U.S. DEPARTMENT Of COMMERCE
National Technical Info-mation S* vice
PB-285 480
DEVELOPMENT DOCUMENT FOR EFFLUENT LIMITATIONS
GUIDELINES FOR THE PESTICIDE CHEMICALS
MANUFACTURING, POINT SOURCE CATEGORY
GEORGE M, JETT
U,S, ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D,C,
APRIL 1978
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EPA 440/l-7fi/06Q-e
Group
Development Document For
Effluent Limitations Guidelines
for the
r ~ ->
PESTICIDE CHEMICALS
MANUFACTURING
Point Source Category
UNITED STATES ENVIRONMENTAL
PROTECTION AGENCY
APRIL 1978
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 440/1-78/060-e
3. RECIPIENT'S ACCESSION"NO.
4. TITLE AND SUBTITLE
nf f9<" final Effluent Limitatioos
nes for the Pesticide Chemicals Manufacture
Point Source Category
ng
5. REPORT DATE
April 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
George M. Jett
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Effluent Guidelines Division
WSM-E, Rrn. 911, WH-552
401 M Street, S.VJ.
Washington, D. C. 20460
10. PROGRAM ELEMENT NO.
2BB156
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D. C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Development Pnrumpnt
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16: ABSTRACT
this document presents the findings of studies of the pesticide chemical manufact-
uring point source category for the purpose of developing effluent limitations
guidelines for existing point sources to implement Sections 301(b) and 304(b) and of
the Federal Water Pollution Control Act as amended (33 U.S.C. 1251 and 1314(b) and
86 Stat. 816 et. seq.) (the "Act"). Effluent limitations guidelines contained herein
represent the application of the Best Practicable Control Technology Currently
Available (BPT) as required by section 301(c) of the Act.
The pesticide chemicals manufacturing point source category is divided into three
subcategories on the basis of the characteristics of the manufacturing processes
involved and the types of products produced. The three subcategories are: the
organic pesticide chemical subcategory, the metallo-organic pesticide chemical
subcategory and'the pesticide chemical formulation and packaging subcategory. Cost
estimates have been developed for model treatment systems which are capable of
attaining the effluent limitations. Supporting data and rationale for development
of the effluent limitations are contained in this report and supporting file records.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Wastewater, Treatment, EPA, Regulations,
BPT, Pesticides, Carbon, Hydrolysis,
Biological Treatment, Herbicide,
Fungicide
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (ThisReport)
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (9-73)
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DEVELOPMENT DOCUMENT
for
FINAL BPT
EFFLUENT LIMITATIONS GUIDELINES
for the
PESTICIDE CHEMICALS MANUFACTURING
POINT SOURCE CATEGORY
George M. Jett
Project Officer
April 1978
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 2016Q.
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ABSTRACT
This document presents the findings of studies of the pesticide
chemicals manufacturing point source category for the purpose of
developing effluent limitations guidelines for existing point
sources to implement Sections 301(b) and 301(b) and of the
Federal Water Pollution Control Act as amended (33 U.S.C. 1251
and 1314(b) and 86 Stat. 816 et. seq.) (the "Act").
Effluent limitations guidelines contained herein set forth the
degree of effluent reduction attainable through the application
of the Best Practicable Control Technology Currently Available
(BPT) as required by section 301 (b) of the Act.
The pesticide chemicals manufacturing point source category was
originally divided into five subcategories on the basis of the
characteristics of the manufacturing processes involved and the
types of products produced. As a result of public comments and a
reevaluation of the Agency's expanded data base, it was concluded
that the subcategories for the halogenated organic, organo-
phosphorus and organo-nitrogen pesticides as defined in the
interim final regulations should be combined into the organic
pesticide chemicals manufacturing subcategory (1). The
subcategories for metallo-organics (2) and formulating and
packaging (3) have remained the same.
Separate effluent limitations for the three subcategories have
been derived based on the degree of treatment achievable by
existing installations. Subcategory 1 plants employ combinations
of biological and physical/chemical treatment methods.
Facilities in subcategory 2 and 3 normally operate without the
discharge of process waste water through recycle, evaporation or
dry manufacturing. Cost estimates have been developed for model
treatment systems which are capable of attaining the effluent
limitations. Supporting data and rationale for development of
the effluent limitations are contained in this report and
supporting file records.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
iii
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TABLE OF CONTENTS
Section Title
Abstract
Table of Contents
List of Figures
List of Tables
I Conclusions
II Recommendations
III Introduction
IV Industrial Categorization
V Vaste Characterization
VI Selection of Pollutant Parameters
VII Control and Treatment Technologies
VIII Cost, Energy, and Non-Water Quality
Aspects
IX Pest Practicable Control Technology
Currently Available
X Index of Common Pesticide
Compounds by Subcategory
XI Acknowledgements
XII Bibliography
XIII Glossary
XIV Abbreviations and Symbols
Page
vi
v
vi
ix
1
3
5
57
63
85
103
155
179
193
267
269
311
315
Preceding page blank
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LIST OF FIGURES
Number Title Page
III-1 Locations of Pesticide
Production Plants 11
III-2 Locations of Formulation
Facilities in U.S. 21
III*-3 General Process Flow Diagram for
DDT and Related Compounds Production
Facilities 22
III-U General Process Flow Diagram for Halo-
genated Phenol Production Facilities 25
III-5 General Process Flow Diagram for Aryl-
oxyalkanoic Acid Production Facilities 26
III-6 General Process Flow Diagram for Aldrin-
Toxaphene Production Facilities 28
III-7 General Process Flow Diagram for Halo-
genated Aliphatic Hydrocarbon
Production Facilities 30
III-8 General Process Flow Diagram for Halo-
genated Aliphatic Acid Production
Facilities 31
III-9 General Process Flow Diagram
for Phosphates and Phbsphonates
Pesticide Production Facilities 33
III-10 General Process Flow Diagram for
Phosphorothioate and Phosphoro-
dithioate Production Facilities 35
III-11 General Process Flow Diagram for Alkyl and
Aryl Carbamate Production Facilities 37
III-12 General Process Flow Diagram for Thio-
carbamate Production Facilities 38
III-13 General Process Flow Diagram for Amide
and Amine Production Facilities 10
VI
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III-1U General Process Flow Diagram for Urea
and Uracils Production Facilities 42
III-15 General Process Flow Diagram for
S-Triazine Production Facilities 44
III-16 General Process Flow Diagram for
Nitro-type Pesticides 45
III-17 General Process Flow Diagram for Arsenic-
type Metallo-Organic Production 47
III-18 General Process Flow Diagram for
Certain Dithiocarbamate Metallo-
Organic Production 49
III-19 Liquid Formulation Unit 51
III-20 Dry Formulation Unit 53
V-1 Flow Raw Waste Load Characteristics,
Pesticides Manufacturers 77
V-2 BOD Raw Waste Load Characteristics,
Pesticides Manufacturers 78
V-3 COD Raw Waste Load Characteristics,
Pesticides Manufacturers 79
V-4 TSS Raw Waste Load Characteristics,
Pesticides Manufacturers 80
V-5 Phenol Raw Waste Load Characteristics,
Pesticides Manufacturers 81
V-6 Pesticide Raw Waste Load Characteristics,
Pesticides Manufacturers 82
VII-1 Effect of pH and Temperature on
Malathion Degradation 121
VII-2 Molecular Structures, Demeton-O
and Demeton-S 122
VII-3 Bronstead Plot of the Second-Order
Alkaline Hydrolysis Rate Constants
of N-phenyl Carbamates versus pKa of
the Resulting Alcohol at 25° C 124
vii
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VII-if Bronstead Plot of the Second-Order
Alkaline Hydrolysis Rate Constant of
the N-alkyl Carbamates versus pKa of
the Resulting Alcohol at 25° C 125
VII-5 Bronstead Free Energy Relationship,
Dimethoxyphosphate Pesticides 133
\ftl-6 Bronstead Free Energy Relationships,
Diethoxyphosphate Pesticides 134
VII-7 Bronstead Free Energy Relationship,
Dimethoxyphosphorothioate Pesticides 136
VII-8 Bronstead Free Energy Relationship,
Diethoxyphospnorothioate Pesticides 137
VII-9 Cost Treatment Technology—:
Subcategory 1 153
viii
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LIST OF TABLES
Number Title Page
II-1 BPT Effluent Limitations Guidelines 4
III-1 Pesticides Classification 12-13
III-2 Structural Chemistry of Typical and
Major Pesticides 14-18
V-l Summary of Potential Process-Associated
Wastewater Sources from Organic
Pesticide Production 64-65
V-2 Raw Waste Loads Organic Pesticide
Manufactures-Subcategory 1 66-69
V-3 Summary of Potential Process-Associated
Wastewater Sources from Metallo-Organic
Pesticide Production 71
V-4 Raw Waste Loads, Metallo-Organic
Pesticide Manufacturers-Subcategory 2 72-74
V-5 Summary of Potential Process-Associated
Wastewater Sources from Pesticide
Formulators and Packagers 75
V-6 Design Criteria, Cost Treatment
Technology-Subcategory 1 83
VII-1 Direct Discharger Profile,
Pesticide Chemicals Industry 105
VII-2 Indirect Discharger Profile,
Pesticide Chemicals Industry 106-109
VII-3 Activated Carbon Design Summary,
Pesticide Chemicals Industry 111
VI I-4 Activated Carbon Summary
Pesticide Industry 113
VII-5 Activated Carbon Isotherm and
Dynamic Data, Pesticide Industry 118-119
IX
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VII-6
VII-7
VI I-8
VI I-9
VII-10
VIII-1
VIII-2
VIII-3
VIII-4
VIII-5
VIII-6
VIII-7
VIII-8
VIII-9
IX-1
IX-2
IX-3
Full Scale Hydrolysis Data
Hydrolysis Literature Data
Organo-Phosphorus Pesticides
Hydrolysis Literature Data
Organo-Nitrogen Pesticides
126
128-131
132
Biologically Treated Effluent Summary -
Organic Pesticide Chemicals Manufacturers-
Manufacturers-Subcategory 1 143-144
Holding Pond Effluent, Plant 34 150
Basis for Computation of Capital
Costs (July, 1977 Dollars) 157
Basis for Computation of. Annual
Costs (July, 1977 Dollars) 158
BPT Cost Itemization
Excluding Pesticide Removal
Units-Subcategory 1 167-168
BPT Cost Itemization, Hydrolysis
12,000 Minutes Detention-Subcategory 1 169
BPT Cost Itemization,
Carbon-750 Minutes Detention-
Subcategory 1 170
BPT Cost Summary, Pesticide Removal-
Subcategory 1 171
BPT Cost Summary,
All Treatment Units-Subcategory 1 172
Land Requirements
Subcategory 1 173-174
BPT Cost Itemization-
Subcategory 3 175
BPT Effluent Limitation Guidelines 181
Development of Long-Term
Averages-Subcategory 1 183
Variability Factors-Subcategory 1 1 85
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IX-U Upgrading of Existing Systems 189-190
X-1 Index of Pesticide Compounds
By Subcategory 19H-266
XIV-1 Metric Table 316
xi
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SECTION I
CONCLUSIONS
This document provides background information for BPT (Best
Practicable Control Technology Currently Available) for the
pesticide chemicals manufacturing point source category. The
initial contractor's draft report was issued in February, 1975.
The interim final report was revised and published in November,
1976. This report represents further revision of that interim
final development document as a result of public comments and
additional studies and data collection by the Agency.
This report marks a change from the earlier studies. The Agency
had previously taken the approach that the major manufacturing
process groups (halogenated organic, organo-phosphorus, and
organo-nitrogen) were a basis for subcategorization. Additional
information collected, combined with the existing data base,
indicates that with the treatment scheme of pesticide removal,
equalization, and biological treatment all waste waters generated
from the manufacture of these pesticide chemicals can be
satisfactorily treated to the same effluent limitations. The
meta11o-organic pesticide chemicals and pesticide chemicals
formulating and packaging subcategories are unchanged from the
interim final regulations.
For purposes of regulation, the three subcategories are:
1. Organic Pesticide Chemicals Manufacturing.
2. Metallo-Organic Pesticide Chemicals Manufacturing.
3. Pesticide Chemicals Formulating and Packaging.
Model treatment systems are presented for each subcategory in
Section VII of this document. Costs for each model were
developed and used to assess the economic impact to the pesticide
industry. The treatment models should not be construed as the
only technology capable of meeting the effluent limitations.
There are many alternative systems which either singly or in
combination are capable of attaining the effluent limitations in
this Development Document.
It is expected that each individual plant will make the choice of
the specific combination of pollution control measures best
suited to its situation in complying with the regulations
supported in this development document.
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Process waste waters from Subcategory 1 may result from the
following steps: decanting, distillation, stripping,
extraction/precipitation, and purification. High organic and
solids loadings may be caused by equipment cleanout, area
washdowns, accidental spillage, or poor operation. Caustic
scrubbers and contact cooling may contribute significantly to
total flow.
For proper control and treatment, Subcategory 1 process waste
waters should be isolated from nonprocess waste waters such as
utility discharges and uncontaminated storm runoff. The BPT
treatment technology for the process waste waters includes an API
separator, pesticide removal by hydrolysis or multimedia
filtration and activated carbon, equalization, neutralization,
and activated sludge. In some cases incineration or suitable
disposal of strong or toxic wastes may be necessary.
Process waste waters produced by facilities within Subcategory 2,
the meta11o-organic pesticide chemicals subcategory, are disposed
of by recycle or suitable containment. BPT control and treatment
of process waste waters for this Subcategory is no discharge of
process waste water pollutants.
Formulators and packagers within Subcategory 3 have been found to
generate either no waste waters or such small volumes that
disposal can be handled adequately by disposal contractors, land
application, evaporation, or other means leading to no discharge
of process waste water pollutants.
Pollutants or pollutant parameters of concern in this industry
are BOD5_, COD, TSS, and pesticide chemicals. Both phenol and
ammonia nitrogen may be found at significant levels at a few
plants. These latter two pollutants should be regulated on an
individual basis.
It is not the intent of this document to cover the manufacture of
intermediates used in the manufacture of the active ingredients.
Like phenol and ammonia, the manufacture of pesticide chemical
intermediates should be covered on a case-by-case basis.
Stormwater that does not commingle with the process waste water
is likewise excluded from coverage by this document. The
document is intended to cover process waste water discharged from
a point source as defined in the Federal Water Pollution Control
Act.
This regulation has also excluded coverage of certain pesticides,
such as symmetrical and asymmetrical triazines, and tin, zinc,
and manganese based metallo-organics. These compounds are under
study, and the Agency intends to publish regulations to cover
them in the future.
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SECTION II
RECOMMENDATIONS
The effluent limitations for each subcategory are presented in
Table II-1.
The effluent limitations consist of two limitations for each
parameter: the maximum average of daily values for thirty
consecutive days and the maximum for any one day. The
limitations were calculated based on the long-term effluent
averages of those plants with the model technologies installed
and properly operating. These long-term averages, presented in
Section IX, were multiplied by the daily and monthly variability
factors presented in Section IX, in order to determine the final
limitations.
Process waste waters subject to these regulations include all
contact process water, but do not include noncontact sources such
as boiler and cooling water blowdowns, sanitary wastes, and other
similar nonprocess sources. This regulation does not include the
waste waters from the manufacture of intermediates used in the
manufacture of pesticide chemicals. Likewise, stormwater which
does not commingle with the process waste water is not covered by
this document.
Paw waste loads developed in Section V form the basis for cost
estimates of the treatment technologies presented in Section VII.
These cost estimates have been applied in Section IX to each
direct discharger not in compliance in order to determine
additional treatment costs due to this regulation. Precautions
in applying these limitations are detailed in Section IX.
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TABLE II-l
BPT EFFLUENT LIMITATIONS GUIDELINES
EFFLUENT LIMITATIONS
SUBCATEGORY!
1
2
3
EFFLUENT
CHARACTERISTIC
BODS
COD
TSS
Pesticide Chemic
PH2
AVERAGE OF DAILY VALUES
FOR 30 CONSECUTIVE DAYS
:als
PROCESS
PROCESS
1.6
9.
1.8
0.0018
WZiQTP WfcTPP t>OT T nTAWFC — -
ijn CTP WZiTFP DOT T TTTfc WPC— .
DAILY
MAXIMUM
7.4
13'.
6'.1
0.010
Note: All units are kg/kkg
1. Subcategory 1: Organic Pesticide Chemicals Manufacturing
Subcategory 2: Metallo-Organic Pesticide Chemicals Manufacturing
Subcateogry 3: Pesticide Chemicals Formulating and Packaging
2. The pH shall be between the values of 6.0 to 9.0
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SECTION III
INTRODUCTION
Purpose and Authority
The Federal Water Pollution Control Act Amendments of 1972 (the
Act) made a number of fundamental changes in the approach to
achieving clean water. One of the most significant changes was a
shift from a reliance on effluent limitations based on water
quality to those based on technology.
The Act requires EPA to establish guidelines for technology-based
effluent limitations which must be achieved by point sources of
discharges into the navigable waters of the United States.
Section 301(b) (1) (A) of the Act requires the achievement by not
later than July 1, 1977, of effluent limitations for point
sources, other than publicly owned treatment works, which are
based on the application of the best practicable control
treatment currently available (BPT) as defined by the
Administrator pursuant to Section 304(b) of the Act. Section
301 (b) (2)(A) also requires the achievement by not later than July
1, 1983 of effluent limitations for point sources, other than
publicly owned treatment works, which are based on the
application of the (BAT) best available technology economically
achievable. This will result in progress toward reaching the
national goal of eliminating the discharge of all pollutants, as
determined in accordance with regulations issued by the
Administrator pursuant to Section 301(b) of the Act. Section 306
of the Act requires new source performance standards. These
standards will reflect the greatest degree of effluent reduction
which the Administrator determines to be achievable through the
application of the new source performance standards (NSPS)
processes, operating methods, or other alternatives, including,
where practicable, a standard permitting no discharge of
pollutants. Section 307 (b) (1) of the Act requires the
Administration to, from time to time, publish pretreatment
standards for new and existing sources.
Section 304 (b) of the Act requires the Administrator to publish
regulations based on the degree of effluent reduction attainable
through the application of the BPT and the best control measures
and practices achievable, including treatment techniques, process
and procedure innovations, operation methods, and other
alternatives.
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This document forms the technical basis for the BPT effluent
limitations and guidelines promulgated pursuant to Sections
301(b) (1) (A) and 304 (b) of the Act.
Methods Used for Development of the Effluent Limitations
Guidelines
The effluent limitations guidelines presented in this document
were developed in the following manner. The Agency completely
reviewed the interim final regulations including the
subcategorization schemes, and the data base presented in the
interim final Development Document (EPA «»UO/1-75/060d) and its
supplements. From this point the Agency began to collect
additional data to determine if any changes needed to be made to
the interim final regulations. Determination was then made as to
whether further subcategorization would aid in description of the
category. Such determinations were made on the basis of the
combined data base including raw materials required, products
manufactured, processes employed, and other factors.
The raw waste characteristics for each subcategory were
identified. This included an analysis of: 1) the source and
volume of water used in the process employed and the sources of
wastes and waste waters in the plant, and 2) the constituents of
all waste waters. The constituents of waste waters which should
te subject to effluent limitations guidelines were identified.
The full range of control and treatment technologies existing
within this industry was identified. This included an
identification of each distinct control and treatment technology,
including both in-plant and end-of-pipe technologies, which
exist. It also included an identification of the effluent level
resulting from the application of each of the treatment and
control technologies in terms of the amount of constituents and
of the chemical, physical, and biological characteristics of
pollutants. The reliability of each treatment and control
technology was also identified. In addition, the non-water
quality environmental impacts (such as the effects of the
application of such technologies upon other pollution problems,
including air, solid waste, radiation, and noise) were also
identified. The energy requirements of each of the control and
treatment technologies were identified, as well as the cost of
the application of such technologies.
This information was then evaluated in order to determine what
level of technology constituted BPT. In identifying such
technologies, factors considered included the total cost of
application of technology in relation to the effluent reduction
benefits to be achieved from such application, the age of equip-
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ment and facilities involved, the process employed, the
engineering aspects of the application of various types of
control techniques, process changes, non-water quality
environmental impacts (including energy requirements) , and other
factors.
During the first phases of the study, an assessment was made of
the availability, adequacy, and usefulness of all existing data
sources. Data on the identity and performance of waste water
treatment systems included the following:
1. NPDES permit applications;
2. Self-reporting discharge data from various states
and regions;
3. Surveys conducted by trade associations or by
agencies under research and development grants.
A preliminary analysis of these data indicated an obvious need
for further information in the following areas: 1) process raw
waste load related to production; 2) currently practiced or
potential in-plant waste control techniques; and 3) the identity
and effectiveness of end-of-pipe treatment systems.
The best source of information was determined to be the
manufacturers themselves. New information was obtained from
telephone surveys, correspondence with the industry, plant
visits, and verification sampling. To date more than 133
pesticide chemicals manufacturing plants have been contacted and
32 visited. Visitations alone have covered more than 90 percent
of the pesticide chemicals quantity manufactured.
The selection of waste water treatment plants to be visited was
developed by identifying information available in the NPDES
permit applications, state self^reporting discharge data, and by
speaking with representatives of the manufacturing segment.
Every effort was made to choose facilities where meaningful
information on both treatment facilities and manufacturing
processes could be obtained.
Collection of the data necessary for development of the effluent
treatment capabilities within dependable confidence limits
required analyses of both production and treatment operations.
In a few cases, plant visits were planned so that the production
operations of a single plant could be studied in association with
an end-of-pipe treatment system which received only the wastes
from that production. No significant differences were observed
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between plants manufacturing a single pesticide chemical and
plants manufacturing multiple pesticides.
Survey teams composed of project engineers and scientists
conducted the actual plant visits. Information on the identity
and performance of waste water treatment systems was obtained
through:
1. Interviews with plant water pollution control personnel
or engineering personnel;
2. Examination of treatment plant design and historical
operating data (flow rates and analyses of influent and
effluent);
3. Treatment plant influent and effluent sampling.
Information on process plant operations was obtained through:
1. Interviews with plant operating personnel;
2. Examination of plant design and operating data (original
design specification, flow sheets, and day-to-day
material balances around individual process modules or
unit operations where possible);
3. Individual process waste water sampling and analysis.
The data base obtained in this manner was then utilized to
develop the effluent limitations for the pesticide chemicals
manufacturing point source category. All of the references
utilized are cited in Section XII of this report. Cost
information is presented in Section VIII. Supporting data are
available for examination at the EPA Public Information Reference
Unit, Room 2922 (EPA Library), Waterside Mall, 401 M St. S.W.,
Washington, D.C. 20U60.
scope of the Document
The basic manufacture of organic pesticides is covered by this
document. Representative pesticides covered by the final
regulations are listed in Section X of this document. Other
operations covered are: (1) establishments primarily engaged in
the formulation and preparation of ready-to-use agricultural and
household pest control chemicals, including insecticides,
fungicides, and herbicides made from technical chemicals or
concentrates; (2) the production of concentrates which require
further processing before use and (3) establishments primarily
engaged in manufacturing or formulating pesticide chemicals, not
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elsewhere classified, such as minor or trace elements and soil
conditioners. The regulations that this document supports cover
the formulation and packaging of all registered (FIFRA) pesticide
chemicals regardless whether or not the manufacture of the active
ingredient has been included.
The use of the term "pesticide" in this document refers to any
chemical used to destroy a specific organism, i.e. an
insecticide, herbicide, fungicide, miticide, etc.
This report does not cover the manufacture of non-pesticide
products (such as plant hormones and soil conditioners) included
in SIC codes 2819, 2869, and 2879. Also not covered in this
document are those miscellaneous pesticide chemicals identified
in Section X of this report. Coverage of the manufacture of
pesticide intermediates used in the manufacture of pesticide
active ingredients or stormwater that does not commingle with the
process waste waters is likewise beyond the scope of this
document.
Individual active ingredients are referred to by generic or
chemical name, predominant trade name, competitive trade names,
or abbreviation (e.g., DDT). This, and the fact that over 500
commercially important pesticides are manufactured, make
individual references extremely difficult, and could be a source
of confusion in this document. Therefore, throughout this
document individual pesticide types will be referred to by their
"common names". In a few instances, the generic or chemical name
matches the common name. The common name is usually: (1) a
hybrid of the original trade name, or (2) an abbreviation based
on the chemical structure.
A better understanding of pesticides nomenclature can be obtained
from the Pesticide Handbook-Entoma, Volume 1, pages 110-134,
where a list of common names, chemical names, and alternative
designations are presented.
It should be understood that specific pesticide manufacturing
operations are unique and generally characteristic only of a
given facility. There are very few, if any, pesticide plants
which manufacture one product or use only one process. Instead,
almost all plants are multiproduct/process facilities where the
final mix of products shipped is unique to that plant. Some
plants (such as batch chemicals complexes) produce hundreds of
products, while other facilities manufacture only two or three
high-volume products. In many instances, even the product mixes
vary from day to day. Furthermore, the production quantities
associated with the product mix shipped from a plant are not
necessarily a true indication of the extent or type of manu-
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factoring activities carried out within that plant,, Frequently,?
products are utilized captiveiy as feedstocks in the manufacture
of other products„ Few facilities manufacture or formulate
pesticides exclusively? other chemicals may constitute a very
minor or a very major portion of total production at a particular
plant,, These factors must be considered since water usage and
waste water generation patterns in the pesticide chemicals point
source category are directly related to the diverse nature of
manufacturing processes and the availability of essential raw
materials.,
Overview of the Industry
The organic pesticide chemicals can be grouped by historical
development- The distribution of major pesticide manufacturers
is illustrated in Figure III-1o Unlike some point source
categories where relatively large plants manufacture essentially
a single product from a limited number of rau materials,? the
pesticide chemicals point source category involves a complex
mixture of raw materials^ processes
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FIGURE III -1
LOCATIONS OF PESTICIDES PRODUCTION PLANTS
SOURCE: ENVIRONMENTAL PROTECTION AGENCY.
TECHNICAL STUDIES REPORT: TS-00-72-04, JUNE 1972
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TABLE III-l
PESTICIDE CLASSIFICATION
NUMBER OF
MAJOR PESTICIDES
Halogenated Organics
DDT and relatives 9
Chlorinated Aryloxyalkanoic Acids 12
Aldrin-toxaphene group 16
Halogenated aliphatic hydrocarbons 20
Halogenated aromatic-type compounds, not elsewhere
classified 29
Other chlorinated compounds
98
Phosphorus-Containing Pesticides
Phosphates and phosphonates 19
Phosphorothioates and phosphorodithioates 61
Phosphorus-nitrogen compounds 8
Other phosphorus compounds _5^
93
Nitrogen-Containing Pesticides
Aryl and alkyl carbamates and related compounds 35
Thiocarbamates 23
Anilides 13
Amides and amines (without sulfur) 24
Ureas and uracils 20
Triazines 14
Amines, heterocyclic (sulfur-containing) 12
Nitro compounds 26
Other nitrogen-containing compounds 42
209
Metallo-Organic Pesticides
Mercury compounds 28
Arsenic compounds 17
Other heavy metal compounds 17
Other inorganic compounds, including cyanides,
phosphides, and related compounds 24
86
12
-------
TABLE III-l
PESTICIDE CLASSIFICATION
Continued
Page 2 of 2 pages
NUMBER OF
MAJOR PESTICIDES
Botanical and Microbiological Pesticides 19
Organic Pesticides, not Elsewhere Classified
Carbon compounds 41
Anticoagulants _4
45
TOTAL 550
13
-------
TABLE 111-2
STRUCTURAL CHEMISTRY OF TYPICAL AND MAJOR PESTICIDES
A. ORGANIC PESTICIDE CHEMICALS
DDT and Relatives
Z
I
I
Y
X=normally Cl Y=noram11y CC13 Z=normally H
DDT, ODD, TDE, Perthane*,Methoxychlor, Prolan, Bulan, Gex, Dicofol,
Chloropropylate, Bromopropylate, Parinol, Chiorobenzilate
Chlorinated Aryloxyalkanoic Acids
Z
V R=normally H or CH3
Y— /Th— OCHR (CH2)m COOH X=normally Cl
M Y=always Cl
X Z=normally H or Cl
2,4-D and its derivatives, 2,4,5-T and its derivatives, Silvex,
Dichloroprop, Sesone, Fruitone CPA*, MCPA, MCPB, MCPP, Erbon
Aldrin - Toxaphene Group
»- Product
(ej) = perchlorinated ring
Kepone*, Heptachlor, Mi rex, Pentac*, Chlorodane, Telodrin, Aldrin,
Dieldrin, Toxaphene, Endrin, Endosulfan, Isodrin, Alodan, Bromodan,
Halogenated Aliphatic Hydrocarbons
X
I
R c X
I .
X
X=halogenated, H and 0
R=Alkyl grouping or halogen
TCA and its salts, Dalapcm and its salts, Fenac, Methyl Bromide, DBCP,
DD*, EDB, Lindane, Glytac*
* Trademark 14
-------
TABLE 111-2
(Continued)
Halogenated Aromatic Compounds
X X
\-J X=C1, and NH2,OCH3, H, etc.
/-(" R=OH, H, CL, RCOOH, ESTER, etc.
A A
Benzene hexachloride, Dichlprbenzenes, Dacthal*, PCP and its salts,
Hexachlorophene, Chloroben, Hexachlorobenzene, Dicamba, Tricamba,
Chloroneb, Probe, Fenac*, Piperalin, 2,3,6-TBA, TCBA, Tiba, Ami ben,
Propanil, Bandane, Strobane
Phosphates and Phosphonates
R], R2=usuany alky! group
R-,0 0 R3?Alkly, halogen, NH2, etc.
\. " Y=ususally halogen on H
J> P-0-C-R3
R2)
Y
Dichlorvos, Dicrotphos, dodrin*, Trichlorofon, Ethephon, Sardona*,
Mevinphos, Naled, Nia 10637, TEPP, Phosphamidon
Phosphorothioates and Phosphorodithioates
S R-i=Alkyl group
A=0 on S
(RiOU-P-A-R? Ro=Alkyl, aryl, NH2, CHBrCBrClo,
CH-CC12, etc.
Parathion, Me-Parathion, Dicapton, Chlorthion, Fenthion, Ronnel, Sumithion,
Demeton, Diazinon, Dioxathion, Guthion*, Malathion, Coumaphos, Dasanit*,
Phorate, Disulfoton, Ekatin, Abate*, Acetellic*, Pyrazophos, Akton*,
Aspon*, Monocrotophos, Betasan*, DEF*, Dimethoate, Chlopyrifos, Dyfonate*,
EPN, Ethion, Folex*, Phentriazophos, Imidan*, Menazon, Demeton-0-methylsulfoxide,
Prophos, Phenthoate, Leptophos, Pirimiphosethyl, Sumithion*, Supracide*,
Surecide*, Dialifor, Carbophenothion, Dichlorofenthion, Zinophos*, Phosalone
* Trademark
15
-------
"
TABLE 1 1 1-2
(Continued)
Phosphorus-Nitrogen Compounds
(S)
0 R-j=Alkyl, aryl group, etc.
R2=A1 kyl , .aryl group, etc.
NR3 R3=Alkyl, aryl, or other cyclic
compounds, etc.
Ruelene, Nellite*, N.emacur*, Cyolane, Cytrolane, Go phacide*, Monitor*
Aryl and Alky1 Carbamates and Related Compounds
R2 0 R2 .0 Ri=Alkyl
| I " R2=Alkyl, H
Rl-N-C-R3 R4-N-C-R3 R3=Alkyl, NH4, Etc.
R4=Aryl group
Propham (IPC), Chlorppropham (CIPC), Barban, Swep, Sirmate*, Azak*,
Isolan, Metacrate*, Carbaryl (Sevin*), Zectran*, Metacil*, Baygon*,
.Mesurol*, Temik*, Banol, Meobal*, Landrin*, Betanol*, Asulox*, BUX,
Carbofuran, Lannate*, Osbac*, Pirimicarb, Tandex*, Mobam*
Thiocarbamates
0 Ri=Alkyl group
R2=Alkyl, H
Rl-N-C-S-R3 R3= Alkyl, NH4, etc.
I
R2
EPTC, SMDC, Vernolate, CDEC, pebulate, Diallate, Triallate, butylate,
Mollnate, Cycloate, Bolero*, Eptam*
Amides and Amines (without sulfur)
0 R1=Alkyl, C1CH2, etc.
" R2=Alkyl, Cyclic compounds
.. Rl-C-N-R3 R3=Alkyl, H
R3
Pronamide, Alachlor, Dicryl, Solan, Propanil, Diphenamid, Propachlor,
CDAA, Naptalam, Cypromid, CDA, Chlonitralid, Benomyl, Deet, Dimetilan,
D1phenylam1ne, Horomodin*, Butachlor, Naphthalene acetamide, Vitavax*
i
* Trademark 1t
-------
TABLE 111-2
(Continued)
Ureas and Uracils
r H
C4H
and
O^V CH3
N
H
Ri=Cl, Br, H, OCH3, etc. Rs=CH3, OCH3, etc.
R2=H, Cl, etc. R4=CH3, Alky!
Fenuron, Monuron, Diuron, Fluometuron, Linuron, Metobromuron, Momolinuron,
Neburon, Siduron, Chloroxuron, Buturon, Chlorbromuron, Norea, Cycluron,
Antu*, Metrobromuron, Monuron TCA, Probe*, Urab*. Bromacil
s-Triazines
Ri=Alkyl
R2=A1kyl
R3=Halogen, SCH3, OCH3, etc.
Ametryne, Atratone, Atrazine, Simazine, Simetone, Simetryne, Prometone,
Prometryne, Propazine, Lambast*, Chlorazine, Bladex*, Prefox*, Sancap*,
Sumitol*, Terbutryn, Dyrene*
Nitro Compounds
R] Ri=OH, AT kyl, Etc.
R XXR R2=N02, H, Alkyl. etc.
4O 2 R3=N02, CF3
•^ R4=N02, H
R3
Benefin, Dinocap, Dinsep (DNSP), DNOC, Mitral in, PCNB, Trifluralin, A-820*,
Dirioseb Acetate, Binapacryl, Dinitramine, Fluorodifen, Isoproplin, Lamprecid*,
Torpedo*, Chloropicrin, DCNA
Other Nitrogen-Containinvg Compounds
These have varied chemical structures
Actellic*, Pyrazophos, Ametrole, Banamite*, Benomyl, Benzomate, Calixin*.
Captan, Carzol*, Chlorodimeform, Cycloheximide, Cycoel*, Cyprex*,
Dexon*, Diquat, Fenazaflor, Maleic hydrazide, M6K 264*,
* Trademark 17
-------
TABLE 111-2
(Continued)
MGK Repellent 326*, Neo-Pyhamin*, Parquat, Thiram, Thipphanate, Thynon*,
Milcurb*, Milstem*, Nia 21844, Nia 21861, Nia 23486, Nicotine, N-Serve*,
Ohric*, Picloram, Piperalin, Plantvax*, Pyramin*, Ronstar*, Towtate*,
SADH, Sencor*, Sicarol*, Stop Scald*, Streptomycin, Tandex*, Thanite*,
Difolatan*, Folpet, Mertect*. Morestan*, Nia 19873, Niacide*,0rdram*,
Terrazole*, Mylone (DMTT)
B. METALLO-ORGANIC
These have varied chemical structures, no generalized formula can
be derived.
Brestan*, Cacodylic Acid, CMA, Manzate 200*, Copoloid*, Copper-8*, Copper
Oleaste, DSMA, Du-Ter*, Ferbam, Maneb, MSMA, Nabam, Niacide*. Plictran*,
Zineb, Ziram
C. BOTANICAL AND MICROBIOLOGICAL
These have varied chemical structures and, therefore, no generalized
formula can be derived.
Bacillus popilliae, Bacillus thuringiensis, Polyhedrus Virus, Pyrethrins,
Ryania
p. MISCELLANEOUS PESTICIDES (Not Elsewhere Classified)
These have varied chemical structures and, therefore, no generalized
formula can be derived.
Cresotw, Nicotine, Rotenone, Petroleum oils, Butoxy, Calamite*, Dexon*,
MGK Repellent 874*, Omite*, Sulfoxide, TCTP, Tetradifon
* Trademark
18
-------
generally are easily hydrolyzed in an alkaline medium to yield
materials of relatively low toxicity.
Several classes of nitrogen-containing compounds have been
produced and successfully marketed since 1945. These have a
broad range of biological activity, and can be applied as
selective herbicides, insecticides, or fungicides. Herbicides
and fungicides which contain nitrogen-compounds continue to
increase their share of the pesticide market, an increase from
i»4.1 percent in 1966 to 57.2 percent in 1970.
Meta11o-organic pesticide chemicals, which are produced by a
relatively limited number of companies, include the sodium
methane arsenate (MSMA) herbicides, and cadmium, mercury, and
copper derivatives of organic compounds. Three major types of
meta11o-organic derivatives, manganese, tin and zinc, are not
included in the scope of this document.
Several botanical and biological insecticides such as Bacillus
thuriigienes, the pyrethrins and rotenone are not covered in this
study. Both production and waste water treatabilities of these
compounds are similar to those of products discussed within the
documents covering the Pharmaceuticals, gum and wood chemicals,
or organic chemicals point source categories. These products
represent a small fraction of the pesticide chemicals industry.
Rotenone is found widely in nature and is quite toxic to fish.
These pesticides must be extracted or obtained through a
fermentation process. Large-volume production (greater than one
million pounds per year) is seldom encountered and limited
treated waste data are available.
There are other pesticides which do not readily fall into the
previously discussed groups. Of these, the rodenticide Warfarin
deserves mention. Its production has exceeded 12 million pounds
per year while none of the other so-called "miscellaneous"
pesticides are produced in quantities greater than 1 million
pounds per year. Warfarin did not fit into the interim final
pesticide chemical groupings and was excluded from the
regulations. It is the intent of the Agency to review this
compound in the near future and publish regulations that will
regulate the discharge from manufacture of Warfarin.
The treatability of the waste waters generated during the
production of sulfur-based compounds is similar to that of their
non-sulfur relatives. Inorganic pesticides such as sodium
chlorate and elemental sulfur have been studied as part of the
inorganic chemicals industry and are not covered in this
document. Likewise, certain organic materials occasionally used
19
-------
as pesticides are more appropriately covered by the organic
chemicals point source category.
In addition to the plants which manufacture active ingredients
there are plants which make pesticide products by formulating,
blending, canning, and packaging operations. Locations of
formulation facilities are shown in Figure III-2. In formulating
and packaging the raw materials used are the pesticide active
ingredients, which may be procured from outside suppliers or may
be manufactured on-site. The processing types in this
subcategory (called formulators and packagers) are mechanical and
physical/ chemical in nature. The levels ' of waste water
generation and contamination are either considerably lower than
in the active-ingredient production and are sometimes
nonexistent. Pesticide formulations and packaged products
generally fall into three classifications: water-based, solvent-
based, and dry-based. Coverage for this subcategory includes all
formulations registered under FIFRA.
Subcategory J^—Organic Pesticide Chemicals
The organic pesticide chemicals can be divided for discussion
into three major groupings: halogen, phosphorus, and nitrogen
based compounds.
Four major halogenated compounds merit discussion. These groups
are:
DDT and its relatives
Chlorinated phenols and aryloxyalkanoic acids
Aldrin and toxaphene
Halogenated aliphatic compounds
Chlorinated compounds are the most common of the halogenated
compounds and, in most cases, are illustrative of the processes
and wastes associated with the other halogenated organic
pesticides.
DDT and its relatives
Although present DDT production is on the decline, its
manufacture is well documented in the literature and serves as a
good example of the production and associated waste waters for
the DDT family of pesticides. Analogs of DDT can be prepared by
changing the substituents on the benzene base (e.g. Methoxychlor
is made from Arisole and Chloral) .
Figure III-3 is a simplified process flow diagram for DDT
production and illustrates the type of waste water generated.
20
-------
FIGURE III-2
LOCATIONS OF FORMULATION
FACILITIES IN U.S.
Source: Environmental Protection Agency,
Technology Series: EPA-660/2-74-094
January, 1975.
7
-------
FIGURE .111-3
GENERAL PROCESS FLOW DIAGRAM FOR DDT AND
RELATED COMPOUNDS PRODUCTION FACILITIES
CHLORO BENZENE.
VENT
ALDEHYDE
H2S04
ro
ro
VENT*-i
2-STAGE
REACTOR
SEPARATOR
WATER-t
SODA ASH
WATER-
SCRUBBER
SPENT ACID
ACID
VENT
RECYCLE ACID
ACID
RECOVERY
UNIT
WASTE ACID
1
:NT
SCRUBBER
VACUUM
COLUMN
NEUTRALIZATION
VENT-h
DUSTSI&
PARTICULATE
AIR
STILL
AIR-1
CRYSTALLIZER
DRYER
FLAKER
TECHNICAL
PRODUCT
CLASS 1
-^DISPOSAL
VENT: GASES ARE SCRUBBED (COLLECTED AND NEUTRALIZED)
DUSTS TO BAGHOUSE (COLLECTED AND RETURNED TO FORMULATION)
-------
The process description that follows is an example of how the
process(es) may be carried out commercially, although
considerable variations exist in process equipment design,
reactant concentrations, amount of recycle acid, and methods of
purification.
An aldehyde, chlorobenzene, and concentrated (95-99 percent)
sulfuric acid or oleum are charged to a steel reactor. Generally
the aldehyde and chlorobenzene are mixed together with part of
the concentrated sulfuric acid. External cooling or cooling by
means of internal coils is generally necessary to maintain the
desired reaction temperature. The batch reaction can take
several hours, or may be run continuously by using a number of
reactors in series.
At the end of the reaction, the crude product goes to separators
where the spent acid separates. This acid contains small amounts
of water and is concentrated for re-use. The product liquor from
the top of the separator goes to a liquid-phase scrubber, where
water is used to remove mechanically entrained sulfuric acid.
The liquor is then washed with dilute caustic or sodium carbonate
solution in a second scrubber and finally washed with water. The
separator and scrubber are maintained at sufficiently high
temperature to prevent product crystallization.
The neutralized product containing chlorobenzene can be run to a
column where it is vacuum-distilled. The chlorobenzene
distillate is passed through a separator and condenser and is
finally pumped to storage for recycling. The molten product
containing a small percent of chlorobenzene can be pumped to a
still, where additional chlorobenzene is removed by continuous
atmospheric distillation. The melt is maintained at a
temperature high enough to prevent crystallization of the
product.
The chlorobenzene-free product melt is generally run to a flaker
(consisting of a chilled drum rotating through a steam heated
feed trough) where it is chilled to flakes. The flaked product
is then pulverized to the proper mesh size and either packaged in
concentrated form or blended with inert extenders.
It is becoming standard practice to recycle as much spent acid as
possible and to raise the acid concentration to the desired level
by the addition of oleum.
In the purification and finishing of the product, the most common
solvents used are petroleum fractions and excess chlorobenzene.
In order to pulverize the product adequately, entrained solvent
must be reduced to as low a concentration as possible. Some
23
-------
manufacturers develop friability by aging the product; others by
grinding in the presence of dry ice.
In summary, the process wastes associated with the production of
DDT and its analogs are:
1. Waste acid from acid recovery unit
2. Scrub water from liquid phase scrubber
3. Dilute caustic waste water from caustic
soda scrubber
U. Production area clean-up wastes
5. scrubber water from vent gas water scrubbers
6. Water of formation from chemical reaction.
Chlorinated Phenols and Aryloxyalkanoic Acids
Chlorobenzenes are used as a starting material in the manufacture
of chlorinated phenols and in the manufacture of chlorinated
aryloxyalkanoic acid pesticides. Figures III-4 and III-5 are
simplified process flow diagrams for the manufacture of the
chlorinated phenols and aryloxyalkanoic acids. Potential waste
water sources are shown.
Chlorobenzene can be converted to a phenol by reacting with
dilute caustic soda or water and a catalyst in a reactor.
Pentachlorophenol (PCP) is prepared by chlorinating the phenol in
the presence of a catalyst (see Figure III-4). Excess hydrogen
chloride and chlorine can be scrubbed with phenol and recycled to
the reactor. The free hydrogen chloride is recycled to the
chlorine plant. The crude PCP is distilled with NaOH to form the
sodium salt.
Halogenated aryloxyalkanoic acids can be prepared by charging
equimolar quantities of a chlorophenol and a monochloroalkyl acid
to a steam-heated closed kettle in the presence of dilute
caustic. The method of synthesis for 2, 1-dichlorophenoxyacetic
acid (2,1-D) is generally applicable to the majority of the
class. The reaction is carried on for several hours under reflux
conditions, after which time the reaction mass is acidified (to
approximately pH = 1.0) with dilute hydrochloric acid. The
acidified liquor is sent to a crystallizer followed by a
centrifuge. The reaction is carried out under optimum conditions
of time, temperature, and rate of addition of reactants to
prevent hydrolysis of unconverted chloroalkyl acid. In one
process variation, unreacted dichlorophenol is removed by
distillation prior to acidification. In still another variation,
the reaction is carried out in anhydrous monochlorobenzene (as a
solvent) at the boiling point of the solvent; water is removed
-------
FIGURE
ro
CAUSTIC SODA
-VENT
GENERAL PROCESS FLOW DIAGRAM FOR
HALOGENATED PHENOL PRODUCTION FACILITIES
CHLORINE
SCRUBBER
PHENOL
CHLORINE
CATALYST
VENT
REACTOR
VENT-«-i
WATER
C6C1XOH
BY-PRODUCT
STILL
TARS TO
INCINERATION
EXCESS-e
WASTEWATER
TO TREATMENT
•PRINCIPAL PROCESSING ROUTE
FOR ALTERNATIVE PRODUCT-TYPE
<_>
o
Ul
C£.
REACTOR
VENT-*]
SCRUBBER
SCRUBBER
SEPARATOR
PRILL
TOWER
DUST & PARTICULATE
DRYER
PRODUCT
(CRYSTAL-
LIZES)
•AIR
^ PRODUCT
(PRILLED)
-------
FIGURE IH-5
GENERAL PROCESS -FLOW DIAGRAM OF ARYLOXYALKANOIC ACID PRODUCTION FACILITIES
DILUTE
DILUTE HYDROCHLORIC ACID
CAUSTIC SODA
, , , ,
CHLOROPHENOL
> REACTOR ** ACIDFIER *- I
n ROOH _
Y
CAUSTIC SODA OR SODA ASH w NEUTRALIZER ^
.^VENT
DUSTS ft
PARTICULATE
;RYSTALIZER — *• CENTRIFUGE •— *• /rRY<-;!;
WASTEWATER
)UCT
\LLIZED)
rM/ENT
DUSTS &
PARTICULATE
H PRODUCT
(SALT OF
PESTICIDE)
i r
WASTEWATER
PRINCIPAL PROCESSING ROUTE FOR ALTERNATIVE PRODUCT-TYPE
VENTS TO RECOVERY
-------
azeotropically. The insoluble product is separated from solvent
by filtration.
Esters and amine salts are prepared by reacting the phenoxy alkyl
acid with an alcohol or amine, respectively. These products have
better formulation and application properties.
Briefly, waste waters generated from the production of this group
of pesticides are:
1. Excess prill tower dust scrubber water
2. Centrate from liquid/solid separation step
3. Vent gas scrubber waters
H. Reactor and processing unit cleanout
waste waters
5. Processing area washdown waste waters
6. Water of formation from chemical reaction.
Aldrin-Toxaphene Group
The insecticides of this group, except for Toxaphene and Strobane
which are discussed below, are polychlorinated cyclic
hydrocarbons with endomethylene-bridged structures, prepared by
the Diels-Alder diene reaction. The development of these
materials resulted from the 1945 discovery of chlordane, the
chlorinated product of hexachlorocyclopentadiene and
cyclopentadiene. Figure III-6, a simplified process flow diagram
for this type of pesticide, illustrates the potential sources of
waste water in this process.
Cyclopentadiene, produced by cracking naphtha, is chlorinated to
yield hexachlorocyclopentadiene (CPD), the raw material basic to
the chemistry of this group of pesticides. Cyclopentadiene and
various vinyl organic compounds can be combined with CPD in the
Diels-Alder reactor.
Certain pesticides in this group can be epoxidized with hydrogen
peroxide or peracids to produce an analogous group of pesticide
compounds.
Toxaphene and Strobane are members of a group of incompletely
characterized, broad-spectrum, insecticidal compounds produced by
the chlorination of naturally occurring terpenes. They are
insoluble in water and generally have long residual effects.
These compounds, are unstable in the presence of alkali. Upon
prolonged exposure to .sunlight, and at temperatures above 155°C
hydrogen chloride is liberated.
27
-------
FIGURE fJi-6
GENERAL PROCESS FLOW DIAGRAM FOR ALDRIN-TOXAPHENE
PRODUCTION FACILITIES
ro
oo
CYCLOPENTADIENE
CHLORINE
CAUSTIC SODA
CHLORINATOR
VENT
1
WET
SCRUBBER
^ CTI TCD ^ DIE
' ' REAC
^
UJ
i CAKE^
£ INC^
3
r
TO
IERATOR
•n.iATcn
NE SOLVENT
TOR STRIPPER
TARS TO
INCINERATOR
PERACID
INTERMEDIATE SOLVENTi
OR
TECHNICAL
PRODUCT
1
OXIDATION
REACTOR
CATALYST
EXCESS TO
REACTOR
SOLVENT
STRIPPER
H20.
EXTRACTOR
PRODUCT
• CHLORINE ^WASTEWATER
I \ VENT-* , STEAM
J
U/ASTEWATER
I
FORMULATING
OR PACKAGING
OPERATIONS
CHLOR-
INATOR
RECOVERY
PRODUCT
-*«
PRODUCT
—RECYCLE,—
DUSTS, ETC.
WASTEWATER
ALTERNATE PRODUCT
-------
Wastewater generated in the production of this family of
pesticides are:
1. Vent gas scrubber water from caustic
soda scrubber
2. Aqueous phase from the epoxidation step
3. Wastewater from the water wash and product
purification units
1. Periodic equipment cleaning waste water
5. Wastes from cleanup of production areas.
Tars, off-specification products and filter cake should
not generate waste waters since they are usually incinerated.
Haloqenated Aliphatic Hydrocarbons
This group includes chlorinated aliphatic acids and their salts
(e.g., TCA, Dalapon, and Fenac herbicides), halogenated hydro-
carbon fumigants (e.g., methyl bromide, DBCP, and EDB), and the
insecticide Lindane. Figures III-7 and III-8 represent
simplified process flow diagrams for the production of
halogenated aliphatics and halogenated aliphatic acid pesticides.
Potential waste water sources are illustrated.
Chlorinated aliphatic acids can be prepared by nitric acid
oxidation of chloral (TCA), or by direct chlorination of the
acid. The acids can be sold as mono- or di-chloro acids, or
neutralized to an aqueous solution with caustic soda. The
neutralized solution is generally fed to a.dryer from which the
powdered product is packaged.
Wastewaters potentially produced during the manufacture of
pesticides in this groups are:
1. Condensate from steam jets
2. Acidic waste water from fractionation units
3. Cooler blowdown water
4. Excess mother liquor from centrifuges
5. Vent gas scrubber water from caustic
soda scrubber
6. Aqueous phase from decanter units
7. scrubber water from dryer units
8. Wash water from equipment cleanout
9. Process area clean up wastes.
Phosphorus-Containing Pesticides
The commercial organo-phosphorus pesticides, composed of
phosphates, phosphonates, phosphorothioates, phosphorodithioates.
29
-------
FIGURE III-7
GENERAL PROCESS FLOW DIAGRAM FOR HALOGENATED
ALIPHATIC HYDROCARBON PRODUCTION FACILITIES
co
o
STEAM
HYDROCARBON
HALOGEN
VENT
JL
EJECTOR
AND
BAROMETRIC
CONDENSER"
OR CAUSTIC
SCRUBBER
ACID
REACTOR
AND
STRIPPER
*SULFUR RELATED COMPOUNDS
FRACTIONATION
SYSTEM
-«- WATER
•*- WASTEWATER
DRYER
(SILICA GEL)
PACKAGING
ACID WASTEWATER TO RECOVERY
SILICA GEL DISPOSAL
OR REGENERATION
* SULFUR RELATED COMPOUNDS IS A RAW MATERIAL FOR PRODUCTS
-------
FIGURE III-8
<*>
WATER
GENERAL PROCESS FLOW DIAGRAM FOR HALOGENATED
ALIPHATIC ACID PRODUCTION FACILITIES
SCRUBBER
HCl.Clp
ALIPHATIC ACID-i I
-*~VENT
-*-WASTEWATER
VENT
t DUSTS & PARTICULATE
CHLORINE
CHLORINATOR
CATALYST
COOLER
WASTEWATER
CAUSTIC SODA
CRYSTALLIZER
CENTRIFUGE
RETURN
MOTHER
LIQUOR
DRYER
PRODUCT
SLOWDOWN
NEUTRALIZER
VENT
i DUSTS & PARTICULATE
PRINCIPAL PROCESSING ROUTE FOR ALTERNATIVE PRODUCT-TYPES
VENTS TO RECOVERY (SCRUBBER OR BAGHOUSE)
PRODUCT
(SALT OF THE
PESTICIDE)
AREA WASHDOWNS & SPILLS
-------
and phosphorus-nitrogen compounds, account for about 95 percent
of the phosphorus-containing pesticides produced today.
Seven of the 10 most popular organo-phosphorus compounds start
with the preparation of a phosphite triester (P (ORD) 3) which
can be readily oxidized to the respective phosphates, but is more
commonly reacted with a ketone or aldehyde having an alpha-carbon
halide. The product thus formed is a phosphate with an
unsaturated aliphatic grouping. These compounds can then be
halogenated across the double bond to form yet another compound
with pesticidal properties.
Phosphates and Phosphonates
Phosphates and phosphonates, such as trichlorfon, dischlovos,
TEPP and ethephon are grouped as phoshpite triesters. Figure
III-9 is a simplified process flow diagram of phosphite triester
production showing potential waste water sources.
In the manufacture of the phosphite triester, an alcohol and
phosphorus trichloride are fed to a reactor using a base (for
example, sodium carbonate) to produce the crude product, with
hydrogen chloride as a by-product. The phosphite triester is
then reacted with a chloroketone or chloraldehyde in a
reactor/stripper vessel. Light-ends are continuously removed
under vacuum. The condensible fraction containing the by-
product, alkyl halide, can be recovered but is generally wasted.
Noncondensibles captured in the steam condensate go to treatment.
The technical-grade intermediate dissolved in an inert solvent is
then halogenated. After halogenation in a batch
reactor/stripper, the vented gas is scrubbed with a solution of
caustic soda. This waste water goes to treatment. Then under
reduced pressure, the solvent is removed, condensed and recycled
back to the reactor. Condensate from the steam jet system is
collected for treatment.
Generally, ketone or aldehyde are manufactured on-site, and the
resulting waste water usually become part of the "pesticide"
process wastes.
Phosphorothioates and Phosphorodithioates
This family of pesticides includes the parathions, malathion,
ronnel, diazinon, Guthion, Dasanit, disulfoton, dimethoate,
chlopyrifos, ethion, Folex, and carbophenothion, each of which is
produced in greater than one million pounds quantity annually.
32
-------
FIGURE ni-9
CO
CO
GENERAL PROCESS FLOW DIAGRAM FOR PHOSPHATES
AND PHOSPHONATES PESTICIDE PRODUCTION FACILITIES
VENT
WATER/NaOH/S02
WATER
VENT
±
SCRUBBER
Na2C03
PCI'
ALCOHOL
STEAM
-WASTEWATER
REACTOR
REACTOR
KETONE OR ALDEHYDE
1
CONDENSER
VACUUM
JET
1 I
ALKYLHALIDE WASTEWATER
STRIPPER
REACTOR
HALOGEN
SCRUBBER
WASTEWATER
STRIPPER
SOLVENT RETURN
STEAM
CONDENSER
VACUUM
JET
I
WASTEWATEF
PRODUCT
STORAGE
-------
Figure III-10 is a generalized process and waste flow diagram for
this group of compounds. In the first step, phosphorus
pentasulfide (P.2S5) is reacted with an alcohol (generally in a
solvent) to form the dialkyl phosphorodithioic acid (dithio
acid). This is an anhydrous reaction.
The dithio acid can then be: (1) converted to a dithio salt, (2)
chlorinated to the dialkyl phosphorochloridothionate (DAPCT), or
(3) reacted, with an aldehyde or an alkene to form a desired
intermediate or product.
Using the production of the dithio salt as an example, caustic
soda is added to the dithio acid in a separate reactor to produce
the dithio salt. The dithio salt in the aqueous phase is
separated to be used in the next reaction step. The organic
phase serves to remove residuals, namely unreacted triester.
Solvent is recovered and returned to the dithio acid unit.
Wastes from the solvent recovery step are sent to treatment.
The dithio acid can also be chlorinated to produce a
phosphorochloriridithionate (PCT) which can combine with the
dithio salt in a condensation step. The crude PCT can be
purified by distillation., Distillation residues are hydrolyzed,
yielding sulfur and phosphoric acid as by-products. Organic
wastes require treatment, usually incineration.
The dithio acid can be further reacted with an aldehyde or alkene
under slightly acidic conditions in a batch process. Caustic
soda is added to maintain the correct pH. In the recovery
system, product is recovered, water-washed, and then air dried.
The recovery step waste products include distillation wastes and
solids (filter cake). Acid waste water from the wash step is
combined with scrubber water from the overhead drier. Together,
these waste waters constitute the major portion of the process
waste stream.
Pesticide removal from process waste water should take place (via
alkaline hydrolysis at elevated temperatures, carbon sorption,
etc.) before combining with other plant waste streams.
In summary, the following waste waters are generated during the
production of organo-phosphorus compounds:
1. Hydrolyzer waste water
2. Aqueous phase from product reactors
3. Wash water from product purification steps
U. Aqueous phase from solvent extractor
5. wastewater from overhead collectors and
caustic soda vent gas scrubbers
-------
FIGURE In_i0
GENERAL PROCESS FLOW DIAGRAM FOR PHOSPHOROTHIOATE
AND PHOSPHORODITHIOATE PRODUCTION FACILITIES
CA>
U1
AQUEOUS NaOH
VENT
SOLVENT
ROH
DITHIO
ACID
SOLVENT
RECOVERY
F
AQUEOUS
PHASE
NEUTRALIZATION
VENT
CHLORINE CHLORINATION * PURIFICATION
|*|
WASTES
I
ORGANIC
PRODUCT
REACTOR
EXTRACTOR
STILL
H
WASH
DISTILLATION
WASTES
FRESH SOLVENT
EXTRACTOR
WATER
DRIER
VENT
L 1
WATER
PRODUCT
STORAGE
AND
PACKAGING
WATER
OVERHEADS
COLLECTOR
ORGANIC
WASTES
HYDROLYZER
BY-PRODUCT WASTEWATER
SULFUR
-*• H3P04
*- ORGANICS TO WASTE TREATMENT
VENT GASES
H2S. THERMAL OXIDIER
HC1. PARTIAL RECOVERY
-------
6. Reactor and process equipment cleanout
waste waters
7. Area washdowns
Organo-Nitrogen Processes
The nitrogenous pesticides include the greatest number of
chemical types, the broadest raw material base, and the most
diverse process schemes. Product and process types to be
described are the aryl- and alkylcarbamates, thiocarbamates,
amides and amines, ureas and uracils, triazines, and the
nitroaromatics.
Aryl and Alkyl Carbamates and Related Compounds
The carbamates in this grouping include carbaryl, carbofuran,
chloropropham, BUX, aldicarb and propoxur. A generalized
production flow diagram is shown in Figure III-11 together with
the principal wastewater sources.
In general, carbamates are synthesized in a combination of batch
and continuous processes. Wastes include liquid streams, vents
and some heavy residues. Pesticide wastes will require
detoxification (via alkaline hydrolysis) before being sent to the
general plant treatment system. Vents are flared or pass through
a caustic scrubber. Heavy residue requires incineration.
Wdstewaters associated with the production of these compounds
are:
1. Brine process waste water from reactors
2. Wastewater from the caustic soda scrubbers
3. Aqueous phase wasted following the isocyanate
reaction
H. Reactor cleanout washwater
5. Area washdowns
Thiocarbamates
This family of pesticides include Eptam, butylate, vernolate,
pebulate and ETPC. In a series of semi-continuous and batch
operations, as shown in Figure III-12, phosgene is reacted with
an amine to give a carbamoyl chloride. Reaction of the cafbamoyl
chloride with a mercaptan gives the corresponding thiocarbamate.
Alternatively, the amine can be reacted with an alkyl
chlorothiolformate to yield the thiocarbamate. Thiocarbamates
are generally volatile compounds, and therefore, can be
distilled.
36
-------
FIGURE
CO
ALKYL CARBAMATE
CAUSTIC SODA
PHOSGENE
NAPHTHOL
ALKYL AMINE
ARYL CARBAMATE
ALKYL ISOCYANATE
CATALYST
GENERAL PROCESS FLOW DIAGRAM FOR ALKYL AND ARYL
CARBAMATE PRODUCTION FACILITIES
FLARE OR SCRUBBER
REACTOR
REACTOR
BRINE
WASTEWATER
CATECHOL
METHALLYL ,
CHCl3-i
REACTOR
CHLORIDE
KETONE (BASF}
i-WATER
PURIFICATION
1
-K;HCI •
DISTILLATION
REACTOR
VENT
DUST
COLLECTOR
PACKAGING
-SOLVENT
REACTOR
DISTILLATION
LIQUID WASTE
PRO
DUCT
WASTEWATER
-------
FIGURE 111-12
GENERAL PROCESS FLOW DIAGRAM FOR
THIOCARBAMATE PRODUCT FACILITIES
MERCAPTAN
CAUSTIC SODA
VENT
CO
oo
AMINE
PHOSGENE
REACTOR
REACTOR
ACID
WASTEWATER
RECYCLE
BRINE
I
VENT
STILL
PACKAGING
TARS
WASTE TREATMENT
-------
Acidic process waste waters from the first reactor are combined
with the brine wastes from the second reactor, and together mixed
with vent gas scrubber water before treatment. Still bottoms are
generally incinerated. Liquid wastes are biodegradable,
especially following acid or alkaline hydrolysis at elevated
temperatures.
In summary, the production of thiocarbamates will generate the
following Waste waters:
1. Acid waste water from the initial
reaction step
2. Brine from the second reaction step
3. wastewater from caustic soda scrubbers
U. Kettle clean-out wash waters
5. Area washdowns.
Amides and Amines (without sulfur)
Compounds in this group include Deet, naptalam, CDAA, propachlor,
alachlor, propanil and diphenamid, each of which has been
produced at greater than one million pounds per year. Typically,
these herbicides include two major groups: herbicides based on
substituted anilide structures and chloroacetamide derivatives.
A generalized process flow diagram, indicating waste water
sources, is presented in Figure 111-13. Briefly, the process is
based on the reaction of an acetyl chloride with a suitable
amine. Generally, the amine is prepared within the same plant.
Wastewater from the preparation of the amine can be included in
the raw waste load for the production of these pesticides. Such
waste waters are generated from the intermediate product
separation and purification steps. If the acetyl chloride is
also prepared on-site, then acidic process waste water from the
purification step and vent gas scrubbers should be considered
part of the overall pesticide raw waste water loads.
In summary, waste waters resulting from the production of the
amide and amine group of pesticides are:
1. Aqueous fractions from reactors
2. Wastewater from purification steps
3. Vacuum jet condensate
U. Wastewater removed in purification step
5. Water from washing steps
6. Kettle cleanout wastes
7. Area washdowns
39
-------
FIGURE III-13
GENERAL PROCESS FLOW DIAGRAM FOR
AMIDE AND AMINE PRODUCTION FACILITIES
ACETYLCHLORIDE
.*»
o
AMINE
ALDEHYDE
OR KETONE
REACTOR
PURIFICATION
WATER
REACTOR
NH4OH
PURIFICATION
WASHING
AND
DRYING
PACKAGING
-WASTEWATER
-------
Ureas and Uracils
Pesticides in this group include diuron, monuron fluometuron,
linuron and norea urea compounds and the herbicide bromacil, each
of which has a production level in excess of one million pounds
per year.
The production of monuron is typical of the general process used
to manufacture this family of pesticides. Figure 111-14 shows
the generalized process flow diagram and waste water sources
associated with the production process. Reaction of para-
chloroaniline in dioxane or another inert solvent with anhydrous
hydrogen chloride and phosgene generates para-chlorophenyl
isocyanate, which then can be reacted with dimethylamine to yield
monuron. Another commercial process involves the reaction of an
aniline and urea, in alcohol or phenol solvent, to generate the
phenyl isocyanate, which is further reacted with an appropriate
amine. The ureas are generally insoluble in the inert solvent
and precipitate out. The inert solvent can be flash-distilled
and recycled to the reactor. Aqueous hydrochloric acid is added
to the crude product to remove insoluble components. The product
is then water washed in a precipitator to yield the final
product.
Uracils are a relatively new class of herbicides whose group is
growing. The process illustrated in Figure 111-14 is as follows:
an alkylamine, phosgene, and ammonia are reacted to yield an
alkyl urea; following a caustic wash purification step, the alkyl
urea is then reacted with an alkyl acetoacetate, caustic washed
and neutralized with sulfuric acid; the uracil can then be
halogenated (commonly with bromine), filtered, dried and finally
packaged.
No solid wastes are generated and no significant quantities of
chemicals are recycled. Liquid wastes from the purification,
neutralization and filtration steps require treatment via either
biological oxidation or incineration technologies.
In summary, waste waters generated in the manufacture of urea and
uracil pesticides can be as follows:
1. Aqueous wastes from precipitator (Urea)
2. Scrubber waters (Urea and Uracil)
3. Brine from purification steps (Uracil)
4. Aqueous sodium sulphate from neutraliz-
ation and intermediate product
separations (Uracil)
5. Brine from filtration
6. Reactor wash water (Urea and Uracil)
7. Production area washdowns (Urea and Uracil)
41
-------
ro
UREAS.
SOLVENT
AMINE
UREA
WATER-INVENT
I
SCRUBBER
FIGURE 111-14
GENERAL PROCESS FLOW DIAGRAM FOR UREA AND URACILS
PRODUCTION FACILITIES
ALKYLANILINE
NH3
•^WASTEWATER
REACTOR
AQUEOUS
HC1 —
DISTILLATION
WASTEWATER
URACILS
ETHYL ACETOACETATE
WATER
EXTRACTOR
tK
t
PRECIPITATOR
PRODUCT
PACKAGING
TARS TO INSOLUBLES WASTEWATER
INCINERATION
HALOGEN
CAUSTIC SODA
I
VENT
PHOSGENE
AMMONIA
ALKYL ANILINE*
UREA
UNIT
PURIFICATION*
URACILj
UNIT
VENT
BRINE
WASTEWATER
NEUTRAL-
PURIFICATIONM CATION
SEPARATION
r
WATER
WASTEWATER
HALOGENATOR
FILTRATION
DRYING
*
PRODUCT
PACKING
r
WASTES
BRINE
WASTEWATER
-------
s-Triazines
The starting material for the production of the s-triazines is
cyanuric chloride. It is obtained industrially by trimerization
of cyanogen chloride. A generalized process flow diagram showing
potential wastewater sources is presented in Figure III-15. One
chlorine atom is replaced by an amine, phenol, alcohol,
mercaptan, thiophenol or a related compound under controlled
reaction conditions. Hydrogen chloride and hydrogen cyanide
gases are evolved and vented. The gases pass through a caustic
soda scrubber, and the resulting scrubber waste water requires
treatment.
Amination of the cyanuric chloride, as depicted in Figure 111-15,
requires one to three steps in a continuous process. Solvent can
be recovered and recycled to the process. The liquid wastes are
combined with the caustic scrubber waters prior to combined
treatment.
Dust generated in formulation and packaging is collected in a
baghouse and then returned to process. Vapors are caustic
scrubbed and combined with other process waste streams.
In summary, waste waters generated in the production of triazine
herbicides generally come from the following sources:
1. Caustic soda scrubbing and filtration of
vented HC1 and HCN gases
2. Aqueous wastes from the solvent recovery
unit
3. Scrubber water from the air pollution
control equipment used in formulation
areas
H. Production area washdowns
5. Reactor clean-out wash waters
Nitro Compounds
This family of organo-nitrogen pesticides includes the nitro
phenols (and their salts), for example, dinoseb, and the
substituted dinitroanilines, trifluralin and nitralin, each of
which amounts to more than one million pounds annually of active
ingredients.
An example of a typical commercial process for the production of
a dinitroaniline herbicide is illustrated in Figure 111-16. In
this example, a chloroaromatic is charged to a nitrator with
cyclic acid and fuming nitric acid. The crude product is then
-------
FIGURE 111-15
GENERAL PROCESS FLOW DIAGRAM FOR S-TRIAZINE
PRODUCTION FACILITIES
SOLVENT ^ ADDITIVES
AMINE
^ OR
> >
CHLORINE _ rVAMIRTP AMTNATTnw —
CHLORINE H;3N3C1 3 — > U^
HYDROGEN CYANIDE UNIT , > TC
HC1 ,HCN
CAUSTIC SODA
,, ,, ^- soi
_ ^_ nrrf
SOLVENTS
PAr.kARTNR . i
JIT (1 ^TRIAZINE— »• FORMULATION U AND -J PRODUCT
i .
> '
VENT 4
\\irrt\j «
SCRUBBER
AND
FILTER
WASTEWATER WAS'
>
DUST -
BAGHOUSE
CAUSTIC SODA
> ' *
f
FEWATER
VENT
SCRUBBER | '
WASTEWATER
-------
FIGURE iIM6
GENERAL PROCESS FLOW DIAGRAM FOR NITRO-TYPE PESTICIDES
CAUSTIC SODA
WATER
AMINE
SOLVENT
NITRIC ACID
CHLORO AROMATIC
MONONITRATOR
SULFURIC ACID
DINITRATOR
SPENT ACID
FILTRATION
AROMATIC
AMINATION
REACTOR
FILTER
AND
DECANTER
VENT
STILL
PRODUCT
VACUUM
EXHAUSTS
WASTEWATER
ACID
RECOVERY
CAUSTIC SODA
NOxGASES
SCRUBBER
T
WASTEWATER
-------
cooled to settle out spent acid, which can be recovered and
recycled. Oxides of nitrogen are vented and caustic scrubbed.
The mono-nitrated product is then charged continuously to another
nitrater containing 100 percent sulfuric acid and fuming nitric
acid at an elevated temperature.
The dinitro product is then cooled and filtered (the spent acid
liquor is recoverable) , the cake is washed with water, and the
resulting wash water is sent to the waste water treatment plant.
The dinitro compound is then dissolved in an appropriate solvent
and added to the amination reactor with water and soda ash. An
a mine is then reacted with the dinitro compound. The crude
ptoduct is passed through a filter press and decanter and finally
vacuum distilled. The salt-water layer from the decanter is
discharged for treatment. The solvent fraction can be recycled
to the reactor, and vacuum exhausts are caustic scrubbed. Still
bottoms are generally incinerated.
In summary, waste waters generated during the production of the
nitro family of pesticides are:
1. Aqueous wastes from the filter and the de-
canting system
2. Distillation vacuum exhaust scrubber wastes
3. Caustic scrubber waste waters
U. Periodic kettle cleanout wastes
5. Production area washdowns
Subcategory 2—Metallo-Qrganic Pesticides
The metallo-organic group of pesticides includes the organic
arsenicals and the dithiocarbamate metal complexes. A discussion
of their manufacture and waste water sources is also applicable
to the production of other compounds in this group.
Monosodium methanearsenate (MSMA) is the most widely produced of
the group of organo-arsenic herbicides (estimated production in
1972 was 2U million pounds) that also includes the octyl- and
dodecyl-ammonium salts, the disodium salt (DSMA), and cacodylic
acid (dimethylarsenic acid) . DSMA can serve as an intermediate
in the manufacture of all the others.
The process is described by the production and waste schematic
flow diagram presented in Figure 111-17.
The first step of the process is performed in a separate,
dedicated building. The drums of arsenic tri-oxide are opened in
an air-evacuated chamber and automatically dumped into 50 percent
-------
FIGURE UI-17
WATER-
GENERAL PROCESS FLOW DIAGRAM FOR ARSENIC-TYPE
METALLO-ORGANIC PRODUCTION
DUST
COLLECTOR
ALKYL CHLORINE
As203
NaOH
WATER
VENT
WET
SCRUBBER
WASTEWATER
WMI
1
PURIFICATION
PRODUCT
STORAGE
REACTOR
INTERMEDIATE
PRODUCT
STORAGE
REACTOR
H2S04
REACTOR
WASTEWATER
PRODUCT
STORAGE
EVAPORATOR
I
AQUEOUS
ALCOHOL WA
CENTRIFUGE
STRIPPER
I
c6h
ALCOHOL
BY-PRODUCT
ER
SOLIDS
LIQUID J,
~~j TO APPROVED
LANDFILL
-------
caustic soda. A dust collection system is employed. The drums
are carefully washed with water, the wash water is added to the
reaction mixture, and the drums are crushed and sold as scrap
metal. The intermediate sodium arsenite is obtained as a 25
percent solution and is stored in large tanks prior to further
reaction. In the next step, the 25 percent sodium arsenite is
treated with methyl chloride to give the disodium salt, DSMA.
DSMA can be sold as a herbicide; however, it is more generally
converted to the monosodium arsenate, MSMA, which has more
favorable application properties.
In order to obtain MSMA, the solution is partially acidified with
sulfuric acid and the resulting solution concentrated by
evaporation. As the aqueous solution is being concentrated, a
mixture of sodium sulfate and sodium chloride precipitates out
(about 0.5 kg per 100 kg of active ingredient) . These salts are
a troublesome disposal problem because they are contaminated with
arsenic. The salts are removed by centrifugation, washed in a
multi-stage, counter-current washing cycle, and then disposed of
in an approved landfill.
Methanol, a side product of methyl chloride hydrolysis, can be
recovered and reused. In addition, recovered water is recycled.
The products are formulated on site as solutions (for example, 48
percent (6 Ib A. I./gal) and 58 percent (8 Ib A. I./gal) and
shipped in 1 to 30-gallon containers.
Figure III-18 is a typical process and waste generation schematic
flow diagram for the production of ethylene bisdithiocarbamate
metal complexes. Raw materials include carbon disulfide,
ethylene diamine and sodium hydroxide (50 percent). These
materials are first reacted in a stainless steel, cooled vessel.
The exothermic reaction is controlled by the feed rate. Excess
carbon disulfide is distilled, collected, and eventually recycled
to the reactor. The sodium hydroxide addition controls pH. The
resulting concentrated Nabam intermediate solution is reacted
(within 24 hours) with a sulfate, and the desired metal organic
complex is precipitated. The slurry is water washed to remove
sodium sulfate and then dried to less than 1 percent water
content. Process by-products include sodium sulfate and small
amounts of carbon disulfide and sodium hydroxide.
Air emissions are controlled by cyclone collectors, bag filters,
and scrubbers. The small amount of hydrogen sulfide from process
vents is caustic scrubbed before release to the atmosphere. The
liquid waste streams contain primarily salt.
-------
FIGURE 111-18
GENERAL PROCESS FLOW DIAGRAM FOR CERTAIN DITHIOCARBAMATE
METALLO-ORGANIC PRODUCTION
V.O
VENT
NaOH
CYCLONE
COLLECTOR
WATER
ETHYLENEDIAMINE
cs2
NaOH
METAL SULFATE
i
REA
T
WASTEWATER
rrnD INTERMEDIATE
^ STORAGE
BINDER
?"7" WATER
-;'••'
- s
— ». REACTOR -*. WA
r-i ^1L
t
1
1
1
|
ATQ
niK
•
LURRY
SH AND
FRATION
IM
> '
VE
WATER-
BAGHOUSE
I—AIR-
DRIER
WASTEWATER
NT
SCRUBBER
T
WASTEWATER
SOLIDS
FORMULATION
AND
PACKAGING
-------
In summary, waste waters generated in the preparation of metallo-
organics are from the following areas:
1. Spillage from drum washing operations
2. Washwater from product purification steps
3. Scrub water from vent gas scrubber unit
4. Process waste water
5. Area washdowns
6. Equipment cleanout wastes.
Subcategory 3--Formulators and Packagers
Pesticide formulations can be classified as liquids, granules,
dusts and powders. There are approximately 3400 formulation
plants registered with the Agency.
The scale on which pesticides are produced covers a broad range.
Undoubtedly, many of the small firms, having only one product
registration, produce only a few hundred pounds of formulated
pesticides each year. At least one plant that operated in the
range of 100,000,000 pounds of formulated product per year has
been identified. The bulk of pesticide formulations, however, is
apparently produced by independent formulators operating in the
20,000,000 to 40,000,000 pounds per year range.
Formulation Processes
Most pesticides are formulated in mixing equipment that is used
only for pesticide formulations. The most important unit opera-
tions involved are dry mixing and grinding of solids, dissolving
solids, and blending. Formulation systems are virtually all
batch mixing operations. Formulation units may be completely
enclosed within a building or may be in the open, depending
primarily on the geographical location of the plant.
Individual formulation units are normally not highly
sophisticated systems. Rather, they are comparatively
uncomplicated batch-blending systems that are designed to meet
the requirements of a given company, location, rate of
production, and available equipment. Production units
representative of the liquid and solid formulation equipment in
use are described in the following subsections.
Liquid Formulation Units: A typical liquid unit is depicted in
Figure III-19. Technical grade pesticide is usually stored in
its original shipping container in the warehouse section of the
plant until it is needed. When technical material is received in
bulk, however, it is transferred to holding tanks for storage.
50
-------
FIGURE 111-19
LIQUID FORMULATION UNIT
PESTICIDE
(55 GAL. DRUM)
.STEAM
-COOLING WATER
PRODUCT
(55 GAL. DRUM)
I m
SCALE I
PUMP
-------
Batch-mixing tanks are frequently open-top vessels with a
standard agitator. The mix tank may or may not be equipped with
a heating/cooling system. When solid technical material is to be
used, a melt tank is required before this material is added to
the mix tank. Solvents are normally stored in bulk tanks. an
exact quantity of an appropriate solvent is either metered into
the mix tank, or determined by measuring the tank level.
Necessary blending agents (emulsifiers, synergists, etc.) are
added directly from the mix tank. The formulated material is
frequently pumped to a holding tank before being put into
containers for shipment. Before being packaged, many liquid
formulations must be filtered by conventional cartridge filters
or equivalent polishing filters.
Air pollution control equipment used on liquid formulation units
typically involves an exhaust system at all potential sources of
emission. Storage and holding tanks, mix tanks, and container—
filling lines are normally provided with an exhaust connection or
hood to remove any vapors. The exhaust from the system normally
discharges to a scrubber system or to the atmosphere.
Dusts and Wettable Powders; Dusts and powders are manufactured
by mixing the technical material with the appropriate inert
carrier, and grinding this mixture to obtain the correct particle
size. Mixing can be affected by a number of rotary or ribbon
blender type mixers. See Figure 111-20.
Particulate emissions from grinding and blending processes can be
most efficiently controlled by baghouse systems. Vents from feed
hoppers, crushers, pulverizers, blenders, mills, and cyclones are
typically routed to baghouses for product recovery. This method
is preferrable to the use of wet scrubbers, however even scrubber
effluent can be largely eliminated by recirculation.
Granules; Granules are formulated in systems similar to the
mixing sections of dust plants. The active ingredient is
adsorbed onto a sized, granular carrier such as clay or a
botanical material. This is accomplished in various capacity
mixers that generally resemble cement mixers.
If the technical material is a liquid, it can be sprayed directly
onto the granules. Solid technical material is usually melted or
dissolved in a solvent in order to provide adequate dispersion on
the granules. The last step in the formulation process, prior to
intermediate storage before packaging, is screening to remove
fines.
Packaging and storage; The last operation conducted at the
formulation plant is packaging the finished pesticide into a
52
-------
Figure II1-20
Dry Formulation Unit
-EEC
4OP
i 1
PERj
X
r £ i
j j SILICE
I J HOPPER
1
1
1
r
CRUSHER
\y
f
i
PULVERIZER
»,
h
i
BAGHOUSE
BLENDER
-€7
1
BARREL
FILLERS
TO
—• ii ••
ATMOSPHERE
a) Premix Grinding
PREMIXED
MATERIAL
SILICA
WETTING
AGENT
TO
•••Waii
ATMOSPHERE
TO
••HMW
ATMOSPHERE
REVERSE -JET
BAGHOUSE
REVERSE-JET
BAGHOUSE
HIGH SPEED
GRINDING
MILL
AIR
TO
(••••(•••H
ATMOSPHERE
AIR
FINISHED PRODUCT
b) Final Grinding and Blending
53
-------
marketable container. This is usually done in conventional
filling and packaging units. Frequently, the same liquid filling
line is used to fill products from several formulation units; the
filling and packaging line is simply moved from one formulation
unit to another. Packages of almost every size and type are
used, including 1, 2, and 5-gallon cans, 30 and 55-gallon drums,
glass bottles, bags, cartons, and plastic jugs.
On-site storage, as a general rule, is minimized. The storage
facility is very often a building completely separate from the
actual formulation and filling operation. In almost all cases,
the storage area is at least located in a part of the building
separate from the formulation units in order to avoid contamin-
ation and other problems. Technical material, except for bulk
shipments, is usually stored in a special section of the product
storage area.
In formulation and packaging plants, waste waters can be
potentially generated at several sources. These sources and
operations are discussed in the following subsection.
Miscellaneous Plant Operations
For housekeeping purposes, most formulators clean buildings which
house formulation units on a routine basis. Prior to washdown,
as much dust, dirt, etc., as possible is swept and vacuumed up.
The waste water from the building washdown is normally contained
within the building, and is disposed of in whatever manner is
used for other contaminated waste water. At least one plant had
raised curbs around all floor drains and across all doorways to
keep spills within the area. Absorbent compounds and vacuum
sweepers are then used to collect the contaminants.
Water-scrubbing devices are often used to control emissions to
the air. Most of these devices generate a waste water stream
that may be contaminated with pesticidal materials. Although the
quantity of water in the system is high, about 20 gallons per
1,000 cfm, water consumption is kept low by a recycle-sludge re-
moval system. Effluent from air pollution control equipment
should be disposed of with other contaminated waste water. One
type of widely used air scrubber is the toro-clone separator, in
which air is cleaned by centrifugal force.
A few formulation plants process used pesticide drums so that
they can be sold to a drum reconditioner or reused by the
formulator for appropriate products, or simply to decontaminate
the drums before they are disposed of. Drum-washing procedures
range from a single rinse with a small volume of caustic solution
or water to complete decontamination and reconditioning
-------
processes. Wastewaters from drum-washing operations are
contained within the processing area and treated with other
processing waste waters.
Most of the larger formulation plants have some type of control
laboratory on the plant site, Wastewater from the control
laboratories, relative to the production operations, can range
from an insignificantly small, slightly contaminated stream to a
rather concentrated source of contamination. In many cases, this
stream can .be discharged into the sanitary waste or municipal
treatment system. Larger, more highly contaminated streams, how-
ever, must be treated along with other contaminated waste waters.
The major source of contaminated waste water from pesticide
formulation plants is equipment cleanup. Formulation lines,
including filling equipment, must be cleaned out periodically to
prevent cross-contamination of one product with another, and
occasionally that needed maintenance may be performed. When
possible, equipment is washed with formula solvent. The
collected solvent can be used in the next formulation of the same
product.
Liquid formulation lines are cleaned out most frequently and
generally require the most water. All parts of the system that
potentially contain pesticidal ingredients must be washed. More
than one rinsing of process vessels and lines is required to get
the system clean. As a general rule, the smaller the capacity of
the line, the more critical cleanup becomes, in order to avoid
cross contamination. Thus, large volumes of washwater are
required, relative to production quantity, for smaller units.
Granule, as well as dust and powder lines, also require cleanup.
Liquid washouts are generally required, however, only in that
portion of the units where liquids are normally present, i.e.,
the active ingredient pumping system, scales, and lines. The
remainder of these production units can normally be cleaned out
.by "dry washing" with an inert material, such as clay.
Spills of technical material or material in process are normally
absorbed on sand or clay, and are disposed of with other
potentially toxic solid wastes in a Class-1 landfill. If the
spill area is washed down, the resultant waste water should be
disposed of with the other contaminated waste waters.
Natural .runoff at formulating and packaging plants, if not
properly handled, can become a major factor in the operation of
waste water systems simply because of the relatively high flow
and the fact that normal plant waste water volumes are generally
extremely low. Isolation of runoff from any contaminated process
55
-------
areas or waste waters, however, eliminates its potential for
becoming significantly contaminated with pesticides.
Uncontaminated runoff is usually allowed to drain naturally from
the plant site.
In some plants, the formulation units, filling lines, and storage
areas are located in the open. The runoff from these potentially
contaminated areas, as a rule, cannot be assumed to be free of
pollutants and should not be allowed to discharge directly from
the plant site.
In summary, waste waters generated at formulator and packaging
plants are:
1. Formulation equipment cleanup
2. Spill washdown
3. Drum washing
U. Air pollution control devices
5. Area runoff
56
-------
SECTION IV
INDUSTRIAL SUBCATEGORIZATION
The purpose of subcategorization is to account for differences in
technological achievement, economic impact and other consequences
when applying limitations to a category. The rationale for
subcategorization of the pesticides category assignment can be
based on factors such as (1) composition and/or quantity of waste
produced; (2) feasibility and effectiveness of treatment; and (3)
the cost of treatment. While mitigating factors such as plant
age and size also affect to a lesser extent the composition and
quantity of waste produced, the important differences were in
waste quantity, treatability, engineering, and cost. The
discussion that follows considers these factors in more detail.
Manufacturing Processes
Pesticide plants manufacturing active ingredient products employ
a number of unit processes in series. The principal processes
utilized include chemical synthesis, separation, recovery,
purification, and product finishing.
Chemical syntheses include chlorination, alkylation, nitration,
as well as many other reactions. Separation processes include
filtration, decantation, extraction and centrifugation. Recovery
and purification are utilized to reclaim solvents or excess
reactants as well as to purify intermediates and final products.
Evaporation and distillation, are also common. Product finishing
includes operations such as blending, dilution, pelletizing,
packaging, and canning.
Since these diverse processes are used by all sectors in the
synthesis of active ingredients, the type of manufacturing
process alone is not a comprehensive basis for subcategory
assignment.
A significant process difference does exist between active
ingredient manufacturing operations and formulating and
packaging. Besides the process differences, less water is used
in formulating and packaging. Less (if any) wastes are
generated, and less treatment is needed.
Product
There are several ways to group pesticides. For example, the
November 1, 1976, regulation for this industry utilized chemical
structure to differentiate halogenated organic, organo-
57
-------
phosphorus, organo-nitrogen, and metallo-organic products. Some
of these groups were further divided, such as the s-triazine
pesticides (exempted from regulation pending further study).
A listing of major pesticide chemicals covered in this regulation
is presented in Table X-l. As this table shows, many pesticides
contain a number of elements such as halogens, phosphorus,
nitrogen, sulfur, and oxygen. Investigation revealed the
disadvantage in establishing separate subcategories for halogen,
phosphorus, and nitrogen pesticides. Certain products contained
combinations of these elements, and thus could only be assigned
to subcategories by greatest similarity to that subcategory. In
addition, many plants produced products in more than one of these
s ubc at egor i es.
It was concluded that placing non-metallic halogenated,
phosphorus, and nitrogen compounds in one group would result in a
more logical and equitable basis for subcategorization. This
conclusion is supported by the nature and treatability of wastes
generated. separate subcategories are maintained for metallo-
organic pesticide chemicals and pesticide chemicals formulating
and packaging which do not need to discharge process waste
waters.
Raw Materials
The raw materials used in the pesticide chemicals industry are
specific to the product being manufactured. Within narrow ranges
of quality and purity, variations in raw material do have a
significant impact on the quantities of waste products generated.
However, the waste loads are so diverse that no groupings
(subcategorization scheme) could be made, (See Section V). The
quantity and composition of wastes generated is also determined
by whether the raw materials are purchased or produced captiveiy.
Irrespective of raw material source, the waste waters were found
to be amenable to pesticide removal, equalization and biological
treatment. Thus, the selection of raw materials is not a
significant factor on which to base further subcategorization.,
58
-------
Plant Size
There are more than 100 plants in the United States engaged in
the production of pesticide active ingredients, and as many as
3,000 facilities formulating the active ingredients into final
products. These are marketed as liquids, dusts, and packaged
aerosols. In order to determine whether plant size is a factor
in subcategorization, the raw waste loads (kg/kkg) for each plant
were plotted versus plant production (1000 Ib/day). No uniform
correlation could be made. Plant size should also not affect the
applicability or performance of treatment technologies as
outlined in later sections of this document, but may affect the
cost of treatment facilities and cost per unit of production.
Accordingly, plant size is not considered as a major criterion
for subcategorization, but has been taken into consideration in
the cost estimates.
Plant Age
Pesticide plants are relatively new, commissioned predominantly
in the post-World War II period, and the general processing
technologies have not changed appreciably. The use of different
processing modes, such as batch, semi-continuous, and continuous,
depends on product type, inherent process requirements, and
economies of scale. The individual process lines are modified as
needed for product or process changes, but plant age is not
reflective of existing process systems at any given plant site
since new processes are normally installed at old and new
facilities alike. Therefore, it is concluded that plant age is
not a significant factor for subcategorization.
Plant Location
As indicated by Figure III-1, pesticide chemicals manufacturing
plants are distributed throughout the United States although they
are primarily concentrated in the eastern and southern regions.
Based on analyses of existing data presented in recent studies
and the results of plant visits to the southern, midwestern, and
northern geographical areas of the country, plant location has
little effect on the quality or quantity of the waste water
generated. Geographic location, however, can influence the
performance of aerated and stabilization lagoons or evaporation
basins. Poor performance problems (temperature related) can be
overcome by adequate sizing or selection of alternative
processes, such as activated sludge. Moisture related problems
can be overcome by coverings.
Most pesticide plants are relatively new, and the trend in the
chemical industry is to locate outside urban areas. Those plants
59
-------
that are located in urban areas tend to occupy and own less land,
with the result that land costs for treatment facilities are
higher than for plants located in rural areas. Urban plants have
alternative technologies available to them which require less
land area, and achieve the same results.
Taking the above points into account, it can be said that, other
than costs associated with land availability, plant location is
not a significant factor for further subcategorization.
Housekeeping
Housekeeping practices vary within the category. However, they
are influenced more by the philosophy of the company and the
personnel involved than by the manufacturing process or product
mix. In many cases, plants with comprehensive treatment
facilities or a history of good treatment also exhibit good
housekeeping techniques. This practice is founded on necessity
and experience which dictate that good treatment requires good
housekeeping.
In view of these findings it is concluded that housekeeping is
not a reasonable factor for subcategorization.
Air Pollution Control Equipment
Air pollution control problems and equipment utilized are not
generally unique to different segments of this point source
category. Vapors and toxic gas fumes are frequently incinerated.
Particulates can be removed by either baghouses or wet scrubbing
devices. In all cases, the wastes produced by air pollution
control devices are readily treatable for all subcategories and
do not serve as a basis for subcategorization.
Nature of the Wastes Generated
The quality and quantity of the wastes generated by the
pesticides chemicals industry are discussed fully in Section V.
Tfye nature of the wastes generated is a supporting basis for
subcategorization. As Figures V-l through V-6 demonstrate, there
are no consistent differences in raw waste loads among the
various chemical families of the organic pesticide chemicals
industry. However, the metallo-organic manufacturers and
formulators/packagers generate smaller volumes, if any at all.
The nature of wastes generated is thus a supporting factor for
subcategori zation.
60
-------
Treatability of Wastewaters
The waste waters generated from the manufacture of organic
pesticide chemicals are currently being treated by combinations
of activated carbon or hydrolysis pesticide removal, equal-
ization, and biological systems. Activated carbon was previously
believed to be used only for halogenated pesticides. It is now
known that it is frequently used in the treatment of nitrogen
based pesticides and is also applicable to phosphorus based
pesticides. No end-of-pipe treatment is required for the
metallo-organic pesticides covered in this document. Recycle
techniques and concentrating waste streams and hauling them to
approved landfills have proven to be an economically sound
technique, resulting in no discharge of process waste waters.
The low flows generated by formulating and packaging can be
suitably controlled by recycle, reuse, or evaporation. Many
formulating operations generate no waste water and therefore
require no treatment.
Summary of Considerations
For the purpose of establishing effluent limitations it was
concluded that the pesticide chemicals point source category
should be grouped into three subcategories. This
subcategorization is based on distinct differences in the volume
of wastes generated, treatability and manufacturing process.
The pesticide chemicals manufacturing point source category has
been grouped into the following subcategories:
1. Organic pesticide chemicals manufacturing.
2. Metallo-organic pesticide chemicals
manufacturing.
3. Pesticide chemicals formulating and packaging.
It should be made clear that the production operations so
categorized occur in combinations at many plants and that it is
possible for a given facility to be associated with all of the
subcategories as well as with other chemical production. It is
further recognized that many plants produce or use intermediate
products. These factors are discussed in Section IX under
"Factors to be Considered in Applying Effluent Guidelines."
61
-------
SECTION V
WASTEWATER CHARACTERISTICS
The purpose of this section is to define the waste water quality
and quantity for plants in those subcategories identified in
Section IV. Based on these data, design criteria are developed
for the model treatment technologies presented in Section VII.
The raw waste load data are thus used only for cost analyses, and
not in the development of effluent guidelines. Under no
conditions should the raw waste load design criteria be construed
to be exemplary or used as a basis for pretreatment guidelines
for industrial discharges into publicly owned treatment works.
The term raw waste load, as utilized in this document, is defined
as the quantity of a pollutant in waste water prior to a
treatment process, whether the process is carbon adsorption,
hydrolysis, or biological treatment. It is normally expressed in
terms of mass (weight) units per day or per production unit. In
several cases plants are producing pesticides, intermediates, and
nonpesticide products concurrently. If monitoring at these
plants was insufficient to separate the waste water contribution
due to the pesticide portion, then the mass unit loading . was
divided by the total plant production. A discussion of the
interpretation of effluent guidelines based on this assumption is
presented in Section IX.
Due to the volume of information available, Subcategory 1 data
remain grouped by chemical structure (i.e., halogenated,
phosphorus, or nitrogen). In the latter part of this section,
however, design criteria are developed using all available data
for the subcategory as defined in Section IV.
Subcateqory _1—Organic Pesticide Chemicals
Process waste waters from Subcategory 1 may result from the
following steps: decanting, distillation, stripping,
extraction/precipitation, and purification. High organic and
solids loadings may be caused by equipment cleanout, area
washdowns, accidental spillage, or poor operation. Caustic
scrubbers and contact cooling may contribute significantly to
total flow. A summary of sources of wastes from processing units
utilized in the manufacturing of organic pesticides unit
operations is contained in Table V-l. A summary of raw waste
loads for organic pesticide manufacturers is presented in Table
V-2.
Preceding page blank 63
-------
TABLE V-l
SUMMARY OF POTENTIAL PROCESS—ASSOCIATED WASTE WATER SOURCES
FROM ORGANIC PESTICIDE PRODUCTION
Processing Unit
Acid recovery unit
Air pollution control equipment
All plant areas
Caustic scrubber
Centrifuges
Crystallizer, dryer, flakers,
prilling
Decanter
Distillation tower
Dust wet scrubbers
Extractor/precipitator
Filtration
Hydrolyzer/extractor
Incinerator exhaust scrubbers
Intermediate product neutralizer
Source
Liquid wastes
Aqueous suspension
Run-off, area
washdowns
Vented process gases
Spent caustic solu-
Mother liqueur
Dusts, mists
Aqueous layer
Organic layer
Distillation residues
and tars
Aqueous suspension
Aqueous wastes
Filtrate
Aqueous layer
Scrubber water
Spillage
Intermediate product purification Neutralized aqueous
Intermediate product reactor Reaction product
Nature of
Waste Water Contaminants
High pH
High suspended solids, relatively low
dissolved organics and solids
Intermittent flow, low organics, variable pH, variable
suspended solids, variable salt content
High pH, possible by-product HCN, high flow, low organics,
low organics, high dissolved solids
High organics, generally toxic
High toxic organics, high
total suspended solids
High salt content, dissolved organics, separable
organic sludge, NH3-N and TKN
High organic, low dissolved organic salt or sludge
High organic, low solubility in water,
frequently high chlorine content
High total suspended solids, high toxic organics
High dissolved and suspended organics, high pH and
frequently high dissolved solids and high NH3-N
High pH, dissolved organics and dissolved solids
High pH, high COD, high dissolved solids, organic sludge
Dissolved inorganics, high pH
Low waste loss, pH variable, high organic,
high dissolved solids
pH, high dissolved organics and dissolved solids
Intermittent flow, high dissolved solids, pH
variable, organic content variable
-------
TABLE V-l (Continued)
Processing Unit
Nitrators
Overheads collector
Product recovery
Product washers
Purification
Reactors
Scrubber from cyanuric
chloride unit
Settling tank
Solvent recovery
Solvent strippers
Vacuum jets
Wet scrubber
Sourca
Vent gas scrubbers
Oust, mists, vapors
Aqueous wastes
Neutralized aqueous
Aqueous wastes
Clean out rinse water,
wasted solvent
Scrubber and filter
water
Spent acid
Aqueous layer
Stripper clean-out
water
Vacuumed gases
Acidic solution
Nature of
Waste Water Contaminants
High nitrates, dissolved solids and high pH
High toxic organics, high total suspended solids
High toxic organics, low flow
Organic product loss, high pH, high dissolved
solids, intermittent flow
High dissolved organics and solids
High dissolved solids and organics.
Variable pH, intermittent flow
High pH, Cyanide waste water, low organics,
high dissolved solids
Low pH, intermittent flow, moderate organic content
High salt content, high pH, intermittent flow rate,
toxic components, some "intermediate" product
High organics, low flow
Low organic, generally acidic
Low pH, moderately high flow rate, little organic wastes
-------
TABLE V-2
RAW WASTE LOADS
ORGANIC PESTICIDE CHEMICALS MANUFACTURERS
SUBCATEGORY 1
CT>
FLOW BOD
Source
COD TSS PESTICIDES of
Plant Product(s) L/Kkg Gal/1000 1b (n) kg/Kkg cng/1 (n) kg/Kkg mg/1 (n) kg/Kkg mg/1 (n) kg/Kkg mg/1 (n) Data
3 1 7250 869 (E
41 252 3 (E
6 2,3,4,5 12800 1540
8 -6,7 3150 377
6,7 15100 1808
6 4210 505
9 1 1760 211
12 8 1060 127
18 1 3810 457
19 9,10 64800 7770
20 11 976 117
11 986 117
21 12 75900 9100
12 50400 6040
17 17600 2110
17 22900 2740
37-45 46300 5550
22 2,13 8060 976
2,13 8760 1050
14 10000 1200
18,19,20 2780 333
18,20 2780 333
5
.-
_-
65.2(E) 9000 (1) 0.159 2.2 (E
N.D. (E
20.0 1630 (3) 70.3 5780
63) --
E)
— 18.3 5766
-- 89.0 5900
5) 0.856 69
11) 4.79 1510
E) 36.4 2410
25) AI AI AI 4.73 881 (7) 1.93 360
E
E
—
_.
E) --
3<
E
E
E
5) 0.793 58.4 (5
11)
E) 1.3 86.2 (3)
7) 0.0655 15.5 (25)
0.001 0.4 (E
— « N.D. E
— ~ N.D. E
\) 5.98 92.0 (34) 30.4 429 (28)
44.1 45200 (6) 144 148000 (6) 1.42 1460 (6) 0.0144 14.8 6)
—
498 6570
30) 211 3880
29) 204 9590
E
E
r
337 , 14700
38.5 832
62.9 7800
30) 62.9 7200
f
c
85.0 8500
1.5 540
1) --
0.0177 18.2 16)
E) 3.75 49
30) 5.50 103
29) 1.5 62.0
E 1.2 52.5
E) -- -- E)
30) 0.79 15.0 30)
29) 1.1 57.0 29)
E)
E -
E 113 14000
30) 125 14300
E) 0.19 24
30) 1.92 220
E) 16.1 2000 (E)
a
b
c
d
e
f
9
h
1
i
i
m
n
s
t
hh)
Q
30) (p
E 160 16000 (E
E 45.0 15200
-- 36.5 13200
46 10000 1200 E) 24.5 2450 (E) 81.3 8120
23 15,16 411000* 49200* (150) —
16
27 21 12600 1510 |
28 21/22 66200 7930
21 50400 6050
22 49500 5730
29 5,7 12800 1530
32 24 107000 12900
25 2660 319
26 60500 7200
-- 43.1 105
E —
1 0.13 47
E 1.81 181
150) 55.0 134
12) 110 8730 (12) 180 14300
8)
61)
31
2
E
C
E
W « M V
V M V W M
«B » •
• 4 « * A
27 10700 1285 (E) —
-- 261 3940
- 185 3670
1)
E)
150) 0.0127 0.031 (150)
— 0.052 0.127 150)
[12) 4.5 360 (12)
7) 9.32 141 (8)
'61) 0.235 4.66 (61)
-- 90.7 1830 (31) 0.454 9.17 (31)
-- 79.0 6100 (2)
- 333 3110 (E) -- --
-- 107 40200
-- 192 3150
M -. -_ -- _-
q
u
y
1 )
r
r
w
X
y
z
ae
bt
bt
E!I (bt
i
i
i
i
-- 96 8910 (E) (bb;
-------
Table V*.2
Page 2 of 4 Pages
o>
28 5170 620 (E
29 62100 7440 E
30 1670 200 (E
31 14700 1760 E
._ ... -
.. .. _
_• »
.. .- -
25 31200 3740 11) —
•- 20
-- 192
- 70
- 46
- 661
24-31 1530U 1840 31) 26.6 1750 (8) 105
24-31 14200 1700 28) 45.2 2780 (6) 118
47 13500 1620 (E
48 51600 6180 (E
_.
..
33 32 -- --
34 33 31400 3760 (E
•14 4500 <>dfl If
JH •* JUU 3*tv IU
3b 21100 253U (E
"*£ 1*105 inn if
- 64
-- 77
—
36 37 32100 3850 11) 3.73 116 (8) 31.5
39 50,51,52 3470 416 t
53 6450 774 E
54 19800 2370 E
55 39300 4718 E
56 1300 156 (E
52 1560 187 4
._
.. _.
.. -. —
._ __ -
.. ~— -
-- 83(A)
-- 154
-- 4562 I
- 7688 I
- 1582 E
1.55 995 (4) 12.9"
41 5/,58,59 23700 2845 61) 24.6 1040 (
57,58,59 31100 3730 209) 50.3 1620
45 60 (C) (C) — (C) 595 (
46 37 35300 4230 (98) -
48 61 -- -- — 58
62 56700 6800 (E) 20.3 358
63 -- -- -- 74.5(b) --
49 64 34500 4140 (E) 167 4840
50 65 (D) (0) — (0) 193
65 NA NA
(n) Number of data points
Not monitored
AI Analytical Interference
* Included noncontact cooling water
(E) Plant estimate
None No waste water discharged to treatment units
N.D. Not detectable
(A) = Portions recovered prior to waste water treatment
(BJ - Portions Incinerated prior to waste water treatment
24) 54.6
118) 99.9
3) (C)
E 97
E 20.3
3850 (E)
3100
4200
3150
21200
6850
7320
4740
1480
5090
E
E
E)
11) 8/.7 2810 (11
31 4.14 269 (21
28) 3.66 Z2I (16
E)
E)
..
...
—
—
0.122 3.» (39)
"* "" -~~
..-
bb)
bb
bb)
bb)
cc
dd
ee
JJJ
UJ
33) - 43 (27) (ff
981
23900
23900
t 231000
! 195000
) 1220000
8310
2300
3050
4750
(99
_ — _B — ••
«B •• _ •••
10) 4.1 128 (11) 2.54 79.0 (11)
E) -
E
E
E
E)
4) 0.26 168 (4)
on
99
99
GO
yy
kk
ID
(ran)
— (ran
(ran
— (mm
— (mm
0.0175 11.3 (4) (nn)
61) 0.528 22.2 (61) 1.51 63.6 (61)
209)
5) (C) 68.6 (5)
4.26 103 200)
(C) 218 (5)
1.04 29.5 (98) 0.664 18.9 (98)
-- (E)
358 (Ej 0.1 1.8 (E)
E 160(b) -- (E) 0.79(b) - (E)
E 676
5 (D)
19600(E
4880 (5) (D) 674 (5)
... -- -- ...
..-
2.4 42.3 (1)
55(b) -- E
20.7 600 E
(D) 8960 5
00
pp]
qq
rr
ss
ss]
tt
uu
vv
(D) 1391 39) (ww)
(C) « Ratios of pollutants to production not calcualted due to batch nature of process and low flow compared
to other non-pesticide products
(D) = Ratios of pollutants to production not calculated since waste water 1s from non-process related washdown only
-------
00
NOTES:
PRODUCT CODE:
1 = Toxaphene
2 - 2,4-D
3 - 2,4-DB
4 = MCPA
5 * MCPB
6 » PCNB
7 = Terrazole
8 » DDT
9 • DCPA
10 « Chlorothalonll
11 = Dlcofol
12 =• Chlorobenzllate
13 • 2,4,5-T
14 * PCP
15 = Endrln
16 «= Heptachlor
17 « Dlazinon
18 • Dursban
19 * Crufomate
20 = Ronnel
21 = Methyl Parathlon
22 » Ethyl Parathlon
23 » Apson
24 • Coumaphos
25 * Dlsulfoton
26 * Fenthlon
27 = Azlnphos Methyl
28 •= Methamldophos
29 = Demeton
30 = Fensulfothlon
31 • Oxydemeton
32 * Glyphosate
33 = Stlrofos
34 « Dlchlorvos
35 » Mevlnphos
36 « Naled
37 = Atrazlne
Table V-2
Page 3 of 4 Pages
SOURCE OF DATA CODE:
(a)
(b
(c
d
e
f
II
1
j
K1
m
n
o
P
q
r
s
t
u
V
w
X
y
z
aa
bb
cc
dd
ee
ff
99
hh
11
Jj
kk
Design criteria based on 1970 sampling. Verified 1n 1975
MRI Toxaphene Report, 2/6/76
Dally time composites, December 13-17, 1976, analyzed by
EPA contractor
Dally composite, 7/1/75 thru 2/29/76
Revised plant estimate 3/15/77 Including supplementary
waste streams not treated by carbon
Dally composites, 8/21/77 thru 10/3/77, analyzed by EPA contractor
MRI Toxaphene Report, 2/6/76
MRI DDT Report, 2/6/76
MRI Toxaphene Report, 2/6/76
Dally composites, 1/5/77 thru 5/16/77, adjusted by total
final product ratio of 1.35:1 due to chloral waste water
Dally composite, 2/77
Dally composite, 3/4/77, analyzed by EPA contractor
Dally average 4/74 thru 3/74
Dally flow proportional composite, 5/21/75 thru 6/19/76
Dally average, 8/74 thru 7/75
Dally composite, 6/75
Dally average, 4/72 thru 3/73
Dally composite, 1/74 thru 5/74
Dally flow proportional composite, 5/5/75 thru 6/3/77
Plant estimate, 4/74 thru 3/75
Plant estimate, 1974
Dally composite, 10/1/74
Twelve dally composites during 6/25/75 thru 9/1/75
Dally composite, 3/21/74 thru 5/9/74, analyzed by outside laboratory
Dally composite, 6/74 and 7/74
Dally composite, 1/74
Two dally composites, 4/74
Plant estimate, 12/16/74
Dally flow proportional composite, 5/31/75 thru 6/13/75
Revised data for Dlsulfoton 3/7/77
Dally average, 1/74
Dally average, 2/74
Dally composites, 2/29/77 thru 3/8/77
Plant estimate, 1975
Plant estimate, 10/24/74
Dally composite, 10/1/74
Plant estimate. 12/1/74
Plant estimate, 4/22/76
-------
VO
38 • Propazlne
39 » S1maz1ne
40 = Proflurallne
41 » Ametryne
42 = Prometryne
43 » Slmetryne
44 = Prometone
45 = Cyanazlne
46 = Dlnoseb
47 « Metrlbuzln
48 » Anllazlne
49 - Aldlcarb
50 » Benfluralln
51 - Ethalfluran
52 - TMfluralln
53 • Isopropalln
54 • Oryzalln
55 - Plperalln
56 • Tebuthluron
57 - Alachlor
58 » Propachlor
59 » Butachlor
60 - DEET
61 « Bromacll
62 • Dluron
63 - Methontyl
64 « Bentazon
65 - Carbofuran
11
ran
nn
(oo)
(PP)
(qq)
Table V-2
Page 4 of 4 Pages
Dally composite, 7/9/75 thru 8/13/75
Plant estimate, 4/5/76
Dally composites, 1/24/77 thru 1/28/77, analyzed by EPA
contractor
Dally composite, 9/76 thru 3/77. adjusted by total: final
production ratio of 1:33:1 to reflect effect of Intermediate
Dally composite. 4/77 thru 5/77. adjusted by total: final
production ratio of 1:33:1 to reflect effect of Intermediate
Dally composite. 12/13/76 thru 12/17/76, analyzed by EPA
contractor
Dally composite, 2/77 thru 4/77
Plant estimate, 5/17/75 and 8/31/77
Plant estimate, 9/9/77
Plant estimate, 7/12/77
Dally composite. 4/77
Dally composite, 10/76 thru 4/77
-------
Data were available for sixteen halogenated products, including
aldrin-toxaphene types, chlorinated aryloxyalkanoic acids and
esters, DDT and relatives, halogenated aromatics, and others.
Seven direct dischargers of organo-phosphorus pesticides
submitted data from in-plant or treatment system influent
monitoring. Phosphates and phosphonates, phosphorothioates and
phosphorodithioates, and phosphorus- nitrogen compounds are
represented among the twenty products with wastewater data
available. Of the organo-nitrogen data ten of the twelve plants
supplying data are direct dischargers. A total of 29
organo-nitrogen pesticide products are covered, including amides,
amide type compounds, carbamates, heterocyclics, nitros, ureas
and uracils, s-triazines, and others.
Subcategory 2—Metallo Organic Pesticides Manufacturers
In the manufacturing process for metallo-organic pesticides, the
principal sources of waste water are: byproduct stripping,
product washing, caustic scrubbing, tank and reactor clean-out
and area washdowns. The waste water characteristics associated
with these operations are summarized in Table V-3.
A summary of raw waste load characteristics for this subcategory
is presented in Table V-U. A total of ten plants submitted data
on arsenic, mercury, copper, zinc, tin, iron, and manganese-based
pesticides.
A continuing effort is underway to better characterize the waste
streams resulting from the manufacture of zinc, iron, manganese,
and tin-based products in this subcategory. These four types of
compounds are not covered but the Agency intends to regulate the
discharge from these manufacturing operations in the future.
Subcategory 3—Formulators and Packagers
Washing and cleaning operations are the principal sources of
waste water in formulating and packaging operations. Table V-5
summarizes the wastewater sources for formulating and packaging
operations.
Because the primary sources of waste water at formulating plants
are associated with cleanup of spills, leaks, area wash-down, and
storm water runoff, there is apparently no basis from which to
correlate the pollutants generated to the product made. This has
been verified at Plant 101. The analyses available indicate that
neither the rate of production nor the type of product formulated
has a direct bearing on the quality or quantity of waste water
generated.
70
-------
TABLE v-3
SUMMARY OF POTENTIAL PROCESS—ASSOCIATED
METALLO-ORGANIC PESTICIDE
PROCESSING UNIT
Caustic scrubber
SOURCE
Spent caustic solution
Intermediate recovery Wash water, washdown
Raw material drum
washer
Slurry wash
Multi-stage counter
current washer
Air pollution control
By-product stripper
Tanks and reactors
All processing areas
Drum wash water, spills
(in recovery)
Product rinse water
Water lost with scrubged
salts, clean-out rinse
water
Scrubber water
Aqueous fraction
Clean-out rinse water
Area washdowns
WASTEWATER SOURCES FROM
PRODUCTION
NATURE OF WASTEWATER CONTAMINANTS
High pH, alkalinity, TDS and sulfur content.
Low average flow rates. Some dissolved
organics.
High TDS, salt content. Arsenic-
contaminant brine. Separate organics.
High arsenic content. No organics. Toxic.
High TDS and sulfidic wastes. Low average
flow rates. Dissolved and separable organics
High suspended and dissolved solids.
Variable heavy metal content. Relatively
low flow rates. Very low organic content.
Toxic
High suspended and dissolved solids. Toxic.
Medium flow rates. Low dissolved and
separable organics.
Dissolved organics. High BOD and TOD.
Neutral pH.
Dissolved organics, and suspended and
dissolved solids. Intermittent flow rate.
Toxic.
Dissolved and separable organics, and
suspended and dissolved solids. Toxic.
-------
TABLE V-4
RAW WASTE LOADS
METALLO-ORGANIC PESTICIDE MANUFACTURERS
SUBCATEGORY 2
ro
PLANT
19
20
48
50
53
54
55
56
57
58
PRODUCT
1
2
2
3,4,5,6
7,8,9
10,11,12
1,13
1,13
14
10
L/Kkg
1300
NM
76310
None
64270
None
None
None
None
None
FLOW
gal/1000 Lb
156
NM
9150
None
8000
None
None
None
None
None
(n)
(E)
(0)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
kg/Kkg
NM
NM
54
None
23.7
None
None
None
None
None
BOD
mg/1
NM
NM
703
None
355
None
None
None
None
None
(n)
(0)
(0)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
kg/Kkg
NM
NM
120
None
47.5
None
None
None
None
None
COD
mg/1
NM
NM
1572
None
711
None
None
None
None
None
(n)
(0)
(0)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
(E) = Plant Estimate
NM = Not Monitored
-------
TABLE V-4
Continued
Page 2 of 3 Pages
CO
PLANT
19
20
48
50
53
54
55
56
57
58
PRODUCT
1
2
2
3,4,5,6
7,8,9
10,11,12
1,13
1,13
14
10
kg/Kkg
NM
NM
137
None
253
None
None
None
None
None
TSS
mg/1
NM
NM
1718
None
3800
None
None
None
None
None
(n)
(0)
(0)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
kg/Kkg
0.0817
NM
37
None
4
None
None
None
None
None
METAL
mg/1
0.359
NM
481
None
60
None
None
None
None
None
(n)
(34)
(0)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
(E)
SOURCE
OF DATA
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(E) = Plant Estimate
NM = Not Monitored
-------
TABLE Y-4
Continued
Page 3 of 3 Pages
PRODUCT CODE:
1 = MSMA
2 = Maneb
3 = Zineb
4 = Ziram
5 = Polyrarn
6 = Ferbam
7 = Tricyclohexyltin Hydroxide
8 = Triphenyltin Hydroxide
9 = Tributyltin Oxide
10 = PMA
11 = Copper Napthenate
12 = CMP
13 = DSMA
14 = Oxine Copper
SOURCE OF DATA CODE:
(a) Daily samples, 1/5/77. Flow
estimate, 8/29/77, includes
stormwater.
(b) Plant visit, 2/15/77.
(c) Plant estimate, 5/21/75.
(d) Plant visit, 1/6/77.
(e) Plant estimate, 5/23/75.
(f) Plant estimate, 5/7/76.
(g) Plant estimate, 5/14/76.
(h) Plant estimate, 5/14/76.
(i) Plant estimate, 5/13/76.
(j) Plant estimate, 4/13/76.
-------
TABLE V-5
SUMMARY OF POTENTIAL PROCESS-ASSOCIATED WASTE WATER SOURCES
FROM PESTICIDE FORMULATORS AND PACKAGERS
PROCESSING UNIT
Mix tank
Air pollution control
equipment
Formulation lines and
filling equipment
All product formulation
and blending areas
Warehouse, technical
active ingredient storage
SOURCE
Condensate from
equipment steam
cleaning
Scrubber water
Wash water and
steam conden-
sate from clean
out
Area washdown
and clean-up
water, spills,
leaks
Spills, leaks,
run-off
NATURE OF
WASTE WATER CONTAMINANTS
Dissolved organics, and
suspended and dissolved
solids. Non-continuous
flow rate, and relatively
low flow. pH variable
High suspended and dissolved
solids, and dissolved organics.
Relatively low flow rate.
Dissolved organics, and sus-
pended and dissolved solids.
A major potential source of
waste water.
Dissolved organics, suspended
and dissolved solids and
intermittent low flow.
Dissolved organics, sus-
pended and dissolved solids
and intermittent low flow.
75
-------
In one survey 75 plants were contacted which formulate wet, dry,
or solvent based pesticides. No plant which solely formulates or
packages was found that discharged waste water to a navigable
waterway. One major formulator operating 38 plants of varying
size and process (wet, dry, and solvent) achieved no discharge
over a thirteen state area through hauling and evaporation.
Other Agency surveys revealed the same results. Waste\vater
volume generated by these plants ranged from zero to 5800
gal/day. A majority of plants surveyed reported from zero to
1000 gal/day generated.
Raw Waste Load Design Criteria
The raw waste load characteristics previously presented form the
basis for the design and cost of the treatment technologies to be
developed in Sections VII and VIII. The purpose for developing
design criteria is solely to allow for subsequent cost
calculations, and is not related to the development of effluent
limitations as documented in Section IX.
Figures V-1 through V-6 show the relative raw waste load values
(kg/kkg) for halogenated, phosphorus, and nitrogen pesticide
producing plants. These figures have been derived from data
presented in previous tables in Section V. The range of values
observed demonstrates the problems of obtaining comparable data
when different products, processes, and methods of disposal are
utilized by each plant. There is no correlation between these
data to justify subcategories.
The design raw waste load selected has been indicated graphically
in each figure. By selecting upper level values for each
parameter, a generous estimate of the raw waste load is made, as
it is highly unlikely that any one plant would exceed these
values in every case. Solid bars indicate an average value for
all products manufactured at a plant. Maximum values for
different products or different estimates for the same products
are represented by empty bars.
A range of production values encountered in the industry has been
utilized in conjunction with the raw waste loads. Flow and
concentration levels have been calculated. The design criteria
to be utilized with the treatment units specified in Section VII
are presented in Table V-6.
76
-------
100000-
9-
8 —
7 —
6-
5
3 —
o
o
o
O
O
10000-
9
8 -
7 -
6
5 -
3 —
2 -
1000
9
8-
7-
6-
5-
3 —
100-
DESIGN RAW WASTE LOAD
3 4 6 8 9 12 18 19 20 21 22 23 27 28 29 22 32 21 34 36 39 41
PLANT
46 32 21 22 48 34 49 32 21
FLOW RAW WASTE LOAD CHARACTERISTICS
PESTICIDES MANUFACTURERS
AVERAGE FOR PARAMETER
MINIMUM AND MAXIMUM FOR PARAMETER
INDICATES LEVEL BELOW 100 QAL/1000 LBS.
77
FIGURE V-1
-------
1900-1
• -
• -
7"
6-
5-
4-
3-
2-
100-
9-
8-
7-
6-
1000LBS)
o» » en
I 1 1
s
ei 2H
0
to
10-
9^
8-
7-
6-
5-
4-
3-
2-
1-
•* «
_— __
••MM
|
/
T
r DESIGN RAW
/ WASTE LOAD
/
/
|
T
6 19 20 21 22 27 22 32 21 36 39 41 21 22 48 49 32 21
PLANT
BOD RAW WASTE LOAD CHARACTERISTICS
PESTICIDES MANUFACTURERS
AVERAGE FOR PARAMETER
MINIMUM AND MAXIMUM FOR PARAMETER
78
FIGURE V-2
-------
1000
O — .
8 —
7 —
6 —
5 -"-
4 —
3 —
2 —
100-
-^ 9 —
0) 8-
00 7_
§ 6-
00 ~
~ 3-
O
O
° 2-
10-
Q
8 —
7 —
6— I
5 —
4 —
2 —
DESIGN RAW
^ WASTE LOAD
LA_
6 8 19 20 22 23 27 28 29 22 32 36 39 41 32 22 48 49 32
PLANT
COD RAW WASTE LOAD CHARACTERISTICS
PESTICIDES MANUFACTURERS
AVERAGE FOR PARAMETER
MINIMUM AND MAXIMUM FOR PARAMETER
79
FIGURE V-3
-------
9-
ft «
7-
6-
5-
3-
2-
10-
9-
8-
7-
6-
03
_j
o
^-
-: 3-
0
I 2-
1.0-
.8-
.7-
.6-
.5-1
.4 —
.2-
••
1
T
/
/- DESIGN RAW W
&
ASTE LOAD
3 6 8 20 21 22 23 27 28 22 32 21 36 39 41 46 22 48 32 21
TSS RAW WASTE LOAD CHARACTERISTICS
PESTICIDES MANUFACTURERS
AVERAGE FOR PARAMETER
MINIMUM AND MAXIMUM FOR PARAMETER
80
FIGURE V-4
-------
Ul
X
Q.
_J
O
100.
9-
8-
7-
6-
5-
4-
3-
2-
10-
9-
8-
7-
6-
5-
4-
2-
1-
9-
8-
7-
6-
5-
4-
3-
2-
DESIGN RAW WASTE LOAD
6 22
PLANT
TOTAL PHENOL RAW WASTE LOAD CHARACTERISTICS
PESTICIDES MANUFACTURERS
AVERAGE FOR PARAMETER
MINIMUM AND MAXIMUM FOR PARAMETER
81
FIGURE V-5
-------
55 —
10 —
9 —
8 —
7 —
6 —
4 —
3 —
2 —
to
3 ">-
o '-
O 8 —
° ' —
T 6 —
O
-I 5 —
cn 4 —
u
0
o 3—
CO
Q. 2 —
0 1 —
OS —
08 —
07 —
06 —
05 —
04 —
03 —
02
T
0
55
t
DESIGN
RAW WASTE
TLOAD
\
_\_.
. ,_ - - -, __.
B
i T
_ ^^_ — ^_
ri
u
T
<
____
1
T
___
_
__ _^ ___ _
6 8 9 20 21 22 23 28 32 21 36 39 41 46 48 49 32
PLANT
PESTICIDES RAW WASTE LOAD CHARACTERISTICS
PESTICIDES MANUFACTURERS
AVERAGE FOR PARAMETER
MINIMUM AND MAXIMUM FOR PARAMETER
INDICATES LEVEL BELOW 0.01 LB./1000 LBS 82
FIGURE V-6
-------
TABLE V-6
DESIGN CRITERIA
COST TREATMENT TECHNOLOGY
SUBCATEGORY 1
Design Loads:
Design Flows:
Design Concentrations:
Flow
BOD
TSS
Pesticides
0.9 MGD
0.2 MGD
0.045 MGD
BOD
TSS
Pesticides
4500 gal/1000 Ib
40 lb/1000 Ib
10 lb/1000 Ib
1.75 lb/1000 Ib
1070 mg/1
266 mg/1
45.5 mg/1
83
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The pollutants which are of primary significance for the
pesticide chemicals industry are as follows:
Organic Pollutants Pesticide Chemicals
Suspended Solids Metals
PH
The adverse effects of primary concern with respect to pesticide
chemicals waste waters are as follows:
the oxygen demanding capacity of organic materials
which will depress dissolved oxygen (DO) levels of
T-or-Ai vi nn wai-^fR;
a.
receiving waters;
b. the aesthetic and physically inhibiting effects of
excessive levels of suspended solids;
'c. the capacity to alter receiving water pH;
d. the potential contribution to eutrophic conditions
in receiving waters;
e. the toxic nature of pesticides, metals, phenol,
and cyanide to aquatic organisms present in
receiving waters; and
f. the danger of long-term buildup in aquatic
organisms and man of persistent pesticides which
may have human health implications.
The pollutants of primary significance are not all likely to be
present at high concentrations in every pesticide plant's waste
water. Organic wastes, suspended solids, pH, and nutrients are
potential pollutants for any of the subcategories. Pesticide
active ingredients are specific to the product manufactured or
used in formulating and packaging. Metals may be present in
waste waters at those facilities where metallo-organic pesticide
chemicals are produced or where metals are employed in the
production process.
Preceding page blank
85
-------
Other pollutants of significance in the pesticide chemicals
industry include the following:
Ammonia Cyanide
Nutrients Phenol
Settleable solids Acidity
Dissolved solids Chloride
Alkalinity Sulfide
Oil and Grease
These pollutants may be of concern in a particular location/ but
they are generally of less importance than the pollutants of
primary significance. They can usually be assessed indirectly by
measurement of pollutants of primary significance.
The following discussion indicates the basis for selection of
parameters to be regulated. Parameters are discussed in terms of
their relevance to the treatment recommended and their validity
as analytical measurements and indicators of environmental
impact.
Pollutants of Primary Significance
Organic Pollutants
Organic pollutants which are amenable to biological and chemical
decomposition in receiving waters exert an oxygen demand on these
waters during the process of decomposition. Oxygen demanding
wastes consume dissolved oxygen (DO). DO is essential for living
organisms and is essential to sustain species reproduction,
vigor, and the development of populations. Organisms undergo
stress at reduced DO concentrations that make them less
competitive and less capable of sustaining their species within
the aquatic environment. For example, reduced DO concentrations
have been shown to interfere with fish populations through
delayed hatching of eggs, reduced size and vigor of embryos,
increased deformities in the young, interference with food
digestion, acceleration of blood clotting, decreased tolerance to
certain toxicants, reduced food utilization efficiency and growth
rate, and reduced maximum sustained swimming speed. Fish food
organisms are likewise affected adversely in conditions of
depressed DO. Since all aerobic aquatic organisms need a certain
amount of oxygen, the occurrence of a total lack of dissolved
oxygen due to a high oxygen demand of wastes can kill all aerobic
inhabitants of the effected area.
The three methods commonly used to measure the organic content of
waste waters are Biochemical Oxygen Demand (BOD), Chemical Oxygen
Demand (COD) and Total Organic Carbon (TOC). Each of these
methods have certain advantages and disadvantages when applied to
industrial waste waters.
86
-------
The BOD test, is essentially a bioassay procedure involving the
measurement of oxygen consumed by living organisms while
utilizing the organic matter present in a waste water under
conditions as similar as possible to those that occur in nature.
Historically, the BOD test has been used to evaluate the
performance of biological waste water treatment facilities and to
establish effluent limitation values. It is important to note
that most state, local and regional authorities have established
water quality regulations utilizing BOD as the major parameter
for determination of oxygen demand on a water body. When
properly performed, the BOD test measures the actual amount of
oxygen consumed by microorganisms in metabolizing the organic
matter present in the waste water. Some limitations to the use
of the BOD test are discussed below (WPCF, 1975, ref. 456).
The standard BOD test takes five days before the results are
available. Although BOD is a good measure of long-term treatment
performance, other parameters which can be determined more
readily are more suitable as treatment system controlling
parameters.
Because the BOD test is sensitive to toxic materials, their
presence in a particular waste water may result in incorrect BOD
values. Toxicity is generally indicated by higher BOD values
measured on repeated dilutions of the samples. This situation
should be remedied by conducting further dilutions, i.e.,
serially diluting the sample until the BOD value reaches a
plateau indicating that the material is at a concentration which
no longer inhibits biological oxidation.
The chemical oxygen demand (COD) determination provides a measure
of the oxygen equivalent of that portion of the organic matter in
a sample that is susceptible to chemical oxidation. The
carbonaceous portion of nitrogenous compounds can be determined
by the COD test, and there is questionable reduction of the
dichromate by ammonia. With certain wastes containing toxic
substances, this test or a total organic carbon (TOC)
determination may be the best method for determination of the
organic load. Since the test utilizes chemical oxidation rather
than a biological process, the result is not always exactly
related to the BOD of a waste water. The test result should be
considered as an independent measurement of organic matter in the
sample, rather than as a substitute for the BOD test (USEPA,
625/6-74-003, 1974, ref. 3261).
The ratio of COD to BOD is an empirical relationship which varies
in each individual waste streams and accordingly has not been
utilized in development of these regulations.
87
-------
The TOC analysis offers a third option for measurement of organic
pollutants in waste waters. The method measures the total
organic carbon content of the waste water by a combustion method.
The results may be used to assess the potential oxygen-demanding
load exterted by the carbonaceous portion of a waste on a
receiving stream. There is generally no correlation among TOC
an<3 BOD or COD for different waste streams. A correlation must
be determined for each waste water by comparison of analytical
results. TOC analysis is rapid and generally accurate and
reproducable. However, it requires analytical instrumentation
which may be relatively expensive if not utilized fully. There
presently does not exist a sufficient data base from which to
regulate TOC in this industry.
The fourth option for measurement of organic pollutants in waste
waters is total oxygen demand (TOD). Like TOC, TOD measures the
parameter by a combustion method. The TOD method is based on the
qu'antitive measurement of the amount of oxygen used to burn the
impurities (pollutants) in a liquid sample. TOD, like TOC,
requires expensive equipment to run and is not cost effective
unless utilized fully. The correlations of BOD and COD with TOD
are the same as with TOC described above.
It is therefore concluded that effluent limitations and
guidelines for organic pollutants in terms of both BOD and COD
are necessary for subcategory 1 of the pesticide chemicals
manufacturing point source category. In certain circumstances
TOD may be substituted for COD and TOC for BOD. However, an
adequate correlation between these parameters should be
established.
88
-------
Total Suspended Solids (TSS)
Suspended solids are usually composed of organic and inorganic
fractions. These fractions, in turn, may be made up of readily
settleable, slowly settleable, or non-settleable materials. The
biodegradable organic fraction will exert an oxygen demand on a
receiving water and is reflected in the analyses for organics
discussed above.
Suspended solids in water interfere with many industrial
processes, causing foaming in boilers and incrustations on
equipment exposed to such water, especially as the temperature
rises. They are undesirable in process water used in the
manufacture of steel, in the textile industry, in launderies, in
dyeing and in cooling systems.
When solids settle to form sludge deposits on a stream or lake
bed, they are often damaging to the life in water. Sludge
deposits may do a variety of damaging things, including
blanketing the stream or lake bed and thereby destroying the
living spaces for those benthic organisms that would otherwise
occupy the habitat. Organic materials also serve as a food
source for sludgeworms and associated organisms.
Solids in suspension are aesthetically displeasing. Suspended
solids may kill fish and shellfish by causing abrasive injuries
and by clogging the gills and respiratory passages. Indirectly,
suspended solids are inimical to aquatic life because they screen
out light and promote and maintain the development of noxious
conditions through oxygen depletion. This results in the killing
of fish and fish food organisms. Suspended solids also reduce
the recreational value of the water.
The control of suspended solids from bioloigcal treatment systems
is especially critical. Not only does the biomass exert an
oxygen demand on receiving waters, but for the pesticide
chemicals industry there is evidence that substantial quantities
of toxic residues are absorbed on or in the floe which, if
carried over^ will potentially cause a toxic effect in the
receiving waters.
Therefore, it is concluded that TSS is an essential pollutant
parameter requiring control for subcategory 1 of the pesticide
chemicals industry.
£H
The pH is related to the acidity or alkalinity of a waste water
stream. Although it is not a linear or direct measure of either,
89
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it may properly be used as a surrogate to control both excess
acidity and excess alkalinity in water. The term pH is used to
describe the hydrogen ion-hydroxyl ion balance in water. pH is
the negative logarithim of the hydrogen ion concentration. A pH
of 7 generally indicates neutrality or a balance between free
hydrogen and free hydroxyl ions. A pH above 7 indicates that a
solution is alkaline, while a pH below 7 indicates that the
solution is acid.
Knowledge of the pH of water or waste water is useful in
determining necessary measures for corrosion control, pollution
control, and disinfection. Waters with a pH below 6.0 are
corrosive to water works structures, distribution lines, and
household plumbing fixtures. Also, corrosion can add
constituents such as iron, copper, zinc, cadmium, and lead to
drinking water. Low pH waters not only tend to dissolve metals
from structures and fixtures but also tend to dissolve or leach
metals from sludges and bottom sediments. The hydrogen ion
concentration can affect the "taste11 of water and, at a low pH,
water tastes "sour".
Extremes of pH or rapid pH changes can exert stress conditions or
kill aguatic life outright. Even moderate changes from
"acceptable" criteria limits of pH are deleterious to some
species. The relative toxicity to aquatic life of many materials
is increased by changes in the pH. For example, metalocyanide
complexes can increase a thousand-fold in toxicity with a drop of
1.5 pH units. Similarly, the toxicity of ammonia is a function
of pH. The bactericidal effect of chlorine is diminished as the
pH increases in most cases. In addition, it is economically
advantageous to keep the pH close to 7, (US EPA, 440/9-76-023,
9/76, ref. U07).
It is therefore concluded that pH is a significant parameter
requiring control in the pesticide chemicals industry.
Pesticide Chemicals
Pesticides are, by their very nature and use, toxic to certain
living organisms. They can be a hazard to aquatic life,
terrestrial life, and man when allowed to enter natural waters in
sufficient amounts. Pesticides may affect the aquatic
environment and water quality in several ways. A pesticide with
a slow rate of degradation will persist in the environment,
suppressing or destroying some organism populations while
allowing others to gain supremacy. An imbalance in the ecosystem
results. Other pesticides will degrade rapidly, some to products
that are more toxic than the parent compound, some to relatively
harmless products and some to products for which toxicity data
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are lacking. Many pesticides have a high potential for
bioaccumulation and biomagnification in the aquatic food chain,
thereby posing a serious threat to a large number of ecologically
important organisms, including man (FWPCA, 1968, ref. 93).
The chlorinated hydrocarbons are among the most widely used
groups of synthetic organic pesticides. They are stable in the
environment, toxic to wildlife and nontarget organisms, and have
adverse physiological effects on humans. These pesticides
readily accumulate in aquatic organisms and in man. They are
stored in fatty tissue and are not rapidly metabolized. Humans
may accumulate chlorinated hydrocarbon residues by direct
ingestion of contaminated water or by consumption of contaminated
organisms. Regardless of how chlorinated hydrocarbons enter
organisms, they induce poisoning having similar symptoms that
differ in severity. The severity is related to the extent and
concentration of the compound in the nervous system, primarily
the brain. Deleterious effects on human health are also
suspected to result from long-term, low-level exposure to this
class of compounds (FWPCA, 1968, ref. 93).
The organo-phosphorus pesticide chemicals typically hydrolyze or
break down into less toxic products more rapidly than the
halogenated compounds. Generally they persist for less than a
year. Some last for only a few days in the environment. They
exhibit a wide range of toxicity, both more and less damaging to
aquatic fauna than the chlorinated hydrocarbons. Some exhibit a
high mammalian toxicity. Accumulation of some of these pesticides
results in a dysfunction of the cholinesterase of the nervous
system when ingested in small quantities over a long period of
time (FWPCA, 1968, ref. 43) .
The organo-nitrogen pesticide chemicals are also generally less
persistent in the environment than the chlorinated hydrocarbons.
They exhibit a wide range of toxicity. The carbamates are
particularly toxic to mammals. They appear to act on the nervous
system in the same manner as the organo-phosphorus pesticides.
Meta11o-organic pesticide chemicals include compounds containing
arsenicals, mercury. The toxicity of these compounds is highly
variable.
Arsenic is notorious for its toxicity to humans. Ingestion of 100
mg usually results in severe poisoning and 130 mg has proved
fatal. The organo-arsenic compounds such as cacodylic acid are
even more toxic to humans and to aquatic organisms. Arsenic
accumulates in the human body so that small doses may become
fatal in time. Mercuro-organic compounds are highly toxic and
exhibit bioaccumulation and biomagnification. They may be
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converted by benthic organisms to the highly-toxic methyl
mercury. They have been shown to reduce photosynthesis at 0.1
ug/1 in lake waters (USEPA, 440/9-76-023, 9/76, ref. 407).
Analyses of pesticides in waste water are generally accomplished
by either colorimetric or gas chromatographic methods with
electron capture detector. For some pesticide chemicals, such as
toxaphene, gas chromatograph - mass spectrometry analysis (GC/MS)
may be required. The colorimetric methods available for certain
of the pesticides are simple and straight forward. Gas
chromatographic methods are more involved and require the
expertise of trained analytical chemists and the use of
relatively costly instrumentation. GC/MS is even more costly and
difficult to run. Procedures for analysis of pesticides in waste
waters can be obtained from the Environmental Monitoring and
Support Laboratory in Cincinnati, Ohio.
Although the pesticide chemicals considered in this document are
organic compounds, they are not adequately measured by BOD, COD,
or TOC. They are often toxic to organisms used in the BOD
analysis. The determination of small quantities of pesticides,
is marked by the presence of large quantities of materials
measured by COD and TOC. Therefore, pesticides should be
specifically measured.
Metals
Metals may enter waste waters of the pesticide chemicals industry
when they are used as a principal constituent of met a 11 o-organic
pesticides, and when used in intermediate production steps or as
catalysts. Metals can be a hazard to both aquatic organisms and
to man. The principal metals of concern with respect to the
pesticide chemicals industry are the following:
Arsenic Lead Nickel
Cadmium Manganese . Tin
Chromium Mercury Zinc
Copper
Arsenic is a cumulative poison with long-term chronic effects on
both aquatic organisms and on mammalian species, and a succession
of small doses may add up to a final lethal dose. It is
moderately toxic to plants and highly toxic to animals,
especially as arsenic hydride. Surface water criteria for public
water supplies have set a permissible level of arsenic in those
waters at 0.05 mg/1 (US EPA, 440/9-76-023, 9/76, ref. 407).
Cadmium in -drinking water supplies is extremely hazardous to
humans. Cadmium accumulates in the liver, kidney, pancreas, and
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thyroid of humans and other animals. A severe bone and kidney
syndrome in Japan has been associated with the ingestion of as
little as 600 ug/day of cadmium. Cadmium may also form organic
compounds which lead to mutagenic or teratogenic effects. It is
known to have acute and chronic effects on aquatic organisms (US
EPA, 440/9-76-023, 9/76, ref. 407) .
Cadmium acts synergistically with other metals. Copper and zinc
substantially increase its toxicity. Cadmium is concentrated in
marine organisms, particularly mollusks, which accumulate cadmium
in calcareous tissues and in the viscera. A concentration factor
of 1,000 for cadmium in fish muscle has been reported, as have
concentration factors of 3,000 in marine plants, and up to 29,600
in certain marine animals. The eggs and larvae of fish are
apparently more sensitive than adult fish to poisoning by
cadmium, and crustaceans appear to be more senitive than fish
eggs and larvae (US EPA, 440-9/76-023, 9/76, ref. 107). The
maximum amount of cadmium allowable in drinking water supplies is
0.01 mg/1 in the United States (US EPA, 440/9-76-023, 9/76, ref.
407) .
Copper salts occur in natural surface waters only in trace
amounts, up to about 0.05 mg/1; consequently, their presence
generally is the result of pollution. This is attributable to
the corrosive action of the water on copper and brass tubing, to
industrial effluents, and frequently to the use of copper
compounds for the control of undersirable plankton organisms
(WPCF, 1975, ref. 456).
Copper is not considered to be a cumulative systemic poison for
humans, but it can cause symptoms of gastroenteritis, with nausea
and intestinal irritations, at relatively low dosages. Excess
copper ingestion is known to cause chronic zinc deficiency.
Copper also affects tastes in waters. Threshold concentrations
for taste have been generally reported in the range of 1.0 to 2.0
mg/1 of copper, while 5 to 7.5 makes the water completely
unpalatable, (WPCF, 1975, ref. 456) .
The toxicity of copper to aquatic organisms varies significantly,
not only with the species but also with the physical and chemical
characteristics of the water, including temperature, hardness,
turbidity, and carbon dioxide content. In hard water, the
toxicity of copper salts is reduced by the precipitation of
copper carbonate or other insoluable compounds. The sulfates of
copper and zinc, and of copper and calcium, are synergistic in
their toxic effect on fish (US EPA, 440/9-76-023, 9/76, ref.
407) .
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Copper concentrations less than 1 mg/1 have been reported to be
toxic (particularly in soft water) to many kinds of fish,
crustaceans, mollusks, insects, phytoplantkon, and zooplankton.
Concentrations of 0.1 mg/1 copper, are detrimental to some
oysters. Oysters cultured in sea water containing 0.13 to 0.5
mg/1 of copper retained the metal in their bodies and became
unfit as food (US EPA, 140/9-76-023, 9/76, ref. 407).
Chromium, in its various valence states (hexavalent and
trivalent), is hazardous to man. Large doses of chromates have
corrosive effects on the intestinal tract and can cause
inflammation of the kidneys. Levels of chromate ions that have no
effect on man appear to be so low as to prohibit determination to
date (US EPA, 440/9-76-023, 9/76, ref. 107).
The toxicity of chromium salts to aquatic life varies widely with
the species, temperature, pH, valence of the chromium, and
synergistic or antagonistic tolerance of chromium salts; however,
fish food organisms and other lower forms of aquatic life are
extremely sensitive. Chromium also inhibits the growth of algae
(US EPA, 440/9-76-023, 9/76, ref. 407).
Lead is foreign to the human body, and tends to accumulate in
bones. A universally safe level of lead has not been
established. Lead poisoning usually results from the cumulative
toxic effects of lead after continuous exposure over a long
period of time, rather than from occasional small doses. Lead is
not considered essential to the nutrition of animals or human
beings. The maximum allowable limit for lead in the DSPHS
Drinking Water Standards is 0.05 mg/1 (US EPA, 440/9-76-023,
9/76, ref. 407).
It is not unusual for cattle to be poisoned by lead in their
water. The lead need not be in solution to be harmful, but may
be in suspension, as for example oxycarbonate. Chronic lead
poisoning among animals has been caused by 0.10 mg/1 of lead in
soft, water. Most authorities agree that 0.5 mg/1 of lead is the
maximum safe limit for lead in a potable supply for animals. The
toxic concentration of lead for aerobic bacteria is reported to
be 1.0 mg/1, and for flagellates and infusoria, 0.5 mg/1. The
bacterial decomposition of organic matter is inhibited by 0.1 to
0.5 mg/1 of lead.
Studies indicate that in water containing lead salts, a film of
coagulated mucus forms first over the gills and then over the
whole body of the fish, probably as a result of a reaction
between lead and an organic constituent of mucus. The death of
the fish is caused by suffocation due to this obstructive layer
(McKee, 1971). Lead is relatively more toxic in soft water than
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hard water. Concentrations of lead as low as 0.1 mg/1 have been
reported toxic or lethal to fish. Other studies have shown that
the toxicity of lead toward rainbow trout increases with a
reduction of the dissolved-oxygen concentration of the water (OS
EPA, 440/9-76-023, 9/76, ref. 401).
Manganese is an essential nutrient in plant and animal life.
Deficiencies of manganese in animals produce lack of growth, bone
abnormalities, and symptoms of central nervous system
disturbance. However, manganese is toxic to humans in extremely
high concentrations. It appears somewhat antagonistic to the
toxic action of nickel on fish.
Manganese may interfere with water usage since it stains
materials, especially when the pH is raised as in laundering,
scouring, or other washing operations. These stains, if not
masked by iron, may be dirty brown, gray or black in color, and
usually occur in spots and streaks. Waters containing manganous
bicarbonate cannot be used in the textile industries, in dyeing,
tanning, laundering, or in many other industrial uses. In the
pulp and paper industry, waters containing above 0.05 mg/1
manganese cannot be tolerated except for low-grade products.
Very small amounts of manganese 0.2 to 0.3 mg/1, may form heavy
encrustations in piping, while even smaller amounts may form
noticable black deposits (US EPA, 440/9-76-023, 9/76, ref. 407).
Mercuric salts are highly toxic to humans and can be readily
absorbed through the gastointestinal tracts. Fatal doses can
vary from 3 to 30 grams. The drinking water criteria for mercury
is 2 ug/1.
Mercuric salts are also extremely toxic to fish and other aquatic
life. Mercuric chloride is more lethal than copper, hexavalent
chromium, zinc, nickel, and lead to fish and aquatic life. In the
food cycle, algae containing mercury in an amount up to 100 times
the concentration of the surrounding sea water are eaten by fish
which further concentrate the mercury, and predators that eat the
fish in turn concentrate the mercury even further. The criterion
for mercury in freshwater is 0.05 ug/1 for protection of aquatic
life. For marine life, the criterion is 0.1 ug/1 (US EPA, 440/9-
76-023, 9/76, ref. 407).
Nickel and tin do not appear to pose as serious threats to
receiving waters as the other heavy metals. Nickel is toxic to
aquatic life and to plants. Little is known about tin as a
pollutant problem. A criteria of 100 ug/1 has been recommended
by EPA. Many of the salts of nickel and tin are soluble in
water. They may be more hazardous to aquatic life than their
parent ions because of their higher level of toxicity.
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In soft water, concentrations of zinc ranging from 0.1 to 1.0
mg/1 have been reported to be lethal to fish. Zinc is thought to
exert its toxic action by forming insoluble compounds with the
mucus that covers the gills, by damage to the gill epithelium, or
possibly by acting as an internal poison (McKee, 1971, ref.
1972) . The sensitivity of fish to zinc varies with species, age,
and condition, as well as with the physical and chemical
characteristics of the water. Some acclimation to the presence
of zinc is possible. It has also been observed that the effects
of zinc poisoning may not become apparent immediately, so that
fish moved from zinc-contaminated (after 4 to 6 hours of
exposure) to zinc-free water may die 48 hours later. The
presence of copper in water may increase the toxicity of zinc to
aquatic organisms, while the presence of calcium or hardness may
decrease the relative toxicity. EPA has recommended a limited
application factor of 0.01 of the 96 hour LC 50 (lethal
concentration for 50 percent of the organisms) for freshwater
life (US EPA, 440/9-76-023, 9/76, ref. 407). The metals listed
above can be analyzed in waste waters by either wet chemical or
atomic absorption methods of analysis (WPCF, 1975, ref. 456) .
Pollutants of Secondary Significance
Nutrients
Aquatic nutrients in this context are various forms of phosphorus
and nitrogen. Both these elements are essential to aquatic
organisms. They are, however, often the limiting nutrients in
natural waters. An excess of these elements in a form that can
be assimilated by aquatic organisms may lead to eutrophication of
surface waters.
An increase in the supply of phosphorus leads to increasing
standing crops of aquatic plant growths, which often interfere
with water uses and are nuisances to man. Such phenomena are
associated with a condition of accelerated eutrophication or
aging of waters. It is generally recognized that phosphorus is
not the sole cause of eutrophication, but there is evidence to
indicate that it is frequently the key element required by fresh
water plants and is generally present in the least amount
relative to need in nature. Therefore, an increase in phosphorus
allows the use of other already present nutrients for plant
growths. For this reason, phosphorus is usually described as a
"limiting nutrient" (US EPA, 440/9-76-023, 9/76, ref. 407).
When plant life is stimulated and attains a nuisance status, a
large number of associated liabilities are immediately apparent.
Growths of pond weeds make swimming dangerous. Boating, water
skiing, and sometimes fishing may be eliminated because the mass
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of vegetation physically impedes such activities. Dense plant
populations have been associated with stunted fish populations
and poor fishing. Decaying nuisance plants emit vile odors,
impart tastes and odors to water supplies, reduce the efficiency
of industrial and municipal water treatment, impair aesthetic
beauty, reduce or restrict resort trade, lower waterfront
property values, cause skin rashes to man during water contact,
and serve as a substrate and breeding ground for flies and other
insects.
Phosphorus concentrations in waste waters are measured by a
colorimetric procedure. Pretreatment of the sample before
analysis allows the measurement of various forms of phosphorus
including orthophosphate, organic phosphates, complex phosphates
and total phosphorus, (WPCF, 1975, ref. 456). In thoroughly
assessing the potential of a waste water to contribute to
eutrophication, all these measurements should be made. However,
soluble orthophosphate concentrations are considered to be the
single most important parameter in measuring nutrients. The
orthophosphate species are the most readily available to aquatic
plants and the most likely to cause water quality problems.
Total phosphorus measurement is the second most useful parameter
in measuring nutrients since it defines the ultimate amount of
the nutrient that may become available to aquatic plants under
the most severe natural conditions.
Nitrogen compounds of concern include ammonia, nitrate, nitrite,
and organic nitrogen. Ammonia is a common product of the
decomposition of organic matter. Dead and decaying animals and
plants along with human and animal body wastes account for much
of the ammonia entering the aquatic ecosystem. Industrial waste
waters are another major source.
Ammonia is a form of nitrogen that readily fulfills the nutrient
requirement of aquatic plants. In those cases where adequate
phosphorus is available, nitrogen may be the limiting nutrient.
In such a case, the discharge of waste waters containing ammonia
will contribute to eutrophication of the receiving water and
consequent nuisance aquatic plant growth. Ammonia can also be
toxic to aquatic animals (US EPA, 140/9-76-023, 9/76, ref. 407).
The toxicity of ammonium solutions is dependent upon the amount
of ammonia, the concentrations of which vary with the pH of the
water. In most natural waters the pH range is such that ammonium
ions predominate; however, in alkaline waters high concentrations
of ammonia increase the toxicity. EPA has recommended a maximum
acceptable concentration of ammonia of 0.02 mg/1 in waters
suitable for aquatic life (US EPA, 440/9-76-023, 9/76, ref. 407).
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In natural waters containing dissolved oxygen, ammonia is
converted to nitrate by nitrifying bacteria. Nitrite, which is
an intermediate product between ammonia and nitrate, sometimes
occurs in large quantities when depressed oxygen conditions
permit. Both nitrate and nitrite are aquatic plant nutrients but
they are not as readily assimilated as ammonia, (Wetzel, 1975,
ref. 440).
Excessive concentrations of nitrate in waters can cause
methemoglobinemia in human infants. Nitrate has been limited by
the United states Public Health Service to 10 mg/1 as nitrogen in
public water supplies (WPCF, 1975, ref. 450).
Ammonia concentrations in waste water may be determined by
colorimetric or specific ion electrode methods. Nitrate and
nitrite are determined colorimetrically. Organic nitrogen
concentrations may be determined by the Kjeldahl procedure, by
which organic nitrogen is reduced chemically to ammonia which is
determined colorimetrically (WPCF, 1975, ref. 456).
In the pesticide industry ammonia nitrogen may be generated up to
levels of 1,500 mg/1 at individual plants. Ammonia is not a
universal pollutant for this industry and should be controlled as
necessary on an individual basis.
Phenols
Phenols and phenolic compounds are a potential waste water
constituent in the pesticide chemicals industry, particularly the
manufacture of halogenated organic pesticides. Because it is not
universally present in this category it should be controlled as
necessary on an individual basis.
Many phenolic compounds such as tetra-chlorodibenzo-p-dioxin are
more toxic than pure phenol; their toxicity varies with the
combinations and general nature of total wastes. The effect of
combinations of different phenolic compounds is cumulative.
Phenols and phenolic compounds are both acutely and chronically
toxic to fish and other aquatic animals. Also, chlorophenols
produce an unpleasant taste in fish flesh, destroying their
commerical value. EPA has recommended a limit of 1 ug/1 of
phenol in freshwater (USEPA, 440/9-76-023, 9/76, ref. 407).
It is necessary to limit phenolic compounds in the raw water used
for supplying drinking water, as conventional treatment methods
used by water supply facilities do not remove phenols.
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Disinfection of drinking water with chlorine when phenol is
present even at very low concentrations, forms chlorophenols,
producing taste and odor problems (WPCF, 1975, ref. 456).
Phenols also reduce the utility of water for certain industrial
uses, notably food and beverage processing, where it creates
unpleasant tastes and odors in the product. Phenols may be
determined in waste waters by colorimetric methods of analysis.
Cyanide
Of all the cyanides, hydrogen cyanide (HCN) is probably the most
acutely lethal compound. HCN dissociates in water to hydrogen
ions and cyanide ions in a pH dependent reaction. The cyanide
ion is less acutely lethal than HCN. The relationship of pH to
HCN shows that as the pH is lowered below 7, less than 1 percent
of the cyanide molecules in the form of the CN ion are present
and the rest are present as HCN. When the pH is increased to 8,
9, and 10, the percentage of cyanide present as CN ion is 6.7,
42, and 87 percent, respectively. The toxicity of cyanides is
also increased by elevations in temperature and reductions in
oxygen concentrations. A temperature rise of 10°C produced a
two- to threefold increase in the rate of the lethal action of
cyanide (US EPA, 440/9-76-023, 9/76, ref. 407).
In the body, the CN ion, except for a small portion exhaled, is
rapidly changed into a relatively non-toxic complex (thiocyanate)
in the liver and eliminated in the urine.
There is no evidence that the CN ion is stored in the body,
(McKee, 1971, ref. 192). The level of cyanide which can be
safely ingested has been estimated at something less than 18
mg/day. The average fatal dose of HCN by ingestion by man is 50
to 60 mg. EPA has been recommended a limit of 0.2 mg/1 cyanide
in public water supply sources.
The harmful effects of the cyanides on aquatic life are affected
by the pH, temperature, dissolved oxygen content, and the
concentration of minerals in the water. The biochemical
degradation of cyanide is not affected by temperature in the
range of 10 to 35° C, while the toxicity of HCN is increased at
higher temperatures.
Cyanide does not seem to be as toxic to lower forms of aquatic
life as it is to fish. The organisms that reduce BOD were found
to be inhibited at between 1.0 mg/1 and 60 mg/1 although the
effect is more one of delay in exertion of BOD than total
reduction.
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Certain metals such as nickel may complex with cyanide to reduce
toxicity, especially at higher pH values. On the other hand,
zinc and cadmium cyanide complexes may be exceedingly toxic (US
EPA, 440/9-76-023, 9/76, ref. U07).
Cyanide is not universally present in pesticide chemicals wastes
and should be controlled as necessary on an individual basis.
Other Pollutants
Settleable solids can be harmful to the aquatic environment in
the same manner as suspended solids. Measurement of total
suspended solid (TSS) includes both the suspended and settleable
solids.
The quantity of total dissolved solids in waste water is of
little meaning unless the nature of the solids are defined. In
fresh water supplies, dissolved solids are usually inorganic
salts with small amounts of dissolved organics, and total
concentrations may often be several thousand milligrams per
liter. It is not considered necessary to recommend limits for
total dissolved solids since they are limited by other
parameters, such as BOD, COD, and TSS.
Acidity is produced by substances that yield hydrogen ions upon
hydrolysis, and alkalinity is produced by substances that yield
hydroxyl ions. The terms "total acidity" and "total alkalinity"
are often used to express the buffering capacity of a solution.
Alkalinity in water is primarily a measure of hydroxide,
carbonate, and bicarbonate ions. Its primary significance in
water chemistry is its indication of a water's capacity to
neutralize acidic solutions. In high concentrations, alkalinity
can cause problems in water treatment facilities. However, by
control of pH, alkalinity is also controlled.
Acidity in natural waters is caused by carbon dioxide, mineral
acids, weakly dissociated acids, and the salts of strong acids
and weak bases.
Chlorides can cause detectable taste in drinking water in salt
(e.g., sodium, calcium, manganese) concentrations greater than
about 150 mg/1; however, the concentrations are not toxic.
Drinking water standards are generally based on palatability
rather than health requirements. A consideration to irrigate
crops with waste water should take into account chloride
concentrations as the salts generally inhibit the growth of
vegetation.
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Extremely high chloride concentrations can cause difficulty in
biological treatment. However, the successful acclimation of
activated sludge organisms to high chloride concentrations has
been demonstrated by several pesticide chemicals plants, as well
as a number of municipal treatment systems, in areas of high
saline water infiltration into sewers. Several pesticide plants
report chloride concentrations as high as 10,000 to 20,000 mg/1.
Oil and grease may result from various solvents used in
processing operations, spills or leaks of fuel oils, and losses
of lubricating fluids. These compounds may settle or float and
may exist as solids or liquids. Even in small quantities, oil
and grease may cause taste and odor problems in water. In
natural waters they can affect aquatic life adversely and exert
an oxygen demand.
Oil and grease have not been observed to be a particular problem
in the pesticide chemicals industry in those cases where adequate
solvent recovery is practiced. As in any industry, oil and
grease in pesticide wastewaters must be controlled by good in-
plant operations.
Sulfides can exert an oxygen demand on receiving streams, impart
an unpleasant taste and odor, and render the water unfit for
other use. Except in extreme cases, sulfides are controlled by
the same mechanisms used to control organics and suspended
solids.
Conclusion
It is concluded from the discussion above that for purposes of
treatment control, for the elimination of adverse environmental
effects, and for the documentation of particular previously
undefined compounds in effluents, that BOD, COD, TSS, pesticide
chemicals and pH should be regulated for this industry, and that
phenol, ammonia, and cyanide should be examined on a case-by-case
basis.
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
This section identifies the range of control and treatment
technologies currently practiced in the industry. A detailed
review is presented of full-scale design and operating
characteristics of the two most frequently utilized pesticide
removal technologies, activated carbon and hydrolysis. Also
included is a summary of pertinent literature. This section
documents the final effluent levels being achieved by the various
treatment technologies employed at plants in the industry. The
components are also defined for the model treatment technology
which is utilized as the basis of cost calculations in Section
VTII.
The data relating to treated effluents that are presented in this
section form the basis for the derivation of effluent limitations
guidelines in Section IX. The treatment technologies presented,
pesticide removal through the application of activated carbon or
hydrolysis technology, equalization, and biological treatment,
represent one of the several treatment schemes capable of meeting
the effluent limitations.
The Agency does not require that any specific technology (ies) be
employed; the requirement is that promulgated effluent
limitations be attained. However, in order to evaluate the
economic impact associated with the implementation of the
standards, model treatment systems are costed for each
subcategory. The installation of well-designed and operated
treatment systems, similar to the model treatment technologies,
will result in attainment of the recommended standards.
Personnel at each facility must decide which specific control
measures are best suited to its situation and needs. It is not
good practice for industrial waste water treatment facilities to
be designed without conducting treatability studies to determine
the optimum design, nor is it good practice that monies be
budgeted without conducting an economic assessment of the various
applicable technologies.
It should be emphasized that the treatment technologies selected
for the basis of cost estimates are not the only systems capable
of attaining the specific effluent limitations. However, the
recommended effluent limitations can be attained through the
application of the unit operations presented in this section.
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INDUSTRY TREATMENT PROFILE
Tables VII-1 and VII-2 present the types of production, methods
of waste water disposal, and types of treatment technologies
employed by the direct and indirect dischargers respectively in
the pesticide chemicals manufacturing industry.
An examination of Table VII-1 and subsequent individual plant
discussions will show that a majority of the direct dischargers
currently employ pollution reduction techniques equivalent to
those which form the basis of the cost estimates. A plant by
plant analysis of the additional costs required for direct
dischargers to meet BPT is presented in Section IX.
Subcategory 1 - Organic Pesticide Chemicals
PESTICIDE REMOVAL TECHNOLOGY REVIEW
Since Interim Final regulations were published on November 1,
1976, a comprehensive review of activated carbon and hydrolysis
pesticide removal technologies was conducted. This study was
used to verify and/or supplement existing design and operating
data concerning these systems and to make appropriate changes to
the effluent limitations and cost analyses included in the
previous development document. Additional sampling and analysis
was undertaken by both the EPA contractor and the plants
involved. The following discussions present the results of this
review.
Activated Carbon
Activated carbon has been used for many years for removing color
and odors from various aqueous streams (i.e., sugar refining).
Adsorption of a molecule within the porous structure of the
activated carbon granule is affected by a variety of factors
including molecular size of the adsorbate, solubility of the
adsorbate, pore structure of the carbon and other factors as
discussed in the following paragraphs.
For sorption to occur, the adsorbate molecule must first travel
from the bulk solution to the surface of the carbon. Once at the
surface, it must diffuse into the inner pores of the carbon where
most of the binding sites are contained. Finally the adsorbate
must align itself with the carbon.surface to allow binding to
occur.
Several parameters affect absorption. Diffusion of the adsorbate
from the bulk solution to the surface of the carbon occurs by two
mechanisms, molecular and eddy diffusion.
104
-------
TABLE Vll-1
DIRECT DISCHARGER PROFILE
PESTICIDE INDUSTRY
PLANT
3
8
9
11
15
16
18
19
2\
22
27
29
31
32
33
34
36
39
40
41
45
47
48
50
53
139
146
149
int.
A
X
X
X
X
X
X
X
X
X
X
X
X
B
X
X
X
X
X
X
X
X
X
PRODUCTION
CATEGORY
C
X
X
x ,
-
X
X
X
X
X
X
X
X
X
X
X
X
X
y
D
X
-
X
X
X
E_
X
X
X
X
X
X
-
X
X
X
X
X
X
X
X
X
X
X
X
X
f_
-
-
X
X
X
X
X
G
X
X
X
X
X
X
X
X
y
X
X
X
X
X
X
X
X
X
X
t
METHODS OF
WASTEWATER
DISPOSAL
1
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
Y
2
xi
X
X
X
:?
1 1
X -
X -
y
X -
X -
X -
TYPES OF TREATMENT
— — — — — — —
------
X. .... y
X - - - - X -
- - - X - - -
X_
- - - X - - -
- - - X - - -
x
X - - - - X
- X -----
X - X - X X -
.
x
X_
- X
- X
y
- X
- X
X X
- X
- X
V
- X
- X
Sk te
x
y
- X
- x-
- X
- X
- X
V
- X
X X
- X
X X
- X
- X
- X
- X
y
- X
X_
y
As.
-
-
X
X
X
X
X
y
X
X
-
Al_ Tf
-
-
v _
- X
X -
X -
X -
X -
-
X -
- X
X X
X -
Ne
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
Note: 1 Method of disposal utilized by plant for products not covered by this regulation.
CODES:
PRODUCTION CATEGORY:
A. Halogenated Organic;
B. Organo Phosphorus
C. Organo Nitrogen
D. Metallo Organic
E. Formula tors/Packagers
F. Non-Categorized Pesticides
G. Non-Pesticide Products
METHODS OF WASTEWATER DISPOSAL:
1. Direct Discharger
2. Deep Well Injection
3. Incineration
4. Contract Truck Hauling
TYPES OF TREATMENT:
Ac
Co
Ev
Hd
le
Mf
Ra
Sp
Eq
Sk
Gs
As
Al
Tf
Ne
Activated Carbon
Chemical Oxidation
Multiple Effect Evaporation
Hydrolysis
Ion Exchange
Multi-Media Filtration
Resin Absorption
Stripping
Equalization
Skinning
Gravity Separation
Activated Sludge
Aerated Lagoon
Trickling Filters
Neutralization
105
-------
TABLE VII-2
INDIRECT DISCHARGER PROFILE
PESTICIDE INDUSTRY
PRODUCTION CATEGORY
METHODS OF
WASTEHATER DISPOSAL
TYPES OF TREATMENT
.ANT
i
4
5
7
10
12
13
14
20
23
24
25
?6
20
in
35
37
38
A1
44
*r
51
52
54
55
56
cl
D/
58
CQ
JJ
cn
61
62
63
65
£•£•
DO
67
68
CQ
by
70
71
72
•7-5
13
7 A
/I
75
A
X
X
x
x
x
x
X
X
x
X
X
X
X
X
-
_
X
.
_
.
-
.
-
.
X
-
-
.
B C
. x
_
x .
- X
X -
K K
X -
- X
- X
Y
- X
V
- X
- X
- X
_
. .
- X
- -
- -
_
D
x
X
.
X
_
-
X
X
X
X
-
-
-
E
Y
x
x
X
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
F G
x
- X
x
- X
¥ .
- X
. -
- X
- X
- X
X -
- -
- -
.
H I
X X
X X
X -
X X
X -
X -
X X
- X
X -
X -
X -
X -
-
X X
X -
XV
A
X -
X -
X -
-
-
X -
J
x
x
X
x
X
X
Y
-
X
.
Y
X
_
1234
x ...
X - - -
x ...
x ...
x ...
- X -
- - - X
X - - -
- - X -
X - - -
X - - -
X - - -
Y Y
X - - -
X.
X - - -
- - X -
- - - X
XV
X - - -
Y -
v
- - A
-
-
5 6 7 8 9 Ac Ca Ej> Fo Hd Mf Ra Ch Dh E^
-----* -- - _
--.__X -- --.. x
--.--. -X --
----x
--.-_. -_• _.
...... -Y -_
x
- -- --xx-x-
---x---- --
---x
--X--- -- -X----X
.K.... -- -.
----x
---x
x x-x
Y
x
Xv y
----x
x- x-x----
x -
x ------ --
Xy y
V
x
x
x
x
y
x
y
x----
x
y
x -
x-----
X .--.-
-------
-------
x
Sk. Gs_ As_ Al_ Ne Ad
-Y-YY
- - - - X -
- X - X - -
X - - - X -
X X - - X -
- X X - X -
- X - - - -
- - - XX-
X
. x - - - -
x -
Y Y
A A
St. Vf Ms Hi No U_k
. - - 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 -
-------
TABLE VII-2
Continued
Page 2 of 4 Pages
PLANT
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
PRODUCTION CATEGORY
A B C D E F G
.... 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 - -
........ y .«
II
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
1
-
X
-
-
-
-
-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
J 1
- -
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
METHODS OF
WASTEWATER DISPOSAL
~2 3 4 5 6 7 S 9 Ac CB Ep Fo Hd Mf
-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
--XX
---x
- - - • X
--XX-
TYPES OF TREATMENT
Ra Ch Dh F_a Sk Gs As Al Ne Ad St Vf Ms Ws No
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--XX--X---
x
x -
x
x
x
X
x
- - - -' x
X
X
x
X
- - • x
X
X
X
X
i----- X
- - - - - X -
X
• . - - x -
[?*L
.
_
.
.
_
_
_
_
.
-
_
-
-
_
_
.
_
.
.
-
.
-
.
.
.
.
.
-
_
-
-
.
-
-
-
-
-
-
-
-
-
-
-
-
-
-------
TABLE VI1-2
Continued
Page 3 of 4 Pages
METHODS OF
PRODUCTION CATEGORY MASTEMATER DISPOSAL TYPES OF TREATMENT
PLANT
12
171
126
177
17fl
i in
1 11
133
1 1/1
1 11^
1 3fi
1 17
i in
110
147
1 A/1
id?
i fin
1 M
1 C1
1R4
1 £A
I'M
1 SO
Ifil
1K7
ABODE
.... X
... x
.... x
- - - X
.... X
.... x
.... x
.... X
x
.... x
X
y - y - x
y
y
Xy -
y
y - .
X_
Xy y
- . y - y
F
y
y
V
Y
y
Y
Y
y
Y
Y
Y
G
y
Y
y
H I
y
X X
x
y
y x
y
y
y
X X
y y
y y
y y
x .
J 1 2 3 4 5 6 7 8 9 Ac Ca Ep Fo lid Mf Ra Ch Dh E
-------
TABLE VI1-2
Continued
Page 4 of 4 Pages
o
VO
CODES:
PRODUCTION CATEGORY:
A. Halogenated Organics
B. Organo Phosphorus
C. Organo Nitrogen
D. Metallo Organic
E. Formulators/Packagers
F. Non-Categorized Pesticides
G. Non-Pesticide Products
II. Solvent Formulation
I. Wet Formulation
0. Dry Formulation
METHODS OF WASTEWATER DISPOSAL:
1. Municipal
2. Direct
3. Other
4. Land
5. Truck Hauling
6. Ocean Discharge
7. Incineration
8. Deep Well Injection
9. No Wastewater Generated
TYPES OF TREATMENT:
Ac = Activated Carbon
Ca = Coagulation
Ep = Evaporation Pond
Fo = Floculation
Hd = Hydrolysis
Mf = Multi-Media Filtration
Ra = Resin Absorption
Ch = Chlorination
Dh = Dehydrochlorination
Eq = Equalization
Sk = Skimming
Ga = Gravity Separation
As = Activated Sludge
Al = Aerated Lagoon
Ne = Neutralization
Ad = Aerobic Digestor
St = Sludge Thickening
Vf = Vacuum Filtration
Ms = Metal Separation
Ws = Wet Scrubber
No = None
Uk = Unknown
-------
Molecular diffusion has a very strong dependency on temperature.
For example, the diffusivity of a component in water at 100°F is
50 percent greater than that for the same component at 70°F.
Eddy diffusion results from transport of the adsorbate molecules
due to turbulent eddies. This phenomenon occurs only in
turbulent flow and is effective up to the laminar boundary layer
near the surface of the carbon granule. Eddy diffusion also
increases with increased temperature. Both are caused by lower
viscosity as a result of the higher temperature resulting in
better contact with the activated sites.
The molecular diameter and structure of the adsorbate molecule
are also important factors in determining the adsorption
characteristics of the solute. Obviously, the molecule must
physically be able to diffuse into the internal pores of the
carbon. Finally, a major factor in determining the adsorption
characteristics of a given solute is its solubility in the waste
water. This, presumably, is the reason for the strong influences
of pH on the adsorption of many molecules.
Full Scale Activated Carbon Treatment Data. There are ten
full-scale carbon systems currently employed or under design in
subcategory 1. Nine are used to reduce pesticide chemicals in
the waste stream and one is used to reduce chlorine. Design data
for these systems are found in Table VII-3. From a review of
this table and the accompanying text it is apparent that under
proper pH and contact time conditions, activated carbon is highly
effective in removing pesticides from waste water.
Activated carbon has been applied primarily to halogenated
organic and organo-nitrogen compounds. The effectiveness of
column configuration has been determined on an empirical basis
(i.e.. Plants 6, 8, and U5 have experimented with counterflow
systems). Long contact times and low loading rates are being
utilized at some facilities to insure high removals of pesticide
active ingredients. For the most part, the pH of the process
water has not been adjusted, nor has extensive testing been
conducted in order to optimize the system. Few plants are known
to practice backwashing.
A weekly air scouring is utilized at Plant 45 in order to prevent
channeling and to remove suspended matter. Plants 45 and 46
employ sand filters used in advance of the carbon columns in
order to improve bed life and to remove solids that could plug
the column. In several cases, carbon replacement is based on
administrative decision rather than maximum pesticide removal.
110
-------
TABLE VII-3
ACTIVIATED CARBON DESIGN 3JMMARY
PESTICIDE INDUSTRY
PLANT PRODUCT(S)
6 2,4-D
2,4-DB
MCPA
MCPB
Bromoxynll Octanoate
8
18
20
22
39
PCNB
Toxaphene
DNBP
Cyanazine
Dicofol
Dalpon
Triflural
45
46
50
Isopropalin
Ethalfluralin
DEET
Piperonyl Butoxlde
Thanite
Atrazine
Carbofuran
1
COLUMN
CONFIGURATION
Upflow
Downflow
NA
Downflow
NA
Downf 1 ow
Downflow
Downflow
Downflow
CONTACT
TIME SLR
CMIN) pjl (GPM/FT2)
760 1 0.60
479 0.5-4.0 0.32
NA NA NA
35 0.5 2.10
NA NA NA
230 9.0 0.66
456 4-5 0.36
120 8-12 1.3
292 7-9 0.51
LBS. CARBON/ TYPE
KGAL TREATED REGENERATION-SYSTEM
110
127
NA
NA
NA
154
21.1
7.8
207
Thermal -Owned
Thermal -Lease
NA
Isopropanol -Owned
NA
Thermal -Lease
Thermal -Lease
Thermal -Lease
Thermal -Lease
SLR = Surface Loading Rate
NA = Not Available
-------
Although flow rates have not been presented, it is important to
note that activated carbon has usually been applied to low flow,
segregated, and concentrated waste streams as a pretreatment
technology. Flows between 1,000 and 150,000 gal/day have been
observed to be pretreated using activated carbon. Personnel at
plant 18 are designing a tertiary carbon system wherein contact
time, loading rate, and carbon usage would be expected to vary
considerably from the levels depicted in Table VII-3.
With the exception of plants 20 and 46, pesticide removals in
excess of 99 percent are being consistently achieved (Table VII-
4) . Plants 20 and 46 operate the carbon to predetermined
discharge levels before either back rinsing with solvent or
changing the carbon. Other plants (e.g. Plants 45 and 50) have
contracts with carbon suppliers and operate the carbon columns
until the supplier changes the carbon according to schedule.
Removal of organic pollutants is a significant benefit in
employing activated carbon, and in most cases the initial design
of existing columns was based on TOC, rather than pesticide
reduction. Utilizing activated carbon generally decreases the
size of subsequent biological treatment processes required. This
is shown in Table VII-4.
At Plant 6, five organic pesticide chemicals are produced: 2,
4-D, 2,4-DB, MCPA, MCPB, and bromoxynil octonoate. Waste water
from these processes enters an 8,000 gallon surge tank at pH 1.5,
passes in series up through two 18,000 gallon wooden tanks
charged with 15,000 pounds of carbon, is neutralized with lime to
pH 6.0 - 8.0, and then goes to a 20,400 gallon holding tank prior
to discharge. Table VII-4 gives the results of sampling
conducted by the EPA contractor while the plant was producing
2,4-D, esters, and dichlorophenol.
At Plant 8 PCNB(parachloronitrobenzene) waste water is treated
using activated carbon. 20,000 Ib adsorbers are operated
downflow in series at pH 0.5 to 4.0. The effluent is neutralized
and discharged to a navigable waterway. Data is presented in
Table VII-4 for periods when PCNB was produced both solely and
together with terrazole. Both are halogenated compounds.
At Plant 19, DCPA, chlorothalonil and an intermediate, chloral,
are produced. The plant operates a carbon column but the purpose
is to remove chlorine from the waste stream not pesticide
chemicals. No known pesticide chemicals are reported removed by
this unit.
At Plant 20 dicofol is produced. Although the waste water is
discharged to a public treatment system, dicofol is pretreated in
112
-------
TABLE VII-4
ACTIVATED CARBON TREATMENT SUMMARY
PESTICIDE INDUSTRY
BOD
COD
TOC
PLANT PRODUCT(S)
6
8
20
39
45
46
50
2,4-D
PCNB
Terrazole
Dlcofol
(1) THflurelln
(2) THfluralln
DEET
Plperonyl
Butoxide
Atrazlne
Carbofuran
PLANT PRODUCT(S)
6
8
20
39
45
46
50
2,4-D
PCNB
Terrazole
Dicofol
(l)Trlfluralln
(2)Triflura11n
DEET
Plperonyl
Butoxide
Atrazlne
Carbofuran
IHF.
mg/1
1630
NM
NM
45200
995
301
NM
NM
NM
193
INK
mg/1
69
1510
1510
1460
168
312
68.6
68.6
29.5
674
EFF.
mg/1
780
NM
NM
37400
1100
109
889
889
NM
9.2
TSS
EFF.
mg/1
109
255
255
2600
165
2.8
46.6
46.8
8.78
6.6
%
REMOVAL
52.1
N/A
N/A
17.4
N/A
63.8
N/A
N/A
N/A
95.2
INF.
mg/1
5780
5770
5770
EFF.
mg/1
2120
320
320
148000 109000
8310
8290
4750
4750
NM
4880
6380
1394
808
808
NM
31.2
REMOVAL
63.2
94.4
94.4
26.7
23.3
83.2
82.9
^82.9
N/A
99.4
INF.
mg/1
2220
698
698
79800
926
1665
1650
1650
NM
2170
TOTAL PHENOL
X
REMOVAL
N/A
83.1
83.1
N/A
1.8
99.1
31.8
31.8
70.2
99.0
INF.
mg/1
77.9
NM
NM
NM
2.02*
NM
129
129
NM
0.28
EFF.
mg/1
2.32
NM
NM
NM
0.51*
NM
4.26
4.26
NM
0.7*
REMOVAL
97.0
N/A
N/A
NN/A
74.8
N/A
96.7
96.7
NM
75.0**
INF.
mg/1
58.4
11.6
NM
17.2
11,3
3.37
218
7.57
18.9
2250
EFF.
mg/1
534
85.7
85.7
66700
1950
291
153
153
NM
15.4
REMOVAL
76.0
97.7
97.7
16.4
N/A
82.5
90.7
90.7
N/A
99.3
PESTICIDES
EFF.
mg/1
0.037
0.0093
NM
10.5
0.104
0.004
1.26
0.01*
2.46
0.46
REMOVAL
99.9
99.9**
N/A
39.1
99.1
99.9
99.4
99.9**
86.9
99.9
(2
EPA Analytical Results
Plant Analytical Results
* = Less Than
**• Greater Than
113
-------
an activated carbon system prior to discharge,, The raw waste is
collected in a 1,000 gallon surge tank? passed through columns {2
feet in diameter by 10 feet high) and stored until analysis has
been completed,. If the total of all chlorinated pesticide
chemicals is less than 5 mg/1, the waste water is discharged to
the municipal treatment systemo If not, it is recycled through
the columns again= The carbon is regenerated with isopropanol
and the solvent is incinerated,, Carbon is replaced infrequently,
approximately twice per year*, This system is inefficient because
of the small detention time and the necessity for more frequent
fresh carbon addition,, Low flows allow frequent recycle in order
that their effluent objective be met* Table VII-1 presents five
and one-half months of pesticide data by the plant, sis days BOD?
COD, TOC, TSS, and pesticide chemicals data by the plant, and
seventeen days of sampling analyzed by the EPA contractor.
Plant 22 submitted one data point (0=2i& kg/kkgj) representing the
average of seven days sampling from the effluent of dalapon waste
water- Neither the operating conditions of the activated carbon
system nor the individual analyses have been supplied by
representatives of the plant=
At Plant 39 waste water from trifluralin, ethalfluralin, and
benfluralin is treated using activated carbon.. These compounds
are nitrogen-based pesticide chemicals,, Process water at pH 8=5
to 9=5 flows through two 20,000 pound adsorbers in series and is
combined with other plant waste water in a biological systemo
Table VII-1 presents data analyzed by both the EPA contractor and
the pi an to
At Plant 45 waste water from DEBT, piparonil butoxide, and
several non-pesticide products is treated ([See Table VIl-4)= Raw
waste water enters a 250,000 gallon equalization basin where the
pH is adjusted to 5=0 to 6=0= It is then passed through a dual
media filter and stored in a 100,000 gallon equalization pondo
Two 20,000 pound carbon columns operated downflow in-series, a
100,000 gallon, and a 250,000 gallon equalization ponds comprise
the remainder of the treatment system prior to discharge to
navigable waterSo
Table VII-4 shows Plant 46 produces atrazine» Waste water from
this plant enters a sump and is pumped to two 0 = 5 million gallon
holding tanks in series= overflow proceeds through two multi-
media filters in parallel, each being four feet in diameter„
Filtered waste water is passed downward through two 20,000 pound
adsorbers in series, neutralized, clarified, and discharged to a
municipal treatment plant= Carbon in the columns is changed only
if the effluent level of atrazine exceeds 10 mg/l=
114
-------
At Plant 50 floor washwater from a carbofuran process is treated
using activated carbon (See Table VII-4) . As such, this waste
water is weaker than the wastes from other pesticide
manufacturing operations and is not representative of the
industry. Washwater at pH 7.0 - 9.0 is stored in a 6,000 gallon
tank. For a period of two to three hours daily the waste water
is passed downward through two 20,000 pound carbon columns in
series. The effluent is currently discharged to a holding pond
and is subsequently reused as washdown water.
Activated Carbon Dynamic Data and Isotherm Data. Isotherm and
dynamic data from the literature and Agency correspondence are
summarized in Table VII-5. These data expand and/or supplement
the documentation of carbon applicability to the following groups
of pesticides: alkanoic acids, DDT and relatives, halogenated
aromatics, phosphorothioates, amides, carbamates, nitros, ureas,
and triazines.
Dynamic carbon data are data obtained from pilot or spill
prevention operations. The units are generally portable and are
used to predict full scale operating conditions. Dynamic data
allow prediction of required contact times to achieve given
reductions in pesticide levels as well as carbon.regeneration
rates.
The Oil and Hazardous Spills Branch of the U.S. EPA in Edison,
New Jersey (Wilder, 1976), operates several mobile carbon columns
which have been used to decontaminate various pesticide chemicals
waste waters. Up to three columns are utilized in series at 100
to 600 gpm and 8 to 60 minutes contact time for a single pass or
up to 240 minutes for recycled streams. The data in Table VII-5
for aldrin, chlordane, kepone, dieldrin, heptachlor, and
toxaphene show extremely high removal efficiencies ranging from
97.2 to 99.99+ percent.
Eichelberger and Lichtenberg (1971) studied the sorption
characteristics of a variety of organochlorine and
organophosphorus pesticides using activated carbon. In each run
a single pesticide was added to a sample of city tap water. The
dynamic data for endosulfan and methoxychlor, included in Table
VII-5, show a fairly good removal efficiency for methoxychlor of
89 percent (from 2 to 0.2 ug/1). The removal efficiency for
endosulfan of 20 percent (from 2 to 1.6 ug/1) was not quite as
good, but was reported to be sufficiently high to warrant further
investigation using longer contact times, different carbons, or
different pH.
Several investigators, including Eichelberger and Lichtenberg
(1971) and Roebeck, (1965), have studied the adsorption
115
-------
characteristics of endrin. The dynamic column test data of
Roebeck, et al., for which endrin was added to a sample of river
water show a very high removal efficiency (greater than 99
percent) using a very short contact time of 7 1/2 minutes. Their
data for dieldrin, although not presented here, corroborate those
of Wilder (1976) for the same compound.
E.M. Froelich (1977) has presented data on the efficiency of
activated carbon on actual pesticide chemicals waste streams.
Pilot data are given along with the results of a full-scale
treatment system. Of the compounds mentioned, all achieved
levels of reduction of better than 99*. Original concentrations
varied from 24 mg/1 to 350 mg/1 with effluent concentrations
varying from less than 0.1 mg/1 to less than 1.0 mg/1. Table
VII-5 presents the results of these studies.
So'rption of 2,U,5-T using granular activated carbon columns was
studied by Roebeck, et al. (1976). River water samples were
spiked with single pesticide chemicals and mixtures of
pesticides. Their data show better than 99 percent removal at a
contact time of around 7.5 minutes (two columns in series). The
investigation results for DDT and lindane show the same high
removal efficiencies as for 2,4,5-T, as evidenced by the data
presented in Table VII-5.
Lambden and sharp (1960) reported on activated carbon treatment
of industrial wastes for the removal of DNOC. Their data
indicate that the reduction of DNOC from 60 mg/1 to trace
quantities with a 16-minute contact time (pH = 7 to 7.5).
Wilder (1976) has treated water contaminated with dinoseb and
achieved extremely good results with a contact time of 26
minutes. This pesticide chemical was reduced from 8 ug/1 to less
than 0.02 ug/1, a removal efficiency of 99.75 percent.
Isotherms respresent adsorption under equilibrium conditions and
indicate the maximum amount of a solute that will be adsorbed
onto the carbon for any concentration of solute in the aqueous
phase. This type of data is useful in selecting carbons for
dynamic column tests and for estimating carbon regeneration
rates. These tests do not account for diffusional effects that
will occur under dynamic column conditions.
Isotherms for alachlor, propachlor, bromacil, and diuron (ESE,
1977) show extremely good adsorption characteristics. The data
summarized in Table VII-5 show pickups ranging from 8 to 19
percent by weight for diuron and alachlor. The tests on these
four compounds were conducted with distilled water using TOC as
the control parameter.
116
-------
Bernardin and Froelich (1975) gave results of their laboratory
analysis of: aldrin, dieldrin, endrin, DDE, DDT, ODD, toxaphene,
and aroclors 1242 and 125U. Procedural analysis consisted of the
addition of varying amounts of individual pesticide chemicals to
a specific quantity of activated carbon in a liter of solution.
The pesticide carbon mixture was shaken four hours and filtered
through a 0.45u millipore filter. The filtrate was then
extracted and concentrated prior to analysis. Analysis was
accomplished via gas-chromatograph techniques employing nickel-63
electron capture. Table VII-5 exhibits the results with the
associated conditions.
In a study by Roebeck, et al. (1965), adsorption isotherms for
dieldrin and lindane (among others) were obtained in samples of
distilled water, river water, and river water containing more
than one pesticide chemical. The isotherms show the effect that
the presence of other organic compounds has on the sorption of a
particular component. As expected, certain organics can occupy
active sites on the carbon granule, thereby suppressing sorption
of the pesticide chemical in question. This is evident on noting
the decreased intercept (ug/mg). However, even in samples of
river water, adsorption of lindane and dieldrin at very low
concentrations was quite high.
Hydrolysis
In hydrolysis, a hydroxyl or hydrogen ion attaches itself to some
part of the pesticide chemical molecule, either displacing part
of the group or breaking a bond thus forming two or more new
compounds. An example of the first type of reaction is found in
the reaction between atrazine and water:
Cl OH
C2H5HN
NHCH(CH3)2 C2H5HN 'NHCH(CH3)2
In this reaction, the chloride ion is displaced by the hydroxyl
ion forming hydroxyatrazine and hydrogen chloride. Hydrolysis of
diazinon provides an example of the second type of reaction:
S
(CH3)2CH N o-P(OCH2CH3)2 (CH3>2CH^|\L OH S
T if Y ll H
1 !l "• ' " + HO-P(OCH2CH3)2
orOH
117
-------
TABLE VII-5
ACTIVATED CARBON ISOTHERM AND DYNAMIC DATA
PESTICIDE INDUSTRY
PESTICIDE
Aldrin
Chlorodane
Chlorodane
Kepone
Dieldrin
Dieldrin
Dieldrin
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
Toxaphene
2,4-D
Sodium Salt
Isopropyl Ester
Butyl Ester
Isooctyl Ester
2,4-D
2,4-D
2,4-D
2,4-5-T
ODD
DDE
DDT
Methoxychlor
0-Dichlorobenzene
P-Dichlorobenzene
lindane
Methyl Parathion
Alachlor
Propachlor
Benomyl
Dinoseb (DNBP)
DNBP
DNOC
Bromacil
Diuron
Atrazine
EH
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
6.5-7.5
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A.
N/A
N/A
N/A
N/A
N/A
Neutral
Neutral
N/A
6.5-7.5
4.0
7-7.5
Neutral
Neutral
N/A
CONTACT
TIME. MIN.
240
17
240
17
45.5
240
17
-
7.5
240
17
26
N/A
-
-
-
-
-
N/A
N/A
N/A
7.5
• -
-
7.5
N/A
N/A
N/A
7.5
N/A
-
-
66
26
300
16
_
_
N/A
INFLUENT
CONC. PPB.
60.5
8.5
1430
13
4000
60.5
11
2
10
80
6.1
36
49000
-
-
-
-
-
35000
350000
0-250000
10
-
-.
10
2
24000
28000
10
108000
-
-
42
8
1200000
60
-
-
45000
EFFLUENT
CONC. PPB.
0.15
0.19
0.43
0.35
1*
0.01*
0.01*
1.6
0.01*
0.1
0.06
1
100*
-
-
-
-
-
100*
1000*
1000*
0.0*
-
-
0.1*
0.2
100*
100*
0.1*
100*
-
-
1*
.002*
5000
Trace
-
-
10*
%
REMOVAL
99.75
97.76
99.99
97.3
99.98**
99.99**
99.99**
20
99**
99.87
99.02
97.22
99.8**
-
-"
-
-
-
99.7**
99.7**
-
99**
-
- -
99**
90
99.6**
99.6**
99**
99.9**
-
-
99**
99.98**
99.6
99**
-
99.9**
N/A = Not Available
** = Greater Than
* = Less Than
118
-------
TABLE VII-5
Page 2 of 2 Pages
Continued
mg/PESTICIDE
mg CARBON
AT FINAL
CONCENTRATION(PPB)
Aldrin
Chlorodane
Chlorodane
Kepone
Dieldrin
Dieldrin
Dieldrin
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
Toxaphene
2,4-D
Sodium Salt
Isopropyl Ester
Butyl Ester
Iscoctyl Ester
2,4-D
2,4-D
2,4-D
2,4,5-T
ODD
DDE
DDE
DDT
Methoxychlor
0-Dichlorobenzene
P-Dichlorobenzene
Lindane
Methyl Parathion
Alachlor
Propachlor
Benomyl
Dinoseb (DNBP)
DNBP
DNOC
Bromacil
Diuron
Atrazine
3% @ 48
N/A
N/A
N/A
1.5% @ 19
1.5% G> 19
1.5% @ 19
N/A
N/A
N/A
N/A
10% @ 300
N/A
3.2% @ 100
6.6% 0 100
6% <<> 100
5.5% @ 100
1.7% @ 100
N/A
N/A
N/A
N/A
18% @ 56
1.1% @ 41
0.9% G> 38
N/A
N/A
N/A
N/A
N/A
N/A
19% @ 5000*
18% @ 5000*
N/A
N/A
12.3% @ 4500
N/A
20% @ 2000*
8% G> 2000*
N/A
WATER
SOURCE
River
N/A
N/A
River
River
River
River
Potable
River
River
River
River
Industrial
N/A
N/A
N/A
N/A
N/A
Industrial
Industrial
Industrial
River
N/A
N/A
N/A
River
N/A
Industrial
Industrial
River
Industrial
Distilled
Distilled
N/A
N/A
Industrial
N/A
Distilled
Distilled
Industrial
REFERENCE
Wilder
Wilder
Wilder
Wilder
Wilder,
Wilder,
Wilder,
1976
1976
1976
1976
1976
1976
1976
Eichelberger & Lichtenberg, 1971
Robeck, et al, 1965
Wilder, 1976
Wilder, 1976
Wilder, 1976
E.M. Froelich, 1977
Aly & Faust, 1965
Aly & Faust, 1965
Aly & Faust, 1965
Aly & Faust, 1965
Aly & Faust, 1965
E.M. Froelich, 1977
E.M. Froelich, 1977
E.M. Froelich, 1977
Robeck, et al, 1965
Bernadine & Froelich, 1975
Bernadine & Froelich, 1975
Robeck, et al, 1965
Eichelberger & Lichtenberg, 1971
E.M. Froelich, 1977
E.M. Froelich, 1977
Robeck, et al, 1965
E.M. Froelich, 1977
ESE, 1977
ESE, 1977
Plant 48
Wilder, 1976
Enviro Labs, 1975
Lamborn & Sharp, 1960
ESE, 1977
ESE, 1977
E.M. Froelich, 1976
Expressed as TOC concentration
119
-------
The primary design parameter to be considered in hydrolysis is
the half-life of the original molecule, which is the time
required to react 50 percent of the original compound. The half-
life is generally a function of (a) the molecule being hydrolyzed
and (b) the temperature and pH of the reaction. This is
illustrated in Figure VII-1 which shows the half- life of
malathion as a function of pH and temperature. The figure shows
that increases in temperature and extremes of pH have significant
effect on the half-life.
The effect of molecular structure on the half- life can also be
quite striking, as for demeton-O and demeton-S. The molecular
structures of these two molecules are presented in Figure VII-2.
The principal difference in their structures is the location of
the phosphorus double bond. In demeton-O, phosphorus and sulfur
are joined by a double bond whereas in demeton-S, phosphorus and
oxygen are connected by a double bond. The half -lives for these
two compounds at 20°C and pH 13 are 75 minutes for Demeton-O and
0.85 minutes for demeton-S (Melnikov, 1971) . This is a
difference of nearly two orders of magnitude.
The half-life of a compound can be determined for first and
second order reactions as follows. For a first order reaction,
the rate (KJ[) is dependent only on the concentration (mg/1) of
the pesticide chemical.
K1
B
The half-life, t(1/2), is determined by the equation:
t(1/2) = 1 In 2 = 0.693
As this equation shows for true first-order kinetics, the half-
life is independent of the concentration of the pesticide
chemical.
As a general rule, hydrolysis follows second-order kinetics,
which depend on the concentration of both the pesticide chemical
and hydrogen ion (or hydroxyl ion). However, if the
concentration of hydrogen or hydroxyl ions is essentially
constant, the above equation is a good approximation.
The reaction constants of hydrolysis for certain classes of
pesticide chemicals, specifically carbamates, phosphorothioates,
120
-------
10*
to
§
o
X
uf
104
10*
6
PH
EFFECT ,OF pH AND TEMPERATURE ON
MALATBION DEGRADATION
* i FIGURE VII-1
121
-------
s
(C2H5O)2 P-O-C2H4-S-C2H5
DEMETON-O
(C2H5O)2P-S-C2H4-S-C2 H5
O
OEMETON-S
MOLECULAR STRUCTURES
DEMETON-O AND DEMETON-S
FIGURE VII-2
122
-------
and phosphates, can be calculated from the Bronsted free energy
equation.1
log K2! = Alog Ka + B
Where = K.2 = second order reaction rate constant,
mole-1 sec-1
Ka = ionization constant for the alcohol formed by
hydrolysis
A = slope of the equation
1. Wolf, Zepp, and Paris, "Use of Structure Reactivity
Relationships to Estimate Hydrolytic Persistance of
Carbamate Pesticides", U.S. EPA; Presented at American
Chemicals Society Meeting, New Orleans, 1977.
The pKa is the negative logarithm of the Ka. A plot of the log
of the reaction rate constant versus the pKa of the alcohol will
be a straight line with negative slope A. Figures VTI-3 and VTI-
U show this relation for four different classes of carbamates.
The value of these relationships lies in the fact that the
ionization constants for many alcohols are known, whereas the
reaction constants for the corresponding carbamates are not.
The reader will notice that a family of lines is shown in these
two figures, each line corresponding to a homologous series. For
example, the line for N-methyl homologes [(HNCH3]COOR) is
different from that of N,N-dimethyl homologes [ (CH3J 2JNCOOR where
R denotes different alkyl and aryl groups. Therefore, for any
homologous series, one need only know the reaction constants and
corresponding pKa1 s for two compounds and the pKa for a third
compound to predict the reaction constant for the third compound.
As with any experimental work, however, the more data points
obtained results in a more accurate prediction.
Full-Scale Hydrolysis Treatment Data. Full scale hydrolysis
systems are operating at Plants 21, 27, 28, 32 and 34. Data
obtained during this study for these plants are presented in
Table VII-6.
At Plant 21 diazinon is hydrolyzed to 0.049 mg/1. The unit is.
maintained at a pH less than 1 by the addition of HCl. The basin
accomodates 8 to 15 days of flow.
At Plant 27 approximately 70,000 gal/day of waste water from the
methyl parathion process are hydrolyzed. The pH is maintained at
greater than 11 until the pesticide level is less than 1 mg/1.
123
-------
O
4
^T
2
i>
" 0
"o
E
i-2
o
«f
-4
-6
p
"V 4-NITROPHENYL-
4-FORMYLPHENYL^% 4-ACETYLPHENYL-
_ 4-CYANOPHENYL- O • 3-NITROPHENYL-
\\3CHLOROrHCNYf-
3-CARBETHOXYPHENYL^O^ 3-FOKMYLPHENYL-
4-CHLOROPHENYL- O\ 4-METHYOXYPHENYL-
— tC*.
PHENYL- C»v 4 METHYLPHENYL-
p= -1.1 A2= 0.99\ O
\ !l
2.2.2-TR/CHLOROETHYL-Q H-N-C-OR
2^2,2- TRIFL UOROE TH YL • ^/^ /-»
2.2-DICHLOFtOETHYL \ C6H5
"**• ^^ 2-HYDROXYETHYL-®\ 0
- — ^^^ \> 2-CHLOROE-
D""~---^ \
- 4-NITROPHENYL- ° ^-^ METHYL^Q „ FTHY
n PHENYL- ^^^^^ otwy
— ^-f?V5c''0
_CH,-N-C--OR P = -0.26 /rrwv/ *V
3 i r2- 1.00 frw/z.- N
I I I I I I I
THYL-
ROPYL
8 10 12
pK. OF ALCOHOL
14
1C
18
AFTER A.WILLIAMS,J.CHEM. SOC.PERKINSII,1244(1973)
O
n
H-N-C-OR : N-PHENYL CARBAMATES
C6H5
o
II
CH3-N-C-OR : N-METHYL-N-PHENYL CARBAMATES
I
BRONSTEAD PLOT OF THE SECOND-ORDER ALKALINE
HYDROLYSIS RATE CONSTANTS OF N-PHENYL CARBAMATES
VERSUS pKa OF THE RESULTING ALCOHOL 25°C
FIGURE VII-3
124
-------
~
s
-
1
6
JC
O
O
-t
b
4
2
0
-2
-6
R
O 4-NITROPHENYL-
0
II
H-N-C-OR
CH3
O 3-TRIMETHYLAMMONIUM-
\ PHENYL-
1-NAPHTHYL- \OPHENYL-
2-ISOPROPYLPHENYL- Ov
o x
« X
-CH3-N-C-OR X
PL, 4-NITROPHENYL- X
V^ tl T
"*"***D "*>t^_ PHENYL-
I-NAPHTHYL- ^^"[P—***^^
3NITROPHENYL- ^^*"***
3-TRIMETHYLAMMONIUMPHENYL-
3-AMINOPHENYL-
p=-0.17 r2 = 0.80
1 1 1 1 I
24 6 8 10 12
pK« OF ALCOHOL
p= -0.91
r2 = 0.99
^
\
X
^k
\,ETHYL-
ETHYL-\^
1 1
14 16 1*
AFTER WOLF.et al,PRESENTED AT THE AMER. CHEM. SOC. MEETING
IN NEW ORLEANS,1977.
O
ii
H-N-C-OR : N-METHYL CARBAMATES
I
CH,
0
n
CH--N-C-OR : N.N-DIMETHYL CARBAMATES
0 I
CH,
BRONSTEAD PLOT OF THE SECOND-ORDER ALKALINE HYDROLYSIS
RATE CONSTANT OF THE N-ALKYL CARBAMATES
VERSUS pKa OF THE RESULTING ALCOHOL 25°C.
FIGURE VII-4
125
-------
ro
cr>
TABLE VII-6
FULL-SCALE HYDROLYSIS DATA
PESTICIDE
DETENTION
PLANT
21
27
28
32
34
PRODUCT(S)
Diazinon
Methyl Parathion
Methyl Parathion 8
Ethyl Parathion
Disulfoton
Nemagon
Stirofos
Dichlorfos
Naled
Phosdrin
Aldicarb
INFL.
mq/1
57.0
N/A
6.91
14.8
N/A
N/A
N/A
N/A
N/A
N/A
EFFL.
mg/1
0.049
*1.0
0.014
0.97
*0.5
*0.01
*0.01
*0.1
*0.1
*0.01
PERCENT
REDUCTION
99.9
N/A
99.8
93.4
_
-
-
-
-
-
£H
*1.0
***1
*10
**12
**12
**12
**12
**12
**12
**12
TIME
HOURS
264
N/A
*120
1
12
12
12
12
12
12
TEMPERATURE
*-F
Ambient
Elevated
Ambient
144-160
no
110
no
no
no
no
* Less Than
** Greater Than
N/A Not Available
-------
This waste is combined with about 1.37 MGD of other plant waste
before discharge to navigable waters.
At Plant 28 parathion is hydrolyzed by first adding caustic in
two 120,000 gallon holding tanks and then aerating the basins for
3 to 5 days. Effluent pesticide concentrations are frequently
less than 0.01 mg/1.
Representatives of Plant 32 have stated that in-plant hydrolysis
of pesticide chemicals is provided. Operating data for
disulfoton have been submitted which show effluent levels of less
than 0.1 mg/1. The disulfoton waste stream is designed to
maintain a pH greater than 12 at 144 to 150 degrees F for one
hour.
At Plant 3U more than 150,000 gal/day of waste water is treated
in a hydrolysis unit (12 hour detention time). Steam is added to
maintain the basin temperature at 110 degrees F, and the pH is
kept above 12. Pesticide chemicals in the effluent are generally
decomposed below the detection limit.
At Plant 148 20,000 gal/day of ethoprophos and 15,000 gal/day of
mephosfolan waste waters are treated via caustic, acid, and
chlorine treatment prior to complete evaporation. No treatment
data were supplied on their system.
Hydrolysis Literature Data. All known available information
relating to the hydrolysis of organic pesticide chemicals has
been collected. These data are presented in Tables VII-7 and
VII-8.
Data are presented in Table VII-7 for ten phosphates and
phosphonates, including the five compounds manufactured by direct
dischargers: dichlorvos, mevinphos, naled, stirofos, and
trichlorfon. At a moderately elevated pH and temperature (pH =
9.0 a 38°C), hydrolysis is effective for all five of these
compounds, and a majority of the others in this group. The
Bronsted free energy relationships for phosphonates, shown in
Figures VII-5 and VII-6, as developed by Wolfe (1977), indicate
that pesticide chemicals of this type are readily hydrolyzed in
alkaline media. For example, in Figure VTI-5, at larger values
of pKa for dimethoxy phosphate the corresponding second-order
rate contact is approximately 10-*mole~lsec-». This value
corresponds to a half-life of 192.5 hours at pH 12 and 25°C. At
higher temperatures and lower pKa» the half-lives would be
shorter.
127
-------
ro
oo
PESTICIDE
Chlorfenvinphos
Crotoxyphos
Dichlorvos
Dicrotophos
Mevinphos
Naled
Phosphamidon
Stirophos
TABLE-VI1-7
HYDROLYSIS LITERATURE DATA
.ORGANO-PHOSPHORUS PESTICIDES
CHEMICAL TYPE
HALF-LIFE MINUTES REFERENCE
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
70
38
38
37.5
37.5
37.5
38
38
70
38
38
23
23
23
43
38
38
23
23
27
50
6.0
1.0
9.0
6.0
7.0
8.0
1.1
9.1
7.0
1.1
9.1
7.0
10.0
11.0
12.5
1.1
9.1
7.0
10.0
11.6
11.6
5,580
5,220
2,100
2,100
462
301
3,600
270
27
144,000
72,000
43,200
480
84
6
3,600
60
19,872
3,168
110
24
Faust & Gomma, 1972
Melnikov, 1971
Melnikov, 1971
Metcalf, et al., 1959
Metcalf, et al., 1959 ;
Metcalf, et al., 1959
Plant 34
Plant 34
Muhlmann & Schrader, 1968-
EPA-670/2-75-057
EPA-670/2-75-057
Plant 34
Plant 34
Plant 34
Plant 34
Plant 34
Plant 34
EPA-670/2-75-057 ;
EPA-670/2-75-057
Plant 34
Plant 34
50
10.5
4,800
EPA-670/2-75-057
-------
TABLE VII-7
Continued
Page 2 of 4 Pages
ro
10
PESTICIDE
Tepp
Trichlorofon
Azinphos Methyl
Bromophos
Carbophenthion
Chlorpyrifos
Coumaphos
Demeton-0
CHEMICAL TYPE
Phosphate
Phosphonate
TEMP. °C
HALF-LIFE MINUTES REFERENCE
Phosphorodithioate
Phosphorothioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
25
38
37.5
37.5
37.5
70.0
70.0
70.0
70.0
20
70
70
70
70
22
20
20
20
7.0
7.0
6.0
7.0
8.0
6.0
7.0
8.0
9.0
(1-5)
6.0
7.0
8.0
9.0
13.0
13.1
6.0
9.96
408
198
5,340
386
63
180
42
36
6
345,600
450
288
144
36
210
180
2,800,000
10,368
EPA-670/2-75-057
EPA-670/2-75-057
Metcalf, et al., 1959
Metcalf, et al., 1959
Metcalf, et al., 1959
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Muhlmann 4 Schrader, 1957
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Melnikov, 1971
Konrad & Chesters, 1969
EPA-670/2-75-057
EPA-670/2-75-057
100
20
37
14.0
13.0
7.9
16
75
318
Kane, et al., 1960
Melnikov, 1971
Crosby, 1969
-------
TABLE VII-7
Continued
Page 3 of 4 Pa
o
PESTICIDE
Demeton-S
Diazinon
Dimethoate
Disulfoton
EPN
Ethion
Fenthion
Fenitrothion
CHEMICAL TYPE
Phosphorothioate
Phosphorothioate
Phos phorod i thi oate
Phosphorodithioate
Phosphorothioate
Phosphorodithioate
Phos phorod i thi oate
Phosphorothioate
TEMP. °C
20
?0
70
70
70
20
20
40
60
70
70
70
70
70
37
20
80
80
30
30
EH HALF-LIFE MINUTES
13.0
(1-5) .
(1-5)
6.0
9.0
3.1
10.4
3.1
3.1
2.0
9.0
5.0
8.0
9.0
13.0
7.0
Acidic
Alkaline
12.0
13.0
0.85
297,000
706
570
252
706
8,690
176
47
1,260
48
3,600
1,290
432
0.5
7,200
2,160
95
272
12
REFERENCE
Melnikov, 1971
Muhlmann & Schrader,
Muhlmann & Schrader,
Muhlmann & Schrader,
Muhlmann & Schrader,
1957
1957
1957
1957
I
Gomma.
Gomma.
Gomna,
et al
et al
et al
1969
1969
1969
Gomma, et al., 1969
Melnikov, 1971
Melnikov, 1971
Melnikov, 1971
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
Metcalf, 1959
Cowart, et al., 1971
Melnikov, 1971
Melnikov, 1971
EPA-670/2-75-057
EPA-670/2-75-057
-------
TABLE VII-7
Continued
Page 4 of 4 Pages
PESTICIDE
Ma lathi on
Parathion Ethyl
CHEMICAL TYPE
Phosphorodithioate
Phosphorothioate
Parathion Methyl
Phorate
P ho sine t
Ronnel
Phosphorothioate
Phosphorodi thioate
Phosphorodithioate
Phosphorothioate
TEMP. °C
20
10
20
20
20
40
40
60
60
70
70
70
20
30
30
70
20
30
40
70
25
20
20
20
HALF-LIFE MINUTES REFERENCE
9.0
12.0
6.5
9.0
7.4
9.0
10.4
3.1
9.0
3.1
9.0
(1-5)
1.0
9.0
(1-5)
12.0
13.0
(1-5)
(1-5)
1-5
(1-5)
8.0
9.3
4.5
7.0
7.0
720
10
12,960
76,900
156,000
31,400
1,992
48,480
7,620
10,860
1,572
2,376
1,200
162
252,000
210
5
660
10,368
2,304
576
120
240
21,600
720
4,320
Melnikov, 1971
Melnikov, 1971
Cowart, et al., 1971
Comma & Faust, 1971
Comma & Faust, 1971
Comma & Faust, 1971
Comma & Faust, 1971
Comma & Faust, 1971
Comma & Faust, 1971
Comma & Faust, 1971
Comma & Faust, 1971
Cowart, et al., 1971
Melnikov, 1971
Melnikov, 1971
Melnikov, 1971
Melnikov, 1971
Melnikov, 1971
Melnikov, 1971
Muhlmann & Schrader, 1957J
Muhlmann & Schrader, 1957
Muhlmann & Schrader, 1957
EPA-670/2-75-057
EPA-670/2-75-057
Melnikov, 1971
Melnikov, 1971
Cowart, et al., 1971
-------
I-
PESTICIDES
Carbaryl
Carbofuran
r,
j Propoxur
Captan
Aldicarb
Propham
Chlorpropham
Mexacarbate
CHEMICAL TYPE
Carbamate
TABLE VII- 8
HYDROLYSIS LITERATURE DATA
ORGANO-NITR06EN PESTICIDES
TEMP °C
Carbamate
Carbamate
Heterocyclic with
nitrogen in ring
Amide
Carbamate
Carbamate
Carbamate
HALF-LIFE MINUTES REFERENCE
25
25
27
27
25
25
25
37.5
20
20
20
28
28
43
80
__
--
__
—
8.0
10.0
7.0
9.0
7.1
8.1
9.1
9.5
8.0
9.0
10.0
1.97
7.0
12.0
7.0
11.0
13.0
11.0
13.0
1,872
192
18,720
20
39,200
4,800
342
70
23,040
2,304
252
645
155
88
205
1,500,000
15,000
150,000
1,500
Wolfe, et al., 1976
Wolfe, et al., 1976
Wolfe, et al., 1976
Waushore & Hague
Plant 50
Plant 50
Plant 50
Metcalf, et al., 1968
Aly & El-Dib, 1971
Aly & El-Dib, 1971
Aly & El-Dib, 1971
Wolfe, et al., 1976
Wolfe, et al., 1976
Plant 34
Plant 34
Wolfe, et al., 1977
Wolfe, et al., 1977
Wolfe, et al., 1977
-Wolfe, et al., 1977
12
9-. 5
2,800
Hosier, 1974
-------
4-
55
>
o
§€
> 9
I W
U* T*
2 *
31
3-
< H
Q £
DC ^
Q O
S"
85
^tt
C5
O
0 -
- 2-
- 4-
l
4
I
6
P =-0.28
8 10
pKa OF ALCOHOL
I
12
1
14
I
16
(CH30)2 P-OR
BRONSTEAD FREE ENERGY RELATIONSHIP
DIMETHOXYPHOSPHATE PESTICIDES
133
FIGURE VII-5
-------
6-
P=-0.40
co
4-
UJ 0
1!
2-
DC <
UJ t-
Q CO
OC Z
o o
§?
O
CO
O
O
0-
-2-
-4-
O
-6-
I
4
I
6
8
10
pKa OF ALCOHOL
O
(EtO)2 - P-OR
I
12
T
14
i
16
BRONSTEAD FREE ENERGY RELATIONSHIP
DIETHOXYPHOSPHATE PESTICIDES
134
FIGURE VII-6
-------
Of the more than 50 phosphorothioates and phosphorodithioates, 17
are manufactured by direct dischargers. These are: aspon,
azinphos-methyl, chlorpyrifos, coumaphos, demeton-O, demeton-S,
diazinon, disulfoton, ethion, fenthion, fensulfothion, malathion,
oxydemeton methyl, parathion ethyl, parathion methyl, phorate,
and ronnel. Table VII-7 presents data that indicate 13 of these
are amenable to hydrolysis. The structure of the molecules is
similiar and hydrolysis rates can be predicted. Of the remaining
four, chlorpyrifos is currently deep well injected at Plant 22,
aspon is deep well injected at Plant 29, and fensulfothion and
oxydemton methyl are being hydrolyzed at Plant 32, although no
data are available.
Wolfe (1977) by refering to Figures VII-7 and VII-8 states that
the following are also amenable to alkaline hydrolysis: bromophos
ethyl, chlormephos, chlorthiophos, cythioate, DBF,
dichlorofenthion, famphur, fensulfothion, IBP, mecarbam, menazon,
methidathion, monocrotophos, morphothion, oxydemeton methyl,
pirimiphos ethyl, piriphos methyl, pyrazophos, quninalphos,
temephos, thiometon, and traizophos.
Three phosphorus-nitrogen pesticides are manufactured by direct
dischargers. Crufomate is being deep-well injected at Plant 22.
Methamidophos is being hydrolyzed at Plant 32. Glyphosate is
undergoing biological treatment at Plant 33. However, the degree
of pesticide chemical removal is unknown at this time.
Four amide and amide-type compounds are manufactured by direct
dischargers. As shown in Table VII-7, aldicarb hydrolyzes
readily in an alkaline environment. Hydrolysis testing for
propachlor and butachlor have been conducted at Plant 41. It has
been reported that they degrade into their corresponding anilines
which are known carcinogens. For these reasons activated carbon
technology was studied and has been shown to be effective (see
Table VII-5). This technology is currently being designed at
this plant. Alachlor, as reported by personnel at Plant U1,
decomposes under acid conditions. The Bronsted free energy
diagrams (Figures VII-3 and VII-U) show that N-phenyl and N-
methyl carbamates hydrolyze very quickly at 25°C as is evidenced
from the fairly large value of the second-order rate constants.
They also show that N-methyl-N-phenyl and N,N-dimethyl carbamates
will also hydrolyze, although the reaction rates are somewhat
slower.
Three carbamates are manufactured by direct dischargers-benomyl
carbofuran, and carbaryl. Benomyl undergoes biological treatment
at Plant 18; however, pesticide reductions have not been
documented. Carbofuran is amenable to both hydrolysis and
activated carbon treatment and is presently treated by the latter
135
-------
6 -
)
o ~
ec i
o o
V- «
X M
I!
O W
oc z
00
o"
Z LU
° t;
0 3
LU EC
M
O
O
0-
- 2-
-4-
- 6-
-8-
Alkaline
Neutral
i
4
P = -0.62
i r i
8 10 12
pKa OF ALCOHOL
14
16
(CH30)2 P -OR
BRONSTEAD FREE ENERGY RELATIONSHIP
DIMETHOXYPHOSPHOROTHIOATE PESTICIDES
136
FIGURE VII-7
-------
CO
c7>
>-
o
tc r-
8 o
> o>
X M
oi •;
z o
il
6-
4-
2-
±* o-
oc z
III <
0
go
o JS
o
o
o
-2 -
-4-
-6-
I
4
I
6
0
O
O
I
8
I
10
T
12
I
14
l
16
18
pKa OF ALCOHOL
S
it
(EtO)2 P-OR
BRONSTEAD FREE ENERGY RELATIONSHIP
DIETHOXYPHOSPOROTHIOATE PESTICIDES
137
FIGURE VII-8
-------
technology at Plant 50. As shown in Table VTI-8, carbaryl
hydrolyzes relatively easily. In addition to literature data
presented in Table VII-8, Wolfe (1977) indicates that aminocarb,
asulum, benomyl, carbetamide, desmedipham, formetanate
hydrochloride, karbutilate, meobal, metalkamate, methiocarb,
pirimicarb and promecarb are also amenable to hydrolysis
treatment techniques.
No hydrolysis information was discovered relative to the two
compounds in the group identifiable as cyanates. Thanite, the
only compound manufactured by a direct discharger, can be removed
using activated carbon.
No hydrolysis information was located for heterocyclic compounds
with nitrogen and oxygen in the ring; nor are any manufactured by
direct dischargers.
Literature data for heterocyclic compounds with nitrogen in the
ring is limited to captan, which has been shown to hydrolyze
readily at neutral pH and room temperature. Two additional
compounds are manufactured by direct dischargers. Piperalin is
treated by both biological and incineration systems at Plant 39.
Maleic hydrazide is treated by a biological system at Plant 116.
Pesticide removal is not monitored by either plant.
The four nitro and nitro-amine pesticides manufactured by direct
dischargers are benfluralin, isopropalin, trifluralin, and
dinoseb. Due to the potential for hydrolysis to produce
dinitrophenols, a more toxic compound, carbon should be
considered as the primary technology. All of the above pesticide
chemicals are amenable to activated carbon treatment.
Two thiocarbamates are manufactured by direct dischargers.
Amobam is treated by an aerated lagoon system at Plant 149.
However, no monitoring has been conducted. Triallate waste water
was inhibitory to the biological system at Plant 33; the waste is
currently being deep-well injected while pretreatment studies are
being conducted.
Chloro and dichloroanilines, suspected carcinogens, are potential
hydrolysis byproducts from the following ureas: monolinuron,
linuron, monuran, monuron-TCA, neburon, siduron, diuron,
fluometuron, and metoxuron. Due to the success of isotherm tests
for diuron and bromacil, ESE (1977), carbon technology should be
considered as the primary technology for both ureas and uracils.
Another nitrogen pesticide manufactured by direct dischargers is
bentazon. Bentazon will be treated in a full-scale oxidation
system at Plant 49. The plant is scheduled to use hydrogen
138
-------
peroxide as the oxidizing agent. Pilot data are presented later
in this section.
Additional Pesticide Removal Processes
Although activated carbon adsorption and hydrolysis are the most
common forms of pesticide removal, other alternatives in practice
or under design in the industry are incineration, resin
adsorption, chemical oxidation, clay adsorption, powdered carbon,
and multiple-effect evaporation.
From the results of incineration studies, Carnes (1976) reached
the following conclusions: 1. most organic pesticide chemicals
can be destroyed (greater than 99.9 percent removal of the active
ingredient) by this method; 2. each pesticide incinerated has a
definite temperature range at which the greatest removal of the
active ingredient is effected; 3. the most important
incineration factors are the temperature and the dwell time in
the combustion chamber; t, conventional waste incinerators are
potentially adequate facilities for pesticide chemicals
incineration; 5. nitrogen based pesticide chemicals can
generate cyanide gas if the incineration temperatures and percent
excess air are not adequate; 6. incinerators burning pesticide
chemicals will require emission control devices; 7. residues
from the incineration of pesticides formulations generally
contain low levels of pesticide chemicals; and 8. odor can be a
problem, especially in the incineration of organo-sulfur
compounds.
One manufacturer utilizes incineration where wastes are
malodorous, not easily biodegraded, inhibitory to biological
microorganisms, and where inorganic salt content is high. BOD,
COD, and TOC reductions exceed 95 percent. TKN (total kjeldahl
nitrogen) reductions are much less due to ammonia in the
scrubbing liquid. The system is acknowledged to be costly and
energy intensive, but the plant has determined it to be justified
in this situation.
Resin adsorption is being installed at Plant 18 for the treatment
of methyl parathion. At Plant 23 a pilot resin adsorption system
has been tested in conjunction with a sand-filtered,
copper-catalyzed, iron powder, reduction bed filter. The
combined system has removed up to 99.9 percent of the pesticide
chemicals.
At Plant 49 a chemical oxidation system has been designed using
hydrogen peroxide (H2O2). A pesticide reduction of 98.8 percent
is predicted using a 1.0 percent by volume solution K2O2. Steam
stripping with solvent recycle is also part of the pretreatment
139
-------
prior to secondary treatment of the combined pesticide and
non-pesticide waste waters.
At Plant 3 a series of settling ponds are operated; more than 95
percent of the pesticide chemical is removed by adsorption onto
clay.
At Plant 36 a powdered carbon adsorption system has been
designed; it includes a wet air-oxidation regeneration of the
spent powdered carbon. Greater than 99 percent pesticide
chemical removal is expected in conjunction with 90 percent TOG
removal.
An evaporation-crystalization system has been installed at Plant
50 to eliminate the discharge of metallo-organic pesticides.,
Evaporator condensate is sent to the municipal treatment system.
IN-PLANT CONTROL TECHNOLOGY
In conjunction with pesticide chemical removal systems, steps
should be be taken to minimize waste water strength and/or
volume. The following discussion addresses techniques which have
general application.
Waste segregation can be an important and fundamental step in
waste reduction. The following factors generally form the
primary basis for waste segregation:
1. Wastes with high organic loadings may be economically
treated or disposed of separately from the main process
waste water. As discussed in more detail later,
segregation for pesticide chemicals removal and specific
parameter control can be both effective and economical.
2. Highly acidic and caustic waste waters can usually be
more effectively adjusted for pH prior to being mixed
with other process waste waters. If both acidic and
caustic streams are being generated, combining these
streams can reduce chemical requirements.
3. Process waste waters with high levels of settleable
solids can be clarified separately.
H. Separate equalization for streams of highly variable
characteristics can be effective and improve overall
treatment efficiency. This highly effective technique
is common practice in the industry.
110
-------
In some cases, waste water generation can be substantially
reduced by the substitution of an organic solvent for water in
the synthesis and separation steps of the production process with
subsequent solvent recovery.
Waste water generation can be reduced by general housekeeping
improvements such as the substitution of dry cleanup methods for
water wash downs of equipment and floors. This is especially
applicable for situations where liquid or solid materials have
been spilled.
Steam jet ejectors and barometric condensers can be replaced in
some cases by vacuum pumps and surface condenser systems.
Barometric condenser systems can be a major source of
contamination and can cause a particularly difficult problem by
producing a high volume, dilute waste stream.
Recycle of waste water is commonly practiced in conjunction with
solvent extraction, steam stripping and distillation materials
recovery operations. Wash water, rainwater runoff, and scrubber
effluent may often be recycled to the process. It is
particularly common in the metallo-organic and the formulating
and packaging subcategories to recycle all wastes to the process.
Biological Treatment
Since the waste waters generated by the pesticide chemicals
industry are for the most part biodegradable, biological
treatment is the most applicable technology. Activated sludge
and aerobic lagooning are the most common types of biological
treatment employed. High-strength industrial waste commonly
requires modifications of the activated sludge design that is
normally applied to treatment of municipal waste. These
modifications include equalization, treatment at essentially a
constant rateff a longer detention times, completely mixed basins,
and larger constant rate, secondary clarifiers. The complete-mix
system is generally preferred over other activated sludge systems
because it is less susceptible to shock loads (the completely
mixed basin partially smooths out organic load variations),
oxygen utilization rate is constant throughout the basin, and
lined earthen basins can be used for economy.
ft. primary disadvantage of any activated sludge system is
operational difficulty. Operators should be adequately trained
to maintain continuous operation and minimize problems and
upsets» Perhaps the most common operating problem is "sludge
bulking" in which rising sludge in final clarifiers causes
floating matter to be discharged in the plant's effluent. The
-------
floating material can considerably increase BOD and suspended
solids concentration in the effluent.
Sludge bulking can often result from poor operation allowing
inadequate aeration or nutrient levels, improper food to
microorganism ratio, or improper sludge age. It is essential
that operators maintain frequent (at least daily) testing of the
dissolved oxygen levels, suspended solids concentrations, and
nutrient concentrations in the effluent, and, of course, the
sludge volume index. If upsets still occur even with the best
operation and most constant monitoring, it may be necessary to
take additional measures such as the addition of filtration,
increased equalization, or greater clarification.
Any biological treatment system requires a period of
stabilization before optimum efficiency can be expected. This
period may range from a few weeks up to a year or more, with the
longer period often resulting in part from the time needed for
operators (even those with previous experience) to learn the
eccentricities of a particular system. During this start-up
period, large variations in both BOD and suspended solids
concentrations can be expected in the discharge.
The period of initial stabilization of a biological system used
for pesticide waste waters can be lengthened by high salt
concentrations requiring special efforts in acclimating a
microbiological culture. Several plants have demonstrated the
achievability of an acclimated culture.
Another problem associated with biological systems is sludge
generation. The sludge from an activated sludge system can be
expected to have a solids content normally ranging from 1.0 to
2.0 percent and, on a dry weight basis, can be generated at a
rate of about 0.5 kg per kg of BOD.
Climatic conditions may also affect biological systems.
Decreased biological activity can be normally expected during
winter months. In extremely cold climates, added cost may be
necessary for the heating of treatment systems.
Table VTI-9 presents a summary of available data relating to
Subcategory 1.
The treatment at Plant 19 consists of pH adjustment,
dechlorination with sodium hydrosulfide, presettling,
equalization, clarification, mixed media filtration, activated
carbon dechlorination, extended aeration, and final clarifi-
cation. Table VII-9 presents five months of data soon after
start-up of the system.
142
-------
TABLE VI1-9
BIOLOGICALLY TREATED EFFLUENT SUMMARY
ORGANIC PESTICIDES CHEMICALS MANUFACTURERS
SUBCATEGORY I
FLOW
BOD
COD
TSS
PESTICIDES
SOURCE
l*>
PLANT PRODUCT(S) L/Kkg Gal/1000 Ib (n) K
19+ 9,10 64800 7770 (34)
21+ 3-14 18900 227(
3 Taj (a
4-12 a a
13.14 (a) (a
' 11
(Oj
27+ 15 N/A N/A (0)
28 15.16 50000 6000 (15)
32+ 17-25 46700 5600 (458)
U) (a) (0)
41+ 26.27,28 23700 2840 (61) 1
31100 3730 (209) 2
g/Kkg . mg/1 (n)
2.53 39.0 (34)
1.11 58.5 (323)
a (a) 0
a (a) 0
a (a) 0
N/A N/A (0)
0.541 10.8 (65)
3.44 73.6 (171)
(a) (a) (0)
.00 42.2 (60
.86 91.9 (118
48+ 29 7000 840 (E) 0.1 N.A. E
30 N.A. N.A. (0) 0.2 N.A. E
Kg/Kkg mg/1 (n) kg/Kkg mg/1 (n) kg/Kkg Blg/l (n)
19.4 299 (28) 1.17 18.0 (28) 0.00430 0.0452 (40
NM NM 0 1..
a) (a) 0 (a
a) a 0 a
a) (a) 0 (a
56 72.1 (329) N/A N/A (0
(a (0) 0.000762 0.0018 (314
(a (0 0.269 3.55 (283
(a (0) 1.27 0.57 (55
OF D/
•
b
N/A N/A (0) N/A N/A (0) 0.00315 0.0129 (36) C
7.01 140 (450) 19.1
381 (184) 0.0007 0.0139 (450) d
59.7 1280 (444) 3.20 68.5 (455) 0.372 2.39 (62
(a) (a) (0) (a) (a) (O) 0.008 N.A. (39
10.2 431 (61 1.08 45.6 (61) 1.13 35.7 (60
23.3 749 (209 4.12 133 (209) 3.77 91.1 (206,
6.4 N.A. E 0.1
6.1 N.A. E 1.1
N.A. (E) 0.3 N.4. (E
N.A. (E) 1.2 N.A. (E
e
9
h
1
(n) number of data points available None - no process wastewater discharged to treatment units
NM not monitored + • discharges to navigable waters
AI analytical Interference (a) • discrete data for Individual products 1n plants with
(E) plant estimate combined flow 1s not applicable except for the pesticide
N/A not applicable • ' parameter
N.A. not available
* less than
-------
TABLE VII-9
NOTES:
PRODUCT CODE:
Continued
Page 2 of 2 pages
SOURCE OF DATA CODE:
1 = DCPA
2 = Chloronthalonil
3 = Diazinon
4 = Anilazine
5 = Propazine
6 = Simazine
7 = Profluraline
8 = Ametryne
9 = Prometryne
10 = Simetryne
11 = Prometone
12 = Cyanazine
13 = Chloropropylate
14 = Chiorobenzilate
15 = Methyl Parathion
16 = Ethyl Parathion
17 = Fensulfothion
18 = Disulfoton
19 = Fenthion
20 = Azinphosmethyl
21 = Oxydemetonmethyl
22 = Methamidophos
23 = Demeton
24 = Phorate
25 = Trichloronate
26 = Alachlor
27 = Propachlor
28 = Butachlor
29 = Methomyl
30 = Diuron
(a) Daily composites, 1/5/77 through 5/16/77.
Ratios developed by using total: final
production ratio of 1.46:1, due to
chloral waste
(b) Daily composites, 4/75 through 2/76.
Ratios developed by utilizing total: final
product ration of 4:1, due to intermed-
iate and non-pesticide production
(c) Weekly average of effluent, 1/9/76 and
7/9/77. Combined plant effluent is not
applicable due to titanium dioxide
and sodiam chlorate representing 92 percent
of flow
(d) Daily composites, 1/74 through 3/75. TSS
5/77 through 10/77
(e) Daily composite, 10/75 through 12/76.
Ratios developed by using total: final
product ratio of 3.33:1 due to manufacture
of intermediates. Disulfoton data,
1/76 through 9/76, weekly composite.
(f) Daily composite, 4/77 through 5/77
(g) Daily composite, 9/76 through 3/77
(h) Plant estimate, 9/9/77
(i) Plant estimate, 8/31/77
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Plant 21, where a variety of pesticide chemicals are
manufactured, hydrolyzes specific pesticide chemical streams and
biologically treats all pesticide chemicals waste waters. A
stripper is used to recover solvent for reuse in the process.
During a representative 30-day period in May 1975, diazinon was
hydrolyzed 99.9 percent to a level of 0.01 kg/day (0.03 Ib/day)
prior to biological treatment. The hydrolysis basin is
maintained at a pH less than 1 at ambient temperature during 8 to
15 days of detention time. The biological system has been
acclimated to a chloride concentration of 20,000 mg/1 and is
designed for 30,000 mg/1. Table VII-9 presents the monthly mean
values from daily sampling for one year of the final effluent.
Parameters monitored include BOD, TSS, and diazinon. The
treatment system achieves consistent removal of the above
parameters.
At Plant 27 methyl parathion waste water is hydrolyzed. Due to
high salinity the waste is then diluted with non-pesticide
effluents and treated in a biological system including final
clarification. Methyl parathion is analyzed at the effluent from
the system as part of NPDES requirements.
Acidic process wastes produced at Plant 28 are discharged through
a limestone pit increasing the pH from a range of 1-2.5 to H -
5. The discharge from the limestone pit is combined with
alkaline waste and the total stream is passed into two agitated
holding tanks which include facilities for caustic addition.
Analyses of samples for parathion, paranitrophenol, pH, and COD
in the holding tank discharge are used to determine the feed rate
to the subsequent aeration basins. The centrifuged sludge from
the activated sludge system is disposed of on land; the treated
waste water is discharged to a municipal system. The treatment
system is reported to remove 95 to 98 percent of the influent
COD, and has a discharge concentration of less than 0.02 mg/1 of
methyl-ethyl parathion. The solvent used in production is
distilled off and recycled.
The effluent COD level averaged 6.137 kg/kkg and ranged from
2.225 to 12.252 kg/kkg. Parathion in the effluent averaged less
than 0.000647 kg/kkg and ranged from less than 0.00005 to 0.00158
kg/kkg. Suspended solids levels presented in Table VII-9 reflect
recent changes in the operation of the treatment system.
Increased plant production has resulted in higher hydraulic
loading. Mixed liquor suspended solids (MLSS) concentrations of
35,000 mg/1 are now being employed. Due to these changes two
additional clarifiers have been added to the two existing units.
At Plant 32, which both manufactures and formulates, a biological
treatment system (pure oxygen) is employed. Pesticide chemical
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reduction at each process line is also practiced in advance of
the biological system. A pure oxygen system was chosen in
preference to an air system because of reduced odor problems„
Waste gases are piped to a thermal oxidation system.
Segregation, phenol recovery and the use of surface condensers
are also practiced.
Due to relatively high salinity (2,000 to 3,000 mg/1 chloride)
the raw waste water is diluted approximately 150 percent prior to
activated sludge treatment. The MLSS concentration is maintained
relatively high (6,000 to 8,000 mg/1). The final clarifiers were
designed at 250 gpd/square foot. Ammonia stripping is practiced
on the non-pesticide streams. A first-phase ammonia stripping
facility was planned to be in operation by 1977 and a second by
1978. The final effluent is discharged to a receiving stream
while sludge, after thickening and vacuum filtration, is hauled
to landfill.
The following percentage removals occur (using kg/kkg); BOD -
82.1%, COD - 32.8% and pesticide 31.1%. As these figures
indicate, the short detention, pure oxygen system is not
achieving the removals possible with longer detention, complete
mix activated sludge systems at plants such as 28 and 41= The
indication is that the design and/or operation of the treatment
facility is insufficient for the type of waste involved,
The hydrolysis pretreatment is not uniformally applied,, as
indicated by the level of hydrolysis for disulfoton compared to
the average level for the entire plant (0.008 to 0.372 kg/kkg).
Table VII-9 reports pesticide levels for two different pesticide
parameters. An average of 0.372 kg/kkg pesticide chemicals was
discharged from the treatment system during the period October
1975 through December 1976. Representatives of the plant have
stated that each pesticide was hydrolyzed to some degree. The
exact operating conditions are not available at this time., The
effluent from hydrolysis of disulfoton was monitored for 9 months
by the plant. The level of 0.008 kg/kkg represents the level
attainable for this specific pesticide under known conditions.,
At Plant 34 an aerated lagoon (90 day detention time) with a
volume of 6,800 cu m (18 million gal) and 140 kw (190 hp) of
aeration is currently under construction. Pilot work at the
plant has indicated that the biological system can be properly
acclimated to the waste water, which contains chloride
concentrations of approximately 30,000 mg/1. Organic reductions
in a 50 cu m (13,000 gal) simulated aerated lagoon were 68
percent for TOC and 88 percent for BOD, resulting in an effluent
BOD concentration of approximately 8 mg/1.
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Plant 39 manufacturers isopropalin and discharges the waste water
to a biological treatment system. The plant did not supply
treated waste load data for this product.
At Plant 11 a treatment system composed of neutralization,
equalization, and activated sludge has recently been started-up.
Representatives of the plant have stated that April and May 1977,
represent normalized operating conditions. Although no pesticide
removal is currently practiced, studies are underway in the areas
of pollutant reductions, granular activated carbon, powdered
carbon, clay adsorption, resin adsorption, wet air oxidation, and
hydrolysis. Table VII-9 presents data from this system. Total
effluent levels have been adjusted by a ratio of 1.33:1 due to
the contribution of three intermediate chemical waste streams.
This ratio was based on raw waste load sampling which indicated
that intermediates contributed only 25 percent of the total load
to the treatment system.
A treatment system operated at Plant HQ is composed of
equalization, activated sludge, and a polishing lagoon. Table
VII-9 contains effluent estimates by the plant personnel for two
compounds: bromacil and diuron. Since this system handles
pesticide and non-pesticide wastes, the effluents represent
existing reductions applied to measured raw wasteloads, or in the
case of pesticide chemicals, predicted effluents from the
application of currently known methods.
Representatives of Plant 49 have submitted predicted effluent
data from their pretreatment and activated sludge treatability
studies on bentazon, as shown in Table VII-9.
Other Treatment
At Plant 3 the production area has been diked to contain all
leaks or spills. Baghouses are used for dust collection and the
dust is recycled. Tank cars are dedicated to a specific product
and their washing is thereby reduced to once per year. The wash
water is recycled. Extensive efforts have been made to improve
housekeeping and reduce water usage by equipment modifications
and better maintenance. All process water, spillage, and floor
washings are treated in a separate tank to separate, recover, and
recycle any free toxaphene or toxaphene solution. A similar
system is used for rainwater runoff and the solution makeup,
packaging, and shipping areas. A special crew is used to clean
up spills. If it is necessary to remove a piece of equipment
from the diked process area, the equipment is first thoroughly
decontaminated. Process waste, neutralized by caustic soda and
limestone, is mixed with clarified storm water and further
clarified. This effluent is then combined with cooling water
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prior to final discharge to a stream. Sludge from the drying
beds is disposed of in a landfill. This system was designed to
remove 90 percent of the toxaphene concentration in the influent
(2 mg/1 to 0.2 mg/1) to an average level of 0.107 mg/1 (0.000943
kg/kkg). According to plant personnel, the system actually
achieves greater than 95 percent removal.
Plant 4 waste water discharge from its toxaphene production area
has been eliminated by dry-cleaning of spills and the use of
solvent instead of water for equipment washing. The cleaning
liquor is recovered and used in the process. The production area
is completely diked.
Plant 9, which is currently closed, employed no waste water
treatment. The plant was meeting its toxaphene discharge
limitation of 0.01 Ib/day (0.001 kg/kkg) through in-plant
control. An official of the plant stated that no discharge is
theoretically achievable through the control of all leaks„ the
recovery of all hydrochloric acid, and the conversion of all
fugitive hydrogen chloride and chlorine gases into bleach.
However, in ordinary operations some discharge would inevitably
be required.
All contaminated and non-reusable process waste water and wet
scrubber effluent discharged at Plant 12 is disposed of in a
sanitary landfill without pretreatment.
The only discharge from the toxaphene process at Plant 18 is
spent caustic which is generated at a rate of about 10 gallons
per minute. A company official has stated that independent
analyses have detected no toxaphene concentrations in this
stream.
At Plant 34, where a variety of pesticide chemicals are
manufactured, processing steps have been selected that minimize
usage of process water. The process streams are segregated, and
the plant provides emergency storage facilities, uses special
pump seals to reduce leakage, and recycles cooling water.
Hydrolysis is provided to remove the pesticide chemicals,
followed by pH adjustment and final holding in a one acre pond
prior to discharge to receiving waters.
Non-aqueous streams at Plant 34 are either trucked to off-site
contract disposal or sent to a liquid/gas incinerator., As a
result, the primary effluent contaminants are inorganic salts
that result from the scrubbing of vent and flue gases. Rain and
wash waters are combined with scrubber waters and tank farm
drainage from several process areas, and the pH is adjusted to 10
with caustic. The combined waste is further combined with other
148
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neutralized process wastes in a settler and phase separator, and
additional caustic is added before removal of insoluble organics
in an API separator. Skimmed oil is incinerated. The separator
effluent is further treated with 20 percent caustic and sent to a
treatment basin; there it is combined with effluent from a
sanitary package plant. Steam is added to bring the temperature
to 43°C and the final alkaline hydrolysis step occurs before
discharge to the final holding pond. The data in Table VII-10
relate to the effluent. Hydrolysis at elevated temperature and
pH during the period November 1975 through March 1976 resulted in
no detectable pesticide chemicals in the effluent.
Plant 48 incinerates Lannate and discharges the incinerator
scrubber water to a biological treatment system.
Subcategory 2; Metallo-Organic Other Treatment
Pesticide Chemical Manufacturers
At Plant 55 all arsenate process waste water is recycled to the
process. No process waste waters are discharged. Condenser
cooling water and storm water are collected in a series of four
evaporation ponds. Sampling reports revealed approximately 1
mg/1 arsenic in the ponds.
All process waste water resulting from the manufacture of
arsenate herbicides is recycled to the process at Plant 56. Only
non-contact cooling water and storm runoff are discharged. Acid
waters are truck hauled to recovery operations, and some solids
are truck hauled to a landfill.
At Plant 58, mercury wastes are totally recycled into the
process.
Complete reuse of all arsonate process waste water was initially
reported for Plant 19. It was indicated that the process
actually had a negative water balance in that all process and
even storm water could be reused. The Agency has since been
advised that the initial information was in error and that a
process waste water discharge was required. The Agency is
presently investigating this report.
Two copper-based pesticide producers. Plants 54 and 57 report no
discharge of waste water. Plant 57 disposes of a small volume by
contract hauling to landfill.
Subcategory 3; Pesticide Chemical Formulators/Packagers
Formulation and blending operations are generally conducted on a
batch basis and the same equipment is used for many products.
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TABLE VII-10
en
o
FLOW
HOLDING POND EFFLUENT
PLANT 34
COD
TOC
TSS
DATE
Nov 75
Dec 75
Jan 76
Feb 76
Mar 76
L/Kkg
47500
19700
17900
29900
51700
Gal/1000 Lb
5700
2360
2150
3580
6200
Kg/Kkg
12.3
7.16
6.83
12.0
11.6
mg/1
259
364
381
402
224
Kg/Kkg
6.85
4.59
4.60
7.14
7.23
mg/1
144
233
256
239
140
Kg/Kkg
0.419
0.172
0.171
0.344
0.507
mg/1
8.81
8.74
9.53
11.5
9.80
Mean
33,400
4000
9.98
299
6.08
182
0.323
9.68
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Vessels are cleaned between batches to avoid cross-contamination.
Many plants use storage tanks to hold wash liquids in order that
they can be used for makeup purposes during the next formulation
of the same product. This procedure reduces the total quantity
of washwater generated and minimizes product losses. It can be
applied in plants where both water and solvent-based products are
manufactured. For example. Plant 101 performs all liquid
equipment cleaning with solvents, which are collected and used in
the next batch formulation.
Housekeeping is particularly important for formulators since
virtually all waste water generated is from equipment and floor
cleanup. Nearly all formulators use dry floor and spill cleanup
techniques and solvent recovery, for example Plants 56-95 and
101.
Evaporation is the predominant disposal technique employed by
formulators which generate some waste water. This method was
noted at Plants 56 through 95 which are located in the Southeast,
Midwest, and Southwest,, Spray recirculation is commonly used in
those areas in which precipitation rates equal or exceed
evaporation rates. Other methods of enhancing evaporation used
in the industry include supplemental heat and coverings. The
flows from these plants range from a few hundred liters per day
to several thousand liters per day. Disposal of waste water to
landfills or by contract operators is also employed by
formulators, as noted in Table VII-2.
Spray irrigation of treated waste water is practiced at Plant
101. The treatment includes oil skimming, chemical coagulation,
vacuum filtration, and aeration. During three to four months of
the year, spray irrigation is prohibited by climatic conditions
and the effluent from the pretreatment system is discharged to a
municipal sewer system. However, it is anticipated (as confirmed
by plant personnel) that with additional effort all waste water
could be excluded from the municipal sewer.
For this study seventy-five formulation facilities registered
under the Federal Insecticide, Fungicide and Rodenticide Act
(FIFRA) were randomly selected. Their operations were reported
to be devoted exclusively to formulation and packaging. Forty-
four were found that currently formulated and all had no
discharge of waste water to navigable waters. In addition, 23
combined manufacturing and formulating facilities which do
discharge to navigable waters report no significant waste water
generation from formulation or packaging activities. Any
facility generating waste water from a formulation or packaging
operation can eliminate the waste water by in-plant controls,
such as re-use or recycle, and/or containment for evaporation,
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and have no discharge. This is routinely accomplished at many
plants in this Subcategory.
MODEL TREATMENT SYSTEMS
In order to allow an assessment of the economic impact of the
limitations, model treatment technologies have been assumed that
are capable of attaining the effluent levels specified by these
limitations. Design and operating data from treatment systems
existing in the industry form the basis for the model
technologies described herein. These systems represent a way of
attaining the recommended effluent limitations. Individual
plants have many options available that are capable of attaining
the effluent limitations such as the implementation of process
modifications and in-plant control techniques, the use of
alternate end-of-pipe technologies, and the use of alternate
methods of disposal.
The following discussions describe the model treatment
technologies which form the basis of the cost estimates to be
used to assess the economic impact of the implementation of the
recommended standards.
Subcategory 1--Organic Pesticide Chemicals
The technology recommended for Subcategory 1 manufacturers
consists generally of pesticide chemicals removal through the
application of hydrolysis or activated carbon techniques (any
method that is applicable to the specific waste being treated
should be considered) , equalization, and biological treatment,
coupled with incineration of incompatible waste streams. A flow
diagram for this treatment system is presented in Figure VII-9.
Subcategory 2—-Metallo-Orqanic Pesticide Chemical Manufacturers
The installation of additional technology is not anticipated at
facilities where metallo-organic pesticide chemicals are
manufactured. The current state-of-the-art is such that no
discharge of process waste water pollutants is being achieved
through the application of recycle technology.
Subcategory 3—Pesticide Chemical Formulators/Packagers
The model treatment technology for Subcategory 3 involves total
evaporation of the small volume of waste water expected after
implementation of a suitable process control system. Landfilling
operations and contract-hauling are considered viable
alternatives at Subcategory 3 plants.
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INCOMPATIBLE
ORGANIC
WASTEWATER
INCINERATOR
SCRUBBER EFFLUENT
OIL SKIMMINGS
CONCENTRATED
PESTICIDE H
WASTEWATER
API SEPARATOR
DUAL MEDIA FILTER
ACTIVATED CARBON
API SEPARATOR
j;
HYDROLYSIS
n
DILUTE
PROCESS
WASTEWATER
en
AERATION BASINS
UJ
O
o
3
_J
V)
FINAL CLARIFIERS
NEUTRALIZATION
EQUALIZATION
THICKENER
AEROBIC DIGESTOR
VACUUM FILTER
FINAL EFFLUENT
SOLIDS TO DISPOSAL
— ALTERNATE TECHNOLOGIES
COST TREATMENT TECHNOLOGY
SUBCATEGORY 1
FIGURE VII-9
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SECTION VIII
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
GENERAL
The purpose of this section is to document the cost, energy, and
nonwater quality aspects of the treatment technology presented in
Section VII.
The costs presented are estimates of the capital and annual
operating expenses expected to be required to attain the effluent
limitations. They are based on the model end-of-line treatment
techniques presented in Section VII applied to the raw waste load
levels developed in Section V. The Agency does not require that
this technology be installed at any plant location. However, the
application of this technology will attain the effluent
limitations presented in section IX and, therefore, cost
estimates are based on the model treatment technology.
Individual plants have the option of utilizing process
modifications, in-plant controls, alternate methods of disposal,
alternate end-of-line treatment units, or any combination of the
above in order to meet the guidelines. A separate economic
analysis of treatment cost impact on the industry will be
prepared and the results will be published in a separate
document.
Annual and capital cost estimates have been prepared for end-of-
pipe treatment technologies for each subcategory to be used in
the evaluation of the economic impact of the recommended effluent
limitations guildelines. The capital costs were generated on a
unit process basis (e.g., equalization, neutralization, etc.).
The total construction costs include the unit process costs, plus
the following:
Percent of Unit Process
Item Capital Cost
Electrical 14
Piping 20
Instrumentation 8
Site Preparation 6
Engineering design and construction surveillance fees of 15
percent and contingencies of 15 percent were also assumed.
Since land costs vary so widely from location to location, the
land requirements for each technology have been estimated so that
Preceding page blank
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these costs can be considered separately in the economic impact
analysis.
All cost data were computed in terms of July, 1977 dollars, which
corresponds to an Engineering News Records Index (ENR) value of
2593. The bases for computation of capital and annual costs are
presented in Tables VIII-1 and VIII-2.
DESIGN BASIS ON WHICH COST ESTIMATES ARE DERIVED
The following discussions present the design criteria which were
assumed in the development of the costs of individual treatment
modules. The designed factors are consistent with those used in
the industry at plants where effluent levels equivalent to the
recommended guidelines are being attained.
Segregation of Individual Streams
As previously noted, waste water segregation provides important
technical and economic advantages. For example:
1. Waste streams not compatible with biological treatment
(i.e., distillation tower bottoms or tars) are most
effectively disposed of by incineration.
2. Activated carbon and hydrolysis techniques, employed to
remove pesticides, are more cost-effective when applied
to concentrated, segregated waste streams rather than to
dilute, combined effluents.
3. High temperatures that may be required for hydrolysis
can be more readily maintained on small volume waste
streams.
4. Chemical costs for pH adjustment are smaller for
concentrated waste streams.
Because these segregation techniques are widely recognized and
practiced in the industry, they have been applied to the design
basis of the model treatment technology. The pesticide removal
unit processes have been sized for segregated waste streams
approximately equal to one-third of the total plant flow based on
'current industry practice. As justification for this assumption,
it is noted that the largest flows in the industry being treated
by carbon and hydrolysis are approximately 150,000 gal/day and
175,000 gal/day respectively. The largest flow used for cost
calculations, 300,000 gal/day, will have this upper range of
reported values. It is further noted that plants currently
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TABLE VIII—1
BASIS FOR COMPUTATION OF CAPITAL COSTS
(JULY 1977 DOLLARS)
CAPITAL COST ITEM
EXCAVATION
REINFORCED CONCRETE
EPOXY COATING FOR HYDROLYSIS BASIN
ACTIVATED CARBON SYSTEM BUILDING
FOR 750 MIN. DETENTION
FOR 600 MIN. DETENTION
FOR 300 MIN. DETENTION
FOR 60 MIN. DETENTION
HYDROLYSIS BASIN ENCLOSURE
SITEWORK, ELECTRICAL, PIPING,
AND INSTRUMENTATION
ENGINEERING
CONTINGENCY
EARTH WORK
CLEARING AND GRUBBING
GRASSING AND MULCHING
LINER
FOR LARGE EVAPORATION POND
FOR MEDIUM EVAPORATION POND
FOR SMALL EVAPORATION POND
CLEAR FIBERGLASS COVER
PIPINGS, FITTINGS, VALVES
(for Subcategory 3)
ENGINEERING AND CONTINGENCY
(for Subcategory 3)
BASIS OF COMPUTATION
$5 per cubic yard
$210 per cubic yard
$2 per square foot
$35 per square foot of floor space
$35 per square foot of floor space
$30 per square foot of floor space
$30 per square foot of floor space
$7 per square foot
48% of total equipment cost
15% of construction cost
15% of construction cost
$5 per cubic yard
$1,000 per acre
$1.10 per square foot
$0.71 per square foot
$0.77 per square foot
$0.89 per square foot
$2.00 per square foot
20% of total equipment cost
15% of construction cost
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TABLE VIII-2
BASIS FOR COMPUTATION OF ANNUAL COSTS
(JULY 1977 DOLLARS)
ANNUAL COST ITEM
MAINTENANCE MATERIALS
TAXES AND INSURANCE
FERRIC CHLORIDE
CAUSTIC SODA, 50%
ACTIVATED CARBON
OPERATING LABOR
OPERATING SUPERVISION
CONTRACT HAULING AND DISPOSAL
OF SLUDGE
ELECTRICITY
THERMAL ENERGY
CAPITAL RECOVERY
MAINTENANCE, TAXES, AND INSURANCE
(FOR SUBCATEGORY 3)
BASIS OF COMPUTATION
4% of capital costs
2% of capital costs
$0.20 per pound
$0.09 per pound
$0.58 per pound
$15,000 per man per year
Including fringe benefits
$20,000 per man per year
including fringe benefits
$5.00 per cubic yard
$0.05 per kilowatt-hour
$2.00 per million BTU
$0.28 for No. II fuel oil
$2.40 per 1000 Ib steam
Based on 10 years at 10%
2% of capital costs
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practicing or designing pesticide chemicals removal units
pretreat only portions of their total flow: Plant 41-7.1 percent.
Plant 49-38 percent, and Plant 21-10 percent.
It is recognized that pesticide chemicals within Subcategory 1
will differ in their resistance to removal through the
application of activated carbon and hydrolysis technologies. For
this reason, four different designs for each technology have been
presented. This will allow all pesticide chemicals to be reduced
to the same level, regardless of the degree of difficulty of
removal of the individual pesticide(s).
&PI Separator
The API type separator is sized based on the following:
Temperature = 40°C
Rise rate of oil globules =0.6 ft/min
Maximum allowable mean horizontal velocity =2.4 ft/min
The API separator precedes either activated carbon or hydrolysis
units. Skimmed organics are incinerated.
Dual Media Filter
A dual media pressure filter is provided in advance of the
activated carbon columns. An influent pumping station loads the
columns at a design rate of 4 gpm/ft2. A terminal head loss of
10 ft is allowed. Backwash pumps operate for 12 minutes at 15
gpm/ft«.
Activated Carbon Adsorption
A downflow, fixed-bed carbon system is assumed, including
backwash pumps and a control building. Based on design
characteristics presented in Table VII-3, contact times of 60,
300, 600, and 750 minutes have been assumed to demonstrate the
range of costs potentially incurred. Hydraulic loading is
assumed to be 0.5 gpm/ft2. Carbon usage is assumed to be 100 Ib
per 1000 gal waste water treated. A minimum of two columns in
series is provided, along with one carbon storage tank.
A regeneration facility is provided, including a furnace (feeder,
scrubber, and after burner), spent carbon dewatering tank, slurry
pumps, regenerated carbon wash tank, make-up carbon wash tank,
and wash water pumps. An eight percent carbon loss during the
regeneration step is assumed.
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Hydrolysis
Hydrolysis units have been designed at four different detention
times (200, 2000, 5000, and 12,000 minutes) in order to estimate
costs for different degrees of difficulty in removing pesticide
chemicals. These detention times are based on a reduction of ten
half-lives, or 99.9 percent for pesticides for which data were
available as identified in Tables VII-7 and VII-8. Chemical
addition has been provided in order to raise the pH of the waste
water from 7.0 to 11.0. Steam from available sources is employed
to raise the waste water temperature from 22°C to UO°C. Mixing
is provided at 30 hp per million gallons of volume. System
components include: basins, mixers, caustic soda feeding and
control, caustic storage tank, temperature control, steam
delivery and control, and basin enclosure.
As noted under activated carbon, the design criteria for
hydrolysis approximate actual operating conditions of plants
capable of attaining effluent levels specified in the guidelines*
In order to insure that the design criteria were valid,
hydrolysis data presented in Tables VI1-7 and VII-8 were used to
calculate the detention times required to achieve 99.9 percent
removal. Since data were available at many different conditions
of pH and temperature, it was necessary to standardize the data.
The methodology utilized to predict the half-lives of all
compounds at one set of conditions is described below.
The data were analyzed using the standard equations available for
second order reactions. The second order rate constant is
assumed to follow Arhenius1 equation:
-Ea/RT
k2_ = Ae
where T = temperature (°K)
R = 1.987 cal/mole - °K
Ea = activation energy (cal/mole)
A = constant (1/mole-min)
k2_ = second order rate constant (1/mole-min)
The pseudo-first order rate constant is defined by the
following equation:
-pOH
kl = k2 X 10
where pOH = - log (OH-)
kl = pseudo-first order rate constant (min-1)
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The half-life can be determined by dividing the natural log of 2
by the pseudo-first order rate constant:
t (1/2) = (In2)/kl where, t (1/2) = half-life (min)
In order to determine the half-life at any pH and temperature, it
is necessary to know the values of the constants A and Ea/R in
the Arhenius equation at the pH and temperature in question. It
was assumed both that Ea/R does not vary significantly with pH,
and that the natural log of A varies linearly with pH.
For each pesticide chemical where sufficient data were available,
Ea/R and the relationship between A and pH were defined. These
results were then used to produce tables showing the half-life at
several temperatures and pH.
For each compound where insufficient data were available, a
relative ease of hydrolysis factor was calculated. This is the
quotient of the half-life of the compound divided by the
half-life of a compound of similar structure for which data were
available. This resulted in the production of a table of
half-liveso
The half-life of any compound at any pH and temperature in the
range in question can then be estimated using the tables of
half-lives and the relative ease of hydrolysis factors.
The half-lives of several of the least and most readily
hydrolizable compounds were determined and at pH 10, 11, and 12
at temperatures of 30, UO, and 50°C. From this information it
was observed that pH = 11 and temperature = 40°C approximated
optimal conditions.
The pesticide chemicals were then divided into four groups
according to ease of hydrolysis:
Group 1: t (1/2) = 500 to 1200 min.
Group 2; t (1/2) = 200 to 500 min.
Group 3: t (1/2) = 20 to 200 min.
Group «*: t (1/2) = 20 min. or less.
Using the upper limit of each of the groups, the necessary
detention time was determined for each group for 99.9 percent
removal. These detention times were then used as the design
basis of the treatment models.
161
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Generally, pesticide hydrolysis proceeds by two mechanisms
simultaneously. One mechanism is at neutral conditions and
follows first order kinetics as defined by the following
equation:
-En/RT
kN = ANe
Where En = activation energy for the neutral mechanism
(cal/mole)
AN = constant for neutral mechanism (min)
kN = first order rate constant for neutral mechanism (min-1).
The other mechanism is at alkaline conditions and follows second
order kinetics as defined by the following equation:
-EB/RT
kB = (OH-) ABe
where EB = activation energy for the alkaline mechanism
(cal/mole)
AB = constant for alkaline mechanism (1/mole-min)
(OH-) = pseudo - first order rate constant for alkaline
mechanism (min-1)
The rate constant observed is the sum of the contributions of
both mechanisms. Therefore,
k = kN + kB
where k = observed first order rate constant
These equations can be used to predict half-lives whenever data
are available at two temperatures for both a neutral and an
alkaline condition. The data in Tables VII-7 and VII-8 were
analyzed according to second order kinetics.
For some pesticides, hydrolysis is catalyzed at acidic rather
than alkaline conditions. Since the purpose of this effort was
to estimate the costs of hydrolysis for pretreatment of pesticide
wastes, acid hydrolysis was not costed in that alkaline
hydrolysis would generally be more expensive and would yield
representative cost data.
Incinerator
The design of the incinerator is based strictly on flow, as the
heat release values of the waste are assumed negligible. Fuel
162
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requirements are based on a heat requirement of 0.5 million gm-
cal/kg (1,000 BTU/lb) of waste. It was assumed that 1 percent of
the total waste water flow is treated by incineration.
Equalization Basins
Equalization basins are sized for a holding time of 36 hours.
The basin is equipped with a floating aerator with an energy
requirement of 75 horsepower per million gallons of volume.
Neutrali zation Basin
The neutralization basin is sized on the basis of an average
detention time of 6 minutes. Either acid or caustic
neutralization may be required. For the purpose of cost
estimation, caustic neutralization was assumed since it is the
more expensive. The size of the caustic soda handling facilities
is determined according to a 100 mg/1 feed rate. Caustic soda
storage is provided based on 30 days capacity. Caustic soda is
fed by positive displacement metering pumps. Fifty horsepower
per million gallons is provided for mixing.
Aeration Basins
The size of aeration basins is based on mixed liquor suspended
solids and food to micro-organism ratios commonly used within the
industry. Mechanical surface aerators are provided in the
aeration basin. Aerators were selected on the basis of 2.0
pounds of oxygen per horsepower-hour.
Final Clarifiers
The clarifiers are assumed to be circular concrete basins with a
depth of 12 feet. They are sized on the basis of an overflow
rate of 400 gpd/sq ft. Allowance is made for a sludge return
capacity of 200 percent.
Aerobic Digest or
The size of the aerobic digester is based on a hydraulic
detention time of 20 days. The size of the aerator-mixers is
based on 150 horsepower per million gallons of digestor volume.
A solids production of 0.6 kg VSS/kg BOD removed and a VSS
reduction of 50 percent were assumed.
Sludge Thickener
The sludge thickener is designed on the basis of a solids loading
of 10 Ib/sq ft/day.
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Vacuum Filtration
The size .of the vacuum filters is based on a solids loading of 4
It/sq ft/ hour with effluent solids at 15 pounds. Average
running times of 12 hours are assumed. Chemical addition (ferric
chloride) at a rate of 7 percent by weight of dry solids is
provided.
Final Sludge Disposal
For all plants, sludge is assumed to be disposed of at a
specially designated landfill.
Evaporation
The earthen evaporation ponds are designed for an evaporation
rate of 21 inches per year. Pond depth of 4.0 feet including
freeboard is assumed. The ponds are lined with plastic and
covered with clear fiberglass roofing to prevent the entrance of
rainfall. It is assumed that no mixing is required.
Control House
Included in the control house is space and equipment necessary
for offices, lockers and showers, pumps, sample receiving, and a
laboratory sufficient to monitor BOD, COD, TSS and pesticide
chemicals.
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COST CALCULATIONS
The following discussions present information relative to the
estimation of capital and operating costs associated with the
installation of the model treatment technology.
Subcategory 1 Cost Calculations
Cost estimates are presented to take into account the potential
range of costs associated with the installation of the model
treatment technology as defined in Section VII. The two
principal factors affecting costs are the size of the treatment
facilities and the degree of difficulty of pesticide removal.
The size of treatment facilities is affected by the volume of
waste water to be treated. Based on information presented in
Table V-10, costs relating to three plant sizes have been
developed. The flow rates corresponding to the various plant
sizes are as follows:
Flow Rate Production
Large plant 0.9 MGD 200,000 Ib/day
Medium plant 0.2 MGD H5,000 Ib/day
Small plant 0.045 MGD 10,000 Ib/day
As discussed earlier in this section, the factors that relate
directly to the degree of difficulty of pesticide removal are the
contact time (activated carbon pretreatment technology) and the
detention time (hydrolysis pretreatment technology). Four
degrees of difficulty of pesticide removal are represented for
both model pretreatment technologies. They are: (a) a contact
time of 60, 300, 600, and 750 minutes for activated carbon and
(b) a detention time of 200, 2000, 5000, and 12,000 minutes for
hydrolysis. The pretreatment units are sized at one-third of the
total plant flow, as discussed previously.
It has been assumed that the size and cost of biological
treatment at any one flow is the same, regardless of the type of
pretreatment employed. As explained in Section VII, activated
carbon would in reality significantly reduce the wasteload of
oxygen demanding materials to the biological system. However,
the most effective type of pretreatment system cannot be
determined without performing treatability studies; therefore, no
reduction of non-pesticide pollutants has been assumed to ensure
that the costs associated with the installation of biological
treatment technology are not understated. Capital and annual
costs of biological treatment (including equalization) are
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presented in Table VIII-3. The costs associated with pesticide
removal units are not included.
Table VIII-4 presents sample capital and annual cost estimates
for hydrolysis pretreatment. Table VIII-5 presents sample
capital and annual cost estimates for activated carbon
pretreatment. Table VIII-6 summarizes the capital and annual
costs for pesticide removal. Table VTII-7 summarizes total
capital and annual costs for pesticide and biological treatment.
Land costs may be added to the above totals by utilizing Table
VIII-8 and multiplying by an appropriate land cost (dollars per
acre) .
Subcateqory 2 Cost Calculations
No cost estimates have been developed for this subcategory. The
state-of-the-art at plants manufacturing metallo-organic
pesticide chemicals is no discharge of process waste water
pollutants. It was originally reported that all plants were "no
discharge" facilities; however, representatives of one facility
(plant 19) recently indicated that there is a discharge from
their manufacture of metallic-organo pesticide chemicals. This
is being investigated by the Agency. The overall impact to this
subcategory is expected to be minimal.
Subcategory .3 Cost Calculations
Table VIII-9 itemizes the capital and operating costs associated
with total evaporation of the waste water generated from
formulating and packaging operations. Three plant sizes are
considered that correspond to the following waste water flow
rates:
Large plant 5000 GPD
Medium plant 500 GPD
Small plant 50 GPD
The quantities of land necessary to install the model treatment
technology, as defined in Section VII, are 1.76, 0.18, and 0.02
acres for the large, medium, and small plants, respectively.
Land costs may be calculated by multiplying these figures by an
appropriate land cost (dollars per acre).
166
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TABLE VI11-3
BPT COST ITEMIZATION
EXCLUDING PESTICIDE REMOVAL UNITS
SUBCATEGORY 1
Average Production
1000 Ib/day
Wastewater Flow
MGD
Capital Costs
Incinerator
Influent Pump Station
for Concentrated Waste
Influent Pump Station
for Dilute Waste
API Separator
Equalization
Transfer Pump Station
Neutralization
Transfer Pump Station
Aerator
Clarifier
Aerobic Digester
Sludge Thickener
Vacuum Filter
Control Building
Monitoring Station
Large Plant
200
0.9
$275,960
28,500
38,000
59,750
360,000
47,000
53,530
47,000
475,000
355,500
305,000
197,000
148,000
87,680
16,390
Medium Plant
45
0.2
$176,790
21,500
23,500
33,920
142,000
25,500
35,680
25,500
146,000
190,000
115,000
128,000
84,000
87,680
16,390
Small Plant
10
0.045
$100,250
19,500
19,800
24,700
65,000
20,500
29,830
20,500
44,800
103,000
38,500
82,000
47,300
87,680
16,390
167
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TABLE VIII-3 (con't)
Subtotal (including sitework,
electrical, piping, and
instrumentation 2,493,810 1,251,460 719,750
Engineering & Contingency 748.140 375.440 215.920
Total Capital Cost 3,241,950 1,626,900 935,670
Annual Cost:
Capital Recovery 528,440 265,180 152,510
Operating/Maintenance 430,770 176,620 85,560
Energy/Power 181.170 46.140 16.480
Total Annual Cost 1,140,380 487,940 254,550
168
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TABLE VIII-4
BPT COST ITEMIZATION
HYDROLYSIS—12,000 MINUTES DETENTION
SUBCATEGORY 1
Large Plant Medium Plant Small Plant
Average Production
1000 Ib/day 200 45 10
Wastewater Flow
MGD 0.3 0.067 0.015
Capital Costs
Basin $ 810,630 $ 215,580 $ 77,260
Mixers 63,420 14,780 9,580
Caustic Soda Feeding
and Control 22,330 22,330 22,330
Caustic Storage Tank 10,440 4,380 1,460
Temperature Control 7,500 7,500 7,500
Steam Delivery and Control 12,190 8.120 4,400
Subtotal 926,510 272,690 122,530
Site Work, Electrical, Piping
and Instrumentation 444,720 130.890 58.810
Subtotal 1,371,230 403,580 181,340
Engineering & Contingency 411.370 121.070 54.400
Total Capital Cost 1,782,600 524,650 235,740
Annual Cost:
Capital Recovery 290,560 85,520 38,430
Operating/Maintenance 147,330 42,580 19,530
Energy/Power 100.270 23.910 5,960
Total Annual Cost 538,160 152,010 63,920
169
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TABLE VIII-5
BPT COST ITEMIZATION
CARBON—750 MINUTES DETENTION
SUBCATEGORY 1
• Large Plant Medium Plant Small Plant
Average Production
1000 Ib/day 200 45 10
Wastewater Flow
MGD 0.3 0.067 0.015
Capital Costs
Adsorption System $2,101,710 $ 475,370 $ 160,070
Regeneration System 1.034.260 393.310 179.170
Subtotal 3,135,970 868,680 339,240
Site Work, Electrical, Piping
and Instrumentation 1.505.270 416.970 162.840
Subtotal 4,614,240 1,285,650 502,080
Dual Media Filter 144,000 93,000 87,000
Influent Pump Station 25.800 21.500 19.500
Subtotal 4,784,040 1,400,150 608,580
Engineer and Contingency 1.435.210 420.040 182.570
Total Capital Cost 6,219,250 1,820,190 791,150
Annual Cost:
Capital Recovery 1,013,740 296,690 128,960
Operating/Maintenance 1,283,950 448,640 200,260
Energy/Power 144.870 25.210 9.660
Total Annual Cost 2,442,560 770,540 338,880
170
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Retention
Time, Minutes
TABLE VIII-6
BPT COST SUMMARY
PESTICIDE REMOVAL
SUBCATEGORY 1
Large Plant
Medium Plant
Small Plant
Hydrolysis
Carbon
12,000
5,000
2,000
200
750
600
300
60
Capital
Annual
Capital
Annual
Capital
Annual
Capital
Annual
Capital
Annual
Capital
Annual
Capital
Annual
Capital
Annual
$1,782,600
538,160
860,040
329,300
448,810
219,390
172,430
153,320
6,219,250
2,442,560
5,293,610
2,230,950
4,256,620
1,999,700
3,079,490
1,734,840
$ 524,650
152,010
293,320
97,130
202,810
74,650
110,760
53,300
1,820,190
770,540
1,558,090
711,810
1,418,480
680,680
1,167,620
624,350
$235,740
63,920
164,630
47,410
115,250
36,070
83,930
28,920
791,150
338,880
727,000
324,390
648,540
306,890
575,110
290,510
171
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TABLE VIII-7
Item; Biological System
BPT COST SUMMARY
ALL TREATMENT UNITS
SUBCATEGORY 1
Large Plant
Including Hydrolysis Capital $5,024,550
12,000 Min. Detention Annual 1,678,540
5,000 Min. Detention Capital 4,101,990
Annual 1,469,680
2,000 Min. Detention Capital 3,690,760
Annual 1,359,770
200 Min. Detention
Including Carbon
750 Min. Detention
600 Min. Detention
300 Min. Detention
60 Min. Detention
Capital 3,414,380
Annual 1,293,700
Capital 9,461,200
Annual 3,582,940
Capital 8,535,560
Annual 3,371,330
Capital 7,498,570
Annual 3,140,080
Capital 6,321,440
Annual 2,875,220
Medium Plant
$2,151,550
639,950
1,920,220
585,070
1,029,710
562,590
1,737,660
541,240
3,447,090
1,258,480
3,184,990
1,199,750
3,045,380
1,168,620
2,794,520
1,112,290
Small Plant
$1,171,410
318,470
1,100,300
301,960
1,050,920
290,620
1,019,600
283,470
1,726,820
593,430
1,662,670
578,940
1,584,210
561,440
1,510,780
545,060
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TABLE VII1-8
LAND REQUIREMENTS
SUBCATEGORY 1
Item
Incinerator
Influent Pump Stations
API Separator
Equalization
Transfer Pump Station
Neutralization
Transfer Pump Station
Aeration
Clarifler
Aerobic Dlgestor
Sludge Thickener
Vacuum Filter
Control Building
Monitoring Station
Total Land Requirement
Hydrolysis,- 12,800 M1n
Hydrolysis - 5,000 M1n.
Large Plant
0.19
0.10
0.07
0.19
0.10
0.19
0.10
0.24
0.24
0.33
0.10
0.10
0.30
0.05
2.30
. Detention 1.29
Detention 0.53
Land Area 1n Acres
Medium Plant
0.11
0.06
0.03
0.11
0.06
0.11
0.06
0.12
0.12
0.17
0.06
0.06
0.30
0.05
1.42
0.35
0.18
Small Plant
0.05
0.03
0.01
0.05
0.03
0.05
0.03
0.05
0.05
0.08
0.03
0.03
0.30
0.05
0.84
0.13
0.08
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TABLE VIII-8 (cont'd)
Hydrolysis - 2,000 Kin. Detention 0.28 0.10 0.05
Hydrolysis - 200 Min. Detention 0.06 0.03 0.03
Carbon - 750 Min. Detention 0.98 0.27 0.09
Carbon - 600 Min. Detention 0.95 0.25 0.08
Carbon - 300 Min. Detention 0.90 0.22 0.07
Carbon - 60 M1n. Detention 0.82 0.18 0.06
174
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TABLE VIII-9
BPT COST ITEMIZATION
SUBCATEGORY 3
Wastewater Flow (GPD)
Capital Costs
Evaporation Pond
Earth Work
Clearing and Grubbing
Grassing and Mulching
Liner
Clear Fiberglass Cover
Pump Station
SUBTOTAL
Piping, Fittings and Valves
SUBTOTAL
Engineering and Contingency
TOTAL CAPITAL COST
Annual Cost
Capital Recovery
Operating/Maintenance
Energy/Power
Large Plant
5,000
$ 25,820
2,400
25,260
56,920
139,429
19,000
268,820
53,760
322,580
48,390
370,970
60,470
7,420
270
Medium Plant
500
$ 2,580
240
7,940
5,690
13,940
4,600
34,990
7,000
41,990
6,300
48,290
7,870
970
270
Small Plant
50
$ 260
20
2490
570
1400
1500
6240
1250
7490
1120
8610
1400
30
270
TOTAL ANNUAL COST
68,160
9,110
1700
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1S1 ON-WATER QUALITY ASPECTS
The non-water quality aspects of the implementation of the
recommended effluent limitations is directly affected by the
various methods employed to treat and dispose of pesticide
chemicals waste waters prior to discharge to surface waters. The
impacts of major importance are related to air and solid waste
considerations. Another area of concern involves protection of
groundwater.
Air Considerations
Incineration is a widely used technology in the pesticide
chemicals industry for combustion of highly concentrated organic
or toxic wastes. Since the off-gases from incineration can be
adequately controlled by scrubbing, with the resultant effluent
being discharged to the waste water treatment facility, air
quality impact need not be significant.
Equipment requirements for control of air pollutant emissions
vary for different applications, waste characteristics,
incinerator performance, and air pollutant emission standards.
Particulate matter can be controlled by the use of cyclones, bag
filters, electrostatic precipitators, or venturi scrubbers.
Emissions from combustion of wastes containing halogen, sulfur,
or phosphorus compounds require the use of aqueous (water or
alkaline solution) scrubbing. Incineration is not applicable to
organic pesticides containing heavy metals such as mercury, lead,
cadmium, or arsenic, nor is it applicable to most inorganic
pesticides or metallo-organic pesticides which have not been
treated for removal of heavy metals.
Land Disposal Considerations
In all cases where incineration is used, provisions must be made
to ensure against the dispersal of hazardous pollutants into the
atmosphere. The disposal of solid wastes generated through the
implementation of water pollution control technology must be done
with proper management. The quantities of sludge generated at
subcategory 1 plants employing the model treatment technology (as
defined in Section VII) are estimated to be:
PLANT SIZE DRY SOLIDS GENERATED
kl/day (MGD) kkq/day
Large 3410 (0.9) 1.51
Medium 760 (0.2) 0.335
Small 170 (O.OU5) 0.0754
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Lime and biological sludges are generally compatible with
ultimate disposal in a specially designated landfill. However,
if land disposal is to be used for materials considered to be
hazardous, the disposal sites must not allow movement of
pollutants to either ground or surface waters. Natural
conditions which must exist include geological insurance that no
hydraulic continuity can occur between liquids and gases from the
waste and natural ground or surface waters. Disposal areas
cannot be subject to washout, nor can they be located over active
fault zones or where geological changes can impair natural
barriers. Any rock fractures or fissures underlying the site
must be sealed.
As a safeguard, liners are often needed at landfill sites. Liner
materials, consisting of clay, rubber, asphalt, concrete, or
plastic, should be pre-tested for compatability with the wastes.
Leachate from the landfill must be collected and treated.
Treatment, which will of course vary with the nature of the
waste, may consist of neutralization, hydrolysis, biological
treatment, or evaporation. Treatment in some cases may be
achieved by recycling the leachate into the landfill.
Landfills for the disposal of hazardous wastes are generally
operated under some form of permit from a state agency. The
regulations and restrictions vary from state to state.
Encapsulation prior to landfilling is recommended for certain
materials such as those containing mercury, lead, cadmium, and
arsenic, and for organic compounds which are highly mobile in the
soil (Federal Register, May 1, 1974, pp 15236-15241).
Where practicable, provision for separate storage of different
classifications of pesticides according to their chemical type,
and for routine container inspection, should be considered.
In general, pesticides or pesticide wastes should only be
disposed of at a "specially designated" landfill, which is
defined as "a landfill at which complete long term protection and
subsurface waters... and against hazard to public health and the
environment. Such sites should be located and engineered to
avoid direct hydraulic continuity with surface and subsurface
waters, and any leachate or subsurface flow into the disposal
area should be contained within the site unless treatment is
provided. Monitoring wells should be established and a sampling
and analysis program conducted. The location...should be
permanently recorded in the appropriate office of legal
jurisdiction" (Federal Register, May 1, 1974, pp 15236-15241).
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Off-site disposal is commonly practiced in the industry for
highly concentrated wastes. It is also common practice for
formulation plants with very low waste water generation to haul
their waste water to other plants that have treatment systems.
Land disposal of residuals should be in conformance with all
applicable federal, state, and local ordinances.
The hauling of pesticide wastes requires special handling
equipment and/or prior containerizatjon.
Activated carbon adsorption can be considered as a land-related
treatment method since in some applications the spent carbon is
disposed of by containerization and surface storage. Also,
thermal regeneration of carbon may be regarded as an incineration
method and subject to the above discussion of incineration,
Protection of Groundwater
Deep-we11 injection has been considered economically attractive
and is employed at several plants in the pesticide chemicals
industry. A deep-well disposal system can only be successful if
a porous, permeable formation of a large area and thickness is
available at sufficient depth to insure continued, permanent
storage. It must be below the lowest ground water aquifer, be
confined above and below by impermeable zones (aquicludes), and
contain no natural fractures or faults. The waste water so
disposed must be physically and chemically compatible with the
formation, and should be completely detoxified prior to
injection. Suspended solids which could result in stratum
plugging must be removed. Well construction must provide
adequate protection against groundwater contamination and include
provisions for continuous monitoring of well performance and
subsurface movement of wastes, including continuous sampling by
monitor wells. Very few deep well injection systems meet all
these requirements.
Evaporation ponds may consist of concrete or earthen basins. In
the latter case, unless the natural soil is impervious, lining
with an impervious material is necessary to ensure that
groundwater is protected.
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
The effluent limitations which must be achieved by July 1, 1977,
specify the degree of effluent reduction attainable through the
application of the Best Practicable Control Technology Currently
Available (BPT). BPT is generally based upon the average
performance of the best existing treatment plants of various
sizes, ages, and unit processes within the industrial category
and/or subcategory. Consideration must also be given to:
a. The total cost of application of technology in
relation to the effluent reduction benefits to
be achieved from such application;
bo The size and age of equipment and facilities
involved;
c. The process employed;
d. The engineering aspects of the application of
various types of control techniques;
e. Process changes;
f. Non-water quality environmental impact (including
energy requirements);
g. Availability of land for use in waste water
treatment-disposal.
BPT emphasizes treatment facilities at the end of a manufacturing
process, but includes the control technologies within the process
itself when these are considered to be normal practices within
the industry.
A further consideration is the degree of economic and engineering
reliability which must be established for the technology to be
"currently available,," As a result of demonstration projects,
pilot plants, and general useff there exists a high degree of
confidence in the engineering and economic practicability of the
technology presented in this document.
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EFFLUENT REDUCTION ATTAINABLE THROUGH THE APPLICATION OF BEST
PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
Based upon the information contained in Sections II through VIII
of this document it has been determined that the degree of
effluent level attainable through the application of the best
practicable control technology currently available is that listed
in Table IX-1. Pesticide chemicals are the sum of all regulated
active ingredients produced in a plant* The pH of the effluent
must be in the range of 6.0 to 9.0.
SUMMARY OF GUIDELINES DEVELOPMENT SUECATEGORY 1_
The effluent limitations guidelines are based on an analysis of
the long term effluent data obtained from existing treatment
plants which have the model treatment,, i.e., pesticide removal,
equalization, and biological treatment that are properly
operated. The limitations are the product of the long term
average performance and a daily maximum or a 30-day maximum
variability factor.
The data base used to set the limitations for subcategory 1 was
derived in the following manner. There are 29 known pesticide
manufacturing plants that discharge process waste water directly.
The products at four plants (33, 36, 53 and 153) were excluded
from coverage at this time,, Plant 9 is closed and no data were
used. Plants 11, 15, 16, 31, 10 and 155 have neither biological
nor pesticide removal treatment. No data from these plants were
used to derive the limitations.
The derivation of the pesticide chemicals limitations will be
described first. Data from Plants 29, 41, 47, 48, 146 and 149
were not used as they had no pesticide treatment. Of the
remaining plants only those with pesticide removal treatment as
described in Section VII were used to determine the pesticide
limitations. These are plants 3, 8, 18, 19, 21, 22, 27, 32, 34,
39, 45 and 50. The data from Plants 6, 20 and 28, which
discharge to publicly owned treatment works, were included
because adequate pesticide removal treatment is practiced prior
to discharge.
Plant 18 did not have data on pesticide levels and was not
further considered. Effluent data and operating conditions were
not supplied by Plant 22, and it was not further considered.
Plant 34 did not detect pesticide active ingredients in the
effluent, and these data were not used. Data from Plant 32 was
not included since it does not have adequate treatment as
described in Section VII. Plant 50 only treats floor washings.
These data are not representative of typical manufacturing
180
-------
TABLE IX-1
EFFLUENT LIMITATIONS
SUBCATE60RY l
1
2
3
EFFLUENT AVERAGE OF DAILY VALUES
CHARACTERISTIC FOR 30 CONSECUTIVE DAYS
BODS
COD
TSS
Pesticide Chemicals
pH?
___Mn HT^PHARGF OF PRHPF^
NO nT^PHARRF OF PROPF^
1.6
9.
1.8
.0018
UA9TF UATFR PHI 1 IITANT^--
UA^TF UIATFR PHI 1 IITANT^
DAILY
MAXIMUM
7.4
13.
6.1
0.010
Note: All units are kg/kkg
1, Subcategory 1: Organic Pesticide Chemicals Manufacturing
Subcategory 2: Metallo-Organic Pesticide Chemicals Manufacturing
Subcateogry 3: Pesticide Chemicals Formulating and Packaging
2. The pH shall be between the values of 6.0 to 9.0
181
-------
process waste water and were not used. Plant 19 uses activated
carbon to remove free chlorine rather than pesticide, hence these
data were not used.
The limitations for BOD, COD and TSS are based on the model of
biological treatment. Of the twenty-five direct dischargers that
are regulated, thirteen plants have biological treatment. These
are Plants 19, 21, 22, 27, 29, 32, 3'*, 39, 41, 47, 48, 146 and
149. Plant 28 discharges to a public owned treatment system but
has the recommended technology \n place. However, since TSS is
not of major concern to the receiving treatment plant, the TSS
removal technology is not as elaborate as for direct dischargers.
Hence, the BOD5 and COD data were used and the TSS data was not
used.
Plants 3, 8, 18, 45 and 50 do not have biological treatment and
they were not used to determine the biological parameter
limitations. Plants 22, 27, 29, 47, 146, and 149 either do not
monitor BOD, COD or TSS or did not supply this data when
requested by the Agency. Plants 34 and 39 submitted BOD, COD and
TSS data only after the pesticide removal treatment. No effluent
discharge data were supplied from the biological system for these
two plants. These data for BOD, COD and TSS were therefore not
used. Plant 48 supplied estimates for BOD, COD and TSS. These
data were not included. Plant 32 as described in Section VTI has
inadequate treatment and these data were not included.
The BOD limitations are derived from plants 19, 21, 28 and 41.
The COD limitations are derived from plants 19, 28 and 41. Plant
21 does not monitor for COD. The TSS limitations are derived
from Plants 19, 21, and 41.
Long-term averages
Subcategory 1 long-term average effluent data are presented in
Table IX-2. Long-term averages represent the average discharge
in units of daily average pounds of pollutants per average 1000
pounds of pesticide chemicals produced for the period for which
effluent data were available from the plants. The overall
long-term average has been weighted according to the number of
observations available, so that the contribution of a particular
plant1 s data is in proportion to the number of observations from
the plant.
All data supplied to the Agency from plants that currently employ
and properly operate the model technology were utilized in
developing long-term averages. These data, and the weighted
long-term averages are presented in Table IX-2.
182
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TABLE IX-2
DEVELOPMENT OF LONG TERM AVERAGES
SUBCATEGORY 1
PARAMETER (NUMBER OF OBSERVATIONS)
PLANT
3
6
8
19
20
21
27
28
39
41
45
BOD (n)
2
I
0
1
~
*
.53
*
.11
-
(34)
(334)
.541(65)
*
.00
*
(60)
COD (n)
19.
7.
10.
*
*
4
*
-
-
01
*
2
*
(28)
(450)
(61)
TSS (n)
*
is
*
1.17
*
1.36
-
***
*
1.08
*
(28)
(329)
(61)
PESTICIDE
CHEMICALS (n)
0
0
0
0
0
0
0
0
0
.000943 (244)
.000505 (5)
.0000765 (25)
**
.00300 (185)
.000762
.00315
.0007
314)
52)
450)
.000162 (4)
**
.031 (5)
Weighted
Average 1.12 (482)
8.01 (539) 1.31 (418) 0.00129 (1284)
Note: All values are kg/kkg
* = Available data do not Include biological treatment
** = Available data do not include pesticide removal
*** = Data from biological treatment prior to clarification
- = No data available
(n) = Number of data points
183
-------
For Subcategory 1, zero discharge facilities were not used in the
computation of the limitations. Plants, at which no detectable
levels of pesticides were found, were not used to determine the
limitations.
The long term averages of plants used to develop the effluent
limitations are not based on deep well injection. If process
waste water from the production of an active ingredient is
disposed into a well, the production of that active ingredient
should not be included in the calculation of discharge levels for
pesticide chemicals.
Development of variability factors
During the development of the interim final limitations
guidelines the Agency used a procedure based on fitting the three
parameter log normal distribution to the effluent data to
determine the variability factors. Subsequent goodness-of-fit
tests on the expanded data base failed to justify the universal
applicability of the normal, two parameter lognormal or three
parameter lognormal distributions to describe the data. Hence,
the Agency adopted the distribution free procedures described
below.
The results of the daily and 30-day variability analyses are
presented in Table IX-3. Pesticide data being monitored at the
effluent of activated carbon or hydrolysis pretreatment, such as
at Plant 20, were not included in the analyses.
Data from plants which did not supply sufficient numbers (more
than 90) of observations to determine variability factors with
specified confidence levels were not used. Hence, the data from
plants 6, 8, 20, 27, 39 and 45 were not used to determine the
variability factors for pesticide chemicals. This was. also the
case for Plant 19 for BOD, COD and TSS and Plant 28 for BOD.
Variability factors at each plant were weight-averaged in the
same manner as the long term values to arrive at one factor for
each parameter. When these factors are multiplied by the long
term values established in Table IX-2, the daily maximum effluent
limitations guidelines given in Table IX-1 result.
Maximum Factor
The daily maximum variability factor is defined as an estimate of
K.99, the 99th percentile of the distribution of daily pollutant
discharge, divided by the average daily pollutant discharge.
Given a set of daily observations the daily variability factor is
-------
TABLE IX-3
VARIABILITY FACTORS
SUBCATEGORY 1
DAILY MAXIMUM PARAMETERS
PLANT
3
21
28
41
Weighted
Average
PLANT
3
21
28
41
Weighted
Average
BOD(n)
7.7 (354)
-
2.6 (95)
6.6 (449)
BOD(n)
1.5 (354)
-
1.2 (95)
1.4 (449)
COD(n)
-
1.8 (92)
1.5 (121)
1.6 (213)
30- DAY
COD(n)
-
1.2 (92)
1.1 (121)
1.2 (213)
ISS(n)
*
5.4 (360)
-.
2.5 (122)
4.7 (482)
MAXIMUM
TSSfrO
*
1.4 (360)
-
1.2 (122)
1.3 (482)
PESTICIDE
CHEMICALS
9.4 (244)
5.0 (341)
12.2 (92)
7.6 (677)
PESTICIDE
CHEMICALS (n)
1.5 (244)
1.3 (341)
1.6 (92)
1.4 (677)
n = number of observations
- = No data available
* = Available data do not include biological treatment
185
-------
U.99/X
where
U.99 = an estimate of K.99
X = arithmetic average of the daily observations
The value for U.99 was obtained as the rth smallest (where r was
less than or equal to n) sample value, denoted by X (r) , chosen so
that the probability that X(r) is greater than or equal to K.99
was at least 0.50. The value of r for which this criterion was
satisfied was determined by nonparametric methods (see, e.g., J.
D. Gibbons, Nonparametric Statistical Inference, McGraw-Hill,
1971). An estimate chosen in this manner is sometimes referred
to as a 50% reliable estimate for the 99th percentile and is
interpreted as the value below which 99% of the values of a
future sample of size n will fall with probability 0.50.
In some cases the number of observations available from a plant
were not sufficient to obtain a nonparametric 50% reliable
estimate of the 99th percentile. In those cases the plant's data
were not used in the calculation of the overall variability
factors.
3J) Day Maximum Variability Factors
The 30 day maximum variability factors were derived on the basis
of the statistical theory which holds that the distribution of
the mean of a sample drawn from a population distributed
according to any one of a large class of different distributional
forms will be approximately normal. In applying the central
limit theory to the derivation of 30 day variability factors, the
sample mean is the average of 30 daily discharge measurements and
the underlying population is the daily discharge. For practical
purposes, the normal distribution provides a good approximation
to the distribution of the sample mean for samples as small as 25
or 30 (see, e.g.. Miller and Fruend, Probability and Statistics
for Engineers, Prentice-Hall, 1965, pp. 132-34). This approach
is distribution free in the sense that no restrictive assumption
is made regarding the form of the population distribution and is
thus consistent with the method used to derive the daily maximum
variability factors. The approach is also in agreement with
industry comments to the effect that 30 day limitations can be
based on this theory.
The 30 day maximum variability factors were calculated as
follows:
30 day maximum factor = X + 2.33 S/ 5.477
X
186
-------
where
X = average daily discharge in pounds
S = standard deviation of the daily discharge observations
Since 5.477 is approximately the square root of 30, the quantity
S/5.477 is an estimate of the standard deviation of the mean of a
sample of size 30 drawn from a population with mean X and
standard deviation S. The numerator of the 30 day variability
factor is an estimate of the 99th percentile of the distribution
of the mean of a sample of size 30 from a population with mean x
and standard deviations. Data not included in the overall
average daily maximum variability factors were not included in
the average 30 day variability factors.
Although the regulations are based on a 99 percentile, the
methodology employed in determining the limitations is
sufficiently conservative that the limits should not be exceeded
by a properly operated treatment system. In fact, many of the
best plants have not exceeded the limits.
Subcateqory 2^
Subcategory 2 manufacturers demonstrate the practice of no
discharge of pollutants via in-process control and recycle of
waste waters.
Subcateqory 3_
Subcategory 3 formulators and packagers demonstrate the practice
of no discharge of pollutants via in-process control and total
evaporation.
Summary of Point Source Discharges
The Agency believes that the regulations presented in this
document are presently or will shortly be attained by sixteen of
the twenty-five affected dischargers. These sixteen plants will
meet the regulations by either the model technology, alternate
treatment technologies or predicted performance from treatment
systems scheduled to be completed prior to the expiration of
existing NPDES permits.
Two of the direct dischargers have not supplied adequate data for
the Agency to make a determination at this time. These plants
are being investigated further. The indication is that these
plants have inadequate treatment but no firm statement can be
187
-------
made from data supplied by these plants. The remaining seven
direct dischargers are expected to incur some cost to comply with
the final regulations. These costs are in the form of capital
and operating costs and are itemized in Table IX-U.
The Agency recognizes that certain conditions may exist which
prevent the monitoring of pesticides at the required levels. For
example, a plant producing a pesticide will receive an allowance
(Ibs) which may require monitoring below current detection
limits-, depending on the amount of dilution by other processes in
the plant.
In situations such as these several options are available in
applying the limitations. First, the analytical method employed
by the plant should be verified with the Environmental Monitoring
and Support Laboratory, Cincinnati. Second, sampling may be done
prior to the dilutions. If the pesticide is being removed in a
particular pretreatment unit (activated carbon, hydrolysis,
etc.), concentrations immediately following that unit operation
may lie within the detectable range. If the pesticide (lb/1000
Ibs) measured at this point is below the levels required, then
the plant has obviously complied with the intention of the
regulations, assuming no pesticide contaminated wastes are
introduced downstream from this point. If the pesticide level
(lb/1000 Ibs) following pretreatment is greater than allowed by
the regulation, then the degree of removal through the biological
system must be determined. The pathway and biological
degradation of the pesticide may require determination by
independents means. Treatability studies or in-depth sampling
may be required to establish the portion of the pesticide
adsorbed onto the sludge, versus that which remains in the
supernatant. The potential for build-up of pesticides in the
treatment system should also be recognized.
ENGINEERING ASPECTS OF CONTROL TECHNOLOGY
As discussed in Section VII, a variety of treatment models other
than those discussed in this document may be employed in the
industry. For particular installations, other models could be
more cost effective. This can only be determined on a case by
case basis.
Application of the best practicable control technology currently
available does not require major changes in existing industrial
processes for the subcategories studied. Water conservation
practices, improved housekeeping and product handling practices,
and improved maintenance programs can be incorporated at
virtually all plants within a given subcategory.
188
-------
TABLE IX-4
UPGRADING OF EXISTING SYSTEMS ANTICIPATED
TO ATTAIN LIMITS
Plant
3
8
9
11
15
16
18
19
21
22
27
29
31
32
33
34
36
Additional
Treatment Required
None
None
None
None
Unknown-Awaiting 308
Responses
None
None
Activated Carbon and
Sand Filtration
Hydrolysis (Nitrogen
Pesticides)
None
Sand Filtration
None
None
Hydrolysis, Tertiary
Sand Filtration and
Activated Carbon
None Applicable
Excluded Products
None
None Applicable
Additional
Capital Costs
None
None
None
None
Unknown
None
None
$ 460,000
$ 430,000
None
$ 167,400
None
None
$6,221,000
None
None
None
Additional
Annual Costs
None
None
None
None
Unknown
None
None
$ 450,000
$ 202,000
None
$ 58,900
None
None
$3,075,700
None
None
None
39
Excluded Products
None
None
None
189
-------
TABLE IX-4
UPGRADING OF EXISTING SYSTEMS ANTICIPATED TO MEET LIMITS
CONTINUED, PAGE 2 OF 2 PAGES
Plant
40
41
45
48
47
50
53
146
149
153
155
Additional
Treatment Required
None
Activated Carbon
None
Activated Carbon
None
None
Not Applicable -
Excluded Product
Activated Cai ';on
Unknown Awaiting
308 Response
Not Applicable
Excluded Product
None
Additional
Capital Costs
None
$1,650,000
None
$ 980,000
None
None
None
None- lease
Unknown
None
None
Additional
Annual Costs
None
$780,000
None
$445,000
None
None
None
$ 55,000
Unknown
None
None
190
-------
The technology to achieve these recommended effluent limitations
is practiced within the subcategories under study or can be
readily transferred from technology in other industries. The
concepts are proven, available for implementation, and applicable
to the wastes in question. However, up to two years may be
required from design initiation to plant start-up. These waste
treatment techniques are also broadly applied within many other
industries. The technology utilized may necessitate improved
monitoring of waste discharges and of additional waste treatment
components on the part of some plants, and may require more
extensive training of personnel in the operation and maintenance
of waste treatment facilities. However, these procedures are
currently practiced in some plants and are common practice in
many other industries.
FACTORS TO BE CONSIDERED IN APPLYING EFFLUENT GUIDELINES
Land Availability /
The above assessment of what constitutes the best practicable
control technology currently available is predecated on the
assumption of a degree of uniformity among plants within each
subcategory that does not necessarily exist in all cases. One of
the more significant variations that must be taken into account
in applying limitations is availability of land for retention
and/or treatment of waste water. While the control technologies
described herein have been formulated for minimal land
requirements, individual cases of extreme lack of land may
present difficulties in applying these technologies. In other
cases, the degree of land availability may dictate one treatment
alternative over another, or allow treatment costs to be
considerably less than those presented.
Production-Discharge Correlation
There are several instances in which no correlation may exist
between the final effluent and the unit of production on a short
term basis due to the batch nature of the process or to the
cleanup periods. For example, while a plant is synthesing
pesticides in a batch process, virtually no waste water may be
generated. During a subsequent period of time, however,
production operations may have completely ceased but a
considerable amount of waste water may be generated by clean-up
procedures. In such cases, it is recommended that plant
capacity, measured on a long term basis, be used in applying the
limitations.
191
-------
Multiple Products
Another production factor which should be considered is that of
intermediate products. The problem might best be illustrated by
three idealized plants:
Plant A receives certain raw materials, processes them through a
number of steps (with each step generating waste water and
resulting in intermediate products which are used in the
subsequent step), and ultimately produces final pesticide
products. The total waste water generated by Plant A can be
related to the quantity of final product, and theoretically other
plants such as Plant A producing the same final products would
generate similar waste water loadings per unit product.
Plant B is similar to Plant A in that it produces the same final
products, but it differs in that it produces more intermediate
than is required and consequently sells a portion. In this case,
if only the final products are considered and the intermediates
ignored, the waste water loading per product unit could be
substantially higher than that of Plant A.
Plant C also produces the same final products as Plants A and B,
but it purchases some of the intermediate products and thereby
eliminates certain processing steps and the corresponding waste
water generation. In this case, the waste water loading per
product unit could be srbstantially lower than that of Plant A.
These, limitations exclude the coverage of intermediates. In
order to evaluate data from plants such as A, B, and C above, the
influent or effluent mass loading (Ibs) has been divided by the
total plant production (pesti :ides, intermediates, and non-
pesticides, if applicable). Ihe assumption that the above
processes contribute equally to waste loading has only been made
when monitoring is insufficient to establish any other
proportion.
There are pesticide manufacturing facilities that also do
formulating and packaging and have a common treatment system.
Such plants should receive no credit for formulating and
packaging. The limitations should be calculated based on the
manufacturing production only.
Storm Runoff
In all cases herein, including those for which no discharge of
waste waters is recommended, it must be recognized that storm
runoff can contain various degrees of contamination. Except for
very new installations, many pesticide plants have contaminated
soil resulting from past spills. Runoff or leachate from that
soil may exhibit contamination, even in cases where there is no
discharge of process -waste water. Extra allowance for this may
be allowed.
192
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SECTION X
LIST OF COMMON PESTICIDE COMPOUNDS
BY SUBCATEGORY
In order to provide readers with a convenient cross reference,
Table X-l lists a number of the major pesticide compounds,
classified by subcategories and defined in this document, i.e.,
organic pesticide chemicals, and metallo-organic pesticide
chemicals. In addition, some compounds, listed as non-
categorized pesticides in Table X-1, have active groups which do
not allow classification in the above-mentioned subcategories and
which are not covered by these guidelines.
Pesticides are alphabetically listed by common name by
subcategory along with their chemical name as defined by
U.S.E.P.A. Report 600/9-76-012, Analytical Reference Standards
and Supplemental Data for Pesticides and Other Organic compounds,
Research Triangle Park, N.C. 27711. These listings are
representative in nature and are not intended to be all inclusive
or to exclude compounds not listed. Mention of trade names or
commercial products does not constitute endorsement or
recommendation for use.
193
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
1 Acephate (Orthene)
0,S-Dimethly acetylphosphora-
midothloate
2 Alachlor (Lasso)
2-Chloro-2',6'-diethyl-N-
(methoxymethyl) acetanll1de
CH,CHj
CH3CH30
^CHjOCHj
"C - CH,
" I
3 Aldlcarb (Temlk)
2-Methyl-2-(methylth1o)-
propionaldehyde-0-
(methylcarbomoyl) oxlme
CH3 O
i ii
CHjS -C -C =N-O-C-N-CH,
™? A
Aldrln
1,2,3,4,10,10-Hexachloro-
l,4,4a,5,8,8a-hexahydro-
1.4-endo-exo-5,8-
dimethanonaphthalene
ci
5 Alodan (Hoechstz)
5,6-B1s(chloromethyl)-|,2,3,4,7,7-
hexachloroblcyclo [2.2,1] hept-
2-ene
ClHjC
cica,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUDCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
6 Ametryn (Ev1k)
2-(Ethylamino)-4-(isopro-
pyl ami no)-6-(methyl -
thio)-s-tr1az1ne
SCHj
N^N H
-l^ JJ-N-CHtCHj),
77 Aininocarb (Matacil)
4-Dimethylami no-m-tolyl
methylcarbamate
H o
i H / \
.
N(CH3)j
CH,
8 Amitrole (Cytrol)
3-Amino-l,2,4-tr1azole
rr
N N
9 Amobam (Chemo-0-Bam)
Diammonium ethylenebisdi
thiocarbamate
CHaNHCS,NH4
10 Ancymidol (A-Rest)
a-Cyclopropyl-a-(p-methoxy-
phenyl)-5-pyrim1dinemethanol
OH
OCH3
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS [W SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
11 Anilazine (Dyrene)
2,4-Di chloro-6-(o-chloroanl1 •
1no)-s-tr1az1ne
TY
Cl
Cl
12 Antu
1-(1-Naphthyl)-2-thlourea
NHCSNH,
13 Aspon
0.0,0,0-Tetrapropyl
pyrophosphate
14 Asulum (Asulox)
Methyl (4-am1no benzene-
sulfonyl)carbamate
H»N-f VsOjNHCOOCHj
15 Atraton (Gesatamin)
2-(Ethy1amino)-4-(1sopropyl-
amino)-6-methoxy-s-tr1az1ne
OCHj
H H
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS 0Y SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
16 Atrazine (Aatrex)
2-chloro-4-(ethylam1no)-6
(1sopropylami no)-s-tr1azi ne
H
17 Azinphos Ethyl
(Ethyl Guthion)
0,0-D1ethyl S-[4-oxq-l,a,3-
penzotr1az1n-3 (4H)
phpsphorQ
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUDCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
2ly Darban (Carbyne)
4-Chloro-2-Butynyl-m-chloro-
carbanilate
H-N-
ci
,-C£C-CHjCI
10
00
22 Benefin (Balan)
N-Butyl-N-etM-a,a,a-tr1
fluoro-2,6-u1n1tro-p-
toluidine
23 Denfluralin (Balan,
Benefin, Bethrodine,
Quilan, Binnell)
N-butyl-N-ethyl-2,6-dlnltro-
4-tr1f1uoro-methylan111ne
24 Bensulide (Prefar)
S-(0,0-D11sopropyl phosphoro-
dith1oate)ester of N-(2-mer-
captoethyl)benzenesu1fonam1de
OH §r ,
0-S-N(CH,)2S-J LOCH(CH,)J,
25 Bentazon (Basagran)
3-Isopropyl-lH-2,l,3-benzo-
th1ad1az1n-(4) 3H-one 2,
2-dioxide
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS 0Y SUDCATEGORY
SUDCATEGORY 1-QRGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
26 Benthiocarb (Bolero)
S-(4-Chlorobenzyl)N,N-d1ethyl-
thlolcarbamate
Cl
IO
27 Benomyl (Benlate)
Methyl 1-(butylcarbamoyl)-
2-benz1m1dazolecarbamate
O H
C-N
N
VN-C-OCHj
I! i H
N H O
28 Bentranll
2-Phenyl-3,l-benzoxaz1none-(4)
29 Benzadox (Topcide)
(Benzamldooxy) acetic add
/\ ° I ?
// V_C_N_O-CH,-C-
OH
30 Benzoylprop Ethyl (Sufflc)
Ethyl N-benzoyl-N-(3,4-
dlchlofophenyl)
-2~ain1noprop1onate
ci-
ci
- o
i
N-C
H,C-C-C-0-C,Hj
H O
-------
TABLE X-l
OF PESTICIDE COMPOUNDS PY SUOCATEGORY
SUQCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
31; BMC and related Isomers
Isomer* of Hexachloro-
cyclohexana
32 BlfenoH (Hodown)
Methyl 6-(2f4-d1chlpro«
phenoxy )-2-
9
H,C-0-C
0,N
C|
33
(Hyvar)
6-Brorao-3-sec-buty1-6-
roethyluracll
CH
34 Bromocyclen
(Bromodan, Alugan)
6-t>romoraethyl-l,2,3,4»7,7t'
hexachl oro-2-norl)ornene
CHjBr
35 Bromopho? (Brofene)
0-(4-Bromo-2,5-d1ch1oro-
phenyl)0,0-dimethyl
phosphorothloate
CH;
CH
Or
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
36 Bromophos Ethyl (Nexagan)
o-(4-Bromo-2,5-d1chloro-
phenyl)0,0-diethyl
phosphorothloate
ro
O
37 Bromopropylate
Isopropyl 4,4'dlbromobenzllate
Bf-
5-CH(CII3>2
38 Bromoxynil (Bromlnal)
3,5-D1 brom.Q-4-hydrQxyi
benzonltrlle
39 Bui an
l,V-(2-N1trobutyl1dene)
bis [4=chlorobenzene]
Cl
40 Butachlor (Machete)
2-Chloro-2',6'-d1ethyl-N-
(butoxymethyl) acetanl11de
,CH2OC4H»
\
COCHjCI
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
o
ro
41 Butralin (Amex 820)
4-(l,l-Dimethylethyl)-N-
(1-methyl propyl)-2,
6-din1tronbenzeneam1 ^e
CH,
H-N-CHCHjCHj
•Q
C(CMj)
42 Butyl ate (Sutan)
43 Captafol (Dlfolaton)
^44) Captan
•> — S
f*\
45) Carbaryl (Sevln)
- — /
S-Ethyl N,N-di1sobutyl- o
th1ocarbamat» CH SCN
c1s-N4(l,l,2,2-Tetra- .*.
chloroethyl) th1o]-4-cyelo- ft
hexene-l,2-d1carbox1n»1de (I
N-[(Trichloromethyl)th1o]-4-
cyclohexene-l,2-d1carbox1m1de J
U^l
p
}l-S-CCI,CHCI,
b
o
| N-S-CCIj
-V
1-Naphthyl N-methylcarbamate O-C-N-CH
r^^)
^J^J
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
46 Carbendazim (Derosal)
2-(Methoxycarbonylam1no)-
benzlmldazol
N
\-NCOOCH3
ro
o
co
47 Carbetamlde (Legurame)
N-Phenyl-1-(ethylcarbamoyl) •
ethylcarbamate, D Isomer
o HO
0 I II
C6H, -N -C -O-C -C -N -C,Hj
A CH3 H
48 Carbofuran (Furadan)
2,3-D1hydro-2,2-d1methyl-7-
benzofuranyl methylcarbamate
49 Carbophenothion (Trlthlon)
S-C(p-Chlorophenylthlo)-
methyl]0,0-d1ethyl
phosphorodithloate
-CHj-S-PtOCjH,),
s
50 Carboxin (Vitavax)
5,6-D1hydro-2-methyl-l,4-
oxathl1n-3-carboxanl11de
cc
O H
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS DY SUDCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
51 CDAA (Randox)
N.N-D1al lyl-2-chloroacetamlde
o
ro
o
52 CDEC (Sulfall ate)
2-Chloroallyl dlethyldlthlo-
carbamate
s ci
(CjHjJjN-C-S-CHjC-CH,
53 Chloramben (Amiben)
3-Am1no-2,5-d1chloro-
benzolc acid
COOH
54 Chloranll (Spergon)
2,3,5.6-Tetrachloro-l,4-
benzoqulnone
*ci
55 Chlorazlne
2-chloro-4,6-bls(dlethylamino)-
1,3,5-trlazlne
C2H5,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS PY SUBCATEGQRY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
56 Chlordecone (Kepone)
Decachloro-octahydro-1,3,
4-metheno-2H-cyclobuta[cd]-
pentalen-2-one
ro
o
in
57 Chlordlmeform
(Chiorphenamldine)
N'-(4-Chloro-o-tolyl)-N, N-
d1methy1formam1d1ne
Cl
58 Chlorfenvlnphos (Supona)
59 Chlormephos (MC 2188)
2-Chloro-l-(2,4-d1ch1orp-
phenyl)vinyl d1ethyl
phosphate
S-Chloromethyl o,o-d1ethyl
phosphorothiolothionate
o
9 O-WOCjHj),
H
60 Chlorobenzene
Monochlorobenzene
Cl
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
61 Chlorobenzilate
(Acarben)
Ethyl 4.4'-dichlorobenzJ|ate
OH
o/Vi/Va
I \=s
COOC,H,
ro
o
Chlorodane (Tech.) and
Components
1,2,4,5,6,7,8,8-Octa-
chloro-2,3,3a,4,7,7a-hexa-
hydro-4,7 methanoindene
63 Chloroneb (Demosan)
t.4-D1chloro-2,5-d1meth-
oxybenzene
ci
CH3O
OCH,
ci
64 Chloropropylate
Isopropyl 4,4'-diChlorobenzilate
CH3 CH3
65 Chiorothaionll (Daconil 2787) 2,4,5,6-TetrachlorolsQRh*
thalonltrlle
CN
CN
*=/ *ci
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name.
Structure
66/ Chlorpropham (CIPC)
Isopropyl N-(3-chlorophenyl)
carbamate
H-N-C
-O-CH(CH,)j
ro
O
67 Chlorpyrlfos (Dursban)
o,o-Diethyl o-(3,5,6-tr1
chloro-2-pyr1dyl) phos-
phorothioate
Cl'X.^O-PtoCjH,),
S
68 Chlorthiophos (CMS 2957)
o,o-D1 ethyl 0-2,4,5-
D1 chl oro- (methyl thlo)
phenyl thionophosphatc
ct
69 Clonitralid (Bayluscide)
2',5-D1chloro-4'-n1trosali-
cylanllide ethanolamlne
O-C
NOfNH2(CH,),CH
70
4 - CPA
4-chlorophenoxyacetlc acid
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUDCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
71 Coumaphos (Co-Ral)
o-(3-Chloro-4-methyl-2-oxo-
2H-l-benzopyran-7-yl)
0,0-d1ethyl phosi horothioate
(C,HjO),P-0
;0
Cl
CH,
ro
o
00
72 Crotoxyphos (C1odr1n)
73 Crufornate (Ruelene)
74 Cyanazlne (Bladex)
75 Cycloate (Ro-Neet)
a-Methylbenzyl 3-hydroxy-
crotonate dimethyl phosphate
0-(4-tert-Butyl-2-chlorophenyl)
0-methyl
N-methyl phosphoroamldate
2-[(4-Chloro-6-(ethyl ami no)-
s-tr1az1n-2-yl) amlno]-
2*methlyprop1on1tr1te
S-Ethyl ethyl eyelohexylthlo-
carbamate
9 9Hj
H-C-(CH3>0-C-C-C-0-P(CH30),
n
O
Cl
O
O-P-OCHj
NHCM,
V V
N
N—C(CH3),
N
N=/
VN-CH3CH,
H
OC,H5
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
76 Cyclohex1m1de (Actldlone)
3[2-(3,5-D1methyl-2-oxo-
cyclohexyl)-2-hydroxy-
ethy1]glutar1m1de
ro
o
vo
77 Cyprazlne (Outfox)
2-Chloro-4-(cyclopropylamino)-
6-(1sopropylamino)-s-tr1az1ne
ci
(CHj)jC-N
H H
H
78 Cythloate (Proban)
o,0-D1methyl 0-p-sulfa-
moylphenyl phosphoro-
thloate
cn,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
81 2,4-DB, Add and Esters
4-{2,4-D1chlorophenoxy)
butyric add, and esters
0(CH,)jCOOH
Cl
ro
»-«
o
82 DBCP (Dlbromochloropropane) 1,2-01bromo-3-chloropro-
pane and related halogen-
ated C3 hydrocarbons
CH,Br-CHBr-CHjCI
83 DCPA (Dacthal)
Dimethyl 2,3,5,6-tetra-
chloroterephthalate
CO,Ch3
ci
84 DD (Nemex, Vidden)
Tech. mixture of 1,3-dichloropropene
and l,2-d1chloropropene
CH2CI-CH-CliCl
CH2C1-CHC1-CH3
85 DDjy, Mixed, Tech. (TOE,
lothane) and Metabolites
2,2-B1s(chloropheny)-l,
l-d1chloroethane and
related compounds
-------
TABLE X-l
INDESC OF PESTICIDE COMPOUNDS
EY SUBCATEGORY
SUDCATEGORV 1-ORGANIC PESTICIDES CHEMICALS
Common
Structure
J6) ODE
l8l-d1chloro-2,2-d1(chlorophenyl)
ethene
ro
W) DDT, Mixed, (Techo) and
Metabolites
Dlchloro dlphenyl trlchloroethane
of metabolites of ca. 80%
and 20% o,£')
a
H
ici^
88
DEET
NN-d1ethyl-m-toluamlde
Me
CO.NEI,
89 DEF
S,S9S-Tr1butyl phosphoro
trlthloate
[90) Demeton-o (Systox-o)
{Thlono)
0,0-01 ethyl o-2-[(ethylthlo-
ethyl]phosphoroth1oate
(Thiono)
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
((91) Demeton-S (Systox-S)
(Thiolo)
o,o-D1ethy1 S-2-[(ethlyth1o)-
ethyl]phosphoroth1oate
(Thiolo)
ro
i—•
ro
92 Demeton-S-Methyl
5-2-ethlyJ.:,1oethyl-0,0-d1methly
phosphorothloate
93 Demeton-S-Methylsulfone
5-2-ethylsulphonylethyl 0,0-d1methyl
phosphorothloate
94 Desmedlpham (Betanex)
Ethyl m-hydroxycarban1late
carbanllate (ester)
9 H
n i
O-C— N
H ' O
95 Desmetryne (Semeron)
2-Methylthlo-4-methylamino-6-
1sopropylami no-s-trlazlne
v
S-CHo
CU3
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
96 D1a11for (Torak)
s-(2-Chloro-1-phthal1mi do-
ethyl )0,0-d1ethyl
phosphorodlthloate
t CH3CI S
N — C— S— P(OCjH5)7
o
CO
97 Dial late (Avadex)
S-(2,3-D1chloroally1)di1so-
propylthiocarbamate
o
[(CH,),CH| N-c-s-CH2-cci=-CHci
98 Dlaphene (Bromsalans)
3,4,5-Tr1bromosa11cyan1l1de,4,5-
d1bromosal1cylan111de and other
bromlnated sa!1cy1an111des
^f§) D1az1non (Spectradde)
0,0-01 ethyl o-(2-1sopropyl-
6-methyl-4-pyr1m1dlnyl)
phosphorothloate
H
IOO) Dlcamba (Banvel D)
2-Methoxy-3,6-d1chloro-
benzoic add
OH_,P
OCH,
//X
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
101 Dlchlobenll (Casoron)
2,6-D1chlorobenzonltrlle
PO
102 Dlchlofenthion (VC-13)
o-2,4-D1chlorophenyl 0,0-
d1ethyl phosphorothioate
103 D1chlone (Phygon XL)
2,3-D1chloro-l,4-naphtho-
qulnone
(104/ Dichloran (Botran)
2,6-Q\chloro-4-nltroanl11ne
NH,
105 Dlchlorbenzene, ortho (ODB) 1,2-Dlchlorobenzene
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
ro
H-"
in
106 Dichlorobenzene, Para (PDB) 1,4-Plchlorobenzene
107 Dlchloroprop (2,4-DP)
2-(2,4-01chlorophenoxy)-
proplonlc add
Q
-CH,
9— C -COOH
fl
Cl
108 Dlchloropropene (Telone) 1,3-plchloropropene
If V c!
H-C-C-C-H
H
109 Dlchlorvos (DDVP)
2,2-D1chlorov1nyl dimethyl
phosphate
CljC-CH-O-P(OCH3),
lio) Dlcofol (kelthane)
1,1-B1s (p-chlorophenyl)-2,
2,2-trlchloroethanol
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
111. Dlcrotophos (B1dr1n)
3-Hyroxy-N,N-d1methyl-c1s
crotonamlde dimethyl phosphate
CH3
ro
/ff2) DleldMn (HEOD)
1,2,3,4,10,10-Hexachloro-
exo-6,7-epoxy-l,4,4a,5,6,7,
8,8a-oct^,./dro-l,4-endo,
exo-5,8-d1methanonaphthalene
H g
113 Dlenochlor (Pentac)
Perchlorobl (cyclopenta-2,4-d1en-
1-yl)
ci
ci
CI
114 01ethyl Phosphate (DEP)
o,o-D1ethyl phosphate
P—OH
115 Dlfenzoquat (Avenge)
l,2-D1methyl-3,5-d1phenyl-
lH-pyrazol1um methyl sulfate
Q
-
CHjOSOj
H3C CH3
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1.-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
116 Oiflubenzuron
(Th-6040,D1m1l1n)
1-(4-Chloropheny1)-3-(2,6-
d1f1uorobenzoyl)urea
H H
=H O O
117 D1meth1rimol (Milcurb)
ro
5-n-Butyl-2-dimethylamino-4-
hydroxy-6-methylpyrlmld1ne
H3C
N N
Y
N(CH3)?
118 Dlmethoate (Cygon)
0,0-D1methyl S-(N-methyl-
carbamoylmethyl) phos-
phorodlthloate
,/s-avco-NH-cn.
l<-R 3
119 Dimethyl Phosphate (DMP) o,o-D1methyl phosphate
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
ro
»—•
oo
121 Dlnocap (Karathane)
2-(1-Methylheptyl)-4,6-
dlnltrophenyl crotonate
9 CH, 9 CH:.
C-CH=CH O-C-CH=CH
ond
NO, CBH,7
20 ratio
122 Dlnoseb (DNBP)
123 Dlnoseb Acetate
(Aretlt)
124 Dloxathlon (Delnav)
125 Dlphcnamld (Enide)
2-( sec-Butyl )-4,6-d1n1trophenol
2-( sec-Butyl )-4,6-d1n1tro-
phenyl acetate
£,£'-p-D1oxane-2,3-d1yl
o,o-diethyl phosphorodi-
thloate (els and trans Isomers)
N,N-D1methyl-2,2-d1phenyl-
acetamlde
OH CHj
°jNT^J A
NO,
I ' "
.##k
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Convnon Name
Chemical Name
Structure
126 Dlpropetryn (Sancap)
2-{ethylth1o)-4,6-b1s-(1sopropylami no)•
1,3,4-triazine
-CH2CH3
ro
127 Dlquat D1bromide
6,7-D1hydrod1pyr1do[l,2-
a:2',l'-c]pyraz1d11n1um
dlbromide, monohydrate
2Br-
•HjO
128) Dlsulfoton (D1-Syston)
0,0-01 ethyl S-[2-(ethylthlo)-
ethyl]phosphorodlth1oate
129 3Uh1anon
2,3-D1carbon1tr1le-l, 4
dUhlaanthraqulnone
o
t
O
Dluron
3-(3.4-D1chlorophenyl)-
dimethyl urea
a
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
131 DNOC
4.6-D1n1tro-o-cresol
NO,
132 Dodine (Carpene)
ro
no
O
n-Dodecylguan1d1ne acetate
NH
D
Ci,H,,-NH-C-NH}- CHrCOOH
133 Drazoxolon (Ganodde)
4-(2-Chlorophenylhydrazono) •
3-methyl-5-1soxazolone
—CM.,
134 Dursban
o.o-DIethyl o-(3,4,6-
Trl-chloro-2-pyridyl)
pt.osphorothloate
Endosulfan (Thlodan) and
Isomers
6,7,8,9,10,iO-Hexachloro-
l,5,5a,6,9,9a-hexahydro-6,
9-methano-2,4,3-benzod1oxa-
thlepon 3-oxlde
s=o
CH-O
*CI
-------
TABLE X-l
OF PESTICIDE COMPOUNDS
BY SUBCATEGOHY
SUBCATEGORY 1-ORGANIC PESTICIDES'CHEMICALS
Common Name
Chemical Name
Structure
136) EndHn
1,2,3,4,10.10-Hexachloro-
6,7-ef)oxy-I,4t4a,5,6,798,
8a-octahydro-l,4-endo,endo-5,
8-d1methanonaphtha1 ene
t«o
137 EPM
0-Ethyl 0-£-n1trophenyl
phenylphosphonothloate
OC3H
138 EPTC (Eptam)
S-Ethyl dlpropylthlocarbamate
CjHrS-C-N{C3H7),
139 Erbon (Baron)
2-(2,4,5-Tr1chlorophenoxy)
ethyl 2,2-d1chloroprop1onate
140 Ethalfluralln
N-ethyl-N-(2-methy)
,N°S
CH
Et
NO.,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
14] Ethephon (Cepha)
(g-Chloroethyl)phosphonlc acid
o
CICH,CH2p'OH)J
142 EtMolate (Prefox)
ro
ro
ro
S-Ethyl d1ethylthtocarbamate
(C,Hj),N-C -S-C,Hj
n
o
143 Ethlon
0,0,0',0-Tetraethyl S,S'-
methylene blsphosphorodl-
thloate
T
(CjHjOjP-S-CHj-S-PlOCjH,),
144 EthlHmol (Milstem)
5-Butyl-2-(ethlyam1no)-6-
hydroxy-4-methylpyrlmld1ne
145 Ethoprop (Mocap)
0-Ethyl S,S,-d1propy1
phosphorodlth1oate
C3H7-S>,0-C2H5
P
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAfrOC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
146 Ethylene D1bromide (Bromo-
fume, Dowfume W-85, So1l-
brom-85, EDB, Nephls)
l,2-d1bromoethane
ro
ro
CO
147 Famphur
0-[p-(dimethylsulfamoyl)
phenyl]0,0-dimethyl
phosphorothloate
148 Fenac
2,3,6-THchlorophenyl-
acetlc add
a ci
CH,-COOH
149 Fenamlnosulf (Dexon)
p-(Dimethyl ami no)benzenediazo
sodium sulfonate
150 Fenltrothlon (Sum1th1on) 0,0-Dlmethyl 0-(4-n1tro-
m-tollyl)phosphorothioate
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
151 Fensulfothlon (Dasanlt)
0.0-D1ethyl 0-[p-(methyl-
sulf1nyl)phenyl]
phosphorothloate
c2n5cx
152 Fenthlon (Baytex)
ro
ro
0,0-D1methyl 0-[4-(methyl-
th1o)-m-toV!]
phosphorothloate
s
\
CH,
(153 JFenuron
1,1-dimethyl-3-phenylurea
H O
N-C-IMCH,),
154) Fenuron-TCA (Urab)
1,1-dimethyl-3-phenyluronium
trlchloroacetate
f V-N—c — N(CH3>2
Cl O
I II
ci-c-c
I II
Cl O
155 Ferbam
Ferric dimethyldlthlocarbamate
ij
(CH3),-N-C-S-
Fe
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUDCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
156 Fluchloralin (Basalln)
N-Propyl-N-(2-chloroethyl)•
a,a,a-tr1fluoro-2,6-
dlnltro-p-toluldine
/ vCH,-CHrCI
ro
PO
in
157 Fluometuron (Cotoran)
1,l-D1methly-3-(a,a,a-tr1-
fluoro-m-tolyl)urea
158 Fluorldamld (Sustar 2-S)
N-4-Methyl-3-[(l,l,l-tr1-
f 1 uoromethyl)sulfonyl]
aminolphenyl]acetam1de
*-x
H-N-£-N(CHj)j
CF,
-0
NHCCHj
NHSO.CF,
CH,
159 Folex (Merphos)
Trlbutyl Phosphorotrlthiotte
(C4H|S),P
160 Folpet (Phaltan)
N-(Trlchloromethylthio)-
phthaHmlde
-P
N-S-CCIj
O
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
161 Fonofos (Dyfonate)
0-Ethyl S-phenyl ethyl -
phosphonodlthloate
/~\sJ:°£Hi
162 Formetanate HydrochloHde
(Carzol SP)
ro
PO
m[ [ (Dlmethlyami no)methyl ene]-
am1no]phenyl -^ethylcarbamate
hydrochlorlae
o
O-C-NH-CH3
H
40
N-i-NlCHj),
163 Formothlon (Anthlo)
o,o-D1methyl S-(N-methyl-N-
fonnylcarbamoyl-methyl)-
phosphorodlth1oate
CH3O.D'.S
CH3Ore-S-Clh -CO- Nr°'3
CH«0
164 Glyphosate (Roundup)
N-(Phosphonomethyl)glyc1ne
HO -C -CHj-N —CH,-P-OH
H OH
165 Glytac (EGT)
ethyleneglycolbls (trlchloroacetate)
CHo-O-CO-CCl3
tu2-o-co-cci3
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS
BY SUBCATEGORY
SUBCATEGORY INORGANIC PESTICIDES'CHEMICALS
Common Mami
Chemical Name
Structure
\166J Heptachlor
1,4,5,6,7,8,8-Heptachloro-
3a,4,7,7a-tetrahydro-40
7-methanolndene
I *c\
ro
ro
167 Hexachlorobenzene (HCB)
Hexachlorobenzene
a
168 Hexachlorphene (Nabac)
2-2'-Methylene b1s(3,4,6-
trlchlorophenol)
:i OH OH a
/VcH,-/\
Cl
CI
169 1-Hydroxychlordene
1-exo, HydroxV-4,5,6,7,8,
8-hexachloro-3a,4,7,7»-
tetrahydro-4(7-ittethano1ndene
••H~\J .
.JX rf OH C1
170 IBP (KUazin)
0,0-D11sopropyl S-benzyl
thlophosphate
-0 ,0
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY ^ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
171 loxynfl (Actrll)
4-Hydroxy-3,5-011odo-
benzonltrlle
CN
OH
ro
ro
oo
172 Isobenzan (TelodHn)
l,3,3a,4,7i7a-hexahydro-4,7-
methanol scl»enzof uran
ci
or
ci1
CCI2
CI
173 Isodrln
1,2,3,4,10,10-Hexachloro-
l,4,4a,5,8,8a-hexahydro-endo,endo-
1,4:5,8-dlmethanonaphtha!ene
See Aldrln which 1s
the endo-exo Isomer
174 Isopropalln (Paarlan)
2,6-D1n1tro-N,N-d1propy-
loumldlne
CHjCHj),
175 Karbutllate (Tandex)
m-(3,3-dlmethylureldo)phenyl
tert-butylcarbamate
O-C-N-C(O
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
ro
ro
Common Nam®
176 Lamprecide (TFN)
177 Lenadl (Venzar)
178 Leptophos (phosvel)
179 Le thane 384
Chemical Name Structure
O— No
3-Tr1fluoromethyl-4-n1tro- JL
phenol, sodium salt (| |
NOi
H
3-Cyc1ohexyl-6,7-dihydro- ^^^ ^ o
IH-cyclopentapyrlmidlne- i if ^f
2,4(3H,5H)-d1one I B & (T)
V
o
0-(4-Bromo-2,5-d1chloro- s Q
phenyl )0-methyl phenyl- / yp-o-fV61-
phosphonothloate \=^^CWj\_..^r
b-Butoxy-B ' -thl ocyanodl ethyl
A^tia ¥• » //-ij \ C r*KJ
\QQ) Llndane
12,22,38,42,52,68-
Hexachlorocyclohexane
Cl
ei
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
Unuron (Lorox)
3-(3,4-D1chlorophenyl)-l-
methoxy-1-methyl urea
i
N-C-N
_ ,!, -0-CH,
Cl
ro
CO
o
\182J Ma lathi on
Dlethyl mercaptosucclnate,
s-ester with 0,0-
dimethyl p«iosphorodithioate
s H
(CHpJjP-S-C-COOCjH,
CH,-COOC,H,
183 Mecarbam (MC-474)
S-[N-Ethoxycarbonyl-N-
methylcarbamoylmethyl]0,0-
dlethly phosphorodlthloate
C2H5O'r^-CH2-CO-N-CO-0
CH
184 MCPA, MCPB, MCPP, Acids
and esters
(4-Chloro-2-methylphenoxy)-aceti c
acids and esters
ci
185 Menazon (Azldlthlon)
S-[(4,6-D1am1no-l,3,5-
tr1az1n-2-yl)methyl]0,0-
dlmethyl phosphorodlthloate
N
NH,
(CH30),P-S-CHJ-
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATE60RY
SUDCATEGORY 1-ORGATOIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
186 Meobal
3,4-Xylyl methylcarbamate
O-CO-NH-CH3
CH,
187 Mephosfolan (Cytrolane)
ro
CO
P,P-D1ethyl cyclic propylene
ester of phosphonodlthlolmldo-
carbonic add
188 Metalkamate (Bux)
Mixture of m-(1-ethylpropyl)-
phenyl methylcarbamate and m-
(1-methylbutyl) phenyl methyl
carbamate (ratio of 1:3)
OCONHCHj
H
H-dCHjCH,),
189 Metham (SMDC)
Sodium N-methy1d1th1ocarbamate
CH,-NH-i-S-No
190 Methamldophos (Monitor) 0-S-01methyl phosphoramldo-
thloate
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
191 Methazole (Probe)
2-(3,4-D1chlorophenyl)-4-Methyl-l,2,4
oxad1azol1d1ne-3,4,-dione
ci
OJ
ro
192 MethldatMon (Supraclde)
Methtocarb (Mesurol)
S-[(2-methoxy-5-oxo-delta-
l,3,4-th1ad
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
Methoxychlor (Marlate)
2,2-B1s (p-methoxyphenyl)-
1,1,1-trlchloroethane
197 Methyl Bromide
ro
CO
CO
Bromomethane
CH.Ur
198 Metoxuron (Dosanex)
3-(3-Chloro-4-methoxyphenyl) •
1,1-dimethyl urea
Cl
CHjO
199 Metr1buz1n (Sencor)
4-amino-6-tert-butyl-3-
(methylth1o)-l,2,4,tr1az1ne-5-one
o
-CH3
200 Mevlnphos (Phosdrln)
Methyl 3-hydroxy-alpha-
crotonate, dimethyl phosphate
HO
C-^
CH, OCHj
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
(201/ Mexacarbate (Zectran)
4-D1methylamino-3,5-xylyl
methylcarbamate
o H
C-N-CH3
NCH,),
202 MH (maletc Hydraztde)
ro
oo
6-Hydroxy-3-(2H)-pyr1dazlnone
OH
N-H
20T) Ml rex (Dechlorane)
DodecacHlorooctdhydro-1,
3,4-metheno-2H-cyclo-
buta [cd] pentalene
204 Mollnate (Ordramj
S-Ethyl hexahydro-lH-azeplne-
l-carboth1ate
0-C-S-C,H,
205 Monallde (Potablan)
N-(4-Chlorophenyl)-2,2-
d1methylpentanamlde
H
N-C-C-CHt-CHj-CH,
II I
O CH3
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
206 Monocrotophos (AzodHn)
Dimethyl phosphate of 3-
hydroxy-N-methyl-cls-
crotonamlde
O-O H
CHj-C=C-C=O
H-N-CHj
207 MonoHnuron (Arestn)
rv>
OJ
in
3-(p-Chlorpheny1)-methoxy-
1-methyl urea
H O O— CH3
Cl-/ \-N-C-N-CH,
\==/
Monuron
3-(p-Ch1orpheny1)-l,l-
dlmethyl urea
H-N-C-N(CHJ,
?09) Monuron-TCA (Urox)
3-(p-Chlorophenyl)-l,l-di-
methyl urea trlchloroacetate
o
H-N-C-N*H(CH,),'OCOCIj
210 Morphothion (Ekatln M)
0,0-Dlmethly S-(morpholino-
carbonylmethyl) phos-
phorodithloate
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBGATEGORY
SUDCATEGORY 1,-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
211 Naled (Dibrom)
l,2-D1bromo-2,2-d1chloror
ethyl dimethyl phosphate
?
(CHjO),P-O-C-CCI3Br
Br
212 Naptalam, Sodium Salt
ro
CO
en
Sodium N-1-naphthylphthamate
o o
it ii
NoO-C C-
H
-N
213 Naphthalene Acetamlde
1-Naphthalene-acetamide
214 Napropamlde (Devrlnol)
2-(a-Naphthoxy)-N,N-d1
ethylproplonamide
O-CH-CN(CjHj)2
Ha Neburon
l-(n-Butyl)-3-(3,4-d1chloro-
phenyl)-l-methyl urea
H-N-C-N-C4H,
c
ci
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY INORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
216 NUrapyrln (N-Serve TG)
2-Chloro-6-tr1chloro-
methylpyMdlne (and re-
lated chlorinated pyrldlnes)
217 Mitral in (Planavln)
ro
CO
4-(Methylsulfonyl)-2,6-
dl n1tro-N,N-d1propylan111ane
NO,
NO,
218 NUrofen (TOK)
2,4-DIchlorophenyl-p-
nltrophenyl ether
a
NO,
219 Norflurazon (Evltal)
4-Chloro-5-(methyl ami no)-2-
(a,a,a-tr1fluoro-m-
toyl)-2H)-pyr1daz1none
,CH,
"H
220 Oxadlazon (Ronstar)
2-tert-Butyl-4-(2,4-d1chloro-
5-1sopropoxyphenyl) delta-
l,3,4-oxad1azo!1n-5-one
V
(CH,)}C-0
b-~\ T II
c,-f "V-N— N
V /
T II
Cl
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
ro
co
oo
221 Oryzalln (Surflan)
222 Oxamyl (Vydate)
3,5-D1n1tro-N4,N4-dipro-
pylsulfanllamTde"
Methyl N',N'-d1omethyl-N-
[(methylcarbomoyl) oxy]-l
thlooxamimldate
o
NOj
N(C3H7),
o —s
NO,
O H
(CH,)7N -C -C =N-0 -C -N - CM,
SCH3
223 Oxydemeton Methyl
S^[2-(ethylsulf1nyl)ethyl
0,0-dimethyl phos-
phorothloate
Cl!30.
'
224 Oxyth1oqu1nox (Morestan) 6-Methyl-2,3-qu1noxalined1-
thlol cycllc-S, S-d1th1o-
carbonate
H,C
c=o
225 Paraquat D1chloride
(Gramoxone)
l,l'-Dimfrthyl-4,4'-b1
pyrldHlum dlchlorlde
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
ro
u>
<£>
(26) Parathion Methyl
127) Parathion Ethyl
228 Partnol (Parnon)
>2|> PCNB (Qulntozene)
0,0-D1methyl 0-p-n1tro-
phenyl phosphorothloate
0,0-01 ethyl-0-p-nltro-
phenyl phosphorothloate
a,a-B1s (p-chlorophenyl)-
3-pyridlne methanol
Pentachloronltrobenzene
s
P(OCHa),
-P(OC:.H,),
OH'
t-/ Vc
ci
Cl
NOi
•a
230 PCP and Us salts
2,3,4,5,6-Pentachlorophenol
OH
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUUCATEGORY
SUDCATEGORY INORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
231 Pebulate (Tillam)
S-Propyl butylethylthlo-
carbamate
O CH2CHj
ro
*»
o
232 Perfluidone (Destun)
1,1,l-Tr1fluoro-N-[2-methyl-
4-(phenylsulfonyl) phenyl]
methanesu"! lonamlde
oo
^=S CH,
MHSO,(.
233) Perthane
l,l-D1ehloro-2,2-b1s
(p-ethylphenyljethane
234 Phenmedlpham (Betanal)
Methyl m-hydroxycarbanllate
m-methy!carbanl1 ate
CHj-O-C-N-H
235 Phencapton
0,0-D1ethyl-S-(2,5-di-
chlorophenylthlomethyl)
phosphorothlolothionate
Cl
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
236 Phenothiazlne
D1benzo-l,4-th1az1ne
INJ
237 Phorate (Thlmet)
0,0-Diethyl S-[(ethylthlo)-
methyl]phosphorod1th1oate
238 Phosalone (Zolone)
S-[(6-Chloro-2-oxo-3-
benzoxazoli nylImethyl]0,
0-diethy1 phosphorodlthloate
o
A
N-CHjS-KOCjH,),
s
CI
239 Phosfolan (Cyolane)
P,P-D1ethyl cyclic ethylene
ester of phosphonod1th1o1m1do-
carbonic acid
240 Phosmet (Imldan)
0,0-D1methyl-S-phthal1ml do-
methyl phosphorodlthloate
H |
N-C-S-P(OCHj),
H
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
241 Phosphamidon (Dlmecron)
2-Chloro-N,N-d1ethyl-3-
hydjoxycrotonaml de
dimethyl phosphate
242 Plcloram (Trodon)
4-Am1no-3,5,6-tr1chloro-
plcollnlc add
NH,
243 Plperalln (Pipron)
3-(2-Methylp1per1d1no)prppyl-3,4
dlchlorobenzoate
N(CH,lp-C
Cl
244 Pirlmicarb (Pirlmor)
2-(Dimethylam1no)-5,6-
dimethyl-4-pyrimid1nyl
dimethylcarbamate
CH.
i ,
i-C-N(GH3)3
245 Plrlmlphos Methyl (Actelllc) 0-[2-{D1ethylam1no)-6-
methy 1 -4-pyr1m1 d1 r\yl ]
0,0-d1methyl phosphorothloate
N(C,H5)7
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-OR6ANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
246 PIHmlphos Ethyl (Pr1m1cid)
0-[2-(D1ethy1ami no)-6-
methyl-4-pyr1m1d1nyl]
0,0-dlethyl phosphorothtoate
CM,
247 Potassium Azlde (Kazoe) Potassium azlde
ro
£»
CO
K—
248 Profluralln
N-cyclopropylmethyl-2,6-d1n1tro-N-
propyl-4-tr1f1uoromethylan111ne
NO
« CH
/
N
NO
249 Promecarb (Carbamult)
m-Cym-5ylmethylcarbamate
CH(CH,),
o H
II l
O-C-N-CH,
CH,
250 Prometon (Pramltol)
2,4-01s(1sopropylami no)-
6-methoxy-s-tr1az1ne
H H
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
25V Prometryn (Caparol)
252 Pronamlde (Kerb)
ro
2,4-B1s(1sopropylam1no)-
6-(methylthio)-s-tr1azine
3,5-D1chloro-N-(l,l-d1meth.yl
2-propynyl) benzamide
SCH3
HI j| H
H H
Cl
H CH3
253 Propachlor (Ramrod)
2-Chloro-N-1sopropylacetani1Ide
N-C-CH,CI
6
254 Propanll (Rogue)
3,4-Dichloroprop1onan1Hde
H
255 Propazlne (MHogard)
2-Chloro-4,6-b1s(1sopro-
pyl amino)-s-tr1azlne
a
H H
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
(256) Propham (IPC)
Isopropyl N-phenylcarbamate
>-CH(CH3),
ro
-P»
en
2&z) Propoxur (Baygon)
o-Isopropoxyphenyl N-methyl-
carbamate
9V
,0-C-N-CH,
( \0-dCHA
\='/ H
258 Prosulfln
N-cyclopropylmethyl-2,6-d1n1tro-
N-propyl-4-tr1thlomethylan111ne
NO.
s.c
w V
259 Pyracarbolld (SIcarol)
3,4-Dihydro-6-methyl-N-phenyl-
2H-pyran-5-carboxam1de
CH3
260 Pyrazon (Pyramln)
5-Ami no-4-chloro-2-phenyl
3(2H)-pyridaz1none
Q P
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUDCATEGORY
SUOCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
261 Pyrazophos (Afugon)
2-(0,0-01 ethyl thionophos-
phoryl)-5-methyl-6-ca be-
thoxy-pyrazolo(l,5a)-
pyrlmldlne
o
CjHjO-C
tv>
-P»
en
262 Quinalphos (Ekalux)
0,0-Dlethyl C-tquinoxa-
Hnyl-(2)] thionophosphate
263 Ronnel
0,0-D1methly 0-(2,4,5-trl-
chlorophenyl) phosphorothloate
a
— a.
264 SaHthion
2-Methoxy-4H-l,3,2-benzod1-
oxaphosphorln-2-sul f1de
CH30;p.
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
265 Secbumeton (Sumltol)
2-sec-butylamino-4-ethylamino-
6-methoxy-l,3,5-s-tr1az1ne
266 Sesone
ro
2-(2,4-D1chlorophenoxy)ethanol hydrogen
sulfate, sodium salt
'Z67/S1duron (Tupersan)
l-(2-Methylcyclohexy1)-
3-phenylurea
I /~~\
NH-C-NH-/ y
CH,
Sllvex. Acid [2-(2,4,5-TP]
and Esters
2-(2,4,5-Tr1chlorophenoxy)
proplonlc add, and esters
O-CH-COOH
a
269 Slmazlne (Prlncep)
2-Chloro-4,5,6-b1s(ethyl-
am1no)-s-tr1az1ne
ci
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
270 Slmetone (Gesadural)
2,4-b1 s(ethyl amino)-6-methoxy
1,3,5-trlazlne
ro
-P.
00
271 Simetryne (Gy-bon)
2-Methylth1o-4,6-b1s-ethylamino-
s-tr1az1ne
CH3
272 Sodium Azlde (Smite)
Sodium Azlde
No —
273 Sodium Pentachlorophenate
(Dow1c1de G)
2,3,4,5,6-Pentachloro-
phenol, sodium salt,
monohydrate
274 Stlrofos (Gardona)
2-Chloro-l-(2,4,5-tr1chloro-
phenyDvlnyl dimethyl
phosphate
Na.H/)
,»
CIHC
Cl
:»c-o-PDCHj),
a
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
275 Streptomycin Sulfate
(Agri-Strep)
D-Streptamlne, 0-2-deoxy-2-
(methyl amino)-a-l-gluco-
pyranosyl-(1-2)-0-5-deoxy-
3-C-formyl-a-1-lyxofuranosyl-
(1-4)-N-V-b1s(am1no1mmo-
methyl-, sulfate (2:3) (salt)
UN l«V -ii.r mi,
1,11-CaliN-/ Von
MO-
ro
•t*
276 Strobane
PolychloH nates of cam-
phene, plnene and related
terpenes
277 Sureclde (S4087)
O-(p-Cyanophenyl) 0-ethyl
phenylphosphonothloate
C3H50-P
CN
(278; Swep
methyl -3 ,4-d1 chl orophenyl carbamate
Cl
OCH
279 2,4,5-T, Add
Esters, and Salts
2,4,5-Tr1chlorophenoxy-acetlc
add, esters, and salts
"CHjCOOH
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
280 4-(2,4,5-TB)
4-(2,4,5-TMchlorophenoxy)
butyric acid
ro
en
o
281 2,36-TBA
2,3,6-Trlchloro benzole acid
and related compounds
COOH
282 TCA and Us salts
trlchloroacetic acid and
Its sodium salt
CC13-COOH
C03-COOW
283 Tebuthluron
l-(5-tert-butyl-l,2,4-th1a-
d1azol-2-y1)-1,3-d1methylurea
B"4I JJ
I.CNHMo
284 Tecnazene (Fusarex)
2,3,5,6-Tetrachloro-
nltrobenzene
NOj
'ci
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUDCATEGORY 1-ORGAN1C PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
285 Temephos (Abate)
0,0-D1methyl phosphoro-
thloate 0,0-d1ester with
4,4'-th1od1phenol
PO
in
286 TEPP
Tetraethyl pyrophosphate
287 Terbadl (Slnbar)
3-(tert-Butyl)-5-chlor-6
methyluracil
H
CHTNT
cHx/N-
II
288 Terbufos (Counter)
5-tert-butylthlomethyl 0, 0-dimethly
phosphorodlthloate
CH
CH
289 Terbuthylazlne (GS-13529)
2-tert-butylam1no-4-ch1oro-
6-ethylam1no-l ,3,5-tr1az1ne
ct
C,H,
CH,
/c^
H CH
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
290 Terbutryn (Igran)
2-(tert-Butylami no)-4-(ethyl
am1no)-6-(methylth1o)-s-
tHazlne
S-CHj
H H
ro
en
291 Terrazole
S-Ethoxy-3-tric1- -•'••o-
methyl-l,2,4-thiaa
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-QRGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
295 TMabendazole (Mertect)
2-(4'-Th1azolyl) benzlmldazole
en
CO
296 Thlofanox (DS-15647)
3,3-D1methyl-l-(methy1th1o)-
2-butamone 0-[(methyl ami no)-
carbony1]ox1me
O H
I! I
M-O-C-N-CH,
-S-Oh
297 Thlometon (Ekatln)
0,0-Dlmethly S-[2-(ethylth1o)
ethyl] phosphorodlthloate
(CHjO),P-S-C2H4-S-C,H1
298 Thlophanate
1,2-B1s(3-ethoxycarbonyl-2-
th1oure1do)benzene
NH-C-NH-C-0-C;Hj
NH-C-NH-
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
300 TMram (Arasan)
Tetramethylthluram dlsulfide
^r \
301; Toxaphene
ro
ui
A mixture of chlorinated camphene
compounds of uncertain Identity
(combined chlorine 67-69%)
302 Tr1ad1mefon (Bayleton)
l-(4-chlorophenoxy)-3,3-d1methyl-l
(1,2,4-tr1azol-l-yl)buton-2-one
ci
CH,
\\ I II I
A_O — C— C — C — CH
I I
N CH
sN '»
3°3 Triallate
S-(2,3,3-Tr1chloroallyl)-
dl1sopropylthlocarbamate
-C-S-CHjCCKCI,
304 Trlazophos (Hostathlon)
0,0-Dlethyl 0-(l-phenyl-
!H-l,2,4-tr1azol-3-
yDphosphorothloate
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY ^-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
305 TMchlorobenzenes (TCB,
TCBA, Polystream)
l,2,4-Tr1ch1orobenzene artd
1somers
ci
306 TMchlorofon (Dylox)
ro
en
en
Dimethyl (2,2,2-trlchloro-l-hydroxyethyl)
phosphonate
OH
307 2,4,5-Trlchlorophenol
(Dowlclde 2)
2,4,5-TH ch1 orophenol
a
308 Tridemorph (Callxln)
N-Tr1 decyl -2 ,6-d1methyl -
morphollne
t
C,;Hj7
309 Trletazlne (Gesafloc)
2-chl oro-4-ethyl ami no-6
d1 ethyl ami no- s-trl az1 ne
-------
TABLE X-l
INDEX CF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 1-ORGANIC PESTICIDES CHEMICALS
Common Name
Chemical Name
Structure
(Treflan)
a,a,a-Tr1fluoro-2,6-d1nitro-
N,N-dipropy1-p-to1uidine
CF,
ro
01
311 TrlfoHne (Cela W524)
N,N'-[l-4-P1peraz1nediyl-b1s-
(2,2,2-trichloroethylene)]-
b1s(formam1de)
ci,-c
CI,-C
H
-NH-CHO
•^NH-CHO
312 Vernolate (Vernam)
S-Propyl N,N-d1propylth1o-
carbamate
-------
TAULE X-l
INDEX OF PESTICIDE COMPOUNDS OY SUOCATEGORY
SUDCATEGORY 2 - METALLO-ORGANIC PESTICIDES
Common Name Chemical Name
Structure
313 Cacodyllc Acid
Dimethylarsinic acid
o
I
(CHj),A»—OH
314 Calcium Arsenate
ro
en
Calcium arsenate
315 Cryolite (Kryocido) Sodium Fluoaluminate
316 Cyhexatin
Tricyclohexytin hydroxide
/ V- SUCH
•» "^
317 Diphenyl Mercury
Diphenyl mercury
318 DSMA
D1sodium methanearsonate,
hexahydrate
CH.,-Ai(ONo),-6HjO
-------
TAULE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 2 - METALLO-ORGANIC PESTICIDES
Common Name Chemical Name
Structure
319 Ethylmercury Chloride
(Ceresan)
Ethylmercury Chloride
ro
(71
oo
320 Fentin Acetate (Orestan) TMphenyltln acetate
322 Lead Arsenate
Acid lead arsenate
—SnO-CO-CHj
c/
321 Fentin Hydroxide (Outer) Trlphenyltln hydroxide
pi
SnOH
323 Maneb
Manganous ethylene-bls-
(dlthlocarbamate)
H H s
i i y
H-C-N-C-S-
H-C-N-C-S-Mn-
i i ii
H H S
324 Methanearsonlc Acid (MAA) Methyl arsonlc acid
o
CHrAs(OHJ,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 2 - METALLO-ORGANIC PESTICIDES
Common Name Chemical Name
Structure
325 Methylmercurlc Chloride Methyl mercury chloride
CHj-Hg-CI
326 Methylmercurlc Iodide Methylmercury loldlde
ro
in
CH,HgI
327 MSMA (Bueno)
Monosodium acid methanearsonate
OH
328 Nabam
01 sodium ethylene b1s(d1th1o-
carbamate)
s
CH,-NH-C-S-Na
CHj-NH-C-S-No
ii
S
329
manganeous benzothlazyl
mercaptlde
330 °henylmercur1c Acetate
(Common name PMA)
Phenylmercury acetate
o
-0-C-CH,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
SUBCATEGORY 2 - METALLO-ORGANIC PESTICIDES
Common Name
Chemical Name
Structure
331 Phenylmercurlc Borate
Phenylmercury borate
•Hg-O-B(OH),
ro
O
332 Phenylmercurlc Chloride Phenylmercury chloride
rw-
333 Phenylmercurlc Hydroxide Phenylmercury hydroxide
HgOH
334 Phenylmercurlc Iodide
Phenylmercury Iodide
Hg-l
335 Vendex
Hexakls (B.B-dimethyl-
phenethyl)-d1stannoxane
336 Zinc Met1 ram
Mixture of [ethyl en el) Is (dlthlo-
carbamato)] zinc ammoniates
with ethylenebis [dithiocarbamic
acid] anhydrosulfides
tCH2N||-CS-S-S-CS-N-M-CII.Oy
where x * 5.2 times v
-------
IAHI.I-: x-i
INULX Ul: I'ESriUUE CUMI'OIHIIlS UY SIMOUi.GO.JY
,-_ HETALLO-OKCANIC PESTICIDE S
Common Name
Chemical Name
Structure
337 Z1ne.b
Zinc ethyleneb1sd1th1ocarbamate
«j
-S-£-NH-CH,
CH,-NH-C-S-Zn-
ro
338 Z1ram
Zinc dimethyldlthlocarbamate
-------
NON-CATEGORIZED PESTICIDES
Common Name
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
Chemical Name
339 Allethrln
2-Allyl-4-hydroxy-3-methyl
2-cyclopenten-l-one ester of
2,2-d1methyl-3-(2-methyl-
propenyl)-cyclopropane-
carboxyllc add
(CH,),C=CHCH O CHj
I NCH-C-O-Ar-CH,-CH=CH,
(CH,),-/
ro
CT»
ro
340 Benzyl Benzoate
Benzyl benzoate
HjC-O-CO
341 Blphenyl (Dlphenyl)
Biphenyl
ff \J/ \
342 Blsethylxanthogen
bis (ethylxanthlc) disulfide
CHj-CHj-O-C-S
343 Chi orophad none (Rozol)
2-[ (p-Chlorophenyl) phenyl-
acetyl]-l,3-lndandlone
344 Coumafuryl (Fumarln)
3-(a-Acetonylfurfuryl)-
4-hydroxycoumar1n
rti
CH
i=o
CH,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
NON-CATEGORIZED PESTICIDES
Common Name
Chemical Name
345 Dimethyl Phthalate
Dimethyl Phthalate
COOCHj
345 Diphacinone
ro
o>
CO
2-01phenylacetyl-1,3-1ndandione
347 Endothall, Add
7-Oxabicycl0(2.2.1)heptane
2,3-d1carboxy11c acid
monohydrate
COOH
348 EXD (Herblsan)
D1 ethyl dithloblsUhlono-
formate)
C2HrOC-S-S-CO-C3H,
s s
349 Glbberelllc Acid
G1bb-3-ene-l,!0-d1carboxylic
ac1d,2,4a,7-trihydroxy-l-
methyl-8-methylene-1,4a-
lactone
1 COOH CH,
350 , Methoprene (Altosid)
Isopropyl (2E,4£)-ll-methoxy-
3,7,ll-tr1methyl-l,4-
dodecadienoate
9|%CH-O-CO-CH=C-CH=9! ,
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS BY SUBCATEGORY
NON-CATEGORIZED PESTICIDES
Common Name
Chemical Name
Structure
351 NAA (Naphthalene Acetic Acid) 1-Naphthalene acetic acid
CH,COOH
po
-P.
352 Phenylphenol (Dowlclde 1) o-Phenylphenol
OH
353 Plperonyl Butoxide
a-[2-(butoxyethoxy)ethoxy]
4,5-methylenedtoxy-2-
propyltoluene
H'C«
354 Proparglte (Omlte)
2-(p-tert-Butylphenoxy)cyclo-
hexyl2-propynyl sufllte
O-VrO-CH,-C»CH
6
(CHj),
355 Protect
1,8-Naphthallc anhydride
V .
356 Pyrethrlns
Standardized mixture of
pyrethrlns I and II (Mixed
esters of pyrethrolone)
faft^^» ***ll_l~LI_/'>^"3 CHj^^» ftms.
__.,i\»^"n~\>n~i'i-_"-p, f*u*S A^7*^
3 V1 OL. J. 91
S> v3 +&
^ ^CdfeCH-Pt NO
-------
TABLE X-J
INDEX OF PESTICIDE COMPOUNDS 3Y SU0CATEGORY
NON-CATEGORIZED PESTICIDES
Common Name
Chemical Name
Structure
357 Qulnomethlonate (Morestan) 6-methly-2-oxo-1,3-d1th1olo
[4,5-b]qu1noxa11ne
358 Resmethrln (SflP-1382)
359 Rotenone
360 Sulfoxlde
(5-Benzy1-3-fury1)methyl-2,
2-d1methyl-3-(2-methy1
propenyl)cyclopropane-
carboxylate (approx. 70*
trans, 30% els Isomers)
l,2,12,12a, Tetrahydro-
2-1sopropeny 1-8,9-dimethoxy-
[1] benzopyrano-[3,4-b]furo
[2,3-b][l] benzopyran-
l-Methy1-2-(3,4-methylane-
dioxyphenyl)ethyl
octyl sulfoxide
361 j
Pheraf
(Ootir1e1d« A)
o-Phenylphenol, sodium salt,
oranohydrate
-------
TABLE X-l
INDEX OF PESTICIDE -COMPOUNDS BY SUBCATEGORY
NON-CATEGORIZED PESTICIDES
Common Name Chemical Name Structure
362 Warfarin 3-(a-Acetonylbenzyl)-4- 5? i
hjrdro*ycoumar1n ^
-------
SECTION XI
ACKNOWLEDGEMENTS
This report was prepared by the Environmental Protection Agency
on the basis of a comprehensive study performed by Environmental
Science and Engineering, Inc., under contract No. 68-01-3297 and
under the direction of John D. Crane, P. E., and the management
of Mr. James B. Cowart, P.E.. Key ESE staff members included Dr.
John D. Bonds, Mr. Edward M. Kellar, Mr. Charles Stratton, Dr.
Don Tang, P. E., Dr. Ruey Lai, Mr. Stu Monplaisir, Mr. Bevin
Beaudet, P.E., Mr. Mark Mangone, Mr. Ernie Frey and Ms. Elizabeth
Brunetti.
The study was conducted under the supervision and guidance of Mr.
George M. Jett, Project Officer. The work was supervised by Dr.
W. Lamar Miller, Organic Chemicals Branch Chief, and Mr. Michael
Kosakowski. Able assistance was provided by Mr. Robert
Dellinger, Mr. Joseph Vitalis and Dr. Hugh Wise of the Organic
Chemicals Branch.
The project officer wishes to acknowledge the assistance of the
personnel at the Environmental Protection Agency's regional
centers who helped identify those plants achieving effective
waste treatment, and whose efforts provided much of the research
necessary for the treatment technology review. Appreciation is
extended to Mr. James Rogers, Mr. Colburn T. Cherney and Mr.
Barry Malter of the EPA Office of General Counsel, to Dr. Henry
Kahn and Dr. Charles Cook for their assistance on the statistical
analyses; Dr. Gregory Kew of the Office of Enforcement; Mr.
Richard Busse of the Office of Planning and Management, Mr.
Charles Gregg and Ms. JoAnn Bassi of the staff of the Office of
Water and Hazardous Materials, and to Mr. Louis DuPuis for his
evaluation of the economic impact of this regulation.
Acknowledgement is made of the cooperation of personnel in many
plants in the pesticide chemicals manufacturing industry who
provided valuable assistance in the collection of data relating
to process raw waste loads and treatment plant performance.
The project personnel would also like to thank Dr. Walt Sanders,
Dr. Lee Wolfe, Dr. James Lichtenburg, Dr. James Longbottom ,
Dr. Dale De,nny, Mr. Dave Oestreich, Dr. Atly Jefcoat, and Mr.
Paul DesRosiers of EPA's Office of Research and Development, for
their technical assistance during this study.
267
-------
Acknowledgement and appreciation is extended to Ms. Kaye Starr,
Ms. Nancy Zrubek, Ms. Carol Swann and Ms. Pearl Smith for
invaluable support in coordinating the preparation and
reproduction of this report; to Mr. Tom Tape, Mr. Todd Williams,
and Mr. Allen Bradley for proofreading, filing, organizing, etc.,
to Mr. Eric Yunker, Ms. Mable Scales, Ms. Middie Jackson and Ms.
Coleen Tresser of the Effluent Guidelines Division secretarial
staff for their efforts in the typing of drafts, necessary
revision, and final preparation of the revised development
document.
268
-------
SECTION XII
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261. Rumker, R. and F. Horay. Pesticide Manual, Vol. I.,
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267. Schacht, R.A. "Pesticides in the Illinois Waters of
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285. Sweeney, K.H., et al. Development of_ Field Applied DDTg
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286. Thompson, J.F. Analysis of Pesticide Residue in Human
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288. Tiedje, J. , Duxbury, J., Alexander, M. , and Daws on, J.
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294. Union Carbide Corp., Chemical and Plastics Physical
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295. Union Carbide Corp. Experimental Procedure for
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296. U.S. Congress. Public Law 92-500, 92nd Congress,
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294
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297., U.S. Department of the Army. Thermal Degradation of
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306. U.S. EPA. "A Catalog of Research in Aquatic Pest
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307. U.S. EPA. Compilation of Municipal and Industrial
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308. U.S. EPA. Control of Hazardous Material Spills,
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310. U.S. EPA. Degradation of Pesticides by Algae, EPA No.
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311. U.S. EPA. Development Document for Effluent Limitations
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312. U.S. EPA. Development Document for Interim Final
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313. U.S. EPA. "Draft Development Document for Interim Final
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314. U.S. EPA. "Effective Hazardous Waste Management (Non-
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315. U.S. EPA. Effects of Pesticides in Water, a report to
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317. U.S. EPA. , The Federal Insecticide, Fungicide, and
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318. U.S. EPA. Final Report of the Task Force on Excess
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319. U.S. EPA. "Flow Equalization," U.S. EPA Technology
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296
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320, U.S. EPA. Guidelines for the Disposal of Small
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321. U.S EPA. "Guidelines for Registering Pesticides in
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322. U.S. EPA. "Handbook for Analytical Quality Control in
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323. U.S. EPA. Herbicide Toxicity in Mangroves, EPA No.
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324. U.S. EPA. Information About Hazardous Waste Management
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325. U.S. EPA. "Methods for Chemical Analysis of Water and
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326. U.S. EPA. Methods for Organic Pesticides in Water and
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327. U.S. EPA. "Monitoring Industrial Wastewater," U.S. EPA
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328. U.S. EPA, Office of Air and Water Programs. Development
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329. U.S. EPA, Office of Air and Water Programs. Development
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330. UoSo EPA, Office of Air and Water Programs. Draft
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297
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Noncontact Coding Water Industries, Effluent Guidelines
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331. U.S. EPA, Office of Air and Water Programs. Effluent
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332. U.S. EPA, Office of Enforcement. Report on an
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333. U.S. EPA, Office of Enforcement. South Dakota Toxaphene
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334. U.S. EPA, Office of Enforcement. Trans locat ion of
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335. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Aldicarb,"
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1975.
336. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Bromacil,"
Substitute Chemicals Program, EPA-540/1-75-006, March,
1975.
337. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Captan,"
Substitute Chemicals Program, EPA-540/1-75-012, April,
1975.
338. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Carbofuran,"
Substitute Chemicals Program, EPA-540/1-76-009, July,
1976.
339. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Malathion,"
Substitute Chemicals Program, March, 1975.
298
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340. U.S. EPA, Office of Pesticide Programs,. "Initial
Scientific and Mini Economic Review of Methyl
Parathion," Substitute Chemicals Program, February,
1975.
341. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Monuran,"
Substitute Chemicals Program, EPA-540/1-75-028,
November, 1975.
342. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Parathion,"
Substitute Chemicals Program, EPA-540/1-75-001, January,
1975.
343. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific Review of Cacodylic Acid," Substitute
Chemical Program, EPA-540/1-75-021, December, 1975.
344. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific and Mini Economic Review of Croto Xyphos,
Substitute Chemical Program, EPA-540/1-75-015, June
1972.
345. U.S. EPA, Office of Pesticide Programs. "Initial
Scientific Review of MSMA/DSMA," Substitute Chemical
Program, EPA-540/1-75-020, December, 1975.
346. U.S. EPA, Office of Pesticide Programs. Substitute
Chemical Program - Initial Scientific Review of PCNB,
EPA-540/1-75-016, April, 1976.
347. U.S. EPA, Office of Research and Development. "An
Analysis of the Dynamics of DDT in Marine Sediments,"
Ecological Research Series, EPA-660/3-75-013, May, 1975.
348. U.S. EPA, Office of Research and Development.
"Chlorinated Hydrocarbons in the Lake Ontario Ecosystem
(IFY.GL)," Ecological Research Series, EPA-660/3-75-
022, June, 1975.
349.- U.S. EPA, Office of Research and Development. "A
Conceptual Model for the Movement of Pesticides Through
the Environment," Ecological Research Series, EPA-
660/3-74-024, December, 1974.
350. U.S. EPA, Office of Research and Development. "A
Conceptual Model for the Movement of Pesticides Through
299
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the Environment," Ecological Researchseries^ EPA-660/3-
75-022. June. 1975.
351. U.S. EPA, Office of Research and Development. "Current
Practices in G.C.-M.S. Analysis of Organics in Water,"
Environmental Protection Technology Series, EPA-R2-73-
277, August, 1973.
352. U.S. EPA, Office of Research and Development.
"Development of Treatment Process for Chlorinated
Hydrocarbon Pesticide Manufacturing and Processing
Wastes," Water Pollution Control Research Series, July,
1973.
353. U.S. EPA, Office of Research and Development. "The
Effect of Mirex and Carbofuram on Estuarine
Microorganisms," Ecological Research Series, EPA-660/3-
75-024, June, 1975.
354. U.S. EPA, Office of Research and Development. Effect of
Pesticides in Water.
355. U.S. EPA, Office of Research and Development.
"Environmental Applications of Advanced Instrumental
Analysis," Environment a1 Protection Technology Series,
EPA-660/2-74-078, August, 1974.
356. U.S. EPA, Office of Research and Development.
"Guidelines for the Disposal of Small Quantities of
Unused Pesticides," Environmental Protection Technology
Series, EPA-670/2-75-057, June, 1975.
357. U.S. EPA, Office of Research and Development.
"Herbicide Runoff From Four Coastal Plain Soil Types,"
Environmental Protection Technology Series, EPA-660/2-
74-017, April, 1974.
358. U.S. EPA, Office of Research and Development. "Methods
for Acute Toxicity Tests with Fish, Macroinvertebrates,
and Amphibians," Ecological Research Series, EPA 660/3-
75-009, April, 1975.
359. U.S. EPA, Office of Research and Development. "The
Occurrence of Organohalides in Chlorinated Drinking
Waters," Environmental Monitoring Series, EPA-670/4-74-
008, November, 1974.
360. U.S. EPA, Office of Research and Development.
"Pesticides Movement from Cropland Into Lake Erie,"
300
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Environmental Protection Technology Seriesg EPA-660/2-
74-032, April, 1974.
361. U.S. EPA, office of Research and Development.
"Pesticide Transport and Runoff Model for Agricultural
Lands," Environmental Protection Technology Series, EPA
660/2-74-013, December, 1973.
362. U.S. EPA, Office of Research and Development.
"Pollution Control Technology for Pesticide Formulators
and Packagers," Environmental Protection Technology
Series, EPA-660/2-74-094, January, 1975.
363. U.S. EPA, Office of Research and Development.
"Promising Technologies for Treatment of Hazardous
Wastes," Environmental Protection Technology Seriesg
EPA-670/2-74-088, November, 1974.
364. U.S. EPA, Office of Research and Development.
"Radiation Treatment of High Strength Chlorinated
Hydrocarbon Wastes," Environmental Protection
Technology Series. EPA-660/2-75-017, June, 1975.
365. U.S. EPA, Office of Research and Development. "Specific
Ion Mass Spectrometric Detection for Gas Chromatographic
Pesticides Analysis," Environmental Protection
Technology Series, EPA-660/2-74-004 January, 1974.
366. U.S. EPA, Office of Research and Development. Summation
of Conditions and Investigations for the Complete
Combustion of Organic Pesticides, EPA-5-03-3516A,
February, 1975.
367. U.S. EPA, Office of Research and Development. "A Tissue
Enzyme Assay for Chlorinated Hydrocarbon Insecticides,"
Environmental Protection Technology Series, EPA-660/2-
73-027, May, 1974.
368. U.S. EPA, Office of Research and Development.
Translation of Reports on Special Problems of Water
Technology, Vol. 9, EPA-600/9-76-030, 1975.
369. U.S. EPA, Office of Research and Development. Toxicity
of selected Pesticides to the Bay Mussel (Mytilus
Edulis)," Ecological Research Series, EPA-660/3-75-016,
May,, 1975.
370. U.S. EPAj, Office of Research and Development. "Use of
Soil Parameters for Describing Pesticide Movement
301
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Through Soils," Environmental Protection Technology
Series, EPA-660/2-75-009, May, 1975.
371. U.S. EPA, Office of Research and Monitoring. "Liquid
Chromatography of Carbonate Pesticides," Environmental
Protection Technology Series, EPA-R2-72-079, October,
1972.
372. U.S. EPA, Office of Research and Monitoring. "Rapid
Detection System for Organophosphates and Carbonate
Insecticides in Water," Environmental Protection
Technology Series, EPA-R2-72-010, August, 1972.
373. U.S. EPA, Office of Research and Monitoring.
"Recondition and Reuse of Organically Contaminated Waste
Sodium Chloride Brines," Environmenta1 Protection
Technology Series, EPA-R2-73-200, May, 1973.
37U. U.S. EPA, Office of Toxic Substances. An Ecological
Study of Hexachlorobenz ene (HCB), Washington, D.C.,
April, 1976.
375. U.S. EPA, Office of Toxic Substances. Preliminary
Assessment of Suspected Carcinogens in Drinking Water,
Washington, D.C., December, 1975.
376. U.S. EPA, Office of Water and Hazardous Materials.
Development Document for Interim Final Effluent
Limitations, Guidelines, and Proposed New Source
Performance Standards for the Pesticide Industry,
Washington, D.C., July, 1976.
377. U.S. EPA, Office of Water Management. "The Use of
Pesticides for Rangeland Sagebrush Control," Pesticide
Study Series-3 (May 1972) .
378. U.S. EPA, Office of Water Planning and Standards.
Economic Analysis of Interim Final Effluent Guidelines
for the Pesticides and Agricultural Chemicals Industry
(Draft Report, Arthur D. Little, Inc., for EPA), EPA-
230/l-76-065f.
379. U.S. EPA, Office of Water Programs. Development of a
Case Study of the Total Effect of Pesticides on the
Environment Non-Irrigated Croplands of the Midwest,
Pesticide Study Series-4 (June, 1972), EP2.25:8.
380. U.S. EPA, Office of Water Programs. The Effects of
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302
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Irrigated Croplands, San Jauquin Valley, P»S0 Series-6
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381. U.S.EPA, Office of Water Programs. Laws and
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11, U.S. Government Printing Office, 1972.
382. U.S.EPA, Office of Water Programs. The Movement and
Impact o_f Pesticides Used in Forest Management on the
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383. U.S. EPA, Office of Water Programs. Patterns of
Pesticide Use and Reduction in Use as RElated to Social
and Economic Factors, P.S. Series-10, 1972.
38t. U.S.EPA, Office of Water Programs. Pesticides in the
Aquatic Environment, EP2.2:PU3/2, April 1972.
385. U.S.EPA, Office of Water Programs. Pesticide Usage and
Its Impact on the Aquatic Environment in the Southeast,
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386. U.S.EPA, Office of Water Program Operations.
Pretreatment of Pollutants Introduced into publicly
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1973.
387. U.S.EPA, Office of Water Programs. The Dse of
Pesticides in Suburban Homes and Gardens and Their
Impact on the Aquatic Environment, P.S. Series-2 (May
1972) , EP2.25-.8.
388. U.S.EPA, Office of Water Quality. "Investigation of
Means for Controlled self-Destruction of Pesticides,"
Water Pollution Control Research Series 88.89.90, ELO
06/70, June 1970.
389. U.S.EPA, Office of Water Quality. A Primer on Waste
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390. U.S.EPA, Organic Compounds, Identified in Drinking Water
in the United states. Health Effects Research
Laboratory, EPA, Cincinnati, Ohio, April 1, 1976.
391. U.S. EPA. "Oxygen Activated Sludge Wastewater Treatment
Systems, Design Criteria and Operating Experience,"
303
-------
U.S. EPA Technology Transfer, EPA, Washington, D.C.
20460, August, 1973.
392. U.S. EPA, Pesticides, Progress Report, Dec. 1970-June
1972, Washington, D.C., November 1972.
393. U.S. EPA, "Pesticides—EPA Proposal on Disposal and
Storage," Part I, Federal Register, Vol. 39, No. 200,
October 15, 1974.
394. U.S. EPA, "Pesticides and Pesticides Containers,"
Federal Register, Part IV, Vol. 39, No. 85 (Washington,
D.C., May 1, 1976) .
395. U.S. EPA. "Pesticide Products Containing Nitrosamines,"
Federal Register, Vol. 42, No. 37, February 24, 1977.
396. U.S. EPA, Pesticide Regulation Division. Acceptable
Common Names and Chemical Names for the Ingredient
Statement on Pesticides Labels, 2nd Edition, June 1972.
397. U.S. EPA. "Physical-Chemical Wastewater Treatment Plant
Design," U.S. EPA Technology Transfer, EPA, Washington,
D.C. 20460, August, 1973.
398. U.S. EPA. "The Pollution Potential in Pesticide
Manufacturing," Pesticide Study Series-5, Technical
Studies Report (T.S.-00-72-04) (June 1972).
399. U.S. EPA. "Procedural Manual for Evaluating the
Performance of Wastewater Treatment Plants," U.S. EPA
Technology Transfer, EPA Washington, D.C. 20460,
October, 1973.
400. U.S. EPA, "Process Design Manual for Carbon
Adsorption," U.S. EPA Technology Transfer, Washington,
D.C., October 1976.
401. U.S. EPA. "Process Design Manual for Sludge Treatment
and Disposal," U.S. EPA Technology Transfer, EPA 625/1-
74-006, Washington, D.C. 20460, October, 1974.
402. U.S. EPA. "Process Design Manual for Suspended Solids
Removal," U.S. EPA Technology Transfer, EPA 625/1-75-
003a, Washington, D.C. 20460, January 1975.
403. U.S. EPA. "Process Design Manual for Upgrading Existing
Waste Water Treatment Plants," U.S. EPA Technology
Transfer, Washington, D.C. 20460, October 1974.
304
-------
404. U.S. EPA. "Projects in the Industrial Pollution Control
Division," Environmenta1 Protection Technology Seriese
EPA 600/2-75-001, Washington, D.C., December 1974.
405. U.S. EPA. "Proposed Toxic Pollutant Effluent
Standards," Federal Register, Vol. 38, No. 247, December
27, 1973.
406. U.S. EPA. "Quality Criteria for Water," EPA-4UO/9-76-
023, September, 1976.
407. U.S. EPA. "A Quantitative Method for Toxaphene By GC-
Cl-M Specific Ion Monitoring, EPA-600/4-76-010f
Environmental Research Laboratory, Athens, Ga. 30601.
408. U.S. EPA, Report of_ Activated Carbon Jar Tests on
Chemagro Wastewater, Surveillance and Analysis Division,
Kansas City, Missouri, January 31, 1973.
409. U.S. EPA. Report of the Aldrin/Dieldrin Advisory
Committee, to William D. Ruckelshaus, Administrator,
EPA, March 28, 1972.
410. U.S. EPA. Report of the Amitrole Advisory Committee,
March 12, 1971.
411. U.S. EPA. Report on Evaluation of Industrial Waste
Discharges at Velsicol Chemical Company, Memphis,
Tennessee, April 1972.
412. U.S. EPA. Report of the Lindane Advisory Committee,
July 12, 1970.
413. U.S. EPA. "Residues of Organo-Chlorine Pesticides in
Surface Waters," Water Pollution Control Notes—No. 36,
(March, 1967) .
414. U.S. EPA, Solid Waste Management Program. Assessment of
Industrial Hazardous Waste Practices; Organic Chemicals,
Pesticides, and Explosive Industries, Washington, D.C.
20460 (1967).
415. U.S. EPA. Spill Prevention Technigues for Hazardous
Polluting Substances, OHM 7102001, Washington, D.C.
20460, February, 1971.
416» U.S. EPA. Tertiary Treatment of Combined Domestic and
Industrial Wastes, EPA-R2-73-236, EPA, Washington, D.C.
20492, 1972.
305
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417. U.S. EPA. "Variability in BOD Concentration from
Bioloqical Treatment Plant," Internal Memorandum, To:
Lilliam Regelson, From: Charles Cook, March 1974.
418. U.S. EPA. "Wastewater Filtration Design Consideration,"
U.S. EPA Technology Transfer, EPA, Washington, D.C.
20460, July, 1974.
419. U.S. EPA. Wastewater Sampling Methodo 1 o gies and Flow
Measurement Technigues, EPA 907/9-74-005, EPA
Surveillance and Analysis, Region VII, Technical Support
Branch, June, 1974.
420. U.S. EPA, Working Group on Pesticides. "Ground Disposal
of Pesticides: The Problem and Criteria for Guidelines,"
Washington, D.C. (March, 1970).
421. U.S. EPA, Working Group on Pesticides. "Proceedings of
the National Working Conference on Pesticide Disposal,
At National Agricultural Library, Beltsville, Maryland,
June 30 and July 1, 1970," Washington, D.C.
422. U.S. Geological Survey, Water Resources Division.
Potential Contamination of the Hydrologic Environment
from the Pesticide Waste Dumps in Hardeman County^
Tennessee, August 1967.
423. U.S. Government Printing Office. Standard Industrial
Classification Manual, Government Printing Office,
Washington, D.C. 20492, 1972.
424. U.S. Government Printing Office. Water Quality Criteria
1972, National Academy of Sciences and National Academy
of Engineering, EPA-R-73-033, No. 5501-00520, March,
1973.
425. Van Valkenburg, J.W. "The Physical and Colloidal
Chemical Aspects of Pesticidal Formulations Research: A
Challenge," Pesticidal Formulations Research, Advances
in Chem. Series 86, Washington, D.C. (1969).
426. Van Walkenburg, J.W. Pesticide Formulation, Marcel
Dekker, Inc., New York, N.Y., 1973.
427. Versar Incorporated. A Study of Pesticide Disposal In A
Sewage Sludge Incinerator, Contract No. 68-01-1587, EPA,
Research and Development Office.
306
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128. Villanueva, E.G. "Evidence of Chlorodifoenzo-p-dioxin
and Chlorodibenzofuran in Hexachlorobenzen,"
Agricultural and Food Chemistry, 22_(5) (Sept./Oct.
1974) .
429. Wang, Lawrence K. Environmental Engineering Glossary
(Draft), Calspan Corporation, Environmental Systems
Division, Buffalo, New York 14221, 1974.
430. Wauchope, R.D. and Hague, R. "Effect of pH, Light and
Temperature on Carbaryl in Aqueous Media," Bulletin of
Environmental Contamination 6 Toxicology, Vol. 9, No. 5
(1973).
431. Way, M.J. , Bardner, R., Van Baer, R. and Aitkenhead, P.
11 A Comparison of High and Low Volume Sprays for Control
of the Buan Aphid, Aphis Pabae Scop, on Field Beans,"
Amrn. Appl. Biol^, 46(3), pp. 399-410.
432. Weast, R., editor. CRC Handbook of Chemistry and
Physics 54th Edition, CRC Press, Cleveland, Ohio 44128,
1973-1974.
433. Weber, C.I., editor. "Biological Field and Laboratory
Methods for Measuring the Quality of Surface Waters and
Effluents," Environmental Monitoring Series, EPA 670/4-
73-001, EPA, Cincinnati, Ohio 45268, July, 1973.
434. Weibel, S.R., et al. "Pesticides and Other Contaminants
in Rainfall and Runoff," J. AWWA, 58_(8) (1966).
435. Weiss, A. and Kramich, W.L. Catalytic Conversion of_
Hazardous and Toxic Chemicals, EPA Grant R-802-857-01,
January 1975.
436. Weiss, C.M. "Organic Pesticides and Water Pollution,"
Public Works, 95 (12):84-87, December 1964.
437. Wershaw, R.L., et. al. "Interaction of Pesticides with
Natural Organic Material," Environmental Science and
Technology, .3(3) (March 1969).
438. Wesvaco. Activated Carbon and Waste Water, Covington,
Virginia 24426, 1973.
439. Wetzel, R.B. Limnology, W.B. Saunders & Co.,
Philadelphia, Pa., 1975, 743 pp.
307
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440. Wiersma, G.B., Tai, H. "Mercury Levels in Soils of the
Eastern United States," Pesticides Monitoring Journal,
7 (3/4) (March 1974) .
441. Wilder, I. Letter to W.L. Miller, Effluent Guidelines
Division (WH552) , U.S. EPA, Washington, D.C. 20460,
August 20, 1976.
442. Wilhelmi, A.R., Ely, R. B. " A two-step process for
toxic waste waters," Chemical Engineering, (Feb. 16,
1976) .
443. Winchester, J.M., Yeo, D. "Future Development in
Pesticide Chemicals and Formulations," Chemistry and
Industry, 27(4) (January 1968).
444. Wincholz, M., editor. The Merck Index, ninth edition.
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(1976).
445. Wolfe, N.L., et. al.. "Exposure of Mosquito Control
Workers to Fenthion," Mosquito News, American Mosquito
Control Assoc., Inc. (Sept. 1974).
446. Wolfe, N.L. , et. al. "Captain Hydrolysis," J_^ Agric.
Food Chem., Vol. 24, No. 5, 1976.
447. Wolfe, N.L., Zepp, R.G. and Pans, D.F. Carbarul,
Propham, and Chlorpropham; A Comparison of the Rate of
Biolysis, U.S. EPA, Environmental Research Laboratory,
Georgia, 1977.
448. Wolfe, N. L. , et^ al._. "Chemical and Photochemical
Transformation of selected Pesticides in Aquatic
Systems," Ecological Research Series, EPA-600/3-76-067,
September 1976.
449. Wolfe, N.L. Correspondence with ESE. Data provided
through EPA Washington Office, July 1, 1977.
450. Wolfe, N.L. "Hydrolysis of Atrazine," inter-office memo
to L. Miller, U.S. EPA, August 13, 1976.
451. Wolfe, N.L, et. al. Methoxychlor and DDT Degradation in
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Research Laboratory, Athens, Georgia, Nov. 9, 1976.
452. Wolfe, Lee N., et. al . "N-Nitrosomine Formation from
Atrazine," for EPA, Bulletin of Environmental
308
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Contamination and Toxicology, Vol.. 15, Wo0 3^ 1976,, p.
342.
453. Wolfe, NoL.„ Zeppr R.G. and Paris„ D.FD Use of
Structure—-Reactivity Relationships to Estimate
Hydrolytic Persistence of Carbamate Pesticides, U.S.
EPA, Environmental Research Laboratory, College Station
Rd., Athens, Georgia 30601, 1976.
454. Woodland, R.G., et^ al . "Process for Disposal of
Chlorinated Organic Residues," Journal of the Air
Pollution Control Assoc._, 15 (2) (Feb. 1965) 0
455. WPCF, APHA, AWWA. "Standard Methods for the Examination
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456. Yader, Jo, et. al. "Lymphocyte Chromosome Analysis of
Agricultural Workers during Extensive Occupational
Exposure to Pesticides," Mutation Research, Vol. 21,
Elsevier Scientific Publishing Company, Amsterdam, 1973.
457. Young, David R., et. al . "DDT in Sediments and
Organisms Around Southern California Outfalls,9' Journal
Water Pollution Control Federation, Vol. 48, No. 8,
August, 1976.
458. Yost, J.F., Frederick, J«B. and Migrdichian, V.
"Malathion and Its Formulations," Agricultural
Chemicals, September 1955.
459. Yost, J.F., Frederick, J.B. and Migrdichian V.
"Malathion Formulations," Agricultural Chemicals,
October 1955.
460. Zepp, R.G., Wolfej, N.L. , Gordon, J»A. and Baughman, G.L.
"Dynamics of 2,4-D Esters in Surface Waters, Hydrolysis,
Photolysis, and Vaporization?" Envi. Scio & Tech.,
9 (13) :1144-1150 (1975).
461. Zindahl,, R0L., Freed, V.H., Montgomery, M.L. and
Furtick, W.R. "The Degradation of Triazine and Uracil
Herbicides in Soil," Weed Res. 10* pp« 18-26 (1970).
462. Zewig, G., editor. Analytical Methods for Pesticides^
Plant Growth Regulations, and Food Additives, Vol. II,
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Fumigantsg Rodenticides and Food and Feed Additives, and
Vol. IV, Herbicides, Academic Press,? New York (1964) ,
309
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SECTION XIII
GLOSSARY
Act. The Federal Water Pollution Control Act Amendments of 1972,,
Public Law 92-500.
Active Ingredient. The ingredient of a pesticide which is
intended to prevent, destroy, repell, or mitigate any pest. The
active ingredients may make up only a small percentage of the
final product which also consists of binders, fillers, diluents,
etc.
BAT Effluent Limitations. Limitations for point sources, other
than publicly owned treatment works, which are based on the
application of the Best Available Technology Economically
Achievable. These limitations must be achieved by July 1, 1983o
BFT Effluent Limitations. Limitations for point sources, other
than publicly owned treatment works, which are based on the
application of the Best Practicable Control Technology Currently
Available. These limitations must be achieved by July 1, 1977.
Contact Process Wastewaters. These are process-generated waste
waters which have come in direct or indirect contact with the
reactants used in the process. These include such streams as
contact cooling water, filtrates, centrates, wash waters, etc.
Dust. T5ry, solid powder. When applied to pesticide production
implies a dry, powder form product.
Formulating. A segment of the Pesticide industry which does not
manufacture pesticides but mixes and blends active ingredients
with binders., fillers, and diluents to produce the final product
for distribution.
Hydrolysis. The degradation of pesticide active ingredients,
most commonly through the application of heat at either acid or
alkaline conditions.
Metallo-Organic Pesticides. A class of organic pesticides
containing one or more metal or metalloid atoms in the structure.
Navigable Waters. Includes all navigable waters of the United
States; tributaries of navigable waters; interstate waters;
intrastate lakes, rivers and streams which are utilized by
interstate travellers for recreational or other purposes;
Preceding page blank 311
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intrastate lakes, rivers and streams from which fish or shellfish
are taken and sold in interstate commerce; and intrastate lakes,
rivers and streams which are utilized for industrial purposes by
industries in interstate commerce.
Non-contact Cooling Water. Water used for cooling that does not
come into direct contact with any raw material, intermediate
product, waste product or finished product.
Noneontact Wastewater. Wastewater which does not come in direct
contact with process materials.
NPDES. National Pollution Discharge Elimination System. A
federal program requiring industry to obtain permits to discharge
plant effluents to the nation's water courses.
Organic Pesticides. Carbon-containing substances used as
pesticides, excluding metallo-organic compounds.
Organo-Nitrogen Pesticides. Pesticides which use nitrdgenous
compounds as the active ingredients.
Organo-Phosphorus Pesticides. Pesticides which use phosphate or
phosphorus compounds as the active ingredients.
Packaging. The last step in preparing a pesticide for
distribution to the consumer. This segment of the industry takes
the final formulated product and puts it into a marketable
container such as drums, bottles, aerosol cans, bags, etc.
Pesticides. (1) Any substance or mixture of substances produced
for preventing, destroying or repelling, any animal or plant
pest. (2) General term describing chemical agents which are used
to destory pests. Ptjticides includes herbicides, insecticides,
fungicides, etc., and each type of pesticide is normally specific
to the pest species it is meant to control.
Pesticides Chemicals. The sum of all active ingredients
manufactured at each facility.
Pretreatment. Any waste water treatment process used to
partially reduce the pollution load before the waste water is
introduced into a main sewer system or delivered to a treatment
plant for substantial reduction of the pollution load.
Process Wastewater. Any water which, during manufacturing or
processing, comes into direct contact with or results from the
312
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production or use of any raw material, intermediate product,
finished product, by-product, or waste product.
Volatile Suspended Solids iVSSJ_. The quantity of suspended
solids lost after the ignition of total suspended solids.
313
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SECTION XIV
ABBREVIATIONS AND SYMBOLS
API American Petroleum Institute
BODJ5 biochemical oxygen demand, five day
Btu British thermal unit
°C degrees Centigrade
cal calorie
cc cubic centimeter
cm centimeter
COD chemical oxygen demand
°F degrees Fahrenheit
F/M BOD (kg/day)/kg MLVSS in aeration basins
fpm feet per minute
fps feet per second
ft feet
gal gallon
gpd gallon per day
gpm gallon per minute
hp horsepower
hr hour
in inch
kg kilogram
kkg 1000 kilograms
kw kilowatt
L(l) liter
lb pound
m meter
M thousand
mg milligram
mgd million gallons daily
min minute
ml milliliter
MLSS mixed-liquor suspended solids
MLVSS mixed-liquor volatile suspended solids
mm millimeter
MM million
POTW public owned treatment works
psi pound per square inch
rpm revolution per minute
sec second
SoI.C. standard Industrial Classification
sq0ft. square foot
TDS total dissolved solids
TKN total Kjeldahl nitrogen
TOC total organic carbon
TOD total oxygen demand
TSS total suspended solids
ug microgram
Preceding page blank
315
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TABLE XIV-1
METRIC TABLE
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
hectares
cubic meters
kilogram - calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilograms)
meter
* Actual conversion, not a multiplier
acre
acre - feet
British Thermal
Unit
British Thermal
Unit/ pound
cubic feet/minute
cubic feet/second
cubic feet
cubic feet
cubic inches
degree Fahrenheit
feet
gallon
gallon/minute
horsepower
inches
inches of mercury
pounds
million gallons/day
mile
pound/square
inch (gauge)
square feet
square inches
ton (short)
yard
ac
ac ft
BTU
BTU/lb
cfm
cfs
cu ft
cu ft
cu in
°F
ft
gal
gpm
hp
in
in Hg
Ib
mgd
mi
psig
sq ft
sq in
ton
yd
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(eF-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
•C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
316
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