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

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                           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

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                             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

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                            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

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"
                          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

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                            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

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                          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

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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

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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

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                                        FIGURE  III-2

                                LOCATIONS OF FORMULATION
                                   FACILITIES  IN U.S.
Source: Environmental Protection Agency,
       Technology Series: EPA-660/2-74-094
       January, 1975.
7

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                                                 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)

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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

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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

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PRODUCT
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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

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> >
CHLORINE _ rVAMIRTP AMTNATTnw —
CHLORINE H;3N3C1 3 — > U^
HYDROGEN CYANIDE UNIT , > TC
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CAUSTIC SODA

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SOLVENTS

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JIT (1 ^TRIAZINE— »• FORMULATION U AND -J PRODUCT

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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

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REA
T
WASTEWATER
rrnD INTERMEDIATE
^ STORAGE


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                                                                                                        VE
                                                                                          WATER-
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                                                                                   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
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          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

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                            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

-------
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     9-
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     9
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          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

-------
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 6  19  20  21  22  27  22 32  21  36  39 41  21  22  48 49  32  21

                           PLANT
            BOD RAW WASTE LOAD CHARACTERISTICS
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AVERAGE FOR PARAMETER

MINIMUM AND MAXIMUM FOR PARAMETER
                              78
FIGURE V-2

-------
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 6   8  19 20 22 23 27  28  29  22 32  36 39 41  32 22 48 49 32

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AVERAGE FOR PARAMETER

MINIMUM AND MAXIMUM FOR PARAMETER
                        79
                                                    FIGURE V-3

-------
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           TSS RAW WASTE LOAD CHARACTERISTICS
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                            80
                                                      FIGURE V-4

-------
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                                      DESIGN RAW WASTE LOAD
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                                 PLANT
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       MINIMUM AND MAXIMUM FOR PARAMETER
                                  81
                                                            FIGURE V-5

-------
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        6  8 9    20  21 22 23  28  32  21 36 39  41  46  48  49   32

                             PLANT
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                    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,
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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.
                                99

-------
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.
                              100

-------
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.
                               101

-------
                           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.
    Preceding page blank
103

-------
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

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                          pKa OF ALCOHOL
14
16
                          (CH30)2 P -OR
              BRONSTEAD FREE ENERGY RELATIONSHIP
            DIMETHOXYPHOSPHOROTHIOATE PESTICIDES
                           136
                                                 FIGURE VII-7

-------
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                          pKa OF ALCOHOL
                                S
                                it
                            (EtO)2 P-OR
                 BRONSTEAD FREE ENERGY RELATIONSHIP
                DIETHOXYPHOSPOROTHIOATE  PESTICIDES
                             137
                                          FIGURE VII-8

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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

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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

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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

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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

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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

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                                                                        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

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                               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
                               144

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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
                               145

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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.
                              146

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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
                               147

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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.
                               149

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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,
                              151

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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.
                              152

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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
                              156

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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
                            157

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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
                                  158

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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.
                               159

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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)
                              160

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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.
                               163

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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.
                              164

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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
                              165

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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
                                 172

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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
      173

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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
                           175

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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
                              176

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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).
                              177

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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.
                              178

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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.
                               179

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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

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                              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

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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

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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

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                              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

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         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

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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

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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

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                             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

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                       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

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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

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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

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                                                 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
                                                                                    
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                                                        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.,

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                                                       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

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                                                      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

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                                                      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

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                                                     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

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                                                      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
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                                                       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
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                                                     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

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                                                      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

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                                                       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

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                                                     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

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                                                     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

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                                                       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

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                                                        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

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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,

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                                                      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! ,

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                                                        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

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                                                   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

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                                                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                                  ^

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                           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

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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

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                           SECTION XII

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-------
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                              270

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                               271

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                              272

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                              273

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                              274

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                               275

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85.      Eichelberger,  J.W.   and  Lichtenberg,   J.J.    "Carbon
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86.      Eisenhauer, H.R.  "Oxidation of Phenolic  Wastes, Part I:
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87.      England,  British  Crop  Protection  Council,  Pesticide
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88.      Enviro-Lab,   Inc.     Completion    Report    Wastewater
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89.      Farmer, W.J. and  Letey,  J.   "Volatization  Losses  of
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90.      Faust, S.D. and Aly, O.M.  "Water Pollution  by  Organic
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91.      Faust, S.D.  and  Comma,  H.M.   Environmenta1  Lettersg
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92.      Faust, S.D. and Comma, H.M.  "Kinetics of Hydrolysis  of
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93.      Federal Water Pollution Control Administration.  "Report
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94.      Federal   Working   Group   on   Pesticide   Management.
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95.      Ferguson,  T.L.     Pollution  Control   Technology   for
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96.      Frear, E.H., Ph.D.   Pesticide  Index,  Fourth  Edition,
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97.      Forestell, W.L., editor-in-chief.  "Get Ready, Hazardous
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98.      Fornwalt, H.J. and  Hutchins,  R.A.   "Purifying  Liquids
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99.      Fox, M., et al.  "  -Chlorobenzene,"  J. of  Amer.  Chem.
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100.     Fox, R.D., "Pollution Control at the Source,"   Chemical
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101.     Gabica, J., et al.  "Rapid Gas Chromatographic Method of
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                               277

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102.      Garrison,  A.W.  Comments  on   Development   Document  for
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103.      Goldstein, J.A., et al.   "Experimental  Hepatic Porphyria
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101.      Golz,  H.H. and Schaffer,  C.B.   Toxicologjcal Information
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105.      Gomma, H. M. and Faust,  S.D.    "Chemical Hydrolysis  and
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106.      Gonzalez, J.G. and Ross,  R.T.   "Interfacing of an Atomic
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107.      Goodrich, P.R. and Monke, E.J.  "Insecticide  Adsorption
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198.      Gould,  M.S.   and  Genetelli,   E.J.     "Heavy   Metal
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109.      Grandjacque, B. Air Pollution Control and  Energy  Saving
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110.      Gunther, F.A.  "Reported  Solubilities of  738  Pesticide
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111.      Gunther, F.A. and  Blinn,  R.C.   Analysis of  Insecticides
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112.      Gunther,  F.A.  and  Gunther,  J.D.,  editors.   Residue
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                              278

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113.      Gysin, H.  and Knuesli,   E.   "Chemistry  and  Herbicidal
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114.      Hagar  and  Rizzo.   "Removal  of  Toxic  Organics  from
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115.      Hannah, S.A., Jelus, M., and Cohen,  J.M.   "Removal  of
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116.      Hague, Rizwanul and Freed, V.H.  'Environmental  Dynamic
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117.      Heath, D.F.  Organophosphorus Poisons,  Pergamon  Press,
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118.      Hemmett, R.B.,  Jr.  and  Faust,  S.D.   "Biodegradation
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119.      Hemphill,    D.D.,   editor.    "Trace   Substances    in
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120.      Henkel, H.G. and Ebing, W.  "A Contribution to  the  Gas
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121.      Hersey,  J.   "Choosing  a   Solvent   for   Insecticide
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122.      Hill, D.w. and Mccarty, P.L.  "Anaerobic Degradation  of
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123.      Hindin, Ervin,  et  al  .   Collection  and  Analysis  of
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         Pullman, Washington.
                              279

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124.      Holden, A.V.,  et  al.   "The  Examination  of Surface Waters
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125.      Honea, F.I.,  et al.   "Pesticides  Industry,"  Task Report,
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126.      Horrobin, S.    "The   Hydrolysis   of   Some  Chloro-1,3,5-
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127.      Hosier, C.F.,  Jr.  "Degradation of Zectran  in  Alkaline
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128.      Howard, P.H.,  Jaxena, J., Durkin, P.R.,   and  Ou,  L.T.
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129.      Huang,  J.C.,   "Organic  Pesticides    in   the   Aquatic
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130.      Huang, J.C. and Liao, C.S.   "Adsorption of Pesticides by
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131.      Hutchins, R.A.   "Activated   Carbon-Economic  Factors  in
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132.      Hutchins,  R.A.   "New  Method  Simplifies   Design   of
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133.      I.C.I. America, Inc.   "Evaluation of Granular  Activated
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135.      I.C.I. America, Inc.   A Symposium on  Activated  Carbon,
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136.      I.C.I. United  States,  Inc.   "Adsorption  Isotherm  of
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137.      I.C.I. United States, Inc.  Gro-Safe Activated  Charcoal
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138.      Ingols,  R.S.,  et  al .   "Biological   Activities   of
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139.      Iowa   State   University   Department   of   Industrial
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110.      Iowa   State   University   Department   of   Industrial
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141.      Jernign, W.M., Georgia Department of Natural  Resources.
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142.      Johnson, D.P. and Stansbury, H.A.,  Jr.   "Determination
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143.      Johnson, O.  "CW Report:  Pesticides '72 Part 1 and Part
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144.      Joiner, R.L., et al.  "Comparative  Inhibition  of  Boll
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145.      Jones,   G.E.,   Dubey,   H.D.,   and   Freeman,    J.F.
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146.      Kane,  P.F.,  et  al  .    "Assay  of  Co-Ralin  Technical
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147.      Karinen,  J.F.,   Lamberton,   J.G.,   Stewart,   N.E.,  and
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148.      Kearney,  P.C.   and  Kaufman,   D.D.    Degradation   of
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149.      Kearney, P.C. and Kaufman,  D.D., editors.     Herbicides,
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150.      Kennedy, D.C.  "Treatment of Effluent  from  Manufacture
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153.      Kerr McGee Chemical Corporation and  Engineering Science,
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154.      Khan,  S.V.,   Greenhalgh,   R.,   and   Cochrane,   W.P.
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155.      Kimbrough,   R.D.    "Review   of    the   Toxicity    of
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156.      Kimbrough,  R.D.   "Toxic  Effects  of   the   Herbicide
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157.      King, P.H., et al.  Bulletin  32,  Removal  of  selected
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158.      Kirk-Othmer.   Encyclopedia of Chemical Technology,  2nd
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159.      Knuesli, E., Berrer,  D.,  Dupuis,  G.,  and  Esser,  H.
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160.      Konrad, J.G. and Chesters, G.  "Degradation in Soils  of
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161.      Konrad, J.G., Chesters, G., and Armstrong,  D.E.   "Soil
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162.      Kozlorowski, B.  and  Kucharski,   J._  Industrial  Waste
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163.      Kutz, F.W., et a^.  "Mirex  Residues  in  Human  Adipose
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164.      Kutz, F.W.,  et  al.   "The  National  Human  Monitoring
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165.      Kutz, F.W.,  et  al.   "Pesticide  Residues  in  Adipose
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166.      LaForge,  F.B.,  et  al.   "Dimerized  Cyclopentadienones
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167.      Lambden,  A.E. and Sharp, D.H.   "Treatment  of  Effluent
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168.      Lanquette, K.H. and Paulson, E.G.  "Treatment  of  Heavy
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169.      Lawless,  E.W., et al.   Guidelines for the  Disposal  of
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                              283

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170.      Lawless,  E.W.,   et   al.     The  Pollution  Potential  in
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171.      Lawless,  E.W.,  et al.  "Production,  Distribution, Use and
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172.      Leigh,  G.M.   "Degradation  of   Selected   Chlorinated
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173.      Leshendok,  Thomas  V.     Hazardous   Waste   Management
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174.      Liang,  T.T.  and  Lichtenstein,  E. P.    "Synergism   of
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175.      Lindner,  G. and Nyberg,  K.  Environmental Engineering, A
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176.      Linder, R.E. , et al.   "The  Effect  of  Polychlorinated
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177.      Liptak, E.G., editor.  Environmental Engineers* Handbook,
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178.      Loos, et al.  "Phenoxyacetate Herbicide Detoxication  by
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179.      Mackay, D. and Wolkoff,  A.W.  "Rate  of  Evaporation  of
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180.      Mahlock,  J.L.   Program Report on Chemical  Fixation  of
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181.      Malin,  H.M.,  Jr.   "Cities  Treat  Industrial  Process
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                              284

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182.      Mann,  J.B.,  et  al.   "Development  of  Sampling   and
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183.      Manufacturing Chemists Association, Inc.  Guidelines fpr
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184.      Manufacturing Chemists Association.    Laboratory  Waste
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185.      Marks, D.R.   "Chlorinated Hydrocarbon Pesticide  Removal
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186.      Marquardt  Company.   Report  on  the   Destruction   of
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187.      Martin, H. and Worthing, C.R.  Pesticide Manual, British
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188.      Martin, J.D., et al.  "Waste  Stabilization  Experiences
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189.      Matsumura, Fumio, et al.   Environmenta1  Technology  of
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190.      Mason,  Thomas  J.,  Ph.D.,  et  al.   Atlas  of  Cancer
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191.      McDermott, G.N.  "Industrial Spill Control and Pollution
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192.      McKee, J.E. and H.W. Wolf.   "Water  Quality  Criteria,"
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193.      Medical College of  Ohio  at  Toledo.   "Report  of  the
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194.      Melnikov,      N.N.       Chemistry      of     Pesticides,
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195.      Metcalf,   R.L.   organic   Insecticides,    Interscience
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196.      Metcalf,  R.L., Fukuto,  T.R.,  Collins,  C.,  Borck, K. , El-
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197.      Metcalf,   R.L.,  et  al .   "Model  Ecosystem  for   the
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198.      Metcalf,   R.L.  and  Fukuto,   T.R.   "Toxic  Action   of
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199.      Mick, D.L.,  et al.   "Organochlorine Insecticide Residues
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200.      Midwest    Research    Institute.      "Aldrin/Dieldrin,"
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201.      Midwest  Research  Institute.    "Endrin,"    Wastewater
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202.      Midwest Research Institute.  Identification  of  Organic
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203.      Midwest Research Institute.  Identification  of  Organic
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205.     Midwest Research Institute.    "Toxaphene,"   Wastewater
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206.     Midwest  Research  Institute.    "Wastewater   Treatment
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207.     Midwest  Research   Institute.    Wastewater   Treatment
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210.     Midwest  Research   Institute.    Wastewater   Treatment
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211.     Miller,  F.M.  and  Gomes,  E.D.   "Detection  of   DCPA
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212.     Mills,  R.E.   "Development  of  Design   Criteria   for
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213.     Minear, R.A. and Patterson, J.W.   Wastewater  Treatment
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214.     Miranowski,  J.A.,  et_ al	.    "Crop    Insurance   and
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215.     Moore, F. L. , et. al.    "Recovery  of   Toxic  Metals  From
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216.      Mounce, L.M.  and  Savage,   E.P.  "The  Epidemiology  of
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217.      Moyer,  J.R.  and  Parmele,  C.S.    "Demonstration   of
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218.      Muhlmann,  R.   and   G.   Schrader.     "Hydrolyse   der
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222.      "New weapons Against Insects,"  Chemical and Engineering
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224.      Novak, S.M.  "Biological Waste  Stabilization  Ponds  at
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225.      Obien, S.P. and Green, R.E.  "Degradation of Atrazine in
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226.      O'Kelley,   J.C.  and  Deason,  T.R.    "Degradation   of
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227.      Otakie, G.F.  A Guide to the Selection of Cost-Effective
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228.      Packer, K.  Nanogen Index, a  dictionary  of  pesticides
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232.     Paris,  D. F. ,  et  al .    Microbial   Degradation   and
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233.     Parker, W.P.  Wastewater Systems Engineering,  Prentice-
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234.     Patterson*  J.W.,  Ph.D.   "State-of-the-Art   for   the
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236=     Perry, J.H. et al.  Chemical  Engineer's  Handbook,  5th
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237.     Pesticide Handbook - Entoma,  Entomological  Society  of
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238o     "Pesticides  972P5'  Chemical Week, Part  1, June  21,  1972.

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240.     Piver,   W.T.    "Organotin    Compounds:      Industrial
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244.     Quirk, T.P.  "Application of  Computerized  Analysis  of
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245.     Pabson  P.  and  Plimmer,  J.R.    "Photoalteration   of
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246.     Reimold, Robert J., et al.   The  Effects  of  Toxaphene
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247.     Reimold, Robert J.  Toxaphene Interactions in  Estuarine
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248.     Riley, B.T., Jr.   The Relationship Between  Temperature
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249.     Rinehart, T^M.  A Symposium  on  Activated  Carbon,  ICI
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250.     Rizzo, J.R. and  Shepherd,  A.R.   "Treating  Industrial
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251.     Rizzo,  J.L.   Use  of  Granular  Activated  Carbon  for
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252.     Robeck, G.G., et al.  "Effectiveness of Water  Treatment
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253.     Rose,  A.  and  Rose,   E.    The   Condensed   Chemical
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255.     Ross, R.T. and Gonzalez,  J.G.   "Short  Communication,"
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256.     Roy F. Weston,  Inc.   Draft  Development  Document  for
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257.     Ruckelshaus, William D.  "Report of the  Mirex  Advisory
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258.     Rudolfs,  W.   Industrial  Wastes,  Their  Disposal  and
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260.     Rumker, V.R., et al.  The Use of Pesticides in  Suburban
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                               291

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261.      Rumker, R.  and F.  Horay.    Pesticide  Manual,  Vol.  I.,
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262.      Ruzo,  L.D.f  et  al .    "Photochemistry  of   Bioactive
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263.      saldick, J.  Biological Treatment of Plant Waste Streams
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261.      Saleh, F.   Monthly Report Dallas,  Texas, Advanced  Waste
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265.      Sanborn, J.R.  "The Fate of  Select  Pesticides  in  the
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266.      Sax, N.I.   Dangerous Properties of Industrial  Material,
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267.      Schacht, R.A.  "Pesticides in  the  Illinois  Waters  of
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268.      Seiber, J.N., et al.  "Determination of  Pesticides  and
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273.     skipper,  H.D.,  Gilmour,  C»M.,   and   Furtick,   W.R.
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279.     Starr, H.G., et al.  "Contribution of Household Dust  to
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280.     Stecher, P.G., editor.  The Merck Index, An Encyclopedia
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281.     Stevens, J.I.   "The  Roles  of  Spillage,  Leakage  and
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282.     Stutz,  C.N.   "Treating  Parathion  Wastes,"   Chemical
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283.     Swanson, C.L.  "Unit Process Operating   and  Maintenance
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284.     Sweeney,  K.H,    "Chlorinated   Hydrocarbon   Pesticide
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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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287.     Thompson,  J.F.    Analytical  Reference  Standards   and
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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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297.,     U.S. Department of the Army.   Thermal   Degradation  of
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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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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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320,     U.S.  EPA.    Guidelines  for  the  Disposal   of   Small
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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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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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         Noncontact Coding Water Industries,  Effluent  Guidelines
         Division, October,  1974.

331.     U.S.  EPA, Office of Air and  Water  Programs.    Effluent
         Limitations  Guidelines  and  Standards  of Performance,
         Metal Finishing Industry,  Draft  Development   Document,
         EPA   440/1-75/040   and   EPA  440/1-75/040a,  Effluent
         Guidelines Division, Washington, D.C. ,  April,  1975.

332.     U.S.   EPA,  Office  of   Enforcement.    Report   on   an
         Investigation   of  Pesticide  Pollution  in  the  Lower
         Colorado   River   Basin   -   1973,   National    Field
         Investigations Center, Denver, Colorado, December, 1973.

333.     U.S.  EPA, Office of Enforcement.  South Dakota Toxaphene
         Use Study, June-September,  1975, EPA/2-75-007,  National
         Enforcement  Investigations  center,  Denver,   Colorado,
         October, 1975.

334.     U.S.   EPA,  Office  of  Enforcement.   Trans locat ion  of
         Heptachlor  and Chlordane trom Indiana Corn Fields,  EPA-
         330/9-75-002,   National   Enforcement    Investigations
         Center, Denver, Colorado, September, 1975.

335.     U.S.   EPA,  Office  of  Pesticide  Programs.    "Initial
         Scientific   and  Mini  Economic  Review  of  Aldicarb,"
         Substitute  Chemicals  Program,  EPA-540/1-75-013,  May,
         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
         Agricultural  Pesticides  in  the  Aquatic  Environment,
                              302

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         Irrigated Croplands, San Jauquin Valley,  P»S0   Series-6
         (June, 1972) EP2.25:8.

381.     U.S.EPA,   Office   of   Water   Programs.    Laws   and
         Institutional  Mechanisms  Controlling  the  Release  of
         Pesticides into the Environment Pesticide  Study  Series
         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
         Aquatic Environment in the  Northeast,  Pesticide  Study
         Series-9  (July, 1972) .

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,
         Pesticide Study Series-8 (September 1972), EP2.25:8.

386.     U.S.EPA,   Office   of   Water    Program    Operations.
         Pretreatment  of  Pollutants  Introduced  into  publicly
         Owned Treatment Works,  Washington, D.C.  20460, October
         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
         Water Treatment,  197U.

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

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         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

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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.
         Published  by  Merck  &   Co.,  Inc. Rahway, N.J., U.S.A.
          (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
         Wat er;  Rates  and  Products,  U.S.  EPA   Environmental
         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
         of  Water and Wastewater,8' 14th edition, 1975.

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,
         Insecticides, Vol° III,  Fungicides,, Nematocides and soil
         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;
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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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