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.

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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

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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

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           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

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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

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                            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

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   • 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)

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          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

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 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

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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).

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         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

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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

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    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

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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

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      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
                               QŁ
          o
       CM,ŁI{ - 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

-------
                            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

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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

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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

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        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

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                           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

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                           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 380-76Ł, 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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