kg/metric ton active ingredient.
There are three main control techniques used for controlling
acidic gases produced from toxaphene manufacture: 1) scrubbing
(alkali or water) , 2) stripping, and 3) adsorption. One plant
uses these techniques to control hydrogen chloride, chlorine
gas, and solvent vapor emissions (13) . The emissions are ini-
tially passed through condensers that remove the majority of the
solvent and the hydrochloric acid. Caustic scrubbers then remove
additional traces of hydrochloric acid and chlorine. The efflu-
ent is finally passed through large towers containing limestone.
The final rate of emissions is not known.
Various control technologies are available in the chemical indus-
try for controlling particulates , such as baghouses, scrubbers,
electrostatic precipitators , etc. Baghouses are used at one
plant to control toxaphene particle emissions (13) . No informa-
tion is available on this plant's uncontrolled or controlled
emissions, nor is control information available from other
toxaphene manufacturing plants.
Methyl Parathion
Methyl parathion is a nonpersistent broad spectrum organophos-
phate insecticide that is highly toxic to humans. It is com-
monly manufactured from sodium p-nitrophenolate by reaction with
0 ,0-dimethyl phosphorothiochloridate and has the following pro-
duction chemistry (12) :
P2S5 + 4ROH - «-2(RO)2PSH + H2S (6)
S
II ...
(R0)2 PSH + C12 - -(RO)2PC1 + HC1 + S (7)
(14) Meiners, A. F., C. E. Mumma, T. L. Ferguson, and G. L. Kelso.
Wastewater Treatment Technology Documentation for Toxaphene
Manufacture. EPA-440/9-76-013, U.S. Environmental Protec-
tion Agency, Washington, D.C., February 1976. 123 pp.
57
-------
(RO) 2P-C1
ONa
NaCl
(8)
NO 2
The raw materials are sodium p-nitrophenolate, methyl alcohol,
chlorine, and phosphorus pentasulfide. In the production of
methyl parathion, byproducts such as sodium chloride (NaCl) and
hydrogen chloride (HC1) are formed along with waste products
such as H2S, mercaptan, and sulfur (S) (13). The production and
waste schematic for methyl parathion is shown in Figure 17 (13).
The odorous compounds (H2S and merqaptan) from the reactor are
flared, and the sulfur-containing species emitted from the chlo-
rinator are incinerated.
so?
—HCI-
CHLORIDOTHIONATE
ACETONE
I PARATHION I
UNIT
NaCl
PARTIAL
' RECOVERY
PARATHION
WASTE
TREATMENT
PLANT
TRACE QUANTITIES
OFHzS, RHS, AND
HCI EMITTED TO AIR
CITY SEWER
Figure 17.
Production and waste handling schematic
for methyl parathion (13).
Air contaminant emission sources include the reactor, the chlo-
rinator, and the parathion unit. Odorous pollutants arise from
vents, liquid wastes, and residues. During the disposal of by-
products (for example, flaring of H2S and mercaptans, and incin-
eration of sulfur), sulfur dioxide is given off. Also, during
wastewater treatment or lagooning, odorous compounds, such as
H2S, mercaptans, etc., are emitted. Emission rates for H2S and S
prior to incineration of off-gases have been calculated as
208.8 kg/hr, 190.7 kg/hr, and 208.8 kg/hr, respectively, on the
basis of 330 days/yr and 24-hr/day operation (13).
58
-------
Sulfur dioxide emission rates based on H2S and S oxidation from
incineration and flaring are estimated to be 703.7 kg/hr from the
following reactions (13):
2H2S + 3O2 -> 2S02 + 2H2O
S + 02 -> SO2
(9)
(10)
Air emission sources, emission species, and emission rates are
presented in Table 24 (13):
TABLE 24. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES FROM
METHYL PARATHION MANUFACTURE AND WASTE TREATMENT (13)
Sources of emission Particulates
Manufacturing processes:
Reactor None
Chlorination Acid mist.
Sulfur
Rates ,
kg/hr
a
208.8
190.7
Gases/ vapors
Diphosphorus pentoxide
Mercaptan
Hydrogen sulfide
Phosphorus trichloride
Rates,
kg/hr Odor
Mercaptan
Xylene
Hydrogen sulfide
-
Thiophosphoryl chloride
Methanol
Methyl chloride
Hydrochloric acid
Parathion unit
Basic mist.
Methyl monochloride
208.8
Waste treatment processes:
Incinerator and
flaring
Waste treatment plant
Lagooning
Phosphorus pentoxide
None
None
Sulfur dioxide
Phosphorus pentoxide
Hydrogen sulfide
Mercaptan
Hydrogen sulfide
Mercaptan
703.7
Hydrogen sulfide
Mercaptan
Hydrogen sulfide
Mercaptan
Not available.
Practical sulfur dioxide emission control processes for H2S,
mercaptan, etc., available for methyl parathion plants are in-
cineration in series with a scrubbing system and carbon adsorp-
tion. Control of visible fumes created by the emission of
diphosphorus pentoxide can be achieved by a mist eliminator,
while H2S and mercaptan emission control during the wastewater
treatment can be achieved by chemical oxidation and deodorization,
The air emission control system used by one plant is shown in
Figure 18. Incineration is used to control the off gases and
residue, while heavy chlorination is used to control the waste-
water odorous emissions. The scrubbing system used to control
the incineration emission is quoted to achieve an efficiency of
95% for the removal of diphosphorus pentoxide. The BRINK® mist
eliminator provides about 99.9% visibility reduction. Incin-
eration of sulfur may be considered a better practical control
59
-------
method than recovery because the sulfur that can be recovered in
this process is inescapably contaminated with toxic methyl
parathion (13).
On the basis of available information, this is the only plant
manufacturing methyl parathion that is controlling air emis-
sions: the sulfur compounds by incineration, diphosphorus
pentoxide by scrubbing, and visibility by a Brink mist elimina-
tor. However, SO2 produced during the incineration of sulfur
compounds is not controlled. An estimated 5.58 x 103 metric
tons of SO2 were emitted in 1974 (13).
TO ATMOSPHERE -~
WATER SUPPLY
INCINERATOR
OFF GAS
RESIDUE -j r -C
FUEL
LIMESTONE NEUTRALIZATION
TO SEWER
RECOVERED
PRODUCT
Figure 18. Parathion residue and off-gas incinerator (13).
Carbaryl
Carbaryl is a moderately toxic, nonpersistent insecticide
classified in the "Carbamates" industry segment. One company
manufactures carbaryl by a combination of batch and continuous
processes with the following production chemistry (12):
OH o
Carbaryl
1-Naphthyl-
chloroformate
CH3NCO
1-Naphthol
(11)
(Alternate Route)
60
-------
A production and waste schematic for carbaryl is shown in
Figure 19 (12).
VENT
FLARE
INCINERATOR
HEAVY RESIDUE
FROM PROCESS
SOLVENT IS USED
FOR SOME STEPS
SECONDARY
WASTE
TREATMENT
PLANT
PRODUCT
Figure 19. Production and waste schematic for carbaryl (12).
Raw materials utilized in the production of carbaryl include
naphthalene, hydrogen, chlorine, oxygen, phosgene, methanol, and
sodium hydroxide (50%) . Byproduct wastes are liquid streams,
vents, and some heavy residues. All toxic vents are flared or
vented to the atmosphere, and standard hood systems with recycle
of recovered material are used in the packaging process (12).
Information concerning sources, rates, and types of emissions
is not available.
Atrazine
Atrazine, estimated to be the largest selling herbicide in the
United States in 1974, is a selective herbicide classified in
the "Triazines" industry segment. Ciba-Geigy Corp., the largest
producer of atrazine, has an estimated annual plant capacity of
9 x 101* metric tons (15) . The estimated production of atrazine
(15) von Rumker, R., E. W. Lawless, and A. F. Meiners Produc-
tion Distribution, Use and Environmental Impact Potential
of Selected Pesticides (PB 238 795). Council on Environ-
mental Quality, Washington, D.C., March 1974. 439 pp.
61
-------
in 1974 was 5 x 104 metric tons (2). Atrazine is produced by a
continuous process; its reaction chemistry is shown below (12):
CI
»AN
3HCN + 3C12 —^ \( )\
,-^v-^S
ci
Uf~\N
(CH3)2CHNH2
CI ^T CI ^* C2H5HN V CI
Cyanuric
chloride
5HC1 or +
10115301 C2H5HN 14 NHCH(CH3)
Atrazine
(12)
Figure 20 presents the production and waste schematic for
atrazine (12).
ADDITIVES
OR SOLVENTS
NaOH
DEEP WELL
DISPOSAL
Figure 20.
DISCHARGE
TO RIVER
Production and waste schematic
for atrazine (12).
VENT
Hydrogen chloride and hydrogen cyanide emissions from the
cyanuric chloride unit are controlled by a scrubber and filter,
as shown in Figure 20 (12). Cyanuric chloride is sublimable and
may possibly be entrained from the cyanuric chloride unit and
62
-------
the amination unit. Possible cocondensation of hydrogen cyanide
(HCN) could result in emissions of lower HCN condensation pro-
ducts. Possible solvent emissions include carbon tetrachloride.
Other potential emissions during the manufacture of atrazine
include ethylamine and isopropylamine.
Available information regarding air pollution control is shown
diagramatically in Figure 20. Hydrogen chloride from the
cyanuric chloride unit is controlled by a scrubber, then dis-
charged to a deep well or river.
Alachlor
Alachlor, a selective herbicide classified in the "Anilides"
industry segment, is produced in a batch process with the fol-
lowing production chemistry (12):
•C2H5 H2CO
Solvent
DiethyIaniline
(13)
Alachlor
Raw materials for the production of alachlor include 2,6-dxethyl
aniline, chloroacetyl chloride (C1CH2COC1), p-formaldehyde,
methanol, ammonia, and aromatic solvents as shown in the pro-
duction and waste schematic (Figure 21) (12).
The alachlor process is said to have no solid product and to
give off no gases. Production equipment requires cleanup only
two to three times per year. No information is available re-
garding types and sources of emissions, but raw material and
solvent losses could occur during handling. Solvents are burned
as fuel, but their emission rates are unknown (12).
63
-------
(HjOMj—»
•HjCO
CICHjCOCI
CH30H
DEA-
AMMMTIC-
SOLVENT
I lit
REA(
HP-
NH4CI
• 'V 1
DISCHARGE
TO RIVER
-AUCHLOR
SOLVENT
Rffl.
Figure 21. Production and waste schematic for alachlor (12).
MSMA
MSMA (monosodium methanearsonate) is an organoarsenic selective
herbicide that degrades fairly readily in soil and is not highly
toxic to animals. Three main compounds are manufactured in the
production of MSMA: sodium arsenite, methylarsonic acid, and
MSMA. Raw materials utilized in MSMA production are arsenic
trioxide, sodium hydroxide, methyl chloride, and sulfuric acid.
Arsenic trioxide is the most toxic species, and it is imperative
that this compound be handled cautiously. The production and
waste schematic for MSMA is shown in Figure 22 (13).
VEUT
58VHSMA
Figure 22. Production and waste handling
schematic for MSMA (13).
64
-------
The main source of air contaminant emissions during the manufac-
ture of MSMA is in the sodium arsenite production during the un-
loading of arsenic trioxide. Minor emissions may occur during
the processing of the MSMA by evaporation from vents of the
reactors.
The main emission during the production of sodium arsenite is
arsenic trioxide, which is very toxic. One plant estimates the
controlled emission of arsenic trioxide (As2C>3) to be
3 x 10"s kg/metric ton or 2.93 x 10~8 kg/hr. During the produc-
tion of DSMA and MSMA, vapors of methyl chloride (CH3C1), sodium
sulfate (Na2SO(+) , and methanol are given off (13) .
The only air pollutant controlled in this industry is As2O3. The
compound is emitted as particulates, for which various control
techniques are available, such as baghouses, scrubbers, and
electrostatic precipitators.
One plant operates the As203 drum opening and dump bin under a
hood equipped with a blower that will pull the As2O3 into a bag
filter for collection. Another plant controls the arsenic
trioxide emission by a scrubbing system. Efficiencies of these
control systems are not known by the firms. The best control
technique for this highly toxic arsenic trioxide is to have both
baghouses and scrubbers in series. The bag filter is useful in
recovering As203, while the scrubber removes the smaller size
particles that normally will not be collected by the bag filter
(13).
Captan
Captan, classified in the "Other Nitrogenous Compounds" industry
segment, is a contact fungicide effective against a fairly broad
spectrum of plant pathogenic fungi. It is estimated that
9 x 103 metric tons of captan were produced in the United States
in 1974 (2). Captan is manufactured in a two-step reaction
process using two intermediates, followed by several purifica-
tion steps.
One of these intermediates is tetrahydrophthalimide, which is
also made by a two-step reaction (16):
(16) Substitute Chemical Program: Initial Scientific and Mini-
economic Review of Captan. EPA-540/1-75-012, U.S. Environ-
mental Protection Agency, Washington, D.C., April 1975.
173 pp.
65
-------
If
E>
CH=CH2
100°C-110''C r || | > (14)
Butadiene Maleic Tetrahydrophthalic
anhydride anhydride
200oC-220°C
Reaction 14 proceeds with a minimum of byproduct. The anhydride
is typically above 99% purity and contains minute quantities of
vinyl cyclohexene and other butadiene polymeric materials as the
major impurities. The reaction is carried out by bubbling buta-
diene gas into molten maleic anhydride at a temperature of 100°C
to 110°C (16) .
In Reaction 15, a small amount of colored maleimide resin poly-
mers is formed from the reaction of ammonia and unreacted maleic
anhydride. The reaction is run at a high temperature to boil
off the water, and, during this process, all of the vinyl cyclo-
hexene and most of the other volatile impurities are removed.
The purity of the imide is typically 98%, with residual water
and tetrahydrophthalic anhydride being the major impurities (16)
The second intermediate is perchloromethyl mercaptan, made by
the following reaction (16) :
CS2 + 3C12 - - ^CC13SC1 + SC12 (16)
Perchloromethyl mercaptan is produced at 0°C to 15 °C by Reaction
16, which is exothermic. The pressure is approximately atmo-
spheric or slightly higher. Iodine is a common catalyst, but
ferric chloride or aluminum chloride may be used. The final
purity is greater than or equal to 96% (16) .
The tetrahydrophthalimide, is mixed with sodium hydroxide, then
reacted with perchloromethyl mercaptan as shown in Reactions 17
and 18 (16) :
o
n
+ NaOH - N-Na + H2O (17)
66
-------
-Na
C1SCC13-
NSCC13 + Nad
(18)
Reaction 17 is a mixing-dissolving step, but Reaction 18 (captan
production) is controlled at a temperature between 10°C and
30°C, and at essentially atmospheric pressure. The reaction,
taking from 10 to 40 minutes, is carried out in an aqueous
medium of pH 10.0 to 10.5, using no catalyst. The pH must be
kept as low as possible to prevent decomposition of the product,
but high enough to drive the reaction to completion by absorbing
the HC1 formed (16).
The production and waste schematic for captan is shown in
Figure 23 (12). Raw materials include carbon disulfide, iodine,
chlorine, ammonia, calcium carbonate, maleic anhydride, butadiene,
and sodium hydroxide. Possible solvents used include ketones
and aromatic, aliphatic or chlorinated hydrocarbons.
r~
BER
1
t
SCRUBBER
1 t
SCRUBBER
CaCOj
—~ CAPTAN UNIT —— CAPTAN-— PACKAGE
r DEEP WELL
DISPOSAL
Figure 23. Production and waste schematic for captan (12).
The only data available on air emissions indicate that captan is
lost in the form of particulates at a rate of about 1.8 kg/day
(2). Possible additional emission species include hydrogen
chloride, ammonia, carbon disulfide, iodine, chlorine, and buta-
diene, due to their volatility. The perchloromethyl mercaptan
67
-------
and sulfur dichloride produced by Reaction 16 are also present
as possible emissions. Other potential emissions include maleic
anhydride, which may sublime; vinyl cyclohexene and other low
molecular weight butadiene polymers, which are also volatile;
and impurities in maleic anhydride, such as succinic anhydride,
which may volatilize during boiling.
Air pollution controls include: 3.78-m3/s baghouse stacks for
controlling captan particulates, a 3.07-m3/s filter hood exhaust
to contain steam and particulates, and a 1.65-m3/s packer bag-
house stack to control particulates (12).
Chlordane
Chlordane is a persistent broad spectrum insecticide classified
in the "Diene-Based" industry segment. Chlordane is manufac-
tured by a continuous process, and the process reactions are
approximately as follows (15):
Naphtha ». Cyclopentadiene (C5H6) (19)
C12 + NaOH (aq.) * NaCIO (aq.) (20)
NaCIO (aq.) + C5H6 >• C5C16 + NaCl (alk. soln.) (21)
C5C16 + C5H6 +• Chlordene (C10H6C16) (22)
Chlordene + C12 *- Tech. chlordane (C10H6C18 +
related epoxides) (23)
The production and waste schematic for chlordane is shown in
Figure 24 (15). The only information found concerning air
emissions is that chlorine from the chlorine tanks is forced
out under pressure with no losses, meeting Chlorine Institute
Specifications (12). Other possible emission species include
naphtha, cyclopentadiene, and lower halogenated "chlordanes",
which are very sublimable. However, emission sources and emis-
sion rates are not known.
Bromacil
Classified as the major pesticide in the "Ureas and Uracils"
industry segment, bromacil is used as a herbicide for general
weed and brush control in noncrop areas. The production steps
are similar for all members of this industry segment, although
starting materials differ. The chemical synthesis for bromacil
is (17):
(17) Substitute Chemical Program: Initial Scientific and
Minieconomic Review of Bromacil. EPA-540/1-75-006, U.S.
Environmental Protection Agency, Washington, D.C.,
March 1975. 79 pp.
68
-------
see-butylamine + phosgene + ammonia -> sec-butylurea + 2HC1 (24)
aec-butylurea + ethyl acetoacetate -» 3-sec-butyl-6-methyluracil
+ H2O + ethanol (25)
3-sec-butyl-6-methyluracil + Br2- pH 5' 5» bromacil + HBr (26)
NAPHTHA •
C5H6
80-90%
RESIN
MANUFACTURE
VENT
NaOH-
CI2
- NaCIO
VACUUM
Figure 24
.. CHIORDANE MIXTURE,
S02CI2?, S02?
CLAY PIT VENT TECHNICAL
CHLORDANE
Production and waste schematic for chlordane (15)
The E. I. du Pont de Nemours Company is the sole manufacturer of
bromacil. The manufacturing plant, located in La Porte, Texas,
has an estimated total capacity of 9 x 103 metric tons per year
for all substituted uracils (17). Actual 1974 bromacil produc-
tion was estimated as approximately 6 x 103 metric tons (2) .
The preparation of bromacil is described as follows (17):
"A solution of 182 parts of 3-see-butyl-6-methyluracil
in 700 parts of acetic acid containing 82 parts of
sodium acetate was treated with 160 parts of bromine.
After standing overnight, the mixture, which contained
some solid, was evaporated to a solid under reduced
pressure. The solid was recrystallized from an ethanol-
water mixture to give, as a white crystalline solid,
2-sea-butyl-5-bromo-6-methyluracil melting at
157.5°C to 160°C".
A proposed schematic for bromacil is presented in Figure 25 (15) .
69
-------
MC-BUTYLAMINE
PHOSGENE
AMMONIA
ETHYL
ACETOACETATE
H2S04
BROMINE
HjO
- DISCHARGE
DISPOSAL AT SEA
— -
BROMACIL
UNIT
FILTRATION
DRYING
1
POSSIBLE
- Br2
RECOVERY
Figure 25. Production and waste schematic for bromacil (15).
No data are available on emission rates or species generated
during bromacil manufacture. Possible emissions include the raw
materials see-butylamine, phosgene, and ammonia from the urea
unit, in addition to the products, sec-butylurea and HCl. Ethyl
acetoacetate and ethanol are possibly emitted from the uracil
unit and bromine from the bromacil unit. Acetic acid, used as a
solvent in the bromacil unit, may also be emitted to the atmos-
phere. A cross reaction product in the manufacture of bromacil
may be acetone, which may also be an emission species.
No information was found concerning air pollution control in the
manufacture of bromacil.
Trifluralin
Trifluralin is a selective preemergence herbicide classified in
the "Nitrated Hydrocarbon"' industry segment. The manufacture of
trifluralin involves two main steps: nitration and amination.
The simple process chemistry is given as follows (13):
CF3
HN03
H2SOi,
O2N
CF3
o
CF3
Dipropylamine
Sodium carbonate
N02 Water.
(27)
p-Chlorobenzo-
trifluoride
3,5-Dinitro-4-chloro
benzotrifluoride
02N
N(C3H7)2
Trifluralin
70
-------
Nitration involves the reaction of the following compounds in
reactors: p-chlorobenzotrifluoride, sulfuric acid, and nitric
acid. The product of the reaction is 3,5-dinitro-4-chloroben-
zotrifluoride, and the byproduct is spent sulfuric acid which is
recycled. The main off gases are nitrogen oxides (13).
Amination, the second-stage reaction, involves the reaction of
3,5-dinitro-4-chlorobenzotrifluoride, dipropylamine, and sodium
carbonate in solution. The product of the reaction is tri-
fluralin and the effluent is brine solution which is treated for
recovery (13) .
The production and waste schematic for trifluralin is presented
in Figure 26 (13).
._ EXCESS ACID
SOLD
WASTE
WATER
-
DECANTER
VACUUM
STILL
SALT WATER
WASTE
AROMATIC
: NAPTHA
VAC EXHAUST
TRIFIURALINIE.C.I
Figure 26.
Production and waste handling
schematic for trifluralin (13).
The main sources of air contaminant emissions are the nitration
reactor and condenser. The main gaseous emissions from the
nitration reactor are sulfur dioxide, sulfur trioxide, hydrogen
fluoride, hydrogen chloride, and nitrogen oxides, while particu-
late emissions from the reactor consist of nitrate, sulfate, and
chloride. Emissions from the condensers are mainly aerosol con-
sisting of chloroform and trifluralin.
71
-------
The raw materials used in the manufacture of trifluralin are
nitric acid, sulfuric acid, sodium carbonate, dipropylamine, and
p-chlorobenzotrifluoride. The main toxic materials are the
acids, and their handling practices in chemical industries are
well known.
Air contaminant emissions from the manufacture of trifluralin
are both gases and particulates. The sole producer of triflura-
lin uses wet scrubbers for emissions control, their quoted effi-
ciency being about 90% (13). Since aqueous waste from triflura-
lin manufacturing has been found to contain nitrosamines,
dipropylnitrosamine could occur as an air emission. Table 25
lists several air contaminant emissions, sources, and rates from
trifluralin manufacture (13).
TABLE 25. AIR CONTAMINANT EMISSIONS, SOURCES, AND
RATES FROM TRIFLURALIN MANUFACTURE (13)
Manufacturing
Process Source
Nitration
Condenser
Particulates
Nitrate
Sulfate
Chloride
Trichloromethane
Rate,
kg/hr
0.454
0.454
0.454
_a
Gases/vapors
Sulfur dioxide
Sulfur tioxide
Hydrogen fluoride
Hydrogen chloride
Nitrogen oxides
_a
~a
Rate,
kg/hr Odor
1.36 None
0.454
0.454
1.36
1.36
None
Rate,
odor
unit/hr
_a
_a
Not available.
Bacillus Thuringiensis
Bacillus thuringiensis, an insecticide (microbial product) con-
taining crystalline toxin as the active ingredient, is produced
by bacillus thuringiensis Berliner in the fermentation process
shown below (12):
Nutrient
Mixture
Sterilize^ Innoculate^ Ferment
Separater Dryr
Solid containing
•\-3% B. t.
The production and waste schematic for baa-Lllus thuringiensis
is shown in Figure 27 (12). The fermentation process uses a
nutrient mixture containing about 75% water in 37.8-m3 to
132.5-m3 tanks. The liquid mix is then sterilized and the
sterile liquid is innoculated (1.9 x 10~2 m3/37.8 m3). The fer-
mentation is submerged, proceeding aerobically as air is bubbled
through for 2 to 3 days. During the process, temperature, pH,
light, and stirring are regulated and turbidity is monitored.
72
-------
INCINERATE
SOYBEAN MEAL [
CORN STEEP LIQUOR f—
MINERALS, ETC. J
WHEAT BRAN
CASEIN I _
MOLASSES 1
VITAMINS, ETC. J
B.t.
AIR
EXC
A
ALTERNATE „„„ BAGHOUSEOR
ES!
[R
' FERMENTATION
TANK
1
• "•'•' ABbUlUlt MUCK
1 I
J~
•• CCNTRirUCE --«• SPRAY . ^ MILL — •- PACKAGF
DRIER
LIQUID
WA
STE
ALTERNATE
STERILIZE
WITH HEAT
WASTE
TREATMENT
PLANT
EVAPORATION
POND
• PRODUCT
DISCHARGE
TO LAKE
Figure 27.
Production and waste schematic for
bacillus thuringiensis (12).
The product, a white milky suspension, is drained from the tank,
centrifuged, and spray dried, and the powder is then milled and
packaged (12).
Raw materials (soybean meal, corn steep liquor, and minerals)
are received by rail and unloaded in a shed equipped with dust
control equipment. Materials are loaded into the fermentation
tank through portholes with no reported dust problems. Excess
air during fermentation, which may contain a variety of fermen-
tation products, goes to an incinerator. The centrifuge and
spray drier are contained so that no bacillus thuringiensis^
escapes to the atmosphere. The milling and packaging area is
enclosed and maintained under negative pressure via vacuum
takeoff through an absolute filter or baghouse, and the
collected dust is recycled. One manufacturer maintains petri
dish cultures throughout the plant to monitor for airborne
biological emissions (12).
Methyl Bromide
Methyl bromide, classified in the "Other Pesticides" industry seg-
ment, is a highly toxic liquefied gas which is probably not persis-
tent in sunlight. The production chemistry is as follows (15):
73
-------
6CH3OH + 3Br2
6CH3Br
Methyl
bromide
2H20
(28!
Figure 28 shows one company's production and waste schematic for
methyl bromide (12). The raw materials are bromine, methanol
and sulfur. Handling of methyl bromide requires a closed refrig-
eration system since the product is a colorless, odorless,
poisonous gas. One possible byproduct is diethyl ether ([CH3]20),
and sulfur bromides may result from cross reactions. The methyl
bromide system is vented through a caustic scrubber and the pro-
duct is dried with silica gel. Emission rates and species are
unknown.
Br2
CH30H
S
NaOH
I
REACTOR
SYSTEM
FRACTIONATION
SYSTEM
H2S04
SCRUBBER
WASTE
TREATMENT
PLANT
DRIER
(SILICA GEL)
PACKAGING
- RECOVERY
SHIPMENT
DISCHARGE
TO RIVER
Figure 28. Production and waste schematic for methyl bromide (12)
74
-------
SECTION 6
PESTICIDE PRIORITIZATION
PRIORITIZATION MODEL
Prioritization listings developed for the Source Assessment Pro-
gram have been used to aid in the selection of specific sources
of emissions for detailed environmental assessment (18) . Air
pollution sources were rank ordered or prioritized by computing a
relative environmental impact factor for each source type. A
priority listing was thus developed for each of four industrial
categories: combustion, organic materials, inorganic materials,
and open sources. Pesticide chemical manufacturing source types
received relatively low impact factors and thus a low rank com-
pared to other organic and inorganic source types. This low
rank, largely due to the smaller production of pesticides com-
pared with other organic chemicals, is not representative of the
potential environmental problem when one considers that pesti-
cides are manufactured specifically to kill certain forms of
life. In addition, a possibility of environmental contamination
exists due to persistent pesticides which may be biologically
accumulated in the food chain and which may produce long-term,
low-level toxic effects on man.
Consequently, a new subcategory was formed to relatively rank
pesticide chemical manufacturing source types, by pesticide
chemical, with regard to their commonly described potential
hazard to the environment from an air pollution standpoint. In
this special project, pesticide source listings and a prioritiz-
ation listing were produced specifically for use in evaluating
pesticide manufacturing source types. A detailed description of
the prioritization model and its development is given in Refer-
ence 18. The basic proposition of this model is that emission
sources can be ranked, based upon the potential degree of hazard
that they impose upon individuals in their environment. Factors
used in the model include downwind concentration of emission
(18) Eimutis, E. C. Source Assessment: Prioritization of
Stationary Air Pollution Sources—Model Description.
EPA-600/2-76-032a, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, February 1976.
77 pp.
75
-------
species and an associated hazard factor, ambient air concentra-
tions, ambient air quality standards, and population densities
surrounding an emission source.
The prioritization model generates an impact factor, Ix, associ-
ated with a given source type, x, and is defined as follows:
1/2
(29)
2
where I = impact factor, person/km
X
K = number of sources emitting materials associated
x with source type x
N = number of materials emitted by each source
P. = population density in the region associated
•^ with the jth source, persons/km2
x". . = calculated time-averaged maximum ground level
13 concentration of the ith material emitted by the
jth source, g/m3
F. = environmental hazard potential factor of the ith
1 material, g/m3
X'.. = ambient concentration of the ith material in the
13 region associated with the jth source, g/m3
S. = corresponding standard for the ith material
1 (used only for criteria emissions, otherwise
set equal to one)
The values for the maximum time-averaged ground level concentra-
tion, 7 , and hazard factor are defined as follows (18):
^max
/t \°-17
Y" = x I — I <30)
Amax Amax \ t /
where x = 2 9? = instantaneous (i.e., 3-min average) maximum
IHclX TTGUll
ground level concentration, g/m3
t = instantaneous averaging time, 3 min
o
t = averaging time, min
3i
Q = emission rate, g/s
h = stack height, m
TT = 3.14
e = 2.72
u = wind speed, m/s
76
-------
For criteria pollutants, the averaging time, ta, is the same as
that for the corresponding ambient air quality standard. For
noncriteria emission species, ta is 1,440 min (24 hr).
For the criteria pollutants—nitrogen oxides (NOX), sulfur oxides
(SOX), carbon monoxide (CO), hydrocarbons, and particulates—F is
the primary ambient air quality standard9. For other emission
species, F is defined by a reduced TLV (19):
F • TLV
where 8/24 normalizes the TLV to a 24-hr exposure and 1/100 is a
safety factor.
PRIORITIZATION BY AIR EMISSIONS
A comprehensive assessment of the environmental significance of
air emissions from pesticide manufacturing plants is inconceiv-
able due to the limited quantitative emissions data available.
The prioritization of major pesticide chemicals was conducted in
order to give an indication of the relative significance of
potential air emissions from these sources. Knowledge of simple
process chemistry is not sufficient to qualify and quantify
emissions because of the variations in production processes among
plants. Detailed process information and production data are
generally not available because this information is considered
proprietary by manufacturers. Sources of emissions may vary _ from
one production facility to another, and very little information
is available concerning emission rates and species because few
companies conduct in-house sampling programs.
The prioritization model is simply one tool used to aid in deci-
sion making regarding further characterization of the pesticide
manufacturing industry. The pesticide ranking should by no
means be considered rigid, but it should highlight areas for
further consideration. For example, four of the highest ranked
pesticides may be emitted from holding ponds or lagoons through
evaporation. Their high rank is due primarily to the lack of
data concerning evaporation emissions and to the fact that these
pesticides may potentially impose a greater environmental burden
than other source types. The impact factors generated by the
prioritization model must not be taken out of context. Pesticide
chemical manufacturing source types with impact factors in the
aThere is no primary ambient air quality standard for hydro-
carbons. The value of 160 ug/m3 used for hydrocarbons is a
recommended guideline for meeting the primary ambient air
quality standard for photochemical oxidants.
(19) TLVs® Threshold Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with Intended
Changes for 1975. American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, 1975. 97 pp.
77
-------
upper 25% of the prioritization listing are likely to impose a
greater environmental burden than those in the lower 25%.
The prioritization of 80 major pesticide chemical manufacturing
source types gives a reasonable overview of the pesticide manu-
facturing industry. In 1974, 37 major organic pesticides
accounted for 74% (4.72 x 105 metric tons) of the total pro-
duction (2). The remaining 26% of production was divided among
some 300 other synthetic organic pesticides, and only about one-
third of these had production greater than 454 metric tons. This
prioritization covers an estimated 81% (5.2 x 105 metric tons) of
total synthetic organic pesticide production based on 1974 esti-
mates. Certain industrial chemicals with minor pesticide uses,
shown in Table 26, were excluded from this prioritization because
they are primarily products of other industries and are predomi-
nantly used for other purposes.
TABLE 26. INDUSTRIAL CHEMICALS, USEFUL AS PESTICIDES,
EXCLUDED FROM THE PESTICIDE PRIORITIZATION
Acrolein
Acrylonitrile
Allyl alcohol
Ammonium thiocyanate
Anthraquinone
Arsenic acid
Biphenyl
Bis(diethylthiocarbamoyl)disulfide
Bis(dimethylthiocarbamoyl)disulfide
Bis(dimethylthiocarbamoyl)sulfide
Sodium borates
Borascu
Borax
Boro-Spray *
Carbon disulfide
Carbon tetrachloride
Copper acetoarsenite (Paris Green)
Copper carbonate
Copper naphthenate
Copper oleate
Copper oxychloride sulfate
Copper sulfate
DHA (dehydroacetic acid)
DMP (dimethyl phthalate)
Dichlorobenzene (ortho and para isomers)
Dimethyldithiocarbamic acid, K salt
Dimethyldithiocarbamic acid, Na salt
Dimethyldithiocarbamic acid, Zn salt
Diphenylamine
Ethylene
Ethylene dibromide
Ethylene dibromide
Ethylene dichloride
Ethylene oxide
Ethyl formate
Formaldehyde, formalin
HCN (hydrocyanic acid)
Mercuric chloride
OPP (o-phenylphenol)
Sodium arsenite
Sodium chlorate
Sodium fluoride
Sulfur
Thiram
The prioritization listing for 80 source types, compiled from the
emissions data summarized in Appendix B, is presented in Table 27.
The column labeled UL is the uncertainty level designation that
is discussed later in Section 6.
As noted earlier, this prioritization should highlight areas
where there is a high potential environmental burden or where key
78
-------
TABLE 27. PRIORITIZATION OF PESTICIDE CHEMICAL MANUFACTURING
SOURCES WITH RESPECT TO SOURCE TYPE
SOURCE TYPE
TOXAPHENE
PHORME
METHOXYCHLOR
OIAZINON
MANEB
ZINEB
DOT
METHYL PARATH10N
PARATHION
OICOFOL
MALATHION
MONOCROTOPHOS
PENTACHLOROPHENOL AND SOOIUH SALTS
CARBOFURAN
OISULFOTON
2.M-0 ACID. ESTERS. SALTS
AZINOPHOS • ETHYL
FENSULFOTHION
BROMACIL
CHLORDANE
TRICHLOROPHENOLS
CARBARYL
NABAM
ALOICARB
PROPANH
OBCP
DiPiETHOATE
CHLORAMBEN
FLUOMETURON
NALEO
HEXAChLOROBENZENE
OICROTOPHOS
AZINOPHOS - METHYL
nsnA
TRIFLURALIN
MEVINPHOS
METHYL BROMIDE
CHLORPYRIFOS
OIURON
DICHLOROVOS
BUTYLATE
OSMA
EPTC
PHOSPHAMIOION
DICHLOROPPOPENE
TERBACIL
OALAPON
SILVEX
LINDANE
VERNOLATE
MERPHOS
PYRETHINS
METALKAMATE (BUX)
DICAHBA
LINURON
BENEFIN
CAPTAN
ATKAZINE
OINOSEB
TEPP
ENORIN
HEPTACHLOR
ENOOSULFAN
MONURON
SODIUM TCA
RONNEL
COEC
CACODYLIC ACID
SIMA2INC
FOLPET
PROPACHLOR
PROPAZINE
BACILLUS THURINGIENSIS
BUTACHLOR
CAPTAFOL
ALACHLOR
CALCIUM ACID METHANEARSONATE
CALCIUM ARSENATE
LEAD ARSENATE
METHANE ARSENIC ACID
IMPACT FACTOR
UL CALC
300,000
70.000
MO. 000
30,000
10,000
7,000
7,000
6.000
5,000
»,000
M.OOO
3,000
2,000
2,000
2.000
2.000
1,000
1,000
1,000
1,000
1,000
900
900
aoo
BOO
aoo
TOO
600
500
500
MOO
MOO
MOO
MOO
300
300
200
200
200
200
100
100
100
100
90
90
60
ao
70
60
60
50
50
50
50
MO
MO
MO
30
50
30
30
20
20
20
20
T
6
5
5
M
M
3
2
2
1
C
D
D
D
0
D
0
B
B
0
C
D
B
0
0
0
D
D
D
0
C
D
0
D
0
D
C
D
0
D
0
0
0
B
B
0
D
D
D
D
D
B
D
D
D
0
D
n
0
D
D
D
0
D
0
D
d
0
C
D
O
0
D
D
D
0
D
0
0
C
D
D
0
D
C
0
D
0
D
0
3
3
3
3
3
3
3
3
3
5
3
3
3
3
3
3
J
3
3
3
3
3
3
3
3
3
S
3
3
3
3
3
5
3
5
J
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
3
3
3
3
J
3
3
3
3
3
3
3
5
3
3
3
3
3
3
3
79
-------
information is lacking. A close look at several pesticides with
the highest impact factors highlights two facts: 1) no informa-
tion is available concerning the environmental burden due to
potential evaporation emissions from holding ponds and evapora-
tion lagoons and 2) sulfur dioxide emissions may be substantial
for some pesticides due to the flaring of H2S and mercaptans and
the incineration of sulfur-containing compounds.
Four pesticides (toxaphene, DDT, methyl parathion, and parathion)
out of the nine pesticides with the highest impact factors are
each potentially emitted to the atmosphere from holding ponds or
lagoons. Emission factors for evaporation of these compounds
were calculated using the methodology presented in Appendix A.
Eight pesticides (phorate, diazinon, maneb, zineb, methyl para-
thion, parathion, malathion, and monocrotophos) appear in the
upper 20% of the prioritization list due primarily to the poten-
tially high emission of S02 resulting from flaring H2S and
mercaptans and from incineration of sulfur-containing compounds.
Methoxychlor received a large impact factor primarily due to the
high county population densities associated with its manufactur-
ing sites.
Methyl parathion and parathion are also ranked in the upper
portion of the prioritization listing, primarily due to the
emission of SO2, a result of flaring H2S and mercaptans and
incinerating sulfur. H2S byproduct has been calculated as 0.12
kg/kg of active ingredient (12). Sulfur dioxide emission rates,
based on H2S and S oxidation, are estimated to be 704 kg/hr (13)
or 0.41 kg S02/kg active ingredient (2). Potential emissions
from wastewater treatment or lagooning include the pesticides,
ammonia (the emission factor for pesticides and ammonia is
calculated using the methodology in Appendix A), mercaptans and
H2S.
Disulfoton, phorate, fensulfothion, diazinon, dursban, and
merphos were all assumed to have the same S02 emission factor
based on their similarities and the fact that 0.06 kg H2S/kg
active ingredient is produced as a reaction byproduct during the
manufacture of disulfoton (12). Based on sulfur dioxide emission
rates calculated for methyl parathion and parathion (H2S by-
product formation was calculated as 0.12 kg/kg active ingredient),
the SO2 emission factor is estimated to be 0.2 kg SO2/kg active
ingredient or 205 kg/metric ton.
It is also noted that atrazine, the largest selling herbicide in
the United States, and captan, with an estimated annual produc-
tion of 9.1 x 103 metric tons, are ranked in the lower half of
the prioritization due to lack of information on which to base
better qualified emission estimates. In general, the existence
of any compound in the lower half of the prioritization list may
well be due to a lack of emissions data.
80
-------
MASS OF EMISSIONS
State-by-state and national listings refer to a compilation of
mass emissions of criteria pollutants (particulates, SOX [report-
ed as SO2], NOX, hydrocarbons [designated HC], and CO) by pesti-
cide source type for specific states and for the nation. The
total mass of emissions of a specific criteria pollutant in a
particular state was obtained by multiplying the pollutant emis-
sion factor (Appendix B) by the annual production rate in the
state. Similarly, the total mass of emissions of a criteria
pollutant in the nation was obtained by multiplying the pollutant
emission factor by the annual total production in the United
States (Table 4).
State-by-State Listing
The state-by-state listing of criteria pollutant emissions from
pesticide manufacturing source types is given in Table 28. This
listing shows the pesticide chemical manufacturing source types
in a particular state that emit one or more of the criteria
pollutants. The first number in each criteria pollutant column
is the annual mass of that emission in the particular state.
For example, the source type entitled "Butylate" emits 0.9 x 103
kg/yr of particulates in Alabama. The second number in each
criteria pollutant column refers to the percentage that the
annual mass of emissions represents in relation to the total
emissions of that pollutant from all pesticide chemical manufac-
turing source types in that state. For the same source type,
"Butylate," in Alabama, 0.9 x 103 kg/yr represent 4.21% of all
particulates emitted from all pesticide chemical manufacturing
sources in Alabama.
National Listing
The national listing of criteria pollutant emissions from pesti-
cide chemical manufacturing source types is shown in Table 29.
For each source type and each criteria pollutant, the first line
represents the annual mass of emissions of each pollutant from
each source type. For example, the source type "Butylate"
accounts for 1.8 x 103 kg/yr of particulate emissions in the
United States. The percentage of emissions which a source type
represents with respect to all pesticide chemical manufacturing
sources is indicated on the second line. For the source type
"Butylate," the 1.8 x 103 kg/yr of particulates represent 0.85%
of the particulate emissions from all pesticide chemical manu-
facturing sources in the United States. The third line shows
the percent of emissions from all sources of air emissions in
the United States represented by this same source type. In the
case of butylate, as well as the majority of source types, the
percentage is too low to be represented by the given number of
decimal places. However, the butylate source does produce
743.9 x 103 kg/yr of sulfur oxide emissions (reported as S02)
which represent 0.00115% of the S02 emissions from all sources in
the United States. In addition, dashes in a criteria pollutant
81
-------
column (for example, the calcium arsenate source type) indicate
that the combined mass of emissions for the particular source
type is not significant to the given number of five decimal
places.
DATA SOURCES, QUALITY, AND METHODOLOGY
Available information regarding principal emission species and
emission rates is listed in Table 22 for seven major pesticides.
Three of these compounds are included in the chlorinated hydro-
carbons industry segment, and one is included in each of four
other industrial segments: organophosphates, organoarsenicals
and organometallics, nitrated hydrocarbons, and other nitrogenous
hydrocarbons. The calculated emission estimates in Table 22 were
used as a basis to derive emission factor estimates for the
remaining pesticides within each industry segment. Additional
input used for organophosphorus pesticides includes: 208.8 kg/hr
hydrogen chloride and 190.7 kg/hr sulfur from the methyl para-
thion chlorination unit prior to incineration and flaring.
Sulfur dioxide emission rates based on H2S and S oxidation from
incineration and flaring are estimated to be 703.7 kg/hr.
For prioritization purposes, several assumptions were made. Pro-
vided that similar assumptions are made throughout the prioritiz-
ation, no added weight would be given to any single pesticide or
industry segment (e.g., organophosphates). For example, detailed
information on emission height is not available; therefore, a
constant emission height of 30.5 m was assumed throughout the
prioritization. Due to the lack of quantitative emission height
data, this value was estimated and provided no added weight to
any source type. The prioritization is thus composed of consist-
ent estimates based on available data and similarities between
pesticide manufacturing processes, raw materials utilized, and
chemical structures.
In certain cases, similarities between pesticides are present,
and their emission estimates are thus assumed to be similar. For
example, dicofol was assumed to have emissions similar to those
of DDT. Dicofol production may be represented by the following
flow diagram:
benzene 1^- monochlorobenzene—y
\ ^ DDT
acetaldehyde ^ chloral ' ' ^ dicofol
Similarly, disulfoton, phorate, fensulfothion and diazinon were
all given similar emission estimates based on the following
diagram:
/-diethyl phosphorodithioic disulfoton
phosphorous / acid or salt phorate
pentasulfide ^""\
*-0,0-diethyl phosphoro- fensulfothion
chloridothioate diazinon
82
-------
Emission factors derived using this methodology should provide
sufficient information to develop the prioritization, although
uncertainty is associated with the emission estimates for each
source type. While the level of uncertainly cannot be quanti-
fied, it can be assumed to vary as a function of the guality of
available information on a specific pesticide. Using this
rationale, a priority index of uncertainty levels may be defined
as follows:
Level Meaning
A Adequate data of reasonable accuracy
B Partially estimated data of intermediate accuracy
C Totally estimated data of intermediate accuracy
D Missing data and unknown emission species
The above defined uncertainty levels are subjective. They
ranged from B to D for the source types in this prioritization.
The pesticides listed in Table 22, in addition to DSMA and para-
thion and excluding toxaphene, were assigned a confidence level
of B. Captafol, dimethoate, dinoseb, folpet, malathion, toxa-
phene, and trichlorophenols were assigned a confidence level of
C, while the remaining pesticides were assigned a D level of
uncertainty.
83
-------
TABLE 28. STATE-BY-STATE LISTING OF CRITERIA POLLUTANT EMISSIONS FROM
PRIORITIZED PESTICIDE CHEMICAL MANUFACTURING SOURCES
STATE EMISSIONS REPORT FOR ALABAMA3
SOURCE
PART
MASS OF EMISSIONS (1000 KO/YR)
PERCENT OF STATE EMISSIONS
802
NOX
HC
CO
00
BUTYLATE
OBCP
OIAZINON
OICHUOROVOS
EPTC
METHYL PARATHION
NCVINPHOS
PARATHION
VERNOLATE
0.9
». 21000
0.0
0.00000
l.«
6.92000
0.1
O.»2100
0.7
S. 16000
IS. 6
63.20000
0.1
0.32700
3.6
16.90000
1.1
9.27000
372.0
». 26000
0.0
0.00000
597.9
6.38000
0.0
0.00000
279.0
3.19000
9979.0
63.60000
0.0
0.00000
itae.o
17.00000
»6<».9
9.32000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2.7
9.96000
2.7
9.96000
0.0
0.00000
0.2
0.63700
2.0
7.17000
13.6
»7. 80000
0.1
0.39SOO
3.7
12.90000
S.H
11.90000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
2
2
2
2
2
2
2
2
STATE TOTALS
21.9
87i»1.0
STATE EMISSIONS REPORT FOR ALASKA
0.0
26.9
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
0.0
CO
(continued)
Producers and plant locations were derived from Reference 2. It must be qualified that
certain prioritized pesticides may not be listed in state emission report due to the
limited quality of data concerning pesticide manufacturer locations.
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR ARIZONA
MASS OF EMISSIONS (1000 K6/TRI
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
CO
STATE EMISSIONS REPORT FOR ARKANSAS
oo
m
SOURCE
2,t-D ACID, ESTERS, SALTS
DALAPON
HCTHYL BROMIDE
SILVEX
TRICHLOROPHENOLS
STATE TOTALS
PART
5.14
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
S02
NOX
HC
0.0
CO
2.3
i«2.00000
0.6
10.50000
0.0
0.00000
0.7
12.60000
1.9
39.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2.3
22.10000
0.6
9.53000
2.3
22.10000
l.t
13.30000
3.6
36.90000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
2
2
2
2
0.0 10.2 0.0
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR CALIFORNIA
oo
cr*
SOURCE
BACILLUS THURINGIENSIS
CAPTAFOL
2.H-0 ACID. ESTERS, SALTS
DOT
METHYL BROMIDE
NALED
PHOSPHAHIDION
STATE TOTALS
PART
16.3
HASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
S02
NOX
HC
0.0
CO
0.2
1.39000
0.1
0.9*900
2.3
13,90000
13.6
as. 20000
0.0
0.00000
0.1
0.69400
0.0
0.2TTOO
0.0
0.00000
0.0
0.00000
0.0
0,00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0,0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
1.4
4.26000
2.3
T. 11000
27.2
as. 30000
0,9
2.8*000
0.1
0.39500
0.0
0.14200
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0,00000
2
2
2
2
2
2
2
0.0 31.9 0.0
(continued)
-------
00
-J
SOURCE
OBCP
OICHLOROVOS
DICROTOPHOS
WEV1NPHQS
HONOCROTOPHOS
STATE TOTALS
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR COLORADO
PART
2.0
MASS OF EMISSIONS (1000 KS/YR)
PERCENT OF STATE EMISSIONS
S02
o.o
NOX
HC
0.0
CO
0.0
0,00000
0.1
t. 60000
0.2
9.20000
0.1
5.75000
1.6
SO. 50000
0.0
o.ooooo
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2.7
56.90000
0.2
3.79000
0.2
B. 79000
0.1
2.37000
1.6
33.20000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
2
2
2
2
0.0
STATE EMISSIONS REPORT FOR CONNECTICUT
SOURCE
CAPTAN
TRICHUOROPHENOLS
STATE TOTALS
PART
2.1
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
S02
NOX
HC
0.0
0.0
CO
0.2
9.54000
1.9
90.50000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
3.0
•m.Hoooo
3.6
55.60000
0.0
0.00000
0.0
0.00000
6.8 0.0
(continued)
-------
SOURCE
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR DELAWARE
BASS OF EMISSIONS (1000 KO/Yft)
PERCENT OF STATE EMISSIONS
PART
802
NOX
HC
CO
STATE EMISSIONS REPORT FOR FLORIDA
00
CO
SOURCE
NALEO
PHOSPHAHIOION
STATE TOTALS
SOURCE
CALCIUM ARSENATE
LEAD ARSENATE
TOXAPHCNE
STATE TOTALS
MASS OF EMISSIONS (1000 K6/YRI
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
0.0
0.0
CO
0.1
Tl.tOOOO
0.0
26.60000
0.2
PORT FOR
PART
0.0
0.00086
0.0
0.00571
0.0
100,00000
. 0.0
0.00000
0.0
0.00000
0.0
GEORGIA
MASS OF
PERCENT
S02
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.1
Tl.HOOOO
0.0
28.60000
0.2
0.0 2
0.00000
0.0 2
0.00000
0.0
EMISSIONS (1000 K8/YRI
OF STATE EMISSIONS
NOX
0.0
0.00000
0.0
0.00000
0.0
0.00000
HC
0.0
0.00000
0.0
0.00000
40.6
100.00000
CO T
0.0 2
0.00000
0.0 2
0,00000
0.0 2
0.00000
0.0 40.6 0.0
(continued)
-------
SOURCE
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR HAWAII
MASS OF EMISSIONS (1000 KS/TR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
CO
SOURCE
STATE EMISSIONS REPORT FOR IDAHO
MASS OF EMISSIONS (1000 KB/YRJ
PERCENT OF STATE EMISSIONS
PART
302
NOX
HC
CO
00
STATE EMISSIONS REPORT FOR ILLINOIS
SOURCE
BACILLUS THURINGIENSIS
CHLORDANC
2.H-0 ACID, ESTERS, SALTS
FLUOBETURON
PENTACHLOROPHENOL AND SODIUM SALTS
STATE TOTALS
PART
15.0
MASS OF EMISSIONS (1000 K6/YRI
PERCENT OF STATE EMISSIONS
SOS
NOX
HC
0.0
CO
0.2
1.52000
0.0
0.00000
2.3
15.20000
0.0
0.00000
12.5
03.90000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
o.o
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
S.H
31.60000
2.3
21.10000
0.6
5.26000
4.3
42.10000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
2
2
2
2
o.o 10.a o.o
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR INDIANA
MASS OF EMISSIONS (1000 KO/YR)
PERCENT OF STATE EMISSIONS
SOURCE
BENEFIN
TRIFLUMLIN
STATE TOTALS
PART
S02
NOX
HC
SOURCE
ALACHLOR
BUTACHLOR
BETALKAHATE (BUX)
PROPACHLOR
STATE TOTALS
SOURCE
DIHETHOATE
PENTACHLOROPHENOL AND SODIUM SALTS
STATE TOTALS
22.6
0.2
0.2
CO
1.3
10.70000
10.9
69.30000
12.2
STATE EMISSIONS REPORT
PART
0.0
0.00000
0.0
0.00000
2.8
100,00000
0.0
0.00000
2.3
1.7
10.70000
14.9
69.30000
16.3
FOR IOWA
MASS OF
PERCENT
802
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0,00000
0.0
STATE EMISSIONS REPORT FOR KANSAS
MASS OF
PERCENT
PART
0.3
1.49000
22. »
96.50000
802
0.2
100.00000
0.0
0.00000
1.3 0.0
10.70000 0.00000
10.9 0.0
69.30000 0.00000
12.2 0.0
EMISSIONS (1000 KG/YRJ
OF STATE EMISSIONS
NOX HC
0.0 0.3
0.00000 1.13000
0.0 6.6
0.00000 26.20000
0.0 6.6
0.00000 26.20000
0.0 10.2
0.00000 »2. 00000
0.0 2».l
EMISSIONS (1000 KG/YRI
OF STATE EMISSIONS
NOX HC
0.2 l.H
100.00000 14.30000
0.0 6.2
0.00000 65.70000
0.0 2
0.00000
0.0 2
0.00000
0.0
CO T
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0
CO T
0.0 2
0.00000
0.0 2
0.00000
9.9 0.0
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR KENTUCKY
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
SOURCE
2.0-0 ACID. ESTERS, SALTS
STATE TOTALS
SOURCE
PART
S02
NOX
HC
ATRAZINE
BUTYLATE
2,4-0 ACID. ESTERS, SALTS
OICHLOROPROPENE
EPTC
FLUOHETURON
PROPAZINE
SIMAZINE
STATE TOTALS
SOURCE
STATE EMISSIONS REPORT FOR MAINE
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
co
H.5
100.00000
4.5
STATE EMISSIONS REPORT FOR
PART
0.0
0.00000
0.9
23.50000
2.3
58.80000
0.0
0.00000
0.7
17.60000
0.0
0.00000
0.0
0.00000
0.0
0.00000
3.9
0.0
0,00000
0.0
0.0
0.00000
0.0
4.3
100.00000
4.5
0.0
0.00000
0.0
a
LOUISIANA
MASS OF EMISSIONS UOOO K6/YR)
PERCENT OF STATE EMISSIONS
soa
0.0
0.00000
372.0
97.10000
0.0
0.00000
0.0
0.00000
279.0
42.90000
0.0
1 0.00000
0.0
0.00000
0.0
0.00000
650.9
NOX
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
HC
74.8
72.60000
2.7
2.64000
2.9
2.20000
3.6
3.92000
2.0
1.98000
0.6
0.55000
6. a
6.60000
10.2
9.90000
103.1
CO
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
T
2
2
2
2
2
2
2
2
PART
S02
NOX
HC
CO
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR MARYLAND
SOURCE
PART
MASS OF EMISSIONS (1000 K6/TRI
PERCENT OF STATE EMISSIONS
S02
NOX
HC
CO
AZINOPHOS - ETHYL
PYRETHINS
0.7
63.30000
0.1
16.70000
0.2
100.00000
0.0
o.ooooo
0.2
100.00000
0.0
0.0004)0
1.0
ee. 20000
0.1
11.80000
0.0
0,00000
0.0
0.00000
2
2
STATE TOTALS
0.6
vo
N)
0.2
0.2
1.2
0.0
STATE EMISSIONS REPORT FOR MASSACHUSETTS
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
CO
(continued)
-------
OJ
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR MICHIGAN
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
SOURCE
CHLORPYRIFOS
2,4-0 ACIOt ESTERS, SALTS
OALAPON
DBCP
DINOSEB
METHYL BROMIDE
PENTACHLOROPHENOL AND SODIUM SALTS
RONNEL
SODIUM TCA
TRICHLOROPHENOLS
ZINEB
STATE TOTALS
PART
S02
NOX
HC
SOURCE
PYRETHINS
STATE TOTALS
0.1
0.0
0.0
CO
1.1
5,76000
2.3
11.60000
0.6
2.89000
0.0
0.00000
2.22000
0.0
0.00000
12.5
63.60000
0.5
2.31000
0.0
0.00000
1.9
9,63000
O.H
2.02000
19.6
DRT FOR
PART
0.1
100,00000
74.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.6
0.09240
0.0
0.00000
0.0
0.00000
0.3
0.04620
0.0
0.00000
0.0
0.00000
162.7
25.90000
626.5
0.0
0.00000
0.0
o.'ooooo
0.0
0.00000
0.0
0.00000
64.00000
0.0
0.00000
0.0
0.00000
0.2
36.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.7
0,0
0.00000
2.3
7.65000
0.6
1.96000
3.6
12.60000
0.9
1.57000
3.9
13.30000
4.5
15.70000
i.e
6.26000
6.6
23.50000
3.6
13.10000
1.2
4.12000
28.9
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
0.0
MINNESOTA
MASS OF EMISSIONS (1000 KS/W
PERCENT OF STATE EMISSIONS
S02
0.0
0,00000
NOX
0.0
0.00000
HC
0.1
100,00000
CO T
0.0 2
0,00000
0.1 0.0
(continued)
-------
VD
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR MISSISSIPPI
MASS OF EMISSIONS (1000 KB/YRI
PERCENT OF STATE EMISSIONS
SOURCE
OINOSEB
METHYL PARATHION
PARATHION
TOXAPHENE
STATE TOTALS
SOURCE
PART
S02
NOX
HC
AZINOPHOS - METHYL
2i*-0 ACIOt ESTERS. SALTS
OISULFOTON
FENSULFOTHION
NALEO
PHOSPHAMIDION
STATE TOTALS
7.0
1488.0
0.2
CO
0.1
6.88000
«.5
71.60000
1.4
21.90000
0.0
0.00072
6.3
STATE EMISSIONS REPORT FOR
PART
0.9
13.00000
2.3
32.60000
2.3
32.60000
l.H
19.50000
0.1
1.63000
0.0
0.69100
0.6
0. 02100
1860.0
76.90000
997.9
23.10000
0.0
0.00000
2*18.0
0.*
100.00000
0.0
0.00000
0.0
o.ooooo
0.0
0.00000
o.«
0.9
2.92000
*.5
29.20000
1.*
7.67000
11.6
6*. 60000
16.0
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
2
t
t
t
MISSOURI
MASS OF EMISSIONS 11000 K8/YRI
PERCENT OF STATE EMISSIONS
S02
0.3
0.01990
0.0
0.00000
929.9
62.90000
9S7.9
37.90000
0.0
0.00000
0.0
0.00000
NOX
0.2
100.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
HC
l.»
39.90000
2.3
99.90000
0.0
0.00000
0.0
0.00000
0.1
2.99000
0.0
1.20000
CO
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
T
*
2
2
2
2
2
c
3.6 0.0
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR MONTANA
MASS Of EMISSIONS (1000 KS/YR)
PERCENT OF STATE EMISSIONS
PART 302 NOX HC CO
SOURCE —
STATE EMISSIONS REPORT FOR NEBRASKA
MASS OF EMISSIONS (1000 KS/YRl
PERCENT OF STATE EMISSIONS
SOURCE
Ul
SOURCE
STATE EMISSIONS REPORT FOR NEVADA
MASS OF i
PERCENT I
PART S02 NOX HC CO
MASS OF EMISSIONS (1000 K8/YR>
PERCENT OF STATE EMISSIONS
STATE EMISSIONS REPORT FOR NEW HAMPSHIRE
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
SOURCE PART SOZ NOX HC CO
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR NEW JERSEY
•ounce
ocoeiLic ncio
CHIORDANC
OUZINON
DIIWTHOATC
DIN01CB
Dt»»
HCXtCHLOKOeCNICNC
LINOANt
IUNCB
HCTHOX'CHLOR
FISK*
HABAM
NALCD
PHCfUTE
PHOSPH»M:OION
PROP»NIL
PTRCTHINS
TOXAPHtNC
I1NEB
ST«Tt TOTALS
N«SS OF CKISSIONI (1000 K«/TK)
PERCENT OF ST«Tt CNISSIONS
0.0
o.ooooo
0.0
0,00000
i.*
9.04000
».»
t.itooo
0.1
a.voooo
0.0
0.00000
0.0
0.00000
0.0
o.otoo
».«
45.90000
0.*
t. 0*000
1.3
10.10000
0.0
0.00000
0.(
J.TTOOO
0.1
O.T9SOO
2.3
19.10000
0.0
0.30100
0.0
0.00000
0.3
1.01000
0.0
0.00090
O.H
t.MOOO
0.0
0.00000
0.0
0.00000
807. »
H.Toooo
o.t
O.OOMI
o.t
O.OHTO
0.0
0.00000
0.0
0.00000
0.0
0.00000
t.«
0.1»BOO
3TI.O
It. 90000
0.0
0.00000
0.0
0.00000
231.9
10.30000
0.0
0.00000
121.1
41.10000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
142. T
T. 20000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0,2
•.20000
0.4
10.10000
0.0
0.00000
0.0
0,00000
0.0
0.00000
J.7
•9, (0000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0,00000
0.0
0.00000
0.0
0.00000
0.0
0,00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
o.t
1.1*000
].*
«.*TOOO
0.0
0.00000
1.*
1.99000
0,8
0.66200
2.t
j.eiooo
1,0
J. 43000
0.4
0.64200
27. 2
9*. 70000
2.7
3.97000
1.9
2.21000
9.0
13.10000
1.7
2.UBOOO
0.1
0.14400
0,0
0.00000
0.0
0. 06.620
2,3
3.31000
0.3
0.39700
11,6
17,00000
1.2
1.7*000
0.0
0,00000
0.0
0.00000
0,0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0,0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
I
2
2
2
2
2
2
2
2
2
2
2
2
2
9
2
2
2
t
19.0
(continued)
-------
SOURCE
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR NEW MEXICO
MASS OF CESSIONS (1000 KG/fR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
CO
SOURCE
STATE EMISSIONS REPORT FOR NEW YORK
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
CO
CARBOFURAN
ENDOSULFAN
HEXACHLOROBEWENE
ZINCS
1.1
7i». 10000
0.0
0.00000
0.0
0.00000
0,t
25.90000
0.0
0.00000
0.0
0.00000
0.0
0.00000
162.7
100,00000
0.0
0.00000
0.0
0,00000
0.0
0.00000
0.0
0.00000
3.t
43.00000
1.*
17.50000
i.a
23.110000
1.2
19.90000
0(0
0,00000
0.0
0.00000*
0.0
0.00000
0.0
0.00000
2
2
2
2
STATE TOTALS
SOURCE
1.9 162.7 0.0
STATE EMISSIONS REPORT FOR NORTH CAROLINA
7.8
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
0.0
CO
SOURCE
STATE EMISSIONS REPORT FOR NORTH DAKOTA
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
CO
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR OHIO
MASS OF EMISSIONS (1000 K6/YRI
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
CO
CAPTAN
FOLPET
HEXACHLOROBENZENE
PENTACHLOROPHENOL AND SODIUM SALTS
0.*
T. 28000
0.1
l.*»000
0.0
0.00000
9.0
91.10000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
6.0
9W.SOOOO
l.H
12.90000
1.8
u.uoooo
i.a
It.ifOOOO
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
2
2
2
co
STATE TOTALS
9.5 0.0
STATE EMISSIONS REPORT FOR OKLAHOMA
0.0
11.0
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
0.0
CO
STATE EMISSIONS REPORT FOR OREGON
SOURCE
PART
MASS OF EMISSIONS (1000 K6/TR)
PERCENT OF STATE EMISSIONS
S02
NOX
HC
CO
2.
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR PENNSYLVANIA
SOURCE
2t4-D ACIDi ESTERS, SALTS
DICOFOL
NANEB
PROPANIL
TEPP
ZINEB
PART
MASS OF EMISSIONS (1000 KB/riU
PERCENT OF STATE EMISSIONS
S02
NOX
HC
CO
2.3
so.toooo
0.9
20.20000
0.9
20.20000
0.0
0.00000
0.0
o.tosoo
0.1
0.S3000
0.0
0.00000
0.0
0.00000
372.0
69.60000
0.0
0.00000
0.0
0.00000
162. 7
30.40000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2.3
24.HOOOO
i.e
19.90000
2.7
29.20000
X.I
12.20000
0.2
1.95000
1.2
12.SOOOO
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2
2
2
t
2
2
VO
STATE TOTALS
SOURCE
4.5 33H.7
STATE EMISSIONS REPORT FOR RHODE ISLAND
o.o
9.3
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
0.0
CO
SOURCE
STATE EMISSIONS REPORT FOR SOUTH CAROLINA
MASS OF EMISSIONS (1000 K6/YRI
PERCENT OF STATE EMISSIONS
PART
302
NOX
HC
CO
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR SOUTH DAKOTA
MASS OF EMISSIONS (1000 K6/TRI
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
CO
STATE EMISSIONS REPORT FOR TENNESSEE
o
o
SOURCE
01CARBA
CWRIN
HEPTACHLOR
HCRPHOS
METHYL PARATHION
PARATH10N
STATE TOTALS
PART
6.3
HASS OF EMISSIONS (1000 KS/YRl
PERCENT OF STATE EMISSIONS
S02
NOX
HC
3069.0
CO
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
4.9
71.40000
l.B
28.60000
0.0
0.00000
0.0
0.00000
0.0
0.00000
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR TEXAS
SOURCt
BROMACIL
DICAMBA
D1CW.OROPROPENE
OIURON
OSHA
LINURON
MANEB
METHYL PARATHION
MONURON
«SMA
PARATHION
TERBACIL
STATE TOTALS
SOURCE
PART
2.7
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
so2
NOX
HC
1116.0
0.0
26.5
STATE EMISSIONS REPORT FOR UTAH
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
CO
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.9
33.30000
0.9
33.30000
0.0
0.00000
0.0
0.00000
0.9
33.90000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
372.0
33.30000
372.0
33.30000
0.0
0.00000
0.0
0.00000
372.0
33.30000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0,00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
2.7
10.30000
i.a
6.S5000
7.7
29.10000
2.3
8.S6000
1.3
H. 92000
0.7
2.97000
2.7
10.30000
0.9
3.K2000
0.2
0.66500
t.6
17.30000
0.9
3. 17000
0.7
2.57000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0,0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0,00000
0.0
0.00000
2
2
2
2
2
2
2
2
2
2
2
2
0.0
PART
302
NOX
HC
CO
(continued)
-------
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR VERMONT
MASS Of EMISSIONS (1000 KG/YRI
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
CO
STATE EMISSIONS REPORT FOR VIRGINIA
MASS OF EMISSIONS (1000 K8/YH)
PERCENT OF STATE EMISSIONS
SOURCE
PART
S02
NOX
HC
co
STATE EMISSIONS REPORT FOR WASHINGTON
SOURCE
PART
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
S02
NOX
HC
CO
CARBOFURAN
PENTACHLOROPHENOL AND SODIUM SALTS
1.1
8.33000
12.5
91.70000
0.0
0.00000
0.0
0.00000
0.0
0.00000
0.0
0.00000
3.t
H2. 90000
4.9
97.10000
0.0
0.00000
0.0
0.00000
2
2
STATE TOTALS
13.6
0.0
0.0
7.» 0.0
(continued)
-------
SOURCE
ALOICARB
CARBARTL
CDEC
HETHOXYCHLOR
NABAM
STATE TOTALS
SOURCE
CACODYLIC ACID
OSMA
HSHA
STATE TOTALS
SOURCE
TABLE 28 (continued)
STATE EMISSIONS REPORT FOR WEST VIRGINIA
"ASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
PART
S02
NOX
HC
0.0
0.0
0.0
6.7
STATE EMISSIONS REPORT FOR WYOMING
"ASS OF EMISSIONS (1000 KG/YR)
PERCENT OF STATE EMISSIONS
PART
CO
1.1
7.16000
13.1
83,30000
0.2
1.15000
0.6
». 79000
0.6
3.59000
15.8
STATE EMISSIONS REPORT FOR
«6t.9
60.20000
0.0
0.00000
7"». »
9.64000
0.0
0.00000
232.5
30.10000
771.8
WISCONSIN
0.0
p. ooooo
0.0
0.00000
o.o
0.00000
0.0
0.00000
0.0
0.00000
0.0
3.H
7.42000
39.5
66.00000
0.5
1.19000
0.6
1.65000
1.7
3.71000
15.9
0.0 2
0.00000
0.0 2
0,00000
0.0 2
0.00000
0,0 2
0.00000
0.0 2
0.00000
0.0
MASS OF EMISSIONS (1000 K6/YR)
PERCENT OF STATE EMISSIONS
PART
0.0
11.70000
0.0
19.50000
0.0
66.60000
S02
0.0
0.00000
0.0
0.00000
0.0
o.ooopo
NOX
0.0
0.00000
0.0
0.00000
0.0
0,00000
HC
0.6
11.70000
1.3
19.50000
1.6
68.80000
CO T
0.0 2
0.00000
0.0 2
0.00000
0.0 2
0.00000
o.o
S02
NOX
HC
CO
18 January 1978
-------
TABLE 29. NATIONAL LISTING OF CRITERIA EMISSIONS FROM PRIORITIZED
PESTICIDE CHEMICAL MANUFACTURING SOURCES
FUSS Of HUSSIONS 11000 K6/TRI
PERCENT Of TOTAL INCLUDING flETALLURGICAL PROCESSING
•ounce
PART
soa
NOX
HC
CO
AtACHLOR
ALDICARB
ATRAZINE
AZINOPHOS - ETHYL
AZINOPHOS - P.ETMYL
BACILLUS THURINBIENSIS
BENEFIN
BROMACIL
BUTACHLOR
BUTYLATE
CACOOYLIC ACIO
CALCIUn ACID HETHANEARSONATE
0.0
0.00000
0.00000
1.1
0. 93600
0.00000
0.0
0.00000
0.00000
O.T
0.92200
0.00000
0.9
0.42900
0.00000
9.9
0.11*00
0.00000
l.S
o.tieoo
0.00000
0.0
0.00000
0.00000
0.0
o.ooooo
0.00000
l.S
0.09000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
***.9
t. 13000
0.00072
0.0
0.00000
0.00000
0.2
0.00100
0.00000
0.9
0.00199
0.00000
0.0
0.00000
0.00000
1.7
0.00797
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
7*9.9
3.»0000
0.00119
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.2
1.01000
0.00000
0.2
1.9*000
0.00000
0.0
0.00000
0.00000
1.3
T.1TOOO
0.00001
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.3
0.05180
0.00000
s.*
0.6*800
0.00002
T».0
1*. 30000
0.000*1
1.0
0.19*00
0.00001
1.*
0.29900
0.00001
0.0
0.00000
0.00000
O.'O
0.00000
0.00000
2.7
0.91000
0.00001
t.e
1.30000
0.0000*
3.*
1.0*000
0.00003
1.4
0.29800
0.00001
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0'
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
2
2
2
2
2
2
2
2
2
2
2
(continued)
-------
TABLE 29 (continued)
SOURCE
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF TOTAL INCLUDING METALLURGICAL PROCESSING
PART
S02
NOX
HC
CO
O
en
CALCIUM ARSENATE
CAPTAFOL
CAPTAN
CARBARYL
CARBOFURAN
CDCC
CHLORAMBEN
CHLORDANE
CHLORPYRIFOS
2,4-0 ACID. ESTERS, SALTS
OALAPON
DBCP
DOT
0.1
0.04250
0.00000
0.6
0.28300
0.00000
13.1
6.22000
0.00001
2.9
1,07000
0.00000
0.2
0.08580
0.00000
0.0
0,00000
0,00000
0,0
0.00000
0.00000
0.0
0,00000
0.00000
0.0
0.00000
0,00000
74.4
0.3*000
0,00011
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
1.4
0.23900
0,00001
9.1
1,73000
0.00005
39.9
7.92000
0,00022
*.s
1.30000
0,00001*
o.s
0,10*00
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
2
2
2
a
2
0.0
0.00000
0.00000
1.1
0.93600
0,00000
24.9
11.80000
0,00002
1.1
0.95600
0.00000
0.0
0,00000
0,00000
13.6
6.43000
0.00001
0.0
0.00000
0.00000
464.9
2.13000
0.00072
0.0
0.00000
0,00000
0.0
0,00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0,00000
0.00000
6,8
1.30000
0.00004
0.0
0,00000
0.00000
2«.9
4.79000
0.00014
1,1
0.21600
0.00001
9.1
1.73000
0,00009
27.2
9.18000
0,00019
0.0
0,00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
(continued)
-------
TABLE 29 (continued) NflS$ QF EHISS10NS (1000 KS/rR,
PCRCENT OF TOTAL INCLUOING METALLURGICAL PROCESSING
SOURCE
PART
S02
NOX
HC
CO
OIAZINON
OIC*«B*
01CHLOROPROPENE
DICHLOROVOS
DICOFOL
DICROTOPH08
OINETHOATC
OINOSEB
DISULFOTON
OIURON
OSMA
ENDOSULFAN
ENDRIN
2.7
1.2*000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.2
0.08900
0.00000
0.9
0.42900
0.00000
0.2
0.06580
0.00000
0.7
0.32200
0.00000
1.3
o.fcisoo
0.00000
2,3
1.07000
0.00000
0.0
0.00000
o.ooooo
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
1116.0
3.11000
0.00172
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000-
0.0
0.00000
0.00000
0.4
0.00199
0.00000
1.7
0.00797
0.00000
929.9
4.25000
0.00144
0.0
0.00000
0.00000
0.0
o.ooooo
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
•0.00000
0.0
2.02000
0.00000
1.3
7.1TOOO
0.00001
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
o.oouoo
0.0
0.00000
0.00000
0.0
0.00000
0.00000
2.7
o.siaoo
0.00001
11. S
2.16000
0.00006
0.4
0.06910
0.00000
i.a
0.3*600
0.00001
0.2
0.03460
0.00000
2.7
o.siaoo
0.00001
1.4
0.2S900
0.00001
0.0
0.00000
0.00000
2.3
0.43200
0.00001
5.2
0.99300
0.00003
1.4
0.25900
0.00001
1,4
0.25900
0.00001
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
o.ooooo
0.00000
2
2
2
2
2
2
2
2
2
2
2
2
2
(continued)
-------
SOURCE
TABLE 29 (continued)
PERCENT OF TOTAL INCLUDING METALLURGICAL PROCESSING
PART soz NOX HC co
EPTC
FENSULFOTHION
FLUOHETURON
FOLPET
HCPTACHLOR
HEXACHLOROBENZENE
LEAD ARSENATE
LINDANE
LINURON
HALATHION
NANEB
HERPHOS
HETALKAMATE (BUX)
1.4
0.64300
0,00000
1.4
0.64300
0.00000
0.0
0.00000
0.00000
0.1
0.04250
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
337.9
2.59000
0.00086
537,9
2.35000
0.00066
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
O.OOOQO
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0,00000
0.00000
0.0
0.00000
0,00000
4.1
0.7T700
0.00002
0.0
0.00000
0.00000
1.1
0.21600
0.00001
1.4
0.25900
0.00001
l.t
0.25900
0.00001
9t4
1. 04000
0.00009
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0,00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
2
2
2
2
2
2
0.0
0.00000
0.00000
0.0
0.00000
0.00000
6.8
9.22000
0.00000
2.7
1.29000
0.00000
0.0
0.00000
0.00000
2.9
1.07000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.01990
0.00001
1116.0
5.11000
0.00172
464.9
2.19000
0.00072
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
3.7
20.20000
0.00002
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.3
0.066*0
0.00000
0.7
0.13000
0.00000
27.2
9.16000
O.OOOlS
8.2
1.55000
0.00004
0.0
0.00000
0.00000
6.6
1.90000
0.00004
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
(continued)
-------
TABLE 29 (continued) nASS Or EMISSIONS 11000 KG/YR)
PERCENT OF TOTAL INCLUDING METALLURGICAL PROCESSING
O
00
SOURCE
METHANE ARSENIC ACID
HCTHOXYCHUOR
METHYL BROMIDE
METHYL PARATHION
MEVJNPHOS
MONOCROTOPHOS
HONURON
MSMA
NABAH
NALCD
PARATHION
PENTACHLOROPHENOL AND SODIUM SALTS
PHORATE
PART
802
NOX
HC
CO
2.3
1.07000
0,00000
0.0
0.00000
0.00000
23.6
11.20000
0.00002
0.2
0.10700
0.00000
1.6
0.79100
0.00000
0,0
0.00000
0.00000
0.0
0.00000
o.ooooo
1.1
0.59600
0.00000
0.5
0.21*00
0.00000
7,7
5.65000
0.00001
6*. 9
30.70000
0,00005
2.3
1.07000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
9671.0
**. 20000
0.01190
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
*6*.»
2.13000
0.00072
0.0
0.00000
0.00000
3162.0
1*. 50000
0.00468
0.0
0.00000
0.00000
929.9
«. 29000
0.001<* "»
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0,00000
0.00000
0.0
0,00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000'
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
2.9
O.*3200
0.00001
7.0
1.34000
o.oooo*
23.6
*.*9000
0.00013
o.e
0.0*320
0.00000
1.6
0.30200
0.00001
0.2
0.03*60
0.00000
18. 1
3. 16000
0.00010
9.*
0.6*800
0.00002
0.5
0.086*0
0.00000
7.8
1.49000
0.0000*
23.6
H. 1*9000
0.00013
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0,00000
0,00000
0.0
0.00000
0.00000
0.0
0,00000
0.00000
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
o.ooooo
0.00000
2
2
2
2
2
2
2
2
2
2
2
2
(continued)
-------
TABLE 29 (continued)
MASS OF EMISSIONS (1000 KG/YR)
PERCENT OF TOTAL INCLUDING rtETALLURGICAL PROCESSING
SOURCE
PART
502
NOX
HC
CO
o
VD
PHOSPHAHIDION
PROPACHLOR
PROPANIL
PROPAZINE
PTRETHINS
RONNCL
SILVEX
SIHAZINE
sooiun TCA
TEPP
TERBACIL
TOXAPHENE
TRICHLOROPHENOLS
0.2
0,06580
0,00000
0.0
0.00000
0,00000
0.0
0,00000
0,00000
0.0
0.00000
0.00000
0.5
0.25700
0.00000
0.5
0. 21*00
0.00000
0.7
0.32200
0.00000
0.0
0,00000
0,00000
0.0
0.00000
0.00000
0.0
0,00858
0.00000
0.0
0.00000
0.00000
0.0
0.00012
0.00000
5.7
2.68000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0,0
0,00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.3
0.00133
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.2
1.34000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0.00-000
0.2
0.03<»60
0.00000
10.2
1.9*000
0.00006
S.H
0.6*800
0.00002
6.6
1.30000
0.00004
0.5
0.10*00
0.00000
1.8
0.3*600
0,00001
1.*
0.25900
0.00001
10.2
1.9*000
0.00006
6.8
1.30000
0.0000*
0.2
0.03*60
0.00000
0.7
0.13000
0.00000
63.9
12.20000
0.00035
11.3
2.16000
0.00006
0.0
0.00000
0.00000
0,0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0,00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
o.ooooo
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
(continued)
-------
TABLE 29 (continued)
MASS OF EMISSIONS (1000 K6/TR)
PERCENT OF TOTAL INCLUDING METALLURGICAL PROCESSING
SOURCE
TRIFLURALIN
VCRNOLATE
ZINEB
TOTALS FOR PESTICIDES
TOTALS FOR ALL U. S. SOURCES
PART
10.9
3.15000
0.00001
1.1
0.93600
0.00000
1.6
0.79100
0.00000
211.9
136200000.0
S02
11.9
0.06640
0.00002
464.9
2.13000
0.00072
690.9
2.96000
0.00101
21860.0
64740000.0
NOX
10,9
99.60000
0.00005
0.0
0.00000
0,00000
0.0
0.00000
0.00000
IS. 2
22360000.0
HC
0.0
0.00000
0.00000
3.4
0.64600
0.00002
4.6
0.90700
0.00003
929.1
16190000.0
CO
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
0.00000
0.00000
0.0
97340000.0
C
2
2
2
-------
SECTION 7
GROWTH AND NATURE OF THE INDUSTRY
GOVERNMENT REGULATION
EPA has assumed federal authority over pesticide regulations,
taking over previous responsibilities belonging to the Depart-
ments of Agriculture (USDA) ; Interior; and Health, Education,
and Welfare. The Office of Pesticide Programs of the EPA has
canceled or suspended some or all uses of certain pesticides,
including many of the chlorinated hydrocarbon insecticides and
mercury-containing fungicides.
Pesticides are presently controlled under the Federal Insecti-
cide, Fungicide, and Rodenticide Act of 1947 (FIFRA) as amended
by the Federal Environmental Pesticide Control Act of 1972
(FEPCA) . FEPCA expanded provisions of the 1947 Act, giving EPA
new authority to classify chemicals for restricted use (only
licensed applicators may apply the pesticide) , to regulate the
use of products in addition to specifying labeling, and to con-
trol products sold in interstate commerce.
In December 1972, acting as the enforcement agency for the Fed-
eral Insecticide, Fungicide and Rodenticide Act of 1947 as
amended in 1972, EPA placed a near-total ban on domestic use of
DDT (11) . The ban resulted partly from the exceptional persist-
ence of DDT. Because it degrades very slowly and is stored in
the fat of living organisms, it tends to build up in the natural
food chain and accumulate in the tissues of fish, wildlife, and
humans. Deciding that the compound is a cancer hazard in humans,
the agency ordered it almost completely off the market. Use of
DDT had already declined greatly, however, due to its ineffec-
tiveness against increasingly resistant insects.
The near-total banning of DDT in the United States has not had
major adverse effects on American agriculture In its largest
uses, on cotton and soybeans, it has been replaced by methyl
e
soybeans is toxaphene. This organochlorine insecticide is often
used in combination with methyl parathion to increase its effec-
tiveness against specific insects and to expand the range of
insects against which the formulation is active (11) .
Ill
-------
For controlling insects on fruit, DDT has been replaced by such
compounds as parathion, malathion, guthion, carbaryl, and phos-
met. For control of insects on vegetables and in home and garden
applications, DDT has been replaced by such compounds as mala-
thion, carbaryl, phosmet, methoxychlor, diazinon, and oxydemeton-
methyl. In controlling forest insects, the leading substitutes
for DDT include carbaryl, trichlorfon, and fenitrothion. For
mosquito control, the chief DDT replacements include malathion,
parathion, methyl parathion, fenthion and dursban (11) . A total
of 24 pesticides have been identified as potential DDT substi-
tutes.
In October 1974, EPA called a halt to formulation and sale of two
organochlorine insecticides, aldrin and dieldrin, for all but a
few uses (11). EPA action was based on findings that laboratory
rats and mice fed dieldrin (a metabolite of aldrin) developed
cancerous liver tumors. Dieldrin has also been found in foods,
such as dairy products, and in human fatty tissue; thus EPA
concluded that aldrin and dieldrin were a cancer threat to humans.
Among available replacements for aldrin and dieldrin in control-
ling insects on corn and other crops are carbaryl, diazinon,
carbofuran, phorate, fensulfothion, fonofos, and chlorpyrifos.
All of these compounds are less persistent than aldrin and diel-
drin (11).
In November 1974, EPA similarly issued a notice of intent to
cancel its registration of two other related organochlorine
insecticides, chlordane and heptachlor, because heptachlor epox-
ide (a metabolite of both insecticides) has been found to cause
cancerous tumors in laboratory rats and mice. Residues of hepta-
chlor epoxide have been found in food, human fatty tissue, and
human milk (11)•
Among the available alternatives to chlordane and heptachlor in
treating corn and other crops are carbofuran, phorate, carbaryl,
diazinon, parathion, methomyl, and disulfoton. These alterna-
tives are not as long-lived in most instances and must be applied
more often (11).
Several uses for the herbicide 2,4,5-T and the fungicides
ethylene dis(dithiocarbamates) (EBDC) have also been restricted.
Similarly, kepone-containing compounds were banned due to their
carcinogenicity. Mirex, which degrades to kepone, was recently
dropped by Allied Chemical and production was left to the State
of Mississippi (5).
EPA has recently initiated a program in cooperation with the
industry to develop more acceptable substitute pesticides. The
29 substitute insecticides shown in Table 30 have been identified
as potential replacements for the five restricted chlorinated
hydrocarbon insecticides shown. In addition, eight herbicides
(bromacil, MSMA/DSMA, cacodylic acid, dinoseb, dicamba, monuron,
112
-------
simazine, and trifluralin) were nominated to replace 2,4,5-T, but
cacodylic acid is currently under a rebuttal presumption against
registration, and monuron has been shown to have carcinogenic
properties. Three fungicides (captan, PCNB, and folpet) are
potential substitutes for EBDC (5).
TABLE 30. PROPOSED SUBSTITUTE INSECTICIDES
(Registrations cancelled)
(5)
Proposed
substitutes
DDT Aldrin Dieldrin Chlordane Heptachlor
Phorate
Demeton
Methyl parathion
Parathion
Malathion
Guthion
Aldicarb
Azodrin
Diazinon
Dimethoate
Fenthion
Met homy 1
Crotoxyphos
Chlorpyrifos
Buxten
Carbonfuran
Counter
Dasanite
Disulfoton
Dyfonate t
Landrin
Trichlorfon
Dacthal
Aspon
Siduron
Ethion
Propoxur
Acephate
Methoxychlor
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X X
X X
X X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
It appears that the EPA will attempt to evaluate both the ben-
efits and the environmental hazards and other risks connected
with pesticide use before granting new registrations or issuing
suspensions or cancellations. For each pesticide under review,
the EPA will examine data regarding the degree of control
achieved and the probable damage that would occur without the use
of the chemical, and will also determine whether safe and effec-
?i^Substitutes are available. Rather than ordering a wide-
spread cancellation of pesticide use, it appears likely that the
113
-------
agency will order reductions in applications of persistent and
hazardous agents without sacrificing essential uses. The degree
of enforcement will largely depend on the availability of econom-
ically feasible alternatives to the chemicals; however, indis-
criminate use of persistent or toxic chemicals will not be
allowed. The EPA will be pressuring the pesticide industry to
develop alternate methods of pest control (20).
ALTERNATIVES TO PESTICIDE CHEMICALS
Due to increasingly stringent regulations, rising costs, and
insect resistance to pesticide chemicals, changes are occurring
in pest control strategies. Emphasis is being placed on effec-
tive or adequate control of pests with minimum environmental
contamination (20).
There have been a variety of new approaches to pest control dur-
ing the last several years. The concept of integrated pest man-
agement dates back to the 1950's and has come to mean the optimum
application of all techniques to realize economical control with
minimum ill effects on nontarget species, the food chain, and the
environment. Integrated pest management techniques, many of
which may grow in importance, are listed in Table 31 (5) .
Behavioral manipulation refers to a technique designed to affect
the communication systems of pests by sending special signals or
altering existing signals. Insects are very sensitive to odors,
and very small quantities of insect attractants can be used to
lure them to traps (21). The attractants, which are usually
food- or sex-based, may be effective for distances up to 1.6 km.
They are usually highly specific, attracting only a few closely
related species, and then often only males. Attractants may be
used either to monitor the presence of a pest or in bait traps,
to which large numbers of males would be drawn and destroyed.
Another promising technique of pest management is the use of
juvenile hormones. Also called insect growth regulators, these
compounds do not kill, but instead interfere with the insect's
normal development. Altosid SR-10, a juvenile hormone recently
approved by the EPA for commercial use, is imbedded in a slow-
release matrix of 1-ym-diameter polymer spheres. The water
suspension has shown low toxicity to nontarget species; it
degrades rapidly, and small volumes are required (5).
Genetic manipulation is another technique of integrated pest
control that is receiving increased attention. It takes two
(20) Connolly, E. M. Pesticides. Stanford Research Institute,
Menlo Park, California, 1973. 24 pp.
(21) Edwards, C. A. Persistent Pesticides in the Environment.
CRC Press, Cleveland, Ohio, 1970. 78 pp.
114
-------
TABLE 31. INTEGRATED PEST MANAGEMENT OPTIONS (5)
Traditional
chemical
manipulation
Behavioral
manipulations
Environmental
manipulations
Genetic
manipulations
Ecology
manipulations
("Herbicides
-------
Living insecticides (bacteria, viruses, fungi, protozoa, and
parasitic nematodes) are also receiving a great deal of attention
as a method of pest control. Baaillus thuringiensis (BA-068), a
strain of spore-forming bacterium, has been mass produced and
tested to suppress a variety of aquatic mosquitoes. Currently,
research and development of viral pesticides (polyhedrosis
viruses) is being conducted, and field tests indicate that their
degree of control is as good as that of chemical pesticides. A
great deal of work remains in developing suitable formulations
for large-scale manufacturing and application.
Opportunities for new pesticide chemicals will, of course, con-
tinue. The average life expectancy of a pesticide is estimated
to be about 10 yr, during which time cheaper, more effective and
safer compounds are developed. Several organic pesticides,
however, are exhibiting life-spans far in excess of 10 yr.
Typical examples are: zineb (1943) ; dinoseb (1945) ; methyl
parathion (1947); captan and parathion (1949) ; maneb and mala-
thion (1950); diazinon (1952); dalapon and guthion (1953);
phorate, diuron, and EPTC (1955); disulfoton, carbaryl, and
simazine (1956); atrazine, chloramben, and paraquat (1958) ; and
fenitrothion (1959) (5).
Many new pesticide chemicals are entering the market. Among the
promising ones are (5):
• Ansar 529 H.C. Ansul was granted an experimental permit in
1975 to test this herbicide aimed at wild oat, green fox-
tail, and mustard weeds in oats.
• Sevin 4 oil carbaryl. Union Carbide obtained registration
in 1976 for this insecticide which protects spruce and fir
foliage against the spruce budworm.
• Galecron. Ciba-Geigy began production of this chemical
(also called chlordimeform) in 1976. It is used against
the budworm, bollworm, and leaf perforator, with insecti-
cide use on a number of fruits indicated.
• Terbufos. Developed early in 1975 by American Cyanamid,
this chemical controls corn rootworm, and EPA approval is
expected for use on seed corn and popcorn.
• Dialifor. Also called Torak®, this product was introduced
in 1973 by Hercules for mite control in citrus orchards.
Registration has since been extended to nut tree insects,
grape leafhoppers, and apple coddling moths.
• NRDC-143 (permethrin). The chemical is a new pyrethroid
tested by FMC that is stable in sunlight for more than
4 days. Success with this product could trigger widespread
interest in pyrethroids.
116
-------
• FMC-25213. The new dioxane preemergence herbicide intro-
duced by FMC controls nutsedge, Johnson grass, and Bermuda
grass.
• Destun®. This product, with a common name of perfluidone
diethanol amine, signals the entry of 3M into the farm
chemicals business. Destun® is used to control nutsedge.
• Elcar. This natural virus insecticide attacks bollworms
and tobacco budworms.
• Glyphosphate. This herbicide, developed by Monsanto and
marketed under the "Roundup®," has received considerable
interest due to its efficacy and unique mode of action as an
inhibitor of the biosynthesis of aromatic amino-acids (22).
Roundup® offers effective postemergent control of many
emerged annual and perennial broadleaves and grasses.
Environmental, economic, and social pressures have led to labor-
atory studies such as synergism, low-volume and ultra-low-volume
application rates, and controlled-release systems such as pest-
icide microencapsulation, promising cheaper and safer products
in the future.
FUTURE PRODUCTION
Chemical pesticides should continue to be significant in pest
management despite changes in pest control strategies. The
primary reason for their continuing use is the inability of
other methods to maintain adequate control. Overall, however,
future developments in chemical pest control may decelerate due
to restrictive conditions dampening the expansion programs of
manufacturers.
Pesticide production beyond the next few years is difficult to
estimate because of diverse changes in government regulation,
the influence of research on new products and on application
rates of products, and a variety of economic factors. The U.S.
pesticide market will largely depend on world agriculture and
population. Presently, agriculture takes 59% of domestic pesti-
cide production to keep pest population below the level at which
crop damage costs exceed control costs (5).
(22) Bronstad, J. O. , and H. O. Friestad. Method for Determin-
ation of Glyphosphate Residues in Natural Waters Based on
Polarography of the tf-Nitroso Derivative. Analyst, 101:
820-824, October 1976.
117
-------
Future agricultural markets are likely to consist of fewer but
larger farms, technically and commercially more sophisticated
farmers, and increasing specialization in application of know-
ledge. . Integration of farm, industrial, and technical-service
labor is likely. There will be shifts in types of major crops
and growing areas, and controlled environments for food produc-
tion may become a factor (20).
The growth of chemical pesticides in the United States is not
likely to continue the fast pace of the 1960's for several
reasons. Growth in the use of herbicides, which are primarily
responsible for the expansion of the pesticide market in recent
years, should be slowing. In addition, many pesticide applica-
tions are nearing the practical saturation level. Moreover,
concern about environmental pollution and hazards, resulting in
stricter regulations and higher costs, should lead to less use
of chemicals as well as more efficient application techniques.
These influences will limit the growth in production of pesti-
cides, primarily insecticides.
Factors that would tend to expand the pesticide market include:
less persistent pesticides will have to be applied more often;
in case of a drought or increased food demand, additional crop
acreage may be needed; rapid infestation in any 1 yr will
increase pesticide need; and some applications have not yet
reached a saturation level (20).
Figure 29 shows the estimated growth of synthetic organic pesti-
cides to 1985 based on an annual average growth rate of 1% for
the total (20). Insecticide production in 1985 should remain at
approximately the current level. Herbicide use will not resume
the dramatic increases of the 1960's but should rise about 2%
annually to 1985. The fungicide market should grow at a compara-
tively slow rate, approximately 1.8% annually, for the following
reasons. Annual fungicide consumption varies much more than
that of other types of pesticides because of the greater varia-
tions in pathogenic activity, making producers less inclined to
undertake costly R&D to meet complex registration requirements.
In addition, several relatively inexpensive, established pro-
ducts are still effective, and current markets are fairly well
saturated (20).
118
-------
100
c
o
10
TOTAL
HERBICI_DES_
INSECTICIDES
8.06 xlO5
4_3_x_105_
3.02x105
FUNGICIDES
8.43 xlO4
1
1975 1976 1977 1978 1979
_L
_L
_L
1980 1981
YEAR
J_
1982 1983 1984 1985
Figure 29.
U.S. estimated average annual growth
of synthetic organic pesticides (20)
119
-------
REFERENCES
1. Pesticides and Pesticide Containers. Federal Register,
39(85):15236, 1974.
2. Kelso, G. L., R. R. Wilkinson, and T. L. Ferguson. The
Pollution Potential in Pesticide Manufacturing—1976 (Draft
Final Report). Contract 68-02-1324, Task 43, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, April 16, 1976. 236 pp.
3. Ouellette, R. P., and J. A. King. Chemical Week Pesticides
Register. McGraw-Hill Book Company, New York, New York,
1977. 346 pp.
4. 1976 Farm Chemicals Handbook. Meister Publishing Co.,
Willoughby, Ohio, 1976. 577 pp.
5. Ouellette, R. P., and J. A. King. Pesticides '76. Chemical
Week, 118(25) :24-38, 1976.
6. Patterson, J. W. State-of-the-Art for the Inorganic
Chemicals Industry: Inorganic Pesticides. EPA-600/2-74-
009a, U.S. Environmental Protection Agency, Washington,
D.C., March 1975. 39 pp.
7. Parsons, T. B. (ed.), and F. I. Honea. Industrial Process
Profiles for Environmental Use: Chapter 8, Pesticides In-
dustry. EPA-600/2-77-023h (PB 266 225), U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
January 1977. 240 pp.
8. Air Pollution Engineering Manual, Second Edition.
J. A. Danielson, ed. Publication No. AP-40, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, May 1973. 987 pp.
9. Sittig, M. Agricultural Chemicals Manufacture - 1971.
Noyes Data Corporation, Park Ridge, New Jersey, 1971.
264 pp.
10. Pesticide Programs: Data Requirements to Support Registra-
tion of Pesticide Active Ingredients and Preliminary
Schedule for Call-ins. Federal Register, 41(32):7218-7376,
1976.
120
-------
11. Sanders, H. J. New Weapons Against Insects. Chemical and
Engineering News, 53(30):18-31, 1975.
12. Lawless, E. W. , R. von Riimker, and T. L. Ferguson. Pesti-
cide Study Series - 5: The Pollution Potential in Pesticide
Manufacturing (PB 213 782). U.S. Environmental Protection
Agency, Cincinnati, Ohio, June 1972. 249 pp.
13. Ifeadi, C. N. Screening Study to Development Background
Information and Determine the Significance of Air Contami-
nant Emissions form Pesticide Plants. EPA-540/9-75026
(PB 244 734), U.S. Environmental Protection Agency,
Washington, D.C., March 1975. 85 pp.
14. Meiners, A. F. , C. E. Mumma, T. L. Ferguson, and G. L.
Kelso. Wastewater Treatment Technology Documentation for
Toxaphene Manufacture. EPA-440/9-76-013, U.S. Environmental
Protection Agency, Washington, D.C., February 1976. 123 pp.
15. von Riimker, R. , E. W. Lawless, and A. F. Meiners. Produc-
tion, Distribution, Use and Environmental Impact Potential
of Selected Pesticides (PB 238 795). Council on Environ-
mental Quality, Washington, D.C., March 1974. 439 pp.
16. Substitute Chemical Program: Initial Scientific and Mini-
economic Review of Captan. EPA-540/1-75-012, U.S. Environ-
mental Protection Agency, Washington, D.C., April 1975.
173 pp.
17. Substitute Chemical Program: Initial Scientific and
Minieconomic Review of Bromacil. EPA-540/1-75-006, U.S.
Environmental Protection Agency, Washington, D.C.,
March 1975. 79 pp.
18. Eimutis, E. C. Source Assessment: Prioritization of
Stationary Air Pollution Sources—Model Description.
EPA-600/2-76-032a, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, February 1976.
77 pp.
19. TLVs® Threshold Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with Intended
Changes for 1975. American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, 1975. 97 pp.
20. Connolly, E. M. Pesticides. Stanford Research Institute,
Menlo Park, California, 1973. 24 pp.
21. Edwards, C. A. Persistent Pesticides in the Environment.
CRC Press, Cleveland, Ohio, 1970. 78 pp.
121
-------
22. Bronstad, J. O., and H. O. Friestad. Method for Determin-
ation of Glyphosphate Residues in Natural Waters Based on
Polarography of the tf-Nitroso Derivative. Analyst, 101:
820-824, October 1976.
23. Glotfelty, D. E., and J. H. Caro. Introduction, Transport,
and Fate of Persistent Pesticides in the Atmosphere. In:
Removal of Trace Contaminants from the Air, V. R. Deitz, ed.
American Chemical Society, Washington, D.C., 1975. 207 pp.
24. Mackay, D., and A. W. Wolkoff. Rate of Evaporation of Low-
Solubility Contaminants from Water Bodies to Atmosphere.
Environmental Science and Technology, 7(7):611-614, 1973.
25. Kenaga, E. E. Pesticide Reference Standards of the Entomo-
logical Society of America. Bulletin of the Entomological
Society of America, 12:117-127, 1966.
26. Paris, D. F., and D. L. Lewis. Chemical and Microbial
Degradation of Ten Selected Pesticides in Aquatic Systems.
Residue Reviews, 45:95-124, 1973.
27. Substitute Chemical Program: Initial Scientific and Mini-
economic Review of Methyl Parathion. EPA-540/1-75-004,
U.S. Environmental Protection Agency, Washington, D.C.,
February 1975. 176 pp.
28. Srinath, E. G., and R. C. Loehr. Ammonia Desorption by
Diffused Aeration. Journal of the Water Pollution Control
Federation, 46 (8) :1939-1957, 1974.
29. Standard for Metric Practice. ANSI/ASTM Designation
E 380-766, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
122
-------
APPENDIX A
PREDICTION OF PESTICIDE AND AMMONIA EMISSIONS^ FROM
HOLDING PONDS AND EVAPORATION LAGOONS
INTRODUCTION
Following chemical treatment, liquid wastes from pesticide manu-
facturing often go to a holding pond or evaporation lagoon where
evaporation of undestroyed hazardous material can occur, result-
ing in emission to the atmosphere. Data regarding pesticide
emissions from ponds and lagoons are virtually nonexistent;
equations were therefore utilized to develop emission factors for
these sources for use in the prioritization of pesticide chemical
source types. This appendix presents background information,
equations, and calculations used to develop emission factors for
both pesticides and ammonia from holding ponds and evaporation
lagoons. The next section of this appendix deals with pesticide
emissions, and the following section deals with ammonia
desorption.
PESTICIDE EMISSIONS FROM HOLDING PONDS AND LAGOONS
Background
Evaporation of a pesticide from the surface of a holding pond
or evaporation lagoon depends upon the vapor pressure of the
compound, its solubility in water, and the amount of Pesticide
truly in solution. The characteristic low solubility of Pesti-
cides in water yields only very dilute ideal solutions for which
Henry's Law is obeyed. Henry's Law specifies that the vapor
pressure over the solution is proportional to both the vapor
^rSssure of the pure compound and the relative saturation of
the solution (23). Evaporation rates of pesticides from water,
however, can be very high (24).
'(23) Glotfelty, D. E. , and J. H. Caro. Introduction, Transport,
and Fate of Persistent Pesticides in the Atmosphers. In:
Removal of Trace Contaminants from the Air, V R Deitz ed.
American Chemical Society, Washington, D.C., 1975. 20/ pp.
Mackav D , and A. W. Wolkoff. Rate of Evaporation of Low-
facility 'contaminants from Water Bodies to At»aophere
Environmental Science and Technology, 7 (9):611-614, 1973.
123
-------
Pesticides are generally of high molecular weight and low vapor
pressure, so it would appear that the evaporation rate would be
slow. A factor that is often overlooked is the remarkably high
activity coefficients of these compounds in water, which cause
unexpectedly high equilibrium vapor partial pressures and, thus,
high evaporation rates (24).
Equations
The approach taken in Reference 24 to predict evaporation rates
from natural waters is to calculate, from equilibrium thermo-
dynamic considerations, the composition of vapor in equilibrium
with the water solution. The following assumptions were made:
• The contaminant concentration is that truly in solution,
not in suspended, colloidal, ionic, complexed, or absorbed
form.
• The vapor formed is in equilibrium with the liquid at the
interface. This is generally accepted as applying to phase
change mass transfer processes such as distillation.
• The water mixing or the pesticide diffusion in water is
sufficiently fast that the concentration at the interface
is close to that of the bulk of the water. The validity
of this assumption depends on the relative rates of evapor-
ation and diffusion or mixing. The slower of these two
will tend to control the overall rate.
• The water evaporation rate is negligibly affected by the
presence of the contaminant. This assumption is valid for
low concentrations of nonsurface-active compounds.
The validity of these assumptions can be confirmed only by ex-
perimental data, few of which are available. The evaporation
equations should represent the physical processes involved with
reasonable accuracy for prioritization.
The equations presented in Reference 24 were modified slightly
by incorporating a surface area factor in order to provide a
total emission rate from the surface of a pond or lagoon. Two
cases are considered: first, evaporation occurs from a satu-
rated solution of pesticide "i" containing excess i as a
separate phase.
Cio - Ci = EPisMitAl°6/(GMwPw) (A-l)
where CiQ = initial concentration of pesticide "i", g/m3
C^ = concentration of "i" at time t, g/m3
E = water evaporation rate, g/m2-day
124
-------
P^s = vapor pressure of pure solid or liquid "i", Pa
M. = molecular weight of "i", g/mole
t = time, days
A - surface area, m2
106 = conversion factor, molar to g/m3
G = weight of water body, g
M = molecular weight of water, g/mole
P = vapor pressure of water, Pa
In the second case, evaporation takes place from a solution in
which "i" is present at a concentration less than saturation:
ln(C. - C.) = EP. M.tA106/(GM P C. ) (A-2)
10 i is i ' w w is
where C. = saturation concentration of i, g/m3
Equation A-2 may be modified to the following form:
(C. - C.) = C. (l ( (A-3)
I exp[(EP. M.tA106)/(GM P C. )]|
I r~l* 1 Q 1 i / \ LJ W "I CS 7
\ JL O •*- W W J- tJ s
In summary, if "i" is present in water at a concentration above
its saturation value and the solution remains saturated, the
change in concentration due to evaporation will be described by
Equation A-l until its concentration equals the saturation value.
The change in concentration will then be described by Equation A-3,
Equations A-l and A-3 give the change in pesticide concentration
due to evaporation from saturated and undersaturated solutions,
respectively. The evaporation rate, dm^/dt is determined by
substituting (C. - C^) into the following equation:
dm. f(C . - C . )~|
_i . [ 1° t Jv (A-4)
where dm./dt = pesticide evaporation rate, g/day
1 (when t = 1 day)
t = time, days (1 day)
V = volume of water body, m3
Simplifying gives Equation A-5 and Equation A-6, which predict
the evaporation rate of pesticide "i" in g/day from a saturated
solution and from a solution in which "i" is present at a con-
centration less than saturation, respectively. Thus, the evapora-
tion rate of pesticide "i" from a saturated solution, in g/day,
is predicted as follows:
125
-------
ditu E
dtT =
w w
Similarly, the evaporation rate of pesticide "i", in g/day, from
a solution in which "i" is present at a concentration less than
saturation is predicted as follows:
dm. VC.
a. VC. r
i _ 10
dt ~ t
exp(EP. M.tA106/GM PC.)
is i ' w w is
Several assumptions were made in order to use Equations A-5 and
A-6 in the prioritization. First, the ambient temperature was
chosen to be 25°C, yielding a water vapor pressure (Pw) equal to
approximately 3.2 x 103 Pa and the physical properties of the
five pesticides listed in Table A-l (24-27). The evaporation
rate of water was chosen as 2,740 g/m2-day, corresponding to a
water evaporation rate of approximately 1,000 mm/yr. Time was
assumed to be 1 day, giving an emission rate in g/day.
TABLE A-l. PESTICIDE PHYSICAL PROPERTIES AT 25°C
Molecular weight, Vapor pressure,
Pesticide g/mole Pa
Aldrin
DDT
Dieldrin
Methyl parathion
Toxaphene
364.
306.
381.
263.
413.
9
5
0
2
8
(25)
(25)
(25)
(27)
(25)
8.
1.
1.
1.
1.
0
3
3
3
3
x 10"*
x 10"5
x 10"5
X 10 1
x 10"!
(24)
(24)
(24)
(27)
Solubility,
g/m3
2
3.7
2.5
4
x
x
X
60
x
lo-1
ID'1
10-1
10-1
(26)
(26)
(26)
(27)
(26)
a
Vapor pressure at 20°C.
b
Actual vapor pressure ranges from 27 Pa to 53 Pa at 25°C, but a
ceiling value of 1.3 x 10"1 Pa was imposed. The ceiling value was
determined by plotting predicted emission rates versus vapor pressure
for several vapor pressures. The results showed an exponential
increase above a vapor pressure of 1.3 x 10"1.
(25) Kenaga, E. E. Pesticide Reference Standards of the Entomo-
logical Society of America. Bulletin of the Entomological
Society of America, 12:117-127, 1966.
(26) Paris, D. F., and D. L. Lewis. Chemical and Microbial
Degradation of Ten Selected Pesticides in Aquatic Systems.
Residue Reviews, 45:95-124, 1973.
(27) Substitute Chemical Program: Initial Scientific and Mini-
economic Review of Methyl Parathion. EPA-540/1-75-004,
U.S. Environmental Protection Agency, Washington, D.C.,
February 1975. 176 pp.
126
-------
Calculations
Dieldrin —
Assume .evaporation takes place from a 4.05 x 10 5 m2 concrete-
lined evaporation lagoon, 1 m deep, with a dieldrin concentration
equal to 5 g/m3 . The lagoon dimensions give the following
parameters:
A = 4.05 x 105 m2
V = 3.70 x 105 m3
G = 3.70 x 1011 g
The dieldrin concentration is above saturation, thus Equation
A-5 is used as follows:
dm. EP. M.AV106
i _ is i , _.
_ _
dt GM P
w w
where dm./dt = evaporation rate of dieldrin, g/day
E = 2,740 g/m2-day
P. = 1.3 x 10~5 Pa
is
M. = 381. 0 g/mole
A = 4.05 x 105 m2
V = 3.70 x 105 m3
106 = conversion factor, g/m3
G = 3.70 x 101 1 g
M = 18 g/mole
w
P = 3.2 x 103 Pa
w
Thus, dmi/dt = 95.4 g/day =34.8 kg/yr.
Assuming dieldrin production to be equal to 340 metric tons/yr,
the emission factor for dieldrin evaporation is calculated as
follows:
34.8 kg/yr = x 1Q-l kg/metric ton
340 metric tons/yr
Aldrin—
Assume evaporation takes place from a 4.05 x 10= mz concrete-
lined evaporation lagoon, 1 m deep, with an aldrin concentration
equal to 5 g/m3. The lagoon dimensions give the following
parameters:
A = 4.05 x 105 m2
V = 3.70 x 105 m3
G = 3.70 x 1011 g
127
-------
The aldrin concentration is above saturation, thus Equation A-5
is used as follows:
dm. EP. M.AV106
i _ is i
dt ~ GM P (A~5>
w w
where dm^/dt = evaporation rate of aldrin, g/day
E = 2,740 g/m2-day
P. = 8.0 x 10~4 Pa
is
M. = 364.9 g/mole
A = 4.05 x 105 m2
V = 3.70 x 105 m3
106 = conversion factor, g/m3
G = 3.70 x 1011 g
MW = 18 g/mole
PW = 3.2 x 103 Pa
Thus
, dnu/dt = 5.6 x 103 g/day = 2.05 x 103 kg/yr.
Annual production of aldrin is estimated as 4.5 x 10 3 metric
tons (2) , giving an aldrin emission factor equal to
4.6 x 10"1 kg/metric ton.
DDT —
Assume evaporation takes place from a holding-recycle pond with
a surface area equal to 348 m2 , depth equal to 4.6 m, and a DDT
concentration of 10 g/m3 to 15 g/in3 . The pond dimensions give
the following parameters :
A = 348 m2
V = 1,590 m3
G = 1.59 x 109 g
The DDT concentration is above saturation, thus Equation A-5 is
used as follows:
dm. EP. M.AV106
is i ,x
_ .
dt GM P
w w
where dm./dt = evaporation rate of aldrin, g/day
E = 2,740 g/m2-day
P. = 1. 3 x 10~5 Pa
is
MA = 306.5 g/mole
A = 348 m2
128
-------
V = 1,590 m3
106 = conversion factor, g/m3
G = 1.59 x 109 g
M = 18 g/mole
VV
P., = 3.2 x 10 3 Pa
W
Thus, dnu/dt = 6.6 x 10~2 g/day = 2.4 x 10~2 kg/yr.
Annual DDT production is estimated to be 27.2 x 10 3 metric tons
(2), giving a DDT emission factor equal to 8.8 x 10~7 kg/metric
ton.
Toxaphene —
Assume evaporation takes place from two settling ponds (each
with dimensions 61 m x 122 m x 1 m deep) at a concentration
above saturation. The ponds' dimensions give the following
parameters :
A = 1.49 x 104 m2
V = 1. 36 x 104 m3
G = 1.36 x 1011 g
The toxaphene concentration is above saturation, thus Equation
A- 5 is used as follows:
dm. EP. M.AV106
i is i .
_ _
dt GM P
w w
where dm./dt = evaporation rate of toxaphene, g/day
E = 2,740 g/m2 -day
P. = 1.3 x 10"1 (from Table A-l)
U_ o
M. = 413.8 g/mole
A = 1.49 x 101* m2
V = 1.36 x 104 m3
106 = conversion factor, g/m3
G = 1.36 x 1010 g
M =18 g/mole
w ^
P = 3.2 x 103 Pa
w
Thus, dm./dt = 3.8 x I0k g/day = 1.4 x 104 kg/yr.
Annual toxaphene production is estimated to be 49.9 x 10 3
metric tons/yr (2) , giving a toxaphene emission factor equal to
2.8 x 10"1 kg/metric ton.
129
-------
Methyl parathion—
Assume evaporation takes place from a holding pond (22.9 m x
15.2 m x 4.6 m deep) and methyl parathion is in solution at a
concentration of 5 g/m3. The pond geometry gives the following
parameters:
A = 348 m2
V = 1.6 x 103 m3
G = 1.6 x 109 g
Methyl parathion is in solution at a concentration below its
saturation value of 60 g/m3, thus use Equation A-6 as follows:
— OVT-. f TTD M +-A in 6 /r?M r> r- T I (A—6)
dm.
dt t I" exp(EP. M.tA10&/GM PC.)
1 c is i ' w w is
i
J
where dn^/dt = evaporation rate of methyl parathion, g/day
V = 1.6 x 103 m3
CiQ = 5 g/m3
E = 2,740 g/m2 -day
P. = 1.3 x 10~3 Pa
X S
M.j^ = 263.2 g/mole
t = 1 day
A = 348 m2 (
106 = conversion factor, g/m3
G = 1.6 x 109 g
M =18 g/mole
w ^'
P = 3.2 x 103 Pa
w
Cis = 60 g/m
Thus, dnu/dt = 4.7 x 10~2 g/day = 1.7 x 10-1 kg/yr.
Methyl parathion annual production is estimated to be 23.1 x 10 3
metric tons (2), and the emission factor for evaporation is
calculated as follows:
= 7.4 x 10-6 kg/metric ton
y/
o. T-. /
23.1 x 10 3 metric tons/yr
AMMONIA EMISSIONS FROM HOLDING PONDS AND LAGOONS
Equation
Ammonia emission to the atmosphere can occur from aerated waste-
water treatment systems as well as from holding ponds and evapora-
tion lagoons. The following equation has been presented in the
130
-------
literature to predict the change in ammonia concentration due to
desorption from a continuous flow system (28):
• Fr ' *HH
where Cj = total ammoniacal nitrogen at time tj , g/m3
C2 = total ammoniacal nitrogen at time t2 , g/m3
KD = operational desorption coefficient, hr"1
Fr = ratio of undissociated ammonia to the total
ammoniacal nitrogen in solution
tHR = hydraulic retention time, hr
The change in ammonia concentration, determined by Equation A-7,
is subsequently multiplied by the volume of water in the treat-
ment unit and the number of hydraulic retention times per day to
give the ammonia desorption rate in g/day.
The operational desorption coefficient (KD) and the ratio of
undissociated ammonia to the total ammoniacal nitrogen in solu-
tion (Fr) must be calculated for use in Equation A-7.
Determination of Kp —
Determined by direct experimentation or semiempirical relation-
ships, KD is a system-dependent desorption coefficient and a
function of both environmental and process conditions. Equation
A-8 is used to calculate KD for quiescent systems.
KD = 0.021 exptO. 062(8-5) ] (A-8)
where 6 = temperature, °C
Determination of Fr~~
The ratio of undissociated ammonia nitrogen, which can be removed
by desorption, to total ammoniacal nitrogen is represented by Fr.
Assuming that total ammoniacal nitrogen may be approximated by
total Kjeldahl nitrogen (TKN) , the following relationship is
developed for Fr :
~ NH3N _ undissociated ammonia nitrogen
Fr ~ TKN ~ total Kjeldahl nitrogen
As shown in Figure A-l, Fr varies with temperature and pH (27).
Little or no desorption occurs below a pH of about 7.
(28) Srinath, E. G, and R. C. Loehr. Ammonia Desorption by
Diffused Aeration. Journal of the Water Pollution Control
Federation, 46 (8):1939-1957, 1974.
131
-------
0.2 -
Figure A-l. Effect of pH and temperature on fraction
of undissociated ammonia (28).
Values of Fr for specific values of pK and temperature are pre-
sented in Table A-2 (28)-
TABLE A-2. VALUES OF F AT DIFFERENT pH AND TEMPERATURES (28)
Temp . ,
°C
10
15
20
25
30
35
7
0.
0.
0.
0.
0.
0.
.0
002
003
004
005
008
014
7.5
0.006
0.009
0.012
0.017
0.025
0.043
8.0
0.020
0.028
0.037
0.052
0.076
0.125
8.5
0.061
0.082
0.110
0.148
0.207
0.312
PH
9.0
0.170
0.221
0.280
0.354
0.452
0.589
9.5
0.393
0.473
0.552
0.634
0.723
0.819
10.0
0.672
0.739
0.796
0.846
0.892
0.935
0
0
0
0
0
0
10.5
.866
.900
.925
.945
.963
.978
11.0
0.953
0.966
0.975
0.982
0.998
0.993
Calculation
For methyl parathion, assume ammonia desorption occurs from a
holding pond (22.9 m x ,15.2 m x 4.6 m deep) with a hydraulic
retention time equal to 24 hr. Assuming a pH of 10 and a
temperature of 25°C, Fr equals 0.846 from Table A-2. From
Equation A-8, K equals 0.073 hr"1 at a temperature of 25°C.
The change in ammonia concentration is calculated by Equation
A-7:
cl ~ C2 =
C2
• F • t
D r HR
(A-7)
132
-------
Assuming that Cx (the total ammoniacal nitrogen at time ti) may
be approximated by TKN and assuming TKN for the untreated waste-
water is 3.0 g/m3, Equation A-7 may be solved for C2-
3.0 g/m3 - C2 = (0>073 hr'1) (0.846) (24 hr)
C-2
.*. C2 = 1-2 g/m3
The change in ammonia concentration (Cj - C2) multiplied by the
volume of the treatment unit and number of hydraulic retention
times per day gives the ammonia emission rate in g/day. From
the pond geometry, the volume equals 1.6 x 103 m3, thus the
ammonia emission rate (dmA/dt) is calculated as follows:
dm
-^ = (3.0 g/m3 - 1.2 g/m3) (1.6 x 103 m3) (I/day)
dm
^^ = 2.88 x 103 g/day = 1.1 x 103 kg/yr
Methyl parathion annual production is estimated to be
23.1 x 103 metric tons (2), and the resulting emission factor
due to ammonia desorption becomes 4.76 x 10~* kg/metric ton.
133
-------
APPENDIX B
EMISSION FACTORS USED IN PRIORITIZATION
This appendix presents the emission factors, emission species,
and subjective data quality used to prioritize 80 major pesti-
cides. Emission factors, as kg pollutant/metric ton pesticide,
are listed in tablular form in Table B-l.
TABLE B-l. EMISSION FACTORS USED IN PRIORITIZATION
Source type *«ttcul4t«
A Itch 1 ox
Aldicarb
Atracine
JUioophoe -ethyl
At inophoe -M thy 1
tVtftfilU* tk*ri*gi***ii 0.5
B***fta 0,9*
- Carbon
BOx »0x Hydrocarbon nonoxide Other
205
0.16 0.13
0.16 0.11
1,28 0.96
1.5
1.5
1.5
0.75
0.75
0.5 Aldricarb
O.S Ethion
O.S Guthion
3.2 Hydrogen chloride
0.32 Hydrogen fluoride
Quality
D
Butachlor
•utylate
Calcium acid
aatt haneazaonate
Calcium areenate
Captafol
C«rb.ryl
Carbofuran
COEC
Chlord«o.
Chlorpyr i f o«
1,4-D acid, ulu,
•>tur>
piaiinon
Dicufc.
pichloropropM*
Dlchloro
Dlcofot
Oicrob
DlMthoat*
0.27
0.56
Dinlfotoo
Diiiron
•ote.—«lank> indicate no
, ettiMtee IMT* "*de.
1.5
1.5
1.5
1.5
1.5
1.0
1.0
1.0
0.5
1.5
1.0
0.5
1.0 Hydrogen broaida
0.5 Bronina
0.5 Butylate
3 x 10'* Arsenic trioxide
0.05 Methyl chloride
0.05 Methyl ketone
0.05 Methanol
3 x 10"B Artenic trioxide
3 x 10"* Arsenic trioxide
0.066 Captafol
1.0 Butadiene
0.5 Carbon diaulfide
0.066 Captan
1.0 Butadiene
0.5 Carbon diaulfide
0.5 Csrbaryl
1.0 Bydrogen chloride
0.5 Chlorine
0.5 Hydrogen chloride
0.5 Dursban
1.0 2,4-Dichlorophenol
1.0 Chloroacatic acid
1.5 AMBonia
0.5 Hydrogen chloride
O.S Propiooic acid
0.5 Dalapon
O.S Hydrogen chloride
0.5 DDT
0.5 Chlorobenxene
0.5 Chloral
8.8 x 10"' DOT (evaporation)
0.5 Diaxinon
0.5 Hydrogen chloride
0.5 Hydrogen chloride
0.5 Dichlorovoe
0.5 Dicofol
0.5 Chlorob*n>en*
0.5 Chloral
O.S Oicrotophoe
0-5
0-5
Toluene
DiJMthoe.te
0.5 Diculfoton
D
D
D
D
C
C
D
D
(continued)
134
-------
TABLE B-l (continued)
Source type
DM*
Endoaulfan
Endrin
EPTC
Fenaulfothion
FluaMturon
rolpet
Heptachlor
Hexachlorobenztfna
Lead areeoate
Lindane
Linuron
Halathion
Maneb
Marphoa
Ketelkanate
id
MethyoxycMor
Methyl bromide
Methyl parathion
Mevinphoe
Monocrotophoa
Monuron
MSMA
Nabea
Haled
Parathion
Pentachlorophenol and
aodiua aelta
Phorate
Pboaphanidion
Propachlor
Propanil
Propaxine
Pyrethina
tonnel
Silvex
Siawcine
SodiuB TCA
TB»P
Terbacil
Toxaphene
Trichloropnenole
Trifluralin
Vernolate
material
Particulate SO. NO. Hydrocarbon
1.0
1.0
1.0
205 l.S
205
O.S
1.0
1.0
1.0
0.5
0.32 0.27 1.5
205 1.5
205
1.S
410
0.5
0.5
0.5
1. 0
205 l.S
0.5
410
205
0.5
0.5
0.5
1.5
0.5 0.5
0.32 0.27 1.5
l.S
1.0
0. 5
0.5
0.96 1.28 0.96
205 1.5
205 1-3
emitted. k«/mtric ton
Carbon
monoxide Other
3 x 10"B Araenic trioxide
0.05 Methyl chloride
0-05 Methyl ketone
0.05 Methanol
0.5 Hydrogen chloride
0.5 Hydrogen chloride
0.5 EPTC
0.5 Feniulfothion
0.5 Fluorine
0.066 Folpet
1.0 Butadiene
0.5 Carbon disulfidc
0.5 Hydrogen chloride
0.5 Hydrogen chloride
3 x 10~8 Araenic trioxide
0.5 Hydrogen chloride
0.5 Chlorine
0.5 Toluene
0.5 Halathion
0.5 Maneb
O.S Metalkamate
3 x 10~8 Arsenic trioxide
0,5 Methoxychior
0.5 An i sole
1.0 Hydrogen bromide
O.S Bromine
0.5 Methyl bromide
1.0 Methyl parathion
1.0 Methyl alcohol
4.76 x 10~2 Anmonia
(evaporation)
7.4 x 10-i Methyl parathion
(evaporation)
0.5 Mevinpho
0 . 5 Monocrotophoa
0.5 Chlorine
3 x 10~8 Arsenic trioxide
0.05 Methyl chloride
0.05 Methyl ketone
0.05 Methanol
0.5 Mabam
0.5 Naled
0.5 Bromine
1.0 Parathion
1.0 Ethyl alcohol
0.68 Ammonia (evaporation)
1.4 x 10~! Parathion
(evaporation)
0.55 Pentachlorophenol
2.2 Sodium pentachlorophenol
1.0 Phenol
1.0 Hydrogen chloride
0.5 Chlorine
0.5 P ho rate
0.5 Phosphamldion
0.5 Toluene
0 . 5 Ronnel
1,0 Phenol
0.5 Trichlorophenol
1.0 Hydrogen chloride
0.5 Hydrogen chloride
0.05 TEPP
1.0 Hydrogen chloride
0.5 Chlorine
2.65 Hydrogen chloride
0.05 Chlorine
1.0 a-Pinene
5 x 10~e Toxaphene
0.28 Toxaphene (evaporation)
1,0 Phenol
0.5 Trichlorophenol
1.0 Hydrogen chloride
3.2 Hydrogen chloride
0.32 Hydrogen fluoride
0.5 Vernolate
0.5 Zineb
Data
quality
B
0
D
D
D
D
C
D
D
D
D
D
C
D
D
D
D
D
D
B
D
D
0
B
D
D
B
B
D
D
D
D
D
0
D
D
D
D
C
C
B
D
D
Mot..—Blanka indicate no emiaaion a.tiutea were Bade.
135
-------
GLOSSARY
active ingredient: Substance contained in a preparation which
will by itself act in the same manner and for the same
purposes as the directions provide for the preparation as
a whole.
attractant: Substance which lures insects from distances to
traps or poison bait stations. The most successful lures,
when available, are the specific secretions of a particular
insect species or their synthetic chemical equivalent
(pheromone).
biological control: Parasitic and predaceous insects and insect
disease organisms which are reared and disseminated
artifically. Biological control includes the use of
insects to control certain weeds as well as the use of any
other living organism in fighting pests.
cholinesterase: Body enzyme necessary for proper nerve function
that is destroyed or damaged by organophosphates or
carbamates taken into the body by any path of entry.
encapsulated pesticides: Pesticides enclosed in tiny capsules
that control release of the chemical and extend the period
of diffusion, thus providing increased safety to appli-
cators as well as the environment.
formulation: Pesticidal substances commercially mixed with
other ingredients, such as carriers, diluents, solvents,
wetting agents, emulsifiers, etc., because the chemicals
are usually too concentrated and immiscible with water to
be prepared directly for use by the purchaser.
juvenile hormone: Hormone produced by an insect in the process
of its immature development which maintains its nymphal or
larval form. Synthetic hormones or similar synthetic
chemicals act as insecticides to control insects by
preventing their maturity.
preemergence herbicide: Herbicide applied after planting the
crop, but before the crop emerges above ground, in order to
kill weed seedlings that appear ahead of the crop.
136
-------
pyrethroids: Synthetic pyrethrin-like compounds produced in an
attempt to duplicate the natural insecticidal activity
derived from pyrethrum flowers.
systemic pesticide: Pesticide that is translocated to parts of
a plant or animal other than those to which the material is
applied.
137
-------
CONVERSION FACTORS AND METRIC PREFIXES (29)
To convert from
Degree Celsius (°C)
Gram/kilogram (g/kg)
Kilogram (kg)
Kilogram (kg)
Kilometer (km)
Kilometer2 (km2)
Meter (m)
(m2)
(m3)
Meter'
Meter;
Metric ton
Pascal (Pa)
CONVERSION FACTORS
To
Multiply by
Degree Fahrenheit
Pound/ton
Pound-mass (avoirdupois)
Ton (short, 2,000 Ib mass)
Mile
Acre
Foot
Foot2
Foot3
Pound
Inches of Hg (60°F)
= 1.8 t° + 32
1.999
2.205
1.102 x 10~3
1.609
2.470 x 102
3.281
1.076 x 101
3.531 x 101
2.205 x 103
2.961 x 10-4
Prefix Symbol
Kilo
Milli
Micro
k
m
METRIC PREFIXES
Multiplication factor
103
io-3
10'6
Example
Ikg=lxl03 grams
1 mm = 1 x 10~3 meter
1 m = 1 x 10~6 meter
(29) Standard for Metric Practice. ANSI/ASTM Designation
E 380-76£, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
138
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-600/2-78-004d
2.
3. RECIPIENT'S ACCESSION-NO.
TITLE AND SUBT.TLE SOURCE ASSESSMENT: Pesticide
Manufacturing Air Emissions—Overview and
Prioritization
5. REPORT DATE
March 1978
6. PERFORMING ORGANIZATION CODE
. AUTHORlSI
!.R. Archer, W.R. McCurley, and G.D.Rawlings
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-766
PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM-071
11. CONTRACT/GRANT NO.
68-02-1874
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD
Task Final; 7/76-1/78
ND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES jERL-RTP task officer is David K. Oestreich, Mail Drop 62 919/'
541-2547. Previous related reports are in the EPA-600/2-76-032 and EPA-600/2-
77-107 series
.__ report is an overview of the pesticide manufacturing industry and
prioritizes 80 major pesticides based on their potential environmental burden from
an air pollution standpoint.JProduction of synthetic organic pesticides was about
640,000 metric tons in 197T. Thirty-seven major synthetic organic pesticides, those
with annual production of 4540 or more tons, accounted for 74% of the market.
Elemental chlorine is common to most pesticides, but other raw materials include
hydrogen cyanide, carbon disulfide, phosgene, phosphorus pentasulfide, hexachloro-
cyclopentadiene, various amines, and concentrated acids and caustics. Air pollution
aspects of the pesticide manufacturing industry are essentially without quantitative
data. For some plants, the pollution caused by loss of active ingredients is less
significant than that caused by unreacted by-products. Evaporation from holding
ponds and evaporation lagoons may also be an emission source, although few quan-
titative data are available. Emissions emanate from various pieces of equipment
and enter the atmosphere as both the active ingredient and as raw materials, inter-
mediates and by-products. Air emission control devices include baghouses,
cyclone separators, electrostatic precipitators, incinerators, and gas scrubbers.
Synthetic organic pesticide production in 1985 will be about 806,000 metric tons.
is.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
PollutionT^esticides "Manufacturing
Organic Compounds, Synthesis, Ponds
Industrial Processes, Lagoons
Gas Filters, Cyclone Separators
Electrostatic Precipitators, Incinerators
Gas Scrubbing, Sulfur Dioxide, Chlorine
b.IDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Source Assessment
Emission Factors
Baghouses
Flaring, Toxaphene
c. COSATI Field/Group
13B, 06F, 05C
07C, 14B, 08H
13H, —
13K, 07A
-,07B, --
13. DISTRIBUTION STATEMENT
Unlimited
EPA Form 2220-1 (9-73)
Unclassified
153
20. SECURITY CLASS {This page)
Unclassified
22. PRICE
139
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