EPA 440/1 -75/060d
Group II
Development Document For Interim
Final Effluent Limitations Guidelines
For The
PESTICIDE CHEMICALS
MANUFACTURING
Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
NOVEMBER 1976
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DEVELOPMENT DOCUMENT
for
INTERIM FINAL
EFFLUENT LIMITATIONS GUIDELINES
for the
PESTICIDE CHEMICALS MANUFACTURING
POINT SOURCE CATEGORY
Russell E. Train
Administrator
Andrew W. Breidenbach, Ph.D.
Assistant Administrator for
Water and Hazardous Materials
Eckardt C. Beck
Deputy Assistant Administrator for
Water Planning and Standards
Robert B. Schaffer
Director, Effluent Guidelines Division
Project Officers
Joseph S. Vitalis
and
George M. Jett
November 1976
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20460
(-
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U,S. Environ;
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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 and
guidelines for existing point sources to implement Sections
301(b), 301(c), 304(b) and 304(c) of the Federal Water
Pollution Control Act, Public Law 92-500 as amended (33
U.S.C. 1251, 1311, 1314(b) and 1314(c), 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) which must be achieved by existing
point sources by July 1, 1977.
The development of data and recommendations in this document
relate to the pesticide chemicals manufacturing point source
category. This category was one of the eight industrial
segments of the miscellaneous chemicals manufacturing point
source category. The pesticide chemicals manufacturing
point source category is divided into five subcategories on
the basis of the characteristics of the manufacturing
processes involved and the types of products produced.
Separate effluent limitations were developed for each
subcategory based on the raw waste loads as well as on the
degree of treatment achievable by existing installations and
suggested model treatment systems. These treatment systems
include biological and physical/chemical treatment methods.
Supporting data and rationales for development of the
proposed effluent limitations and guidelines are contained
in this report and supporting file records. Mention of
trade names or commercial products does not constitute
endorsement or recommendation for use.
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TABLE OF CONTENTS
Section Title Page
Abstract
Table of Contents
List of Figures
List of Tables
I Conclusions 1
II Recommendations 6
III Introduction 9
IV Industrial Categorization 29
V Waste Characterization 72
VI Selection of Pollutant Parameters 117
VII Control and Treatment Technologies 135
VIII Cost, Energy, and Non-Water Quality 199
Aspects
IX Best Practicable Control Technology 217
Currently Available
X Index of common Pesticide 238
Compounds by Subcategory
XI Acknowledgements 264
XII Bibliography 266
XIII Glossary 296
XIV Abbreviations and Symbols 329-330
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LIST OF FIGURES
Number Title
III-1 Locations of Pesticide 17
Production Plants
III-2 Locations of Formulation 28
Facilities in U.S.
IV-1 General Process Flow Diagram for
DDT and Related Compounds Production 36
Facilities
IV-2 General Process Flow Diagram for Halo- 38
genated Phenol Production Facilities
IV-3 General Process Flow Diagram Aryl- 40
oxyalkanoic Acid Production Facilities
IV-1 General Process Flow Diagram for Aldrin- 42
Toxaphene Production Facilities
IV-5 General Process Flow Diagram for Halo- 44
genated Aliphatic Hydrocarbon
Production Facilities
IV-6 General Process Flow Diagram for Halo-
genated Aliphatic Acid Production 45
Facilities
IV-7 General Process Flow Diagram
for Phosphates and Phosphonates 47
Pesticide Production Facilities
IV-8 General Process Flow Diagram for
Phosphorothioate and Phosphoro- 49
dithioate Production Facilities
IV-9 General Process Flow Diagram for Aryl and 51
Alkyl Carbamate Production Facilities
IV-10 General Process Flow Diagram for Thio- 53
carbamate Production Facilities
IV-11 General Process Flow Diagram for Amide 54
and Amine Production Facilities
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IV-12 General Process Flow Diagram for Urea 56
and Uracils Production Facilities
IV-13 General Process Flow Diagram for 58
S-Triazine Production Facilities
IV-14 General Process Flow Diagram for 60
Nitro-type Pesticides
IV-15 General Process Flow Diagram for Arsenic- 62
type Metallo-organic Production
IV-16 General Process Flow Diagram for 63
Certain Dithiocarbamate Metallo-
organic Production
IV-17 Liquid Formulation Unit 65
IV-18 Dry Formulation Unit 67
VII-1 Effect of pH and Temperature on 139
Malathion Degradation
VII-2 Hydrolysis of Methyl Parathion at 15°C 140
VII-3 pH-Half-Life Profile for Captan 141
Hydrolysis in Water at 28°C
VII-4 BPT Cost Model - Subcategory A 188
VII-5 BPT Cost Model - Subcategory B 189
VII-6 BPT Cost Model - Subcategory C 190
vm
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LIST OF TABLES
Number Title Page
1-1 Summary Table 4-5
II-1 BPT Effluent Limitations Guidelines 8
III-1 Pesticides Classification 19-20
III-2 Structural Chemistry of Typical and 21-25
Major Pesticides
V-l Summary of Potential Process-Associated 74-75
Wastewater Sources from Halogenated
Organic Pesticide Production
V-2 Raw Waste Loads, Halogenated 77-80
Organic Pesticide Plants -
Subcategory A
V-3 Summary of Potential Process-Associated 84-85
Wastewater Sources from Organo-
Phosphorus Pesticide Production
V-U Raw Waste Loads, Organo-Phosphorus 87-91
Pesticide Plants - Subcategory E
V-5 Summary of Potential Process-Associated 96-97
Wastewater Sources from Organo-
Nitrogen Pesticide Production
V-6 Raw Waste Loads, Organo-Nitrogen 100-103
Pesticide Plants - Subcategory C
V-7 Summary of Potential Process-Associated 105
Wastewater Sources from Metallo-
Organic Pesticide Production
V-8 Raw Waste Loads, Metallo-Organic 107-108
Pesticide Plants - Subcategory D
V-9 Potential Process-Associated Wastewater ]]Q
Sources from Pesticide Formulators
and Packagers
V-10 Raw Waste Loads, Pesticide Formulators ]-\-\
and Packagers - Subcategory E
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Page
V-11 Raw Waste Load, Multi-Category 113-114
Pesticide Producer, Plant M1
V-12 Raw Waste Load, Multi-Category 115-116
Pesticide Producer, Plant M2
VII-1 Holding Pond (Final) Effluent, 152-153
Plant M2
VII-2 Oxygen Activated Sludge Final 156-157
Effluent, Plant M8
VII-3 Biological Treatment System 159-160
Clarifier Overflow, Plant M9
VII-U Settling Pond Final Effluent, 153
Plant A3
VII-5 Neutralized Activated Carbon 164-165
(Final) Effluent, Plant A6
VII-6 Activated Carbon (Final) ^57
Effluent, Plant A8
VII-7 Holding Pond (Final) 159
Effluent, Plant A19
VII-8 Halogenated Organic Pesticide 170-171
Plants, Treated Effluent Summary,
Subcategory A
VII-9 Monthly Activated Sludge Effluent 174
Summary, Plant B2
VII-10 Effluent Daily Variability, 175
Plant B2
VII-11 Selected Daily Activated 176-177
Sludge Effluent, Plant B2
VII-12 Primary Treatment Effluent, 178-179
Plant B7
VII-13 Organo-Phosphorus Pesticide
Plants, Treated Effluent
Summary, Subcategory B
VII-14 Organo-Nitrogen Pesticide
Plants, Treated Effluent
Summary, Subcategory C
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VII-15
VII-16
VIII-1
VIII-2
VIII-3
viu-a
VIII-5
VIII-6
VIII-7
VIII-8
VIII-9
IX-1
IX-2
IX-3
X-1
XIII-1
Page
BPT Treatment System Design Summary 193
Summary of BPT Model Treatment 198
Systems Effluents
Basis for Computation of Annual 201-202
Costs (August 1972 Dollars)
BPT Capital Cost Itemization 204
Subcategory A
BPT Capital Cost Itemization 205-206
Subcategory B
BPT Capital Cost Itemization 207-208
Subcategory C
BPT Capital Cost Itemization 209
Subcategory E
BPT Cost Summary - Subcategory A 211
BPT Cost Summary - Subcategory B 212
BPT Cost Summary - Subcategory C 213
BPT Cost Summary - Subcategory E 214
BPT Effluent Limitation Guidelines 219
BPT Treatment Technology 224
Potential Methods for Upgrading 234-235
Existing Systems
Index of Pesticide Compounds 239-263
By Subcategory
Metric Table 331
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SECTION I
CONCLUSIONS
The miscellaneous chemicals industry encompassed eight
industrial categories, grouped together for administrative
purposes. This document provides background information for
the pesticide chemicals point source category, sometimes
referred to as the pesticide chemicals industry, and
represents a revision of a portion of the initial
contractor's draft document issued in February, 1975. The
revisions have been made as the result of additional studies
and data collection by two additional contractors to the
Agency.
It is pointed out that each category differs from the others
in raw materials, manufacturing processes, and final
products. Water usage and subsequent wastewater discharges
also vary considerably from category to category.
Consequently, for the purpose of the development of the
effluent limitations guidelines and corresponding BPT (Best
Practicable Control Technology Currently Available)
requirements, each category is treated independently. This
document addresses the pesticide chemicals manufacturing
point source category.
It should be emphasized that the proposed treatment model
technology is used as a guideline primarily for cost
development and may not be the most appropriate technology
for use in every case, and that the cost models for BPT were
developed to facilitate the economic analysis and should not
be construed as the only technology capable of meeting the
effluent limitations guidelines. There are many alternative
systems which either singly or in combination are capable of
attaining the effluent limitation guidelines recommended in
this development document.
A representative treatment model is presented for each
subcategory.
It is expected that each individual plant will make the
choice of the specific combinations of pollution control
measures best suited to its situation in complying with the
regulations proposed in this development document.
This report encompasses five major subcategories of the
pesticide chemicals point source category. These
subcategories are:
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A. Halogenated Organic Pesticides.
B. Organo-Phosphorus Pesticides.
C. Organo-Nitrogen Pesticides.
D. Metallo-Organic Pesticides.
E. Formulators and Packagers.
Process wastewaters from production of halogenated organic
pesticides result from wet scrubbing, caustic soda
scrubbing, and contact cooling systems. Organic compounds
result from decanting, distillation, and strippincr
operations. Poor operation may result in process wastewater
streams becoming contaminated from spillage, washdowns, and
runoff.
For proper control and treatment, Subcategory A process
wastewaters should be isolated from nonprocess wastewaters
such as utility discharges and uncontaminated storm runoff.
The BPT treatment model of the process wastewaters includes
equalization, pH adjustment, skimming of separable organics,
filtration, carbon adsorption, and biological treatment.
Incineration or suitable disposal of strong or toxic wastes
may be necessary.
The organo-phosphorus pesticides facilities produce
wastewaters with high organic loadings from decanter units,
distillation towers, overhead collectors, and solvent
strippers. Caustic scrubbing and contact cooling are the
major contributors to total flow. Highly alkaline wastes
result from caustic scrubbing, in-process hydrolysis units,
and product washing.
The BPT technologies necessary to control and treat
wastewaters from this category include isolation of process
streams, separation of insoluble organics, alkaline
hydrolysis, equalization, pH adjustment, and biological
treatment. Incineration or other suitable disposal systems
may be required for very strong or toxic wastes.
Scrubbing operations are the major contributor to the total
effluent flow rate for facilities producing pesticides of
the organo-nitrogen subcategory. Nitrogen loadings are due
primarily to decanting operations and extractor/precipitator
units. Organic loadings result from solvent stripping anc!
purification steps. High organic and solids loadings can
caused by poor operation, accidental spillage, equipment
cleanout, and area washdowns.
The model treatment system for process wastewaters from
organo-nitrogen pesticide facilities includes pH adjustment,
separation of insoluble organics, hydrolysis, equalization,
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and biological treatment. Incineration or other suitable
disposal of very strong or toxic wastes may be required.
Process wastewaters produced by facilities within the
metallo-organic subcategory covered by this regulation are
disposed of by recycle or suitable containment.
BPT control and treatment of process wastewaters for this
subcategory is no discharge of process wastewater
pollutants.
Formulators and packagers have been found to generate either
no wastewaters or such small volumes that disposal can be
handled adequately by disposal contractors, land
application, evaporation, or other means leadina to no
discharge of process wastewater pollutants.
Table 1-1 summarizes the contaminants of interest, raw waste
loads, and recommended treatment technologies for BPT for
each subcategory. An index for determining the subcategory
for each pesticide is published in Section X of this
development document.
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TABLE 1-1
SUMMARY TABLES
SUBCATEGORY
A
D
E
CONTAMINANTS OF INTEREST
BOD, COD, TSS, Phenol, Total
Pesticides
BOD, COD, TSS, NH3.-N, Total
Pesticides
BOD, COD, TSS, NH3.-N, Total
Pesticides
TREATMENT TECHNOLOGY
Neutralization, API separation, equalization,
filtration, carbon adsorption, activated
sludge, and incineration of strong organic
wastes.
API separation, hydrolysis, neutralization,
equalization, activated sludge, ammonia
stripping for segregated waste streams, and
incineration of strong organic wastes.
API separation, hydrolysis, neutralization,
equalization, activated sludge, ammonia
stripping for segregated waste streams, aerobic
digesters and incineration ot strong organic
wastes.
In-plant controls, water conservation, and
water reuse.
Recycle, containment and evaporation.
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TABLE 1-1
Continued
Page 2 of 2 Pages
MODEL PLANT RAW WASTE LOADS*
SUBCATEGORY
A
B
C
FLOW
L/Kkg
35,300
43,900
35,400
BOD
97.2
67.7
45.5
COD
183
267
103
SS
3.49
11.7
2.50
NH3-N PHENOL
1.92
81.8
60.2
TOTAL
PESTICIDES
0.327
0.454
2.82
*A11 units Kg/Kkg unless otherwise noted
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SECTION II
RECOMMENDATIONS
The recommendations for effluent limitations guidelines
commensurate with the BPT and end-of-pipe treatment
technology for BPT are presented in the following text.
Exemplary in-process controls are discussed in the later
sections of this document.
The effluent regulations corresponding to BPT, as proposed
for each subcategory, are presented in Table IT-1. The
effluent limitations guidelines were derived on a basis with
two limitations for each parameter; the maximum average of
daily values for thirty consecutive days and the maximum for
any one day. These values were derived on the basis of the
observed performance of treatment plant operations as
discussed in Section IX of this document. Process
wastewaters 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.
Implicit in BPT standards is the segregation of noncontact
wastewaters from process wastewaters and the maximum
utilization of applicable in-plant pollution abatement
technologies required to minimize capital expenditures for
end-of-pipe wastewater treatment facilities. Segregation
and incineration of extremely toxic wastewaters or very
strong wastewaters are recommended.
End-of-pipe treatment model technology for BPT involves the
application of biological treatment, preceded by various
types of in-process control and pretreatment, depending on
the particular subcategory. Extensive pretreatment systems
are required due to the toxic nature of many pesticide
wastewaters. Equalization with pH control and oil
separation will be required to provide optimal, as well as
uniform, levels of treatment.
Subcategory A, "Halogenated Organics", includes carbon
adsorption followed by biological treatment. The model
treatment systems for organo-phosphorus and organo-nitrogen
subcategories include hydrolysis units prior to equalization
and biological treatment. Chemical flocculation aids, when
necessary, should be added to the clarification system in
order to control suspended solids levels. The metallo-
organic subcategory covered by this regulation was found to
effectively control in-plant processes to a level of no
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discharge of process wastewater pollutants. This is
attained by recycle or suitable containment of wastes. No
treatment model is presented for formulators and packagers
as this study found that economical in-plant recovery,
reuse, evaporation systems or contract disposal results in
no discharge of process wastewater pollutants.
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SUBCATEGORY
TABLE II-l
BPT EFFLUENT LIMITATIONS GUIDELINES
EFFLUENT LIMITATIONS
EFFLUENT
CHARACTERISTICS
AVERAGE OF DAILY VALUES
FOR 30 CONSECUTIVE DAYS
DAILY
MAXIMUM
B
BOD
COD
TSS
Phenol
Total Pesticides
BOD
COD
TSS
NH3-N
Total Pesticides
BOD
COD
TSS
NH3-N
Total Pesticides
8.70
21.2
6.30
0.00170
0.00306
1.52
11.9
7.05
4.41
0.00175
8.64
21.1
9.51
4.88
0.00705
D
E
—NO DISCHARGE OF PROCESS WASTEWATER K)LLUTANTS-
—NO DISCHARGE OF PROCESS WASTEWATER K)LLUTANTS-
15.2
30.7
9.03
0.00480
0.00622
2.65
17.3
10.1
5.14
0.00392
15.1
30.4
13.6
5.69
0.0158
Note: All units are kg/Kkg
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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 to shift from a reliance on effluent
limitations related to water quality to an additional
reliance on technology-based effluent limitations.
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) 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
BPT as defined by the Administrator pursuant to Section
304 (b) of the Act. Section 301(b) 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. This will result in progress towards reaching the
national goal of eliminating the discharge of all
pollutants, as determined in accordance with regulations
issued by the Administrator pursuant to Section 304 (b) of
the Act. Section 306 of the Act requires the achievement by
new sources of federal standards of performance providing
for the control of the discharge of pollutants. This
reflects the greatest degree of effluent reduction which the
Administrator determines to be achievable through the
application of the NSPS processes, operating methods, or
other alternatives, including, where practicable, a standard
permitting no discharge of pollutants.
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. The
regulations proposed herein set forth effluent limitations
and guidelines pursuant to Section 304(b) of the Act.
Section 304(c) of the Act requires the Administrator to
issue information on the processes, procedures, or operatincr
methods which result in the elimination or reduction in the
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discharge of pollutants to implement standards of
performance under Section 306 of the Act. Such information
is to include technical and other data, including costs, as
are available on alternative methods of elimination or
reduction of the discharge of pollutants.
Section 306 of the Act requires the Administrator, within
one year after a category of sources is included in a list
published pursuant to Section 306 (b) (1) (A) of the Act, to
propose regulations establishing federal standards of
performances for new sources within such categories. The
Administrator published in the Federal Register of January
16, 1973 (38 F.R. 1624) a list of 27 source categories.
Publication of the list constituted announcement of the
Administrator's intention of establishing, under section
306, standards of performance applicable to new sources.
Furthermore, Section 307(b) provides that:
1. The Administrator shall, from time to time, publish
proposed regulations establishing pretreatment
standards for introduction of pollutants into
treatment works (as defined in Section 212 of this
Act) which are publicly owned, for those pollutants
which are determined not to be susceptible to
treatment by such treatment works or which would
interfere with the operation of such treatment
works. Not later than ninety days after such
publication, and after opportunity for public hear-
ing, the Administrator shall promulgate such
pretreatment standards. Pretreatment standards
under this subsection shall specify a time for
compliance not to exceed three years from the date
of promulgation and shall be established to prevent
the discharge of any pollutant through treatment
works (as defined in Section 212 of the "Act")
which are publicly owned, which pollutant inter-
feres with, passes through, or otherwise is
incompatible with such works.
2. The Administrator shall, from time to time, as
control technology, processes, operatina methods,
or other alternatives change,, revise such
standards, following the procedure established by
the subsection for promulgation of such standards.
3. When proposing or promulgating any pretreatment
standard under section 307 (b), the Administrator
shall designate the category or categories of
sources to which such standard shall apply.
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U. Nothing in this subsection shall affect any
pretreatment requirement established by any State
or local law not in conflict with any pretreatment
standard established under this subsection.
In order to insure that any source introducing pollutants
into a publicly owned treatment works, which would be a new
source subject to Section 306 if it were to discharge
pollutants, will not cause a violation of the effluent
limitations established for any such treatment works, the
Administrator is required to promulgate pretreatment
standards for the category of such sources simultaneously
with the promulgation of standards of performance under
Section 306 for the equivalent category of new sources.
Such pretreatment standards shall prevent the discharge into
such treatment works of any pollutant which may interfere
with, pass through, or otherwise be incompatible with such
works.
The Act defines a new source to mean any source the
construction of which is commenced after the publication of
proposed regulations prescribing a standard of performance.
Construction means any placement, assembly, or installation
of facilities or equipment (including contractual obliga-
tions to purchase such facilities or equipment) at the
premises where such equipment will be used, including
preparation work at such premises.
Methods Used for Development of the Effluent Limitations and
Standards for Performance
The effluent limitations, guidelines and standards of
performance proposed in this document were developed in the
following manner. The pesticide chemicals manufacturing
point source category was first divided into industrial
categories based on type of manufacturing and products
manufactured. Determination was then made as to whether
further subcategorization would aid in description of the
category. Such determinations were made on the basis of raw
materials required, products manufactured, processes
employed, and other factors.
The raw waste characteristics for each category and/or
subcategory were then identified. This included an analysis
of: 1) the source and volume of water used in the process
employed and the sources of wastes and wastewaters in the
plant; and 2) the constituents of all wastewaters
(including toxic constituents) which result in taste, odor,
and color in water or aquatic organisms. The constituents
of wastewaters which should be subject to effluent
11
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limitations, guidelines and standards of performance were
identified.
The full range of control and treatment technologies
existing within each category and/or subcategory was
identified. This included an identification of each dis-
tinct control and treatment technology, including both in-
plant and end- of-pipe technologies, which exist or are
capable of being designed for each subcategory. 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 and the required implementation time 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
wel] as the cost of the application of such technologies.
The information, as outlined above, 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 equipment 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 initial 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 wastewater treatment systems were known to be included in
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)
12
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process Raw Waste Load (RWL) 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. During the course of the
study to date, more than 166 plants have been contacted and
27 visited. Visitations alone have covered more than 90
percent of the pesticide products manufactured.
Collection of the data necessary for development of RWL and
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. The
RWL for this plant and associated treatment technology would
therefore fall within a single subcategory. However, the
wide variety of products manufactured by most of the
industrial plants usually prohibited this approach.
Thus, in the majority of cases, it was necessary to visit
individual facilities where the products manufactured fell
into several subcategories. The end-of-pipe treatment
facilities often received combined wastewaters associated
with several subcategories (several products, processes, or
even unrelated manufacturing operations). It was necessary
to analyze separately the production (waste-generating)
facilities and the effluent (waste treatment) facilities.
This approach required establishment of a common basis, the
Raw Waste Load (RWL), for common levels of treatment
technology for the products within a subcategory and for the
translation of treatment technology between categories
and/or subcategories.
The selection of wastewater 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.
Survey teams composed of project engineers and scientists
conducted the actual plant visits. Information on the
13
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identity and performance of wastewater 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 and the associated
RWL 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 wastewater sampling and
analysis.
The data base obtained in this manner was then utilized by
the methodology previously described to develop recommended
effluent limitations, guidelines and standards of
performance for the pesticide manufacturing point source
category. All of the references utilized are included in
Section XII of this report. The data obtained during the
field data collection program are included in Supplement B.
Cost information is presented in Supplement A. The
documents are available for examination by interested
parties at the EPA Public Information Reference Unit, Room
2922 (EPA Library), Waterside Mall, 401 M St. S.W.,
Washington, D.C. 20460.
of the Study
SIC 2879, Pesticides and Agricultural Chemicals not
Elsewhere Classified, covers: (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 elsewhere classified,
such as minor or trace elements and soil conditioners.
14
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The basic manufacture of inorganic metallic pesticides,
herbicides, etc. is included in SIC 2819 and the basic
manufacture of organic pesticides is included in SIC 2869.
It can be seen, therefore, that 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.
The coverage of non-pesticide products (such as plant
hormones and soil conditioners) in SIC codes 2819, 2869, and
2879 is beyond the scope of this study. Also not covered in
this study are those miscellaneous pesticides not
identifiable by their active molecular group as halogenated
organic, organo-nitrogen, organo-phosphorous or metallo-
organic.
Individual pesticides 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
110-13U, where a list of common names, chemical names, and
alternative designations are presented. This list is the
basis for the pesticide references employed in this
document.
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 hicrh-
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 manufacturing activities carried out within that
15
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plant. Frequently, products are utilized captively 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 wastewater
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 distribution of major pesticide manufacturers is
illustrated in Figure III-1. Unlike some point source
categories where relatively large plants manufacture es-
sentially a single product from a limited number of raw
materials, the pesticide chemicals point source category
involves a complex mixture of raw materials, processes,
product mixes, and product formulations. To understand this
completely, it is necessary to examine selected chemical
groupings and product categorizations in detail. Of over
500 individual pesticides of commercial importance, and
perhaps as many as 34,000 distinct major formulated
products, the following pesticide product divisions can be
made:
1. Halogenated organic
2. Organo-phosphorus
3. Organo-nitrogen
U. Metallo-organic
5. Botanical and microbiological
6. Miscellaneous (not covered in the preceding groups)
During the course of the study every known manufacturer of
technical pesticides was contacted. The distribution of
plants by product division was as follows:
16
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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
-------
Single Multi-
Category Category
Manu facturers Manu facturers
Halogenated
Organic 22 33
Phosphorus
Containing 7 1U
Nitrogen
Containing 19 34
Metallo
Organic 4 17
Other or
Unknown
TOTAL
*Discrete Plants
The grouping above further expedites discussion of the
relationships and differences among the various chemical
groups. Some examples of these differences include the
prolonged persistence of chlorinated hydrocarbons versus
shorter half lives of organo-phosphorus and organo-nitrogen
compounds in the environment; the amenability of organo—
phosphates and organo-nitrogen compounds to chemical
hydrolysis; the various physical properties of pesticides
(for example, oily versus crystalline) which may affect the
selection of control and treatment processes; and the
amenability of particular chlorinated hydrocarbons to
recovery (for example, by steam stripping).
The distribution of the pesticide chemicals among the
preceding product groups or families is presented in Table
III-1. It can be seen that the nitrogen-containing group is
the most diverse, and that the halogenated, phosphorus-
containing, and metallo-organic families are approximately
equal in diversity. Table III-2 lists the majority of the
pesticides manufactured in the U.S. according to family tree
and chemical structure. Their chemical configuration is
also illustrated in the table.
The halogenated organic group of pesticides includes many
first generation organic pesticides, e.g., DDT, and has a
broad spectrum of insecticidal action with prolonged
stability and residual activity. This, along with
18
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TABLE III-l
PESTICIDE CLASSIFICATION
NUMBER OF
MAJOR PESTICIDES
A. 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
B. Phosphorus-Containing Pesticides
Phosphates and phosphonates 19
Phosphorothioates and phosphorodithioates 61
Phosphorus-nitrogen compounds 8
Other phosphorus compounds _5_
93
C. Nitrogen-Containing Pesticides
Aryl and alky! carbamates and related compounds 35
Thiocarbamates 23
Anil ides 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
D. 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
19
-------
TABLE III-l
PESTICIDE CLASSIFICATION
Continued
NUMBER OF
MAJOR PESTICIDES
E. Botanical and Microbiological Pesticides 19
F. Organic Pesticides, not Elsewhere Classified
Carbon compounds 41
Anticoagulants _4
45
TOTAL 550
20
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TABLE II1-2
STRUCTURAL CHEMISTRY OF TYPICAL AND MAJOR PESTICIDES
A. HALOGENATED ORGANICS
X=normally Cl
DDT and Relatives
Z
I
I
Y
Y=noramlly CC13
Z=normally H
DDT, ODD, TDE, Perthane* ,Methoxychi or, Prolan, Bulan, Gex, Dicofol,
Chloropropylate, Bromopropylate, Parinol, Chiorobenzilate
Chlorinated Aryloxyalkanoic Acids
>_ OCHR (CH2)m COOH
R=normally H or CH3
X=normally Cl
Y=always Cl
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
(cj) = perch!orinated ring
Kepone*, Heptachlor, Mirex, Pentac*, Chlorodane, Telodrin, Aldrin,
Dieldrin, Toxaphene, Endrin, Endosulfan, Isodrin, Alodan, Bromodan,
Strobane
Halogenated Aliphatic Hydrocarbons
C
X
X=halogenated, H and 0
R=Alkyl grouping or halogen
TCA and its salts, Dalapan and its salts, Fenac, Methyl Bromide, DBCP,
DD*, EDB, Lindane, Glytac*
* Trademark
21
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TABLE 1 1 1-2
(Continued)
Halogenated Aromatic Compounds
X=C1, and NH?,OCH-,, H, etc.
*
R=OH, H, CL, RCOOH, ESTER, etc,
A A
Benzene hexachloride, Dichlorbenzenes, 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
B. PHOSPHORUS-CONTAINING
Phosphates and Phosphonates
R] , Ro=usuany alkyl group
RjO 0 R3=Alkly, halogen, NH2, etc.
^ " Y=ususally halogen on H
"
R2)
Y
Dichlorvos, Dicrotphos, Ciodrin*, Trichlorofon, Ethephon, Gardona*,
Mevinphos, Naled, Nia 10637, TEPP, Phosphamidon
Phosphorothioates and Phosphorodithioates
S Rl=Alkyl group
A=0 on S
(RlO)?-P-A-R2 R2=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-methyl sul foxi de,
Prophos, Phenthoate, Leptophos, Pirimiphosethyl , Sumithion*, Supracide*,
Surecide*, Dialifor, Carbophenothion, Dichlorofenthion, Zinophos*, Phosalone
* Trademark
22
-------
TABLE II I -2
(Continued)
Phosphorus-Nitrogen Compounds
(S)
0 R-|=Alkyl, aryl group, etc.
^ " R2=Alkyl, aryl group, etc.
j\ p - pjR3 R3=Alkyl, aryl, or other cyclic
"^^ compounds, etc.
Ruelene, Nellite*, Nemacur*, Cyolane, Cytrolctne, Go phacide*, Monitor*
C. NITROGEN-CONTAINING
Aryl and Alky! 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), Chloropropham (CIPC), Barban, Swep, Sirmate*, Azak*,
I sol an, 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.
R2
EPTC, SMDC, Vernolate, CDEC, pebulate, Diallate, Triallate, butylate,
Molinate, Cycloate, Bolero*, Eptam*
Amides and Amines (without sulfur)
0 R1=Alkyl, C1CH2, etc.
" R2=Alkyl, Cyclic compounds
R]-C-N-R3 R3=Alkyl, H
Pronamide, Alachlor, Dicryl, Solan, Propanil, Diphenamid, Propachlor,
CDAA, Naptalam, Cypromid, CDA, Chlonitralid, Benomyl , Deet, Dimetilan,
Diphenylamine, Horomodin*, Butachlor, Naphthalene acetamide, Vitavax*
* Trademark
23
-------
TABLE II1-2
(Continued)
Ureas and Uracils
C4
and IN Y^Y !
(K Vs CHS
N
I
H
Ri=Cl, Br, H, OCH3, etc. R3=CH3, OCH3, etc.
R2=H, Cl, etc. R4=CH3, Alkyl
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=A1 kyl
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, Alkyl, Etc.
P ^\n R2=N02, H, Alkyl, etc.
4O 2 R3=N02, CF3
k^J R4=N02, H
«3
Benefin, Dinocap, Dinsep (DNSP), DNOC, Nitralin, PCNB, Trifluralin, A-820*,
Dinoseb 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*,
24
* Trademark
-------
TABLE 111-2
(Continued)
MGK Repellent 326*, Neo-Pynamin*, Parquat, Thiram, Thiophanate, 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)
D. 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
E. BOTANICAL AND MICROBIOLOGICAL
These have varied chemical structures, and, therefore, no generalized
formula can be derived.
Bacillus popilliae, Bacillus thuringiensis, Polyhedrus Virus, Pyrethrins,
Ryania
F. 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
25
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competition from new products which are more economical,
less toxic to higher animals, and more environmentally de-
gradable, has caused a decline in the use of the halogenated
organic group of pesticides since the mid-1960»s.
The phosphorus-containing insecticides are among the fastest
growing products in the pesticide chemicals industry.
Thousands of phosphorus-containing compounds have been
evaluated for pesticidal properties, and commercial products
currently used include insecticides that are marketed in
multimillion-pound quantities. The number of highly toxic,
phosphorus-containing compounds is virtually limitless.
Their suitability as insecticides, however, depends on their
specific physical and chemical properties, and on how safely
they can be employed. Although they are very toxic,
phosphorus-containing compounds generally are easily
hydrolyzed in an alkaline medium to yield materials of
relatively low toxicity. Generally, these pesticides are
also environmentally degradable.
Several classes of nitrogen-containing compounds have been
produced and successfully marketed since 1945. These have
the broadest range of biological activity, and can be
applied as selective herbicides, insecticides, or
fungicides. Herbicides and fungicides for which nitrogen-
containing compounds have recently been synthesized have
continued to increase their share of the pesticide market,
an increase from 44.1 percent in 1966 to 57.2 percent in
1970.
Metallo-organic pesticides, which are produced by a
relatively limited number of companies, include the sodium
methane arsenate herbicides, and cadmium, mercury, and
copper derivatives of organic compounds. The three major
types of metallo-organic derivatives, manganese, tin and
zinc, are not included in the scope of this document.
Three of the botanical and biological insecticides, Bacillus
thuringienes, rotenone, and the pyrethrins,, though quite
effective and useful in insecticide formulations, are
nontoxic to mammals. Rotenone is quite toxic to fish and
are found widely in nature. These pesticides must be
extracted or obtained through a fermentation process.
Large-volume production (greater than one million pounds per
year) is seldom encountered. Thus, these insecticides are
not covered in this study.
There are other pesticides which do not readily fall into
the previously discussed subcategories. Of these, the
rodenticide Warfarin deserves mention. Its production has
26
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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.
A small group, called the sulfur pesticides, contains
halogen, nitrogen, or are produced as a metal salt, and have
been categorized as halogenated organic, nitrogen-
containing, or metallo-organics, respectively. The
treatability of the wastewaters generated during the
production of these sulfur-based compounds is similar to
that of their non-sulfur relatives. Inorganic pesticides,
for example sodium chlorate and elemental sulfur, have been
studied as part of the inorganic industry and are not
covered in this document. Likewise, certain organic
materials, occasionally used as pesticides, are more
appropriately covered by the organic chemicals point source
category. Both production and wastewater treatabilities of
the botanical (pyrethrins), microbiological (Bacillus
thuringienes), and the anticoagulants (Warfarin) 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.
In addition to the plants which manufacture active
ingredients for pesticides, 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 this sector of the category,
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
wastewater generation and contamination are considerably
lower than in the active-ingredient production facilities.
Pesticide formulations and packaged products generally fall
into three classifications: water-based, solvent-based, and
dry-based.
27
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FIGURE III-2
LOCATIONS OF FORMULATION
FACILITIES IN U.S.
PO
00
Source: Environmental Protection Agency,
Technology Series: EPA-660/2-74-094
January, 1975.
-------
SECTION IV
INDUSTRIAL CATEGORIZATION
Rationale of Categorization
In the development of effluent limitation guidelines and
standards of performance for the pesticide chemicals point
source category, it was necessary to determine whether
significant differences exist which may form a basis for
subcategorization. The rationale for subcategorization was
based on emphasized differences and similarities in such
factors as (1) constituents and/or quantity of waste
produced; (2) the engineering feasibility of treatment and
resulting effluent reduction; and (3) the cost of treatment.
While factors such as plant age and size tend to affect the
constituents and quantity of waste produced, the emphasis
herein is not merely on an analysis of these factors, but on
the resulting differences in waste production, engineering
feasibility, and cost.
Among the factors or elements which were considered in
regard to identifying any relevant subcategories were the
following items.
Manufacturing Processes
Pesticide plants which manufacture active ingredient
products use many diverse manufacturing processes. Rarely
does a plant employ all of the processes found in the
category, but most plants use several processes in series.
The principal processes utilized include chemical synthesis,
separation, recovery, purification, and product finishing,
such as drying.
Chemical synthesis can include chlorination, alkylation,
nitration, and many other substitution 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,
distillation, and extraction are common processes in the
pesticide chemicals industry. Product finishing can include
blending, dilution, pelletizing, packaging, and canning.
Since diverse processes are used by all sectors of the
active ingredient industry, as discussed above, the type of
manufacturing process alone is not a comprehensive basis for
subcategorization.
29
-------
This study indicated the manufacturing segment differed from
the formulating/packaging segment in the basic operations,
water/solvent utilized, and waste load generated. These
differences require separate subcategorization of the active
ingredient manufacturing sectors from the formulation and
packaging operation.
Product
Four fundamental pesticide subcategories are evident based
on the generic class of the product and the process
chemistry employed. These are halogenated organic, organo-
phosphorus, organo-nitrogen, and metallo-organic products.
As shown in Section V of this document, the characteristics
of the wastewaters from the production of these products can
differ appreciably. Also, as detailed in Section VII, the
treatment technologies required for the wastewaters differ.
Certainly the subcategorization does leave some ambiguities.
This is especially true of compounds containing chlorine
which are not grouped as halogenated organics but elsewhere
due to greater similarity of functional groups. An example
is the organo-phosphorus compound Dursban. This compound
contains sulfur, chlorine, nitrogen and phosphorus. The
readers are directed to Section X of this development
document for guidance in which subcategory a particular
pesticide belongs.
A number of pesticides cannot be classified in any of the
above classes. These are referred to as non-categorized
pesticides hereafter. Examples of these are also in Section
X.
Raw Materials
Since it can be assumed that the raw materials used in the
pesticides chemicals industry are feedstocks specific to the
product being manufactured and with narrow ranges of quality
and purity, the choice of raw material does not have a
significant impact on the nature or quantities of waste
products generated within any one subcategory. Accordingly,
wastewater volumes and qualities are not effected by choice
of raw materials. Thus, the selection of raw materials is
not a significant factor on which to base further
subcategorization.
Plant Size
There are more than 100 plants in the United States engaged
in the production of pesticidal active ingredients, and
30
-------
possibly as many as about 3,000 facilities formulating the
active ingredients into final products, such as liquids,
dusts, and packaged aerosols. The sizes of process units,
production complexes, and individual companies in the
pesticide chemicals point source category sector are not
published, and this information was not available for the
purposes of this study. Based on information obtained
during plant visits, it is obvious that plant size can vary
appreciably. Plant size should not affect the applicability
or performance of control and treatment technologies as
outlined in later sections of this document, but potentially
will 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 on 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, continuous, depend 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 plants are
distributed throughout the United States. 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 wastewater
generated. Geographic location, however, can influence the
performance of aerated and stabilization lagoons, but low
performance problems can be overcome by adequate sizing or
selection of alternative processes, such as activated
sludge.
Since most pesticide plants are relatively new, and the
trend in the chemical industry is to locate plants outside
of urban areas, the tend to be located in rural areas.
Those plants that are located in urban areas tend to occupy
and own less land with the result that land costs for
31
-------
treatment facilities are higher than plants located in rural
areas.
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 philosophy of the company and
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 can be concluded that
housekeeping alone is not a reasonable factor for
subcategori zation.
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 type and characteristics of the wastes generated by the
various sectors of the pesticide chemicals industry are
discussed fully in Section V. In brief, the nature of the
generated wastes is a supporting basis for subcategorizatinq
the industry. The rationale behind such a subcategorization
is adequately covered in the process descriptions
subsections.
Treatability of Wastewaters
The wastewaters generated by the various sectors of the
industry exhibit different treatability characteristics.
The waste types and treatabilities are irelated to the
industry sector and its products and processes; no
32
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generalized conclusions can be drawn. The impact of the
product mix and processes is discussed in the subsections
dealing with the industry process descriptions in the
following pages.
Summary of Considerations
It was concluded, for the purpose of establishing effluent
limitations guidelines and standards, that the pesticide
chemicals industry should be grouped into five
subcategories. This subcategorization is based on distinct
differences in raw material, manufacturing processes,
products, and wastewater characteristics and treatability.
It is concluded that the pesticide chemicals point source
category should be grouped into the following subcategories:
A. Halogenated organics production
B. Organo-phosphorus production
C. Organo-nitrogen production
D. Metallo-organics production
E. Formulation or packaging of pesticides
F. Production of botanical, microbiological, or
miscellaneous pesticides. (not within the
scope of this document.)
It is recognized, and it should be made clear, that the
production operations so categorized occur in combinations
at many plants and that it is in fact possible for a given
facility to be associated with all of the subcategories as
well as with other chemical production. It is however,
generally true that a given plant does not produce both
insecticides and herbicides.
It is further recognized that many plants produce or use
intermediate products. This complicating factor is
discussed in Section IX under "Factors to be Considered in
Applying Effluent Guidelines."
Description of Subcategories
Subcategory A - Halogenated Organic Pesticides
Representative products included under Subcategory A are
those pesticides listed under halogenated organics in
Section X. In most cases the halogen component is chlorine.
The chlorine groups generally are added via direct
chlorination or via substitution from another chlorinated
organic.
33
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Subcategory B - Orqano-Phosphorus Pesticides
Representative products under Subcategory B includes those
pesticide products listed under organo-phosphorus compounds
in Section X. The subcategory includes phosphates, phos-
phonates, phosphorothioates, phosphorodithioates, and
phosphorus-nitrogen pesticide types.
Subcategory C - Organo-Nitrogen Pesticides
Representative pesticides included under Subcategory C are
listed in Section X under organo-nitrogen compounds. This
subcategory has more family groups and is the most diverse
of all the pesticide subcategories.
Subcategory D - Metallo-Orqanic Pesticides
The metallo-organic pesticide subcategory could be
considered a part of the inorganic and metallo-organic
sector of the industry. However, since most inorganic
pesticides are essentially simple inorganic chemicals, they
are not covered in this document. Representative metallo-
organic pesticides included in subcategory D are listed in
Section X.
Subcategory E - Formulators and Packagers
Subcategory E includes all types of pesticide formulating,
blending, packaging, canning, etc. It should be emphasized
that the manufacture or production of active ingredients
material is excluded from this subcategory.
Subcategory F - Non-Categorized Pesticides
Subcategory F includes the manufacture of all pesticides not
included in Subcategories A through D. These products are
not addressed in this document.
Process Descriptions
Halogenated Organic Pesticides
Four major halogenated organic pesticide groups merit
process descriptions and process flow diagrams. These
groups are:
34
-------
DDT and its relatives
Chlorinated phenols and aryloxyalkanoic acids
Aldrin and toxaphene
Halogenated aliphatic compounds
Although halogenated organic pesticides can involve other
halogens, chlorinated compounds are more common 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
wastewaters for the DDT family of pesticides. Analogs of
DDT can be prepared by changing the substituents on the
benzene (e.g. methoxychlor is made from Arisole and
Chloral).
Figure IV-1 is a simplified process flow diagram for DDT
production and illustrates the type of wastewater generated.
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 it may also 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
35
-------
FIGURE IV-1
GENERAL PROCESS FLOW DIAGRAM FOR DDT AND
RELATED COMPOUNDS PRODUCTION FACILITIES
CHLORO BENZENE
VENT
VENT
VENT-«-
ALDEHYDE
H2S04
en
2-STAGE
.REACTOR
SEPARATOR
WATER-i
SCRUBBER
SPENT ACID
ACID
VENT
SODA ASH
WATER-i
I
RECYCLE ACID
ACID
RECOVERY
UNIT
WASTE ACID
SCRUBBER
VACUUM
COLUMN
NEUTRALIZATION
VENT^i
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)
-------
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 throuorh 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 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 wastewater from caustic
soda scrubber
i». 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 IV-2
and IV-3 are simplified process flow diagrams for the
manufacture of the chlorinated phenols and aryloxyalkanoic
acids. Potential wastewater sources are shown.
Chlorobenzene can be converted to a phenol by reacting with
dilute caustic soda or water and a catalyst in a reactor.
Pentachloropheno1 (PCP) is prepared by chlorinating the
37
-------
FIGURE IV-2
OJ
oo
CAUSTIC SODA
-VENT
CHLORINE
SCRUBBER
PHENOL
CHLORINE
CATALYST
VENT
C6C1XOH
BY-PRODUCT
REACTOR
J
STILL
TARS TO
INCINERATION
EXCESS-e
WASTEWATER
TO TREATMENT
•PRINCIPAL PROCESSING ROUTE
FOR ALTERNATIVE PRODUCT-TYPE
GENERAL PROCESS FLOW DIAGRAM FOR
HALOGENATED PHENOL PRODUCTION FACILITIES
>-
LU
a:
I
REACTOR
o
u_
o
VENT-*i
SCRUBBER
SEPARATOR
PRILL
TOWER
VENT-
1
WATER
SCRUBBER
DUST & PARTICULATE
DRYER
PRODUCT
(CRYSTAL-
LIZES)
•AIR
PRODUCT
(PRILLED)
-------
phenol in the presence of a catalyst (see Figure IV-2).
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,
4-dichlorophenoxyacetic acid (2,4-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
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, wastewaters 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
4. Reactor and processing unit cleanout
wastewaters
5. Processing area washdown wastewaters
6. Water of formation from chemical reaction.
It should be mentioned that 2, 4, 5 trichlorophenol (the
feedstock for 2, U, 5 -T) may be contaminated with 2, 3, 7,
8 tetrachlorodibenzo-p-dioxin.
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.
39
-------
FIGURE IV-3
GENERAL PROCESS FLOW DIAGRAM OF ARYLOXYALKANOIC ACID PRODUCTION FACILITIES
DILUTE
CAUSTIC SODA
CHLOROPHENOL
CLROOH
REACTOR
CAUSTIC SODA OR SODA ASH
DILUTE
HYDROCHLORIC ACID
ACIDFIER
CRYSTALIZER
CENTRIFUGE
WASTEWATER
NEUTRALIZER
CRYSTALIZER
CENTRIFUGE
WASTEWATER
-VENT
DUSTS &
PARTICULATE
PRODUCT
(CRYSTALLIZED)
-
-»-VENT
DUSTS &
PARTICULATE
PRODUCT
(SALT OF
PESTICIDE)
PRINCIPAL PROCESSING ROUTE FOR ALTERNATIVE PRODUCT-TYPE
VENTS TO RECOVERY
-------
prepared by the Diels-Alder diene reaction. The development
of these materials resulted from the 1945 discovery of
chlordane, the chlorinated product of hexa-
chlorocyclopentadiene and cyclopentadiene. ^igure IV-4, a
simplified process flow diagram for this type of pesticide,
illustrates the potential sources of wastewater in this
process.
Cyclopentadiene, produced by cracking naphtha, is
chlorinated to yield hexachlorocyclopentadlene (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.
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
4. Periodic equipment cleaning wastewater
5. Wastes from cleanup of production areas.
Tars, off-specification products and filter cake should
not generate wastewaters since they are usually incinerated.
Halogenated Aliphatic Hydrocarbons
This group includes chlorinated aliphatic acids and their
salts (e.g., TCA, Dalapon, and Fenac herbicides),
halogenated hydrocarbon fumigants (e.g., methyl bromide,
DBCP, and EDB) , and the insecticide Lindane. figures IV-5
and IV-6 represent simplified process flow diagrams for the
production of halogenated aliphatics and halogenated
41
-------
FIGURE IV-4
GENERAL PROCESS FLOW DIAGRAM FOR ALDRIN-TOXAPHENE
PRODUCTION FACILITIES
-ti-
ro
CYCLOPENTADIENE
CHLORINE
CHLORINATOR
VENT
CAUSTIC SODA
WET
SCRUBBER
FILTER
o:
LU
I—
oo
DIENE
REACTOR
CAKE TO
INCINERATOR
-»-WASTEWATER
EXCESS TO
HoO.
SOLVENT
STRIPPER
TARS TO
INCINERATOR
INTERMEDIATE
OR
TECHNICAL
PRODUCT
SOLVENT
i
1 CHLORINE
1 1
1 CHLOR-
INATOR
>— i r— LMiMLYii REACTOR ^
OXIDATION . SOLVENT
REACTOR
' STRIPPER
U-WASTEWATER
VENT -« 1 STEAM-
pprnvFRY
PRODUCT
EXTR/
UWASTEWATER
PRODUCT
i i- n r-n
irTfip > prcnniiri
r
r r-i +A TFT*
FORMULATING
OR PACKAGING
OPERATIONS
— RECYCLE —
DUSTS, ETC.
ALTERNATE PRODUCT
-------
aliphatic acid pesticides. Potential wastewater 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 wastewater from fractionation units
3. Cooler blowdown water
t». 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, phosphoro-
dithioates, 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 IV-7 is a simplified process flow diagram
of phosphite triester production showing potential
wastewater sources.
43
-------
FIGURE IV-5
GENERAL PROCESS FLOW DIAGRAM FOR HALOGENATED
ALIPHATIC HYDROCARBON PRODUCTION FACILITIES
STEAM
HYDROCARBON
HALOGEN
VENT
EJECTOR
AND
BAROMETRIC
CONDENSER'
OR CAUSTIC
SCRUBBER
ACID
REACTOR
AND
STRIPPER
*SULFUR RELATED COMPOUNDS
FRACTIONATION
SYSTEM
«- WATER
-*- WASTEWATER
DRYER
(SILICA GEL)
T
PACKAGING
ACID WASTEWATER TO RECOVERY
SILICA GEL DISPOSAL
OR REGENERATION
* SULFUR RELATED COMPOUNDS IS A RAW MATERIAL FOR PRODUCTS
-------
FIGURE IV-6
en
WATER
GENERAL PROCESS FLOW DIAGRAM FOR HALOGENATED
ALIPHATIC ACID PRODUCTION FACILITIES
SCRUBBER
HCl.Clp
ALIPHATIC ACID-i I
• WASTEWATER
VENT
t DUSTS & PARTICULATE
CHLORINE
CHLORINATOR
CATALYST
COOLER
WASTEWATER
CAUSTIC SODA
CRYSTALLIZER
CENTRIFUGE
DRYER
PRODUCT
RETURN
MOTHER
LIQUOR
SLOWDOWN
NEUTRALIZER
VENT
1 DUSTS & PARTICULATE
PRINCIPAL PROCESSING ROUTE FOR ALTERNATIVE PRODUCT-TYPES
VENTS TO RECOVERY (SCRUBBER OR BAGHOUSE)
PRODUCT
(SALT OF THE
PESTICIDE)
AREA WASHDOWNS & SPILLS
-------
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 wastewater 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 wastewater 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.
Figure IV-8 is a generalized process and waste flow diagram
for this group of compounds. In the first step, phosphorus
pentasulfide (P2S5) is reacted with an alcohol (generally in
a solvent) to form the dialkyl phospheredithioic 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
46
-------
FIGURE IV-7
GENERAL PROCESS FLOW DIAGRAM FOR PHOSPHATES
AND PHOSPHONATES PESTICIDE PRODUCTION FACILITIES
VENT
WATER/NaOH/S02
LL
WATER
VENT
SCRUBBER
Na2C03
PCI'
ALCOHOL
STEAM
-WASTEWATER
REACTOR
REACTOR
KETONE OR ALDEHYDE
CONDENSER
VACUUM
JET
GO
ALKYLHALIDE WASTEWATER
STRIPPER
REACTOR
HALOGEN
-»| SCRUBBER],
WASTEWATER
CONDENSER
STRIPPER
SOLVENT RETURN
STEAM
1
VACUUM
JET
WASTEWATER
PRODUCT
STORAGE
-------
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
wastewater from the wash step is combined with scrubber
water from the overhead drier. Together, these wastewaters
constitute the major portion of the process waste stream.
Process wastewater can be detoxified (via alkaline
hydrolysis at elevated temperatures) before combining with
other plant waste streams.
In summary, the following wastewaters are generated during
the production of organo-phosphorus compounds:
1. Hydrolyzer wastewater
2. Aqueous phase from product reactors
3. Wash water from product purification steps
H. Aqueous phase from solvent extractor
5. Wastewater from overhead collectors and
caustic soda vent gas scrubbers
6. Reactor and process equipment cleanout
wastewaters
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.
48
-------
FIGURE IV-8
GENERAL PROCESS FLOW DIAGRAM FOR PHOSPHOROTHIOATE
AND PHOSPHORODITHIOATE PRODUCTION FACILITIES
AQUEOUS NaOH
FRESH SOLVENT
VENT
SOLVENT
ROH
DITHIO
ACID
SOLVENT
RECOVERY
f
AQUEOUS
PHASE
ORGANIC
NEUTRALIZATION
EXTRACTOR
EXTRACTOR
WATER
VENT
CHLORINE ..
CHLORINATION W PURIFICATION
WASTES
I
PRODUCT
STORAGE
AND
PACKAGING
ACID
DISTILLATION WASTES
WASTES
WATER
VENT
ORGANIC
WASTES
J
OVERHEADS
COLLECTOR
HYDROLYZER
BY-PRODUCT WASTEWATER
SULFUR
•*• H3P04
*• ORGANICS TO WASTE TREATMENT
VENT GASES
H2S. THERMAL OXIDIER
HC1. PARTIAL RECOVERY
-------
Aryl and Alkyl Carbamates and Related
Compounds
The carbamates in this grouping include carbaryl,
carbofuran, chloroprophamr BUX, aldicarb and propoxur. A
generalized production flow diagram is shown in Figure IV-9
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. Potentially toxic
wastewaters 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.
Wastewaters associated with the production of these
compounds are:
1. Brine process wastewater from reactors
2. Wastewater from the caustic soda scrubbers
3. Aqueous phase wasted following the isocyanate
reaction
4. 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 IV-10,
phosgene is reacted with an amine to give a carbamoyl
chloride. Reaction of the carbamoyl chloride with a mer-
captan 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.
Acidic process wastewaters 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 alka-
line hydrolysis at elevated temperatures.
In summary, the production of thiocarbamates will generate
the following wastewaters:
50
-------
FIGURE IV-9
ALKYL CARBAMATE
CAUSTIC SODA
PHOSGENE
NAPHTHOL
ALKYL AMINE
ARYL CARBAMATE
ALKYL ISOCYANATE
CATALYST
CATECHQL
METHALLYL
CHLORIDE
KETONE (BASE)
GENERAL PROCESS FLOW DIAGRAM FOR ALKYL AND ARYL
CARBAMATE PRODUCTION FACILITIES
FLARE OR SCRUBBER
REACTOR
REACTOR
BRINE
WASTEWATER
CHC1'
REACTOR
I
WATER
PURIFICATION
-M;HC1-
DISTILLATION
REACTOR
LIQUID WASTE
VENT
DUST
COLLECTOR
PACKAGING
-SOLVENT
REACTOR
DISTILLATION
PRODUCT
WASTEWATER
-------
1. Acid wastewater 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 Deetr 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 wastewater
sources, is presented in Figure IV-11. 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 wastewaters are generated from the
intermediate product separation and purification steps. If
the acetyl chloride is also prepared on-site, then acidic
process wastewater from the purification step and vent gas
scrubbers should be considered part of the overall pesticide
raw wastewater loads.
In summary, wastewaters 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
Ureas and Uracils
Pesticides in this group include diuron, 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 IV-12
shows the generalized process flow diagram and wastewater
52
-------
FIGURE IV-10
GENERAL PROCESS FLOW DIAGRAM FOR
THIOCARBAMATE PRODUCT FACILITIES
MERCAPTAN
CAUSTIC SODA
AMINE
>
PHOSGENE
W^
VE
NT
REACTOR
ACI
(STEk
D
ATER
' i
REACTOR
t
RECYCLE
V
S'
T)
INT
1 ILL T rALI\MullNb
\RS
BRINE
I
-WASTE TREATMENT
-------
FIGURE IV-11
GENERAL PROCESS FLOW DIAGRAM FOR
AMIDE AND AMINE PRODUCTION FACILITIES
ACETYLCHLORIDE
en
AMINE
ALDEHYDE
OR KETONE
REACTOR
PURIFICATION
WATER
REACTOR
NH4OH
PURIFICATION
WASHING
AND
DRYING
PACKAGING
-WASTEWATER
-------
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. Agueous 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 IV-12 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. Liguid wastes from the
purification, neutralization and filtration steps reguire
treatment via either biological oxidation or incineration
technologies.
In summary, wastewaters 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)
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 IV-13. One chlorine atom is replaced by
55
-------
tn
CTl
UREAS
WATER-,H/ENT
r
SCRUBBER
FIGURE IV-12
GENERAL PROCESS FLOW DIAGRAM FOR UREA AND URACILS
PRODUCTION FACILITIES
SOLVENT
AMINE
UREA
ALKYLANILINE
TU
NH3
IASTE WATER
AQUEOUS
REACTOR
OR
-*•
nil
DISTILLATION
>
EXTRACTOR
WATER-
PRECIPITATOR
WASTEWATER
URACILS
ETHYL ACETOACETATE
CAUSTIC SODA
rEWATER I
TARS TO INSOLUBLES
INCINERATION
PRODUCT
PACKAGING
WASTEWATER
H2S04-, HALOGEN—i ,— WATER
VENT
PHOSGENE
AMMONIA
ALKYL ANILINt
UREA
UNIT
PURIFICATION
URACILj
UNIT
VENT
PURIFICATION
BR NE
WASTEWATER
NEUTRAL-
IZATION
SEPARATION
WASTEWATER
HALOGENATOR
FILTRATION
DRYING
•>
PRODUCT
PACKING
WASTES
BRINE
WASTEWATER
-------
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 wastewater requires treatment.
Amination of the cyanuric chloride, as depicted in Figure
IV-13, 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, wastewaters generated in the production of
triazine herbicides generally come from the following
sources:
1. Caustic soda scrubbing and filtration of
vented HCl and HCN gases
2. Aqueous wastes from the solvent recovery
unit
3. Scrubber water from the air pollution
control equipment used in formulation
areas
4. Production area washdowns
5. Reactor clean-out wash waters
Nitro Compounds
This family of organo-nitrogen pesticides includes the nitro
phenols (and their salts)r 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 IV-14. In this example, a chloroaromatic is charged
to a nitrator with cyclic acid and fuming nitric acid. The
crude product is then 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.
57
-------
FIGURE IV-13
GENERAL PROCESS FLOW DIAGRAM FOR S-TRIAZINE
PRODUCTION FACILITIES
01
00
SOLVENT
AMINE
CHLORINE
HYDROGEN CYANIDE
CYANURIC
CHLORINE
UNIT
HC1 ,HCN
CAUSTIC SODA
>
>
SCRUBBER
AND
FILTER
T
WASTEWATER
ADDITIVES
OR SOLVENTS
AMINATION
UNIT (1
TO 3 STEPS)
SOLVENT
RECOVERY
-TRIAZINE
WASTEWATER
FORMULATION
PACKAGING
AND
STORAGE
PRODUCT
DUST
BAGHOUSE
CAUSTIC SODA
VENT
SCRUBBER
WASTEWATER
-------
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 wastewater
treatment plant.
The dinitro compound is then dissolved in an appropriate
solvent and added to the amination reactor with water and
soda ash. An amine is then reacted with the dinitro
compound. The crude product 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, wastewaters 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 wastewaters
H. Periodic kettle cleanout wastes
5. Production area washdowns
MetallQ-Organic Pesticides
The metallo-organic group of pesticides includes the organic
arsenicals and the dithiocarbamate metal complexes. A
discussion of their manufacture and wastewater sources is
also applicable to the production of other compounds in this
group.
MSMA is the most widely produced of the group of organo-
arsenic herbicides (estimated production in 1972 was 24
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 IV-15.
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 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
59
-------
FIGURE IV-14
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
-------
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 IV-16 is a typical process and waste generation
schematic flow diagram for the production of ethylene
bisdithiocarbamate metal complexes. Paw 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
2U 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, baa
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;.
61
-------
FIGURE IV-15
WATER-
DUST
COLLECTOR
ALKYL CHLORINE
en
ro
As203
NaOH
WATER
GENERAL PROCESS FLOW DIAGRAM FOR ARSENIC-TYPE
METALLO-ORGANIC PRODUCTION
VENT
WET
SCRUBBER
WASTEWATER
REACTOR
INTERMEDIATE
PRODUCT
STORAGE
REACTOR
WH 1
1
1
1
Lt\
>
PURIFICATION
>
PRODUCT
STORAGE
— fcJJASTFUflTFD
REACTOR
PRODUCT
STORAGE
EVAPORATOR
CENTRIFUGE
AQUEOUS
ALCOHOL WATER
i
STRIPPER
COH
ALCOHOL
BY-PRODUCT
WASH
SOLIDS
LIQUID I
) TO APPROVED
LANDFILL
-------
FIGURE IV-16
en
CO
GENERAL PROCESS FLOW DIAGRAM FOR CERTAIN DITHIOCARBAMATE
METALLO-ORGANIC PRODUCTION
WATER
ETHYLENEDIAMINE
CS,
NaOH
REACTOR
METAL SULFATE
VENT
SCRUBBER
I
WASTEWATER
INTERMEDIATE
STORAGE
BINDER
NaOH
WATER
REACTOR
CYCLONE
COLLECTOR
AIR
SLURRY
WASH AND
FILTRATION
WASTEWATER
VE
WATER-
BAGHOUSE
SCRUBBER
WASTEWATER
-^SOLIDS
• AIR-
DRIER
FORMULATION
AND
PACKAGING
-------
In summary, wastewaters 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 wastewater
5. Area washdowns
6. Equipment cleanout wastes.
Formulators and Packagers
Pesticide formulations can be classified as liquids,
granules, dusts and powders. There are 92 major formulation
plants according to this classification.
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 UO,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 operations 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 IV-17. Technical grade pesticide is usually
stored in its original shipping container in the warehouse
section of the plant until it is needed. When technical
-------
FIGURE IV-17
LIQUID FORMULATION UNIT
EXHAUST VENT
en
HOOD
. PESTICIDE
(55 GAL. DRUM)
SCALE
PUMP
SOLVENT STORAGE
AGITATOR
MANHOLE
EMULSIFIER
T
. . STEAM
-COOLING WATER
FILTER
PUMP
PRODUCT
(55 GAL. DRUM)
I
I SCALE j
PUMP
-------
material is received in bulk, however, it is transferred to
holding tanks for storage.
a
Batch-mixing tanks are frequently open-top vessels with
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, 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 IV-18.
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
66
-------
FEED
Figure IV-18
Dry Formulation Unit
ATMOSPHERE
a) Premix Grinding
PREMIXED
MATERIAL
SILICA
WETTING
AGENT
TO
ATMOSPHERE
TO
ATMOSPHERE
TO
ATMOSPHERE
REVERSE-JET
BAGHOUSE
REVERSE-JET.
BAGHOUSE
r- — *
1
BLENDER
FLUID
ENERGY
MILL
HIGH PRESSURE |
AIR
b) Final Grinding and Blending
67
FINISHED PRODUCT
-------
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
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 contamination 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, wastewaters 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 wastewater from the building washdown is
normally contained within the building, and is disposed of
in whatever manner is used for other contaminated
wastewater. 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 wastewater
stream that is potentially 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 removal system. Effluent from
air pollution control equipment should be disposed of with
other contaminated wastewater. One type of widely used air
68
-------
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
decontaminante 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
wastewaters.
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, however, must be
treated along with other contaminated wastewaters.
The major source of contaminated wastewater from pesticide
formulation plants is equipment cleanup. Formulation ?.ines,
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.
69
-------
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 wastewater
should be disposed of with the other contaminated
wastewaters.
Natural runoff at formulating and packaging plants, if not
properly handled, can become a major factor in the operation
of wastewater systems simply because of the relatively high
flow and the fact that normal plant wastewater volumes are
generally extremely low. Isolation of runoff from any
contaminated process areas or wastewaters, however,
eliminates its potential for becoming significantly con-
taminated 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, wastewaters 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
Basis for Assignment to Subcategories
The assignment of subcategories to pesticide plants
manufacturing active ingredient products (that is,
Subcategories A through D) can best be described by Table X-
1, where most pesticides are listed by common name and basic
chemical structure. Pesticides not listed in Table x-1
because they are small production-volume commodities, or
because they were first manufactured after preparation of
this document, can be assigned based on their chemical
structure or nature of the active component (halogen,
phosphorus, etc.). Additionally, subcategory assignment can
be made based on the production process similarities with
other pesticides in the same chemical family or homoloa
group.
70
-------
Plants not producing active ingredient commodities, but
using the premanufactured active ingredient for a formulated
or packaged product, obviously fall into Subcategory E.
71
-------
SECTION V
WASTEWATER CHARACTEPISTICS
The purpose of this section is to define the wastewater
quantity and quality for plants in those subcateqories
identified in Section IV. Raw waste load (RWL) data are
also presented for plants which produce in more than one
subcategory, and which have sampling procedures or process
flows that produce data extending across more than one
subcategory.
The term raw waste load, as utilized in this document, is
defined as the quantity of a pollutant in wastewater 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 the development of the ratio of
raw waste load to production, the production used was that
of final (technical) product, not including the production
of intermediates. A discussion of the interpretation of
effluent limitations guidelines, based on the element of
active ingredient production, is presented in Section IX.
For the purpose of cost analysis, a model plant for each
subcategory has been defined in terms of production and
wastewater characteristics. Based on the range of
production encountered in each subcategory, a small and
large plant are presented in order to demonstrate in Section
VIII the range of probable costs for suggested treatment.
Similarly, raw waste load characteristics have been
developed for each subcategory in order to estimate the cost
of the treatment modules. Under no conditions should these
values be construed to be exemplary nor used as a basis for
pretreatment guidelines for industrial discharges into
publicly owned treatment works.
The effluent limitations guidelines were developed on the
basis of observed operating treatment systems and the
resulting pollutant loads. Accepted engineering judgements
were made to apply those results and operating efficiencies
observed to similar plants which do not currently practice
the model treatment technologies or do not obtain the
observed efficiencies. A detailed discussion of this
approach is presented in Sections VII and IX.
The data presented in this document is based on the most
current, representative information available from each
plant contacted. Sufficient long term data was available at
72
-------
each plant such that verification sampling data was not
utilized in the derivation of the recommended effluent
guidelines.
Subcategory A - Halogenated Organic Pesticides
In the manufacturing processes for halogenated organic
pesticides, the principal sources of high organic wastes are
decanting, distillation, and stripping operations.
Spillage, washdowns, and run-off can also be significant
sources of high organic and solids loadings if suitable
operational control is not maintained. A summary of sources
of wastes from processing units utilized in the
manufacturing of halogenated organic pesticides is contained
in Table V-l.
A summary of raw waste loads for Subcategory A is presented
in Table V-2. Data were collected on a total of eleven
plants during production of thirteen halogenated organic
products. These data are considered to be relevant since
nine of the eleven plants provide some form of wastewater
treatment, and they are judged to be representative since
the major types of halogenated organics, both polar and non-
polar compounds, are included in the production observed.
Of the eleven pollutant parameters presented in Table V-2,
the most significant are considered to be BOD, COD,
suspended solids, phenol, and pesticides for reasons
presented in Section VI. While chloride concentrations are
reported in some cases to be high (approaching 80,000 mg/1
in one case), it can be reasonably expected that process
modifications or in-plant recovery, prior to introduction
into a properly operated biological system (including the
acclimation of the biological system to the particular
waste), can prevent detrimental effects to the biological
system by these chloride concentrations.
The considerable variability of data from plant to plant
which is indicated by Table V-2 and which results from
operational and other differences, is lessened by the
consideration that the flow from Plant A6 includes a
substantial amount of cooling water. Daily variability in
raw waste load for an individual pesticide plant sampled for
30 consecutive days is presented below:
BOD TSS TKN TP CHLORIDE CHLOROBENZILATE
Minimum 52.6 1.3 0.05 0.01 82 0.02
Mean 211 5.5 1.0 0.05 160 0.8
Maximum 513.0 22.7 5.85 0.14 349 3.39
73
-------
TABLE V-l
SUMMARY OF POTENTIAL PROCESS - ASSOCIATED WASTEWATER SOURCES FROM
HAL06ENATED ORGANIC PESTICIDE PRODUCTION
PROCESSING UNIT
Wet scrubber
SOURCE
Acidic solution
Caustic soda scrubber Spent caustic solution
Intermediate product
neutralizer
Decanter
Distillation tower
Settling tank
Product washers
Crystallizer, dryer,
flakers, prilling
Dust wet scrubbers
Spillage
Aqueous layer
Organic Layer
Distillation residues and
tars
Spent acid
Neutralized aqueous wastes
Dusts, mists
Aqueous suspension
NATURE OF WASTEWATER CONTAMINANTS
Low pH, moderately high flow rate, little
organic wastes
High pH, low average flow rate, high
dissolved solids, low organics
Low waste loss, pH varible, high organic,
high alkalinity, high dissolved solids
High salt content, generally low dissolved
organic, separable organics sludge
High organic, low dissolved organic salt or
sludge
High organic, low solubility in water, high
chlorine content
Low pH, intermittent flow, moderate organic
content
High salt content, organic product loss,
high pH, high alkalinity, high dissolved
solids
High toxic organics, high total suspended
solids
High total suspended solids, high toxic
organics
-------
en
PROCESSING UNIT
Solvent strippers
Acid recovery unit
Tanks and reactors
Centrifuges
Vacuum jets
All plant areas
TABLE V-l
Continued
Page 2 of 2 Pages
SOURCE
Stripper clean out rinse
water
Liquid wastes
Cleanout rinse water and
wasted solvents
Mother liquor
Vacuumed gases
Run-off, area washdowns
NATURE OF WASTEWATER CONTAMINANTS
High organics, low flow
High pH
Intermittent flows, high organics, high salt
content (condensation reactions &
neutralization), high dissolved solids
High organics, generally toxic
Low organics, highly acidic
Intermittent flow, low organics, variable
pH, variable suspended solids, variable
salt content
-------
St. Dev. 149 4.5 1.3 0.03 68 1.0
All units in kg/kkg
Daily maximum to mean ratios for BOD and Chlorobenzilate of
2.43:1 and 1.25:1 indicate that there is a need for
equalization but that it is not particularly extensive for
this type of product.
Based on the data presented in Table V-2 and the following
discussion, model plant raw waste load values for
halogenated organic pesticide plants have been developed for
cost calculations as outlined below:
Production (Small Plant) =16.2 kkg/day = 35,900 Lb/day
Production (Large Plant) = 85.7 kkg/day = 189,000 Lb/day
Flow = 35,300 L/kkg = 4230 Gal/1000 Lb
BOD = 97.2 Kg/kkg = 2750 ma/1
COD =183 Kg/kkg = 5190 mg/1
TSS =3.49 Kg/kkg = 98.8 mg/1
Phenol = 1.92 Kg/kkg = 54.4 mg/1
Total Pesticide = 0.327 Kg/kkg = 9.27 mg/1
The model plant defined above does not represent any one
plant, nor does it represent merely the average of all data
presented. Additional factors which required consideration
were reliability of data, specific process influences (such
as the production of intermediates of any one plant), and
relationship between parameters (BOD/COD ratios, TKN/NF3-NT
comparisons, etc.). The model plant does represent the
average of available, reliable, and comparable data which
may currently be expected to exist in plants from this
subcategory. The rationale for not utilizing all reported
data is explained in the text for each parameter.
In establishing the model plants, the Agency acknowledged
that the ranges are wide and -that cost calculations may be
more exact if a less wide segment of the data were used.
For instance, in the flow calculation, three plants are
grouped at 8,340 1/kkg (1,000 Gal/1000 Lb). The use of the
average 35,300 1/kkg (4230 Gal/1000 Lb) results in a cost
calculation which is generous for large production units amd
somewhat less generous for small production units. The cost
calculations given in Section VIII are judged to be within
acceptable engineering practice. It should be noted that
Plants A8 through All have eliminated the discharge of
pesticides to navigable waters by in-process controls or
total containment procedures as outlined in section VIT.
These plants are not considered relevant to the development
of cost models. However, the means by which they reduce
76
-------
TABLE V-2
RAW WASTE LOADS
HALOGENATED ORGANIC PESTICIDE PLANTS
SUBCATEGORY A
LANT
Al
A2
A3
A4
A5
A6
A7
A8
A9
A10
All
PRODUCT
1,2
3
4,5
6
6
7,8
7,8
9
10,11
7,12
3
3
3
13
FLOW
L/Kkg gal /1 000 Ib
3150
8757
85900
75900
50400
8060
8760
10000
411000*
9560
3810
252
1760
1060
377
1050
10300
9100
6040
967
1050
1200
49200*
1146
457
3
211
127
BOD COD TOC
kg/Kkg mg/1 kg/Kkg mg/1 kg/Kkg mg/1
18.3 5766 2.31 698
______
60.8 706
498 6570 -
211 3880 -
62.9 7800 113 14000 64.5 8000
62.9 7200 125 14300 41.1 4700
85.0 8500 160 16000
43.1 105
______
______
______
______
______
SOURCE OF
DATA
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(D
(m)
(n)
* Includes cooling water
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Ib X 8.34)
-------
00
TABLE V-2
Continued
Page 2 of 4 Pages
PLANT
Al
A2
A3
A4
A5
A6
A7
A8
A9
A10
All
PRODUCT
1,2
3
4,5
6
6
7,8
7,8
9
10,11
7,12
3
3
3
13
TOD TSS
kg/Kkg mg/1 kg/Kkg
4.79
65.2
_
796 10500 3.75
5.50
0.19
1.92
55.0
_
_
_
- -
_
mg/1
1510
9000
-
49
103
24
220
134
-
-
-
-
-
TDS TOTAL PHOSPHATE SOURCE OF
kg/Kkg mg/1 kg/Kkg mg/1 DATA
(a)
(b)
(c)
(d)
0.05 1.00 (e)
(f)
(g)
950 9500 - - (h)
(1)
(j)
(k)
(1)
(m)
(n)
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 !£> X 8.34)
-------
UD
TABLE V-2
Continued
Page 3 of 4 Pages
TKN CHLORIDE PHENOL
PLANT
Al
A2
A3
A4
A5
A6
A7
A8
A9
A10
All
PRODUCT
1,2
3
4,5
6
6
7,8
7,8
9
10
11
7,12
3
3
3
13
kg/Kkg mg/1 kg/Kkg
22.9
_
_
0.83 10.9 207
0.90 17.1 170
0.087 10.0 331
0.087 10.0
720
_
667
_
_
- - -
- - -
mg/1 kg/Kkg mg/1
7234
_
_
2730
3180
14000 1.61 200
2.75 315
72000
_
80000 1.67 200
_
_
_
_
PESTICIDES*
kg/Kkg
0.159
-
0.79
16.1
0.0127
0.052
-
N.D.
N.D.
0.001
0.504
mg/1
2.2
-
15
2000
0.031
0.127
-
N.D.**
N.D.**
0.4
0.423
SOURCE OF
DATA
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(1)
(m)
(n)
* Pesticide values represent the sum of products listed
** N.D. - Not Detectable
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MOD/1000 tb X 8.34)
-------
TABLE V-2
Continued
Page 4 of 4 Pages
NOTES:
PRODUCT CODE:
1 = PCNB
2 = Terrazole
3 = Toxaphene
4 = DCPA
5 = Chlorothalonil
6 = Chlorobenzilate
7 = 2,4D
8 = 2,4D, 5T
9 = PCP
10 = Endrin
11 = Heptachlor
12 = MCPA
13 = DDT
SOURCE OF DATA CODE:
(a) Daily composite, 7/1/75 through 2/29/76.
(b) Plant estimate, 1975.
(c) Plant estimate, summation of seven waste
streams, 10/74.
(d) Daily average, 4/74 through 3/75.
(e) Daily flow proportional composite, 5/21/75
through 6/19/76.
(f) Daily average, 8/74 through 7/75.
(g) Daily composite, 6/75.
(h) Daily average, 4/72 through 3/73.
(i) Daily composite, 1/74 through 5/74.
(j) Plant estimate, 3/23/76.
k) MRI toxaphene report, 2/6/76.
.1) MRI toxaphene report, 2/6/76.
(m) MRI toxaphene report, 2/6/76.
(n) MRI DDT report, 2/6/76.
-------
their discharges is quite significant.
discussion of each parameter is as follows:
A detailed
Flow — With two exceptions. Plants Al and A2, flow data was
considered reliable. Plant Al measured flow across an
activated carbon unit; however, this rate was controlled by
pumping capacity and preceded by an extensive holding pond.
Plant A6 discharged to a municipality, but did not exclude
all cooling waters. Plants A2, A3, A4, and A7 all operate
treatment systems and monitor flow continuously. Plant A5
discharges to deep well disposal and monitors continuously.
Data reported and utilized are given below:
PLANT
FLOW REPORTED
1/kkg (Gal/1000 Lb)
FLOW UTILIZED
1/kkg (Gal/1000 Lb)
Al 3,150
A2 8,757
A3 85,900
AH 75,900
50,400
A5 8,060
8,760
10,000
A6 411,000
A7 9,560
Average
377
1,050
10,300
9,100
6,040
967
1,050
1,200
49,200
1,146
8,800
86,000
6,300
8,900
10,000
1,050
10,300
7,570*
1,072*
1,146
35,200 L/kkg 4,227
Gal/1000 Lb
* Average of reported values
BOD/COD — Due to differences in monitoring, few plants
reported data for both BOD and COD. In order to derive
ratios for both parameters a BOD/COD ratio of 0.53
established from Plant A5 data was used to complement
existing figures. Data reported and utilized are given
below:
PLANT
Al
A2
A4
A5
BOD
REPORTED
(kg/kkg)
498
211
62.9
62.9
85.0
BOD COD
UTILIZED REPORTED
(kg/kkg) (kg/kkg)
9.24
30.7
354*
70.3*
18.3
60.8
113
125
160
COD
UTILIZED
(kg/kkg)
18.3
60.8
668
133*
81
-------
A6 — 21.8 43.1 43.1
Average 97.2 kg/kkg 183 kg/kkg
* Average of reported values
TSS — Suspended solids data were considered accurate for
all plants except Plant A2r for which the value reported was
back-calculated from the amount of sludge produced, and
Plant A6 for which suspended solids have since been reduced
from the reported value of 55.0 kg/kkg but were not
available for preparation of this document. Data reported
and utilized are given below:
TSS TSS
REPORTED UTILIZED
PLANT (kg/kkg) (kg/kkg)
Al 4.79 4.79
A2 65.2
A4 4.75 4.62*
5.50
A5 0.19 1.05*
1.92
A6 55.0 --
Average 3.49 kg/kkg
* Average of reported values
Phenol — Only two plants presented phenol data. Plant A7
monitors phenol every four hours as a control parameter for
activated carbon, hence these data are considered quite
reliable. Data reported and utilized are given below:
PHENOL PHENOL
REPORTED UTILIZED
PLANT (kg/kkg) (kg/kkg)
A5 1.61
2.75
A7 1.67
Average 1.92 kg/kkg
* Average of reported values
Pesticides -- Few plants monitor pesticides in the raw
wastewater. Plant A4 conducted 30 day sampling of one
process waste stream, and Plant A6 monitored its discharge
82
-------
daily to a municipal sewer. These data are considered to be
reliable. The pesticides from Plant A5 were disposed of by
deep well injection, and are not included in calculations
since it is acknowledged that in the absence of a deep well
system it would be necessary to incinerate the wastes rather
than treat them biologically. Data reported and utilized
are given below:
PESTICIDES PESTICIDES
REPORTED UTILIZED
PLANT (kg/kkg) (kg/kkg)
A2 0.159 0.159
A4 0.79 0.79
A5 16.1
A6 0.0127 0.0323*
0.052
Average 0.327 kg/kkg
* Average of reported values
Subcategory B - Organo-Phosphorus Pesticides
Sources of wastewater from the manufacture of organo-
phosphorus pesticides include decanter units, distillation
towers, overhead collectors, solvent strippers, caustic
scrubbers, contact cooling, hydrolysis units, and equipment
washing. Table V-3 contains a summary of wastewater sources
from processing units commonly used in the production of
organo-phosphorus pesticides.
A summary of raw waste load data for organo-phosphorus
pesticide plants is presented in Table V-H. Data was
collected from seven plants manufacturing 18 products. Five
of the seven plants operate full-scale treatment facilities.
One of the five treatment plants receives only orqano-
phosphorous wastes. For those plants operating treatment
systems the data is guite extensive, ranging from one month
to more than a year of daily, flow-proportional, composited
samples.
Of the twelve pollutant parameters reported for Subcategory
B, the significant parameters are considered to be BOD, COD,
suspended solids, ammonia nitrogen, phosphates, and
pesticides for reasons outlined in section VI.
High chloride concentrations are experienced in this
Subcategory, but concentrations in excess of 7,000 mg/1 are
not adversely affecting biological treatment at two plants,
83
-------
TABLE V-3
SUMMARY OF POTENTIAL PROCESS - ASSOCIATED WASTEWATER SOURCES FROM
ORGANO-PHOSPHORUS PESTICIDE PRODUCTION
oo
PROCESSING UNIT
Solvent recovery
Caustic scrubbers
Hydrolyzer/extractor
Decanter
Overheads collector
Distillation tower
Intermediate product
reactor
Product washers
Product recovery
Solvent strippers
SOURCE
Aqueous layer
Vented gases
Aqueous layer
Aqueous layer
Organic layer
Dusts, mists, vapors
Residues and tars
Reaction product residues
Neutralized aqueous wastes
Aqueous wastes
Stripper clean-out rinse
watei
NATURE OF WASTEWATER CONTAMINANTS
High salt content, high pH, intermittent flow
rate, toxic components, some "intermediate"
product
High pH, high volume, low organics
High pH, high COD, high dissolved solids,
possible separate organic sludge
High salt content, generally low dissolved
organics, separable organic sludge
High organics, low dissolved organic-salt
and sludge
High toxic organics, high total suspended
solids
High organics, low water solubility
Intermittent flow, high dissolved solids,
pH variable, organic content variable
High salt content, organic product loss,
high pH, high alkalinity, high dissolved
solids, intermittent flow
High toxic organics, low flow
High organics, low flow
-------
PROCESSING UNIT
Tank and reactors
Vacuum jets
All plant areas
TABLE V-3
Continued
Page 2 of 2 Pages
SOURCE
Clean-out rinse water and
wasted solvent
Vacuumed gases
Run-off, area washdowns
NATURE OF WASTEWATER CONTAMINANTS
Intermittent flow, high organics, high salt
content (condensation and neutralization
reactions), high dissolved solids
Low organic, generally acidic
Intermittent flow, low organics, variable
pH, suspended solids, and salt content
CO
01
-------
and in the case of Plant B2 the treatment system has been
acclimated to operate at approximately 20rOOO mg/1.
Depending on the product, total nitrogen concentrations in
excess of 1,000 mg/1 can be expected as reported by Plants
Bl and B2, although a portion of this is a result of the use
of ammonia in neutralizing operations and can be eliminated
as discussed in Section VII.
Phosphorus concentrations of 200 to 800 mg/1 were reported.
Pesticide concentrations up to 10 mg/1 are being treated
biologically at Plant B3, which monitors influent and
effluent daily for COD and parathion. Raw waste load
monitoring for phenol was submitted by Plant Bl for a period
of one month. Average concentrations less than 5 mg/1 were
found.
Plant Bl submitted data representing long term plant
estimates for eight specific products. In addition, its
disulfoton process was sampled daily for 14 days. By
comparing these values to the daily average at the influent
to the treatment system for January and February, 1974, it
can be seen that fluctuations in each parameter are dampened
as a result of overlapping production. Flow ratios of
individual lines are much greater than ratios of flow in the
sum of the individual lines due to process control, in-
process pretreatment systems, and non-process related events
such as cleanup. An analysis of six months of raw waste
load data from five process lines at Plant Bl during the
production of more than eight products demonstrates this
reduction in variability. Peak to mean ratios for flow and
COD were 2.60:1 and 3.39:1, respectively compared to those
listed for individual products in Table V-4. Consequently,
equalization will be required prior to treatment in a
biological system, a necessity recognized by this plant in
the design of its treatment system described in Section VII.
Plant B2 presented data for diazinon taken prior to caustic
destruction and biological treatment. Consequently, these
values are higher than those data from lines which are
directed to biological plants after a detoxification
process.
Plant B3, which treats wastes from methyl and ethyl
parathion, monitors daily for COD and parathion in the raw
wastewater. Based on data from January, June, and July,
1974 , a substantial difference in raw waste load exists
between products as would be expected when individual
process lines are directly compared to one another.
86
-------
TABLE V-4
RAW WASTE LOADS
ORGANO-PHOSPHORUS PESTICIDE
SUBCATEGORY B
PLANTS
00
FLOW
PLANT PRODUCT L/Kkg gal /1 000 Ib
Bl
1
1
B2
B3
B4
B5
B6
B7
1 1
2
3
4
5
6
7
8
2
,2,3,5,6,7,9
,2,3,5,6,7,9
10
10
11 or 12
11
12
13,14,15
13,15
11,16
17
18
11
07000
8250
60500
55700
11900
62100
7510
54400
31170
60480
51620
17600
22870
66171
50444
49506
2780
2780
12800
30000
4300
12600
12900
989
7200
6680
1430
7440
800
6530
3737
7253
6180
2110
2742
7932
6047
5734
333
333
1530
3600
516
1510
BOD COD TOD SOURCE OF
kg/Kkg mg/1 kg/Kkg
333
332
192
499
46
192
315
170
661
105 1750 414
378
204 9590
337 14700
260.7
185.1
90.7
1.5 540 45
36.5
79
— — —
_
110 8730 180
mg/1 kg/Kkg mg/1
3110
40200
3150
8910
3850
3100
42000
3150
21200
6850
7320
— — —
626 27370
3938
3669
1831
15200
13200
6100
_ — —
_
14300 28 2220
DATA
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(1)
(m)
(m)
(n)
Note: Mean concentrations are calculated by the equation: mg/l = kg/Kkg divided by (MGD/1000 tb X 8.34)
-------
TABLE V-4
Continued
Page 2 of 5 Pages
CO
CO
TOC TSS
Plant PRODUCT kg/Kkg rng/1 kq/Kkq mq/1
Bl
B2
B3
B4
B5
B6
B7
Note:
1
2
3
4
5
6
7
8
2
1,2,3,5,6,7,9
1,2,3,5,6,7,9, -
10
10
11 or 12 111
11
12
13,14,15
13,15
11,16
17
18
11
Mean concentrations
— — —
-
-
-
-
-
-
-
87.7 2810
16.3 269
11.7 227
1.5 62.0
1.2 52.5
1670 9.32 140.9
- - -
- - —
-
0.13 47
- - -
-
- _ _
4.5 360
are calculated by the ecru
TDS
kg/Kkg mg/1
763
1750
565
2780
702
1030
941
1040
-
1363
-
_
-
-
-
-
240
281
-
-
-
-
ation: i
7130
210000
9420
49800
58500
16600
125000
19250
-
22500
-
—
-
-
-
-
86000
79684
-
-
-
-
TW/1 = kd
T-P
kg/Kkg mg/1
5.5
57.0
18.6
43.0
14.0
7.2
32.0
105.0
76.8
46.6
-
2.6
-
13.3
-
-
53
6.1
-
_
-
7.6
f/Kka di\
51
6900
304
770
1170
115
4260
1930
2460
770
157
201
-
-
19000
2200
-
_
-
600
rided bv fiv
SOURCE OF
DATA
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(b)
(c)
Id)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(1)
(m)
(m)
(n)
ICD/1000 Th
-------
TABLE V-4
Continued
Page 3 of 5 Pages
00
ID
TKN NH3-N
PLANT
Bl
B2
B3
B4
B5
B6
B7
PRODUCT kg/Kkg
1
2
3
4
5
6
7
8
2
1,2,3,5,6,7,9
1,2,3,5,6,7,9
10 20.1
10 27.0
11 or 12 0.182
11
12
13,14,15
13,15 0.711
11,16
17
18
11
mg/1 kg/Kkg mg/1
_ — —
_ - —
295 5300
242 20200
_ _ —
_ -
122 2200
_ _ _
91.6 1514
72.1 1397
1011
1180
2.74
_ _ _
_
.
256
_
— _ •«
_
_
CHLORIDE
kg/Kkg
242
1220
394
1830
527
357
563
396
641
448
-
427
447
428
_
-
_
91
195
_
-
-
mg/1
2260
147000
6500
37000
44000
5700
75000
700
20500
7413
-
19480
19500
6690
-
-
_
32800
-
—
-
-
SOURCE OF
DATA
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(b)
!cl
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(D
(m)
(m)
(n)
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Ib X 8.34)
-------
TABLE V-4
Continued
Page 4 of 5 Pages
PLANT
Bl
B2
B3
B4
B5
B6
B7
PHENOL PESTICIDE*
PRODUCT kg/Kkg mq/1 kg/Kkq mq/1
1 - -
2 -
3 -
4 -
5 - - -
6 - -
7 - -
8 - -
2 0.14 4.48 0.02 0.64
1,2,3,5,6,7,9 0.193 3.20
1,2,3,5,6,7,9 - -
10 - - 1.1 57.0
10 - -
11 or 12 0.024 0.375
11 - - 0.235 4.66
12 - - 0.454 9.17
13,14,15 - -
13,15 0.068 24.7
11,16 - -
17 - N.D. N.D.**
18 - - N.D. N.D.
11 - 0.0126 1.0
SOURCE OF
DATA
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(a)
(b)
(d)
(e)
(f)
(g)
(h)
(D
(j)
(k)
(D
(m)
(m)
(n)
^Pesticide values represent sum of products listed
**N.D. = Not detectable
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 lib X 8.34)
-------
TABLE V-4
Continued
Page 5 of 5 Pages
PRODUCT CODE:
1 = COUMAPHOS
2 = DISULFOTON
3 = AZINPHOSMETHYL
4 = MATHAMIDOPHOS
5 = FENSULFOTHION
6 = FENTHION
7 = DEMETON
8 = METHYL DEMENTON
9 = MONITOR
10 = DIAZINON
11 = METHYL PARATHION
12 = ETHYL PARATHION
13 = DURSBAN
14 = CRUFOMATE
15 = RONNEL
16 = ASPON
17 = RABON
18 = VAPONA
(c)
(d
(e
(d) =
(e) =
SOURCE OF DATA CODE:
(a) = PLANT ESTIMATE, 12/16/74.
(b) = DAILY FLOW PROPORTIONAL COMPOSITE,
5/31/75 THROUGH 6/13/75.
DAILY AVERAGE, 1/74.
DAILY AVERAGE, 2/74.
DAILY FLOW PROPORTIONAL COMPOSITE,
5/5/75 THROUGH 6/3/75.
(f) = DAILY AVERAGE, 4/74 THROUGH 3/75.
(g) = 4 TO 9 DAILY COMPOSITES,
3/21/74 THROUGH 5/9/74.
(h) = DAILY COMPOSITE, 6/74 AND 7/74.
(i) = DAILY COMPOSITE, 1/74.
(j) = PLANT ESTIMATE.
(k) = VERIFICATION SAMPLING, 10/1/74.
(1) = COMBINATION OF TWO COMPOSITE SAMPLES, 4/74.
(m) = FLOW-MATERIAL BALANCE, MDL FOR RABON = 10 ppb,
MDL FOR VAPONA = 100 ppb.
(n) = PLANT ESTIMATE, 4/20/76.
-------
Plant B4, which disposes of organo-phosphorus pesticide
wastewater by deep well injection, does not routinely
monitor this particular waste stream. The data which are
available are substantially lower than those from plants
utilizing biological treatment.
Plant B6 submitted flow estimates and pesticide analyses
after hydrolysis. Rabon was not detected above 10 ppb and
Vapona was not detected above 100 ppb. Plant B6 currently
plans to construct a biological treatment plant to follow
the hydrolysis unit. The flow data from Plant B6 has been
excluded from cost calculations pending confirmation of
material balances by sampling.
Plant B7 presented methyl parathion data which compared
closely with COD ratios for Plant B3. The flow ratio at
Plant B7, however, was much lower and the concentrations
much higher, such that dilution of the waste is predicted as
a requirement to biological treatment. Data from Plant B7
has been excluded from cost calculations pending
confirmation by sampling.
Based on the data presented in Table V-4 and the following
discussion, model plant values for organophosphorus
pesticide plants have been developed for cost calculations
as outlined below:
Production (Small Plant) =6.57 kkg/day = 11,900 Lb/day
Production (Large Plant) = 72.0 kkg/day = 134,000 Lb/day
Flow = 43,900 L/kkg = 5,260 Gal/1000 Lb
BOD = 67.7 kg/kkg = 1,540 mg/1
COD = 267 kg/kkg = 6,080 mg/1
TSS =11.7 kg/kkg =267 mq/1
NH3-N =81.8 kg/kkg = 1,860 mg/1
Total Pesticide = 0.454 kg/kkg = 10.3 mg/1
The model plant defined above, as in the case of halogenated
organics, does not represent any one plant, nor does it
represent merely the average of all data presented.
Additional factors which required consideration for the
model plant definition were reliability of data, specific
process influences (such as the production of intermediates
at any one plant), and relationships among parameters
(BOD/COD ratios, TKN/NH3-N comparisons, etc.). The model
plant does represent the average of available, reliable, and
comparable raw waste load data which may currently be
expected to exist in plants from this subcategory. A
detailed discussion of each parameter so defined is as
follows: The rationale for not utilizing all reported data
is explained in the text for each parameter.
92
-------
Flow — Data from Plant Bl indicate that flows for
individual products vary by a factor of 16, but that monthly
averages are considerably dampened, ranging from 52rOOO to
60,000 1/kkg (6,180 to 7,253 Gal/1000 Lb) during production
of seven different pesticides. Hence, an average of 56,000
1/kkg (6,716 Gal/1000 Lb) was utilized. Values for Plant B3
are monitored continuously at treatment system influent and,
although only one product is manufactured, the values are
quite similar to Plant Bl. Data from Plant B4 were based on
an assumed flow and have been deleted, as were data from
Plant B5, which were based on two samples. Data reported
and utilized are given below:
FLOW REPORTED FLOW UTILIZED
PLANT 1/kkg (Gal/1000 Lb) 1/kkg (Gal/1000 Lb)
Bl 107,000 12,900 56,000 6,716 (1)
8,250 989
60,500 7,200
55,700 6,680
11,900 1,430
62,100 7,440
7,510 800
54,400 6,530
31,170 3,737
60,480 7,253
51,620 6,180
B2 17,600 2,110 20,000 2,428 (2)
22 870 2 742 —~ ~~
B3 66^171 7'932 55,000 6,638 (2)
50,444 6,047
49,506 5,934
B4 2,780 333
2,780 333
B5 12,800 1,530 -- —
Average 44,000 L/kkg 5,260 Gal/1000 Lb
(1) Average of 60,000 and 52,000 1/kkg, two month average of
influent to treatment system
(2) Average of reported values
BOD/COD — Although long term data from BOD and COD were
available, most plants do not monitor both parameters.
Consequently, a BOD/COD ratio of 0.254 from Plant Bl was
utilized to complement existing data. Data from Plant B2
were deleted because monitoring took place before diazinon
destruction and subsequent biological treatment values for
Plants B4 and B5 were excluded due to an inadequate number
of data points. Data reported and utilized are given below:
93
-------
PLANT
Bl
BOD
REPORTED
(kg/kkq)
105
BOD
UTILIZED
(kq/kkq)
105
B2
B3
204
337
1.5
35.0
B5
COD
REPORTED
(kg/kkg)
333
332
192
499
46
192
315
170
661
414
378
260.7
185.1
90.7
45.0
365
79
COD
UTILIZED
(kq/kkq)
396 (1)
138 (2)
Average
67.8 kg/kkg
267 kg/kkg
(1) Average of 414 and 378r two month average of influent to
treatment system
(2) Average of 185.1 and 90.7, three month average of
influent to treatment system representing two different
products.
TSS — Data for Plants Bl and B3 were considered
representative. Data from Plants B2 and B4 were not
considered reliable or comparable, for reasons previously
stated. Data reported and utilized are given below:
PLANT
Bl
B2
B3
B4
TSS
REPORTED
(kq/kkq)
87.7
16.3
11.7
1.5
1.2
9.32
0.13
Average
TSS
UTILIZED
(kq/kkq)
14.0 (1)
9.32
11.7 kg/kkg
94
-------
(1) Average of 16.3 and 11.7, two month influent to treatment
system
NH3-N -- Few plants monitor ammonia nitrogen in the raw
wastewater. Data from Plant Bl, which produces four to five
organo-phosphorus compounds with high wastewater ammonia
concentrations, have been utilized as the basis for the
model plant in order to demonstrate the maximum economic
impact for treatment technology. For some plants, however,
the designated ammonia removal technology would not be
required. For example, Plant B3 (in Table V-4) shows a
total nitrogen concentration insufficient to support
biological treatment; this plant would have to add nitrogen,
probably in the form of anhydrous ammonia, to its raw
wastewater. Data reported and utilized are given below:
NH3-N NH3-N
REPORTED UTILIZED
PLANT (kg/kkg) (kg/kkg)
Bl 91.6 81.8
72.1
Average 81.8 kg/kka
Pesticides — Plant Bl has recently submitted data over a
six month period showing total pesticides for five product
lines to range from 0.4 to 11.5 mg/1. As noted previously,
data from Plant B2 was taken from a segregated waste stream
which does not represent the total influent to bioloqical
treatment, and hence has been excluded. Plant B3 has
presented averages for two different products which enter
biological treatment. Plant B6 has reduced two pesticide
products below detection limits by hydrolysis. For purposes
of cost calculations only, the value of 0.454 kg/kkg has
been selected from Plant B3 to demonstrate the maximum
economic impact for the hydrolysis unit recommended in
Section VII.
Subcategory C - Organo-Nitrogen Pesticides
The principal sources of wastewater in the manufacturing
processes of organo-nitrogen pesticides are: decantinq
operations, extractor/precipitator units, scrubbina
operations, solvent stripping, product purification, vessel
rinsing, spillage, and equipment washdown. A summary of the
wastewater sources associated with these unit operations is
contained in Table V-5. A summary of raw waste loads for
this subcategory is presented in Table V-6. A total of
-------
TABLE V-5
SUMMARY OF POTENTIAL PROCESS - ASSOCIATED WASTEWATER SOURCES FROM
ORGANO-NITROGEN PESTICIDE PRODUCTION
PROCESSING UNIT
Caustic scrubber
Solvent stripper
Air pollution control
equipment
SOURCE
Vented process gases
Aqueous fraction
Aqueous suspension
Extractor/precipitator Aqueous wastes
Intermediate product
purification
Filtration
Tanks and reactors
Reactors
Purification
Extractor
Neutralized aqueous wastes
Filtrate
Cleanout rinse water and
wasted solvents
Aqueous wastes
Aqueous wastes
Aqueous phase
NATURE OF WASTEWATER CONTAMINANTS
High pH, possible by-product HCN, high flow,
low organics
High dissolved organics
High suspended solids, relatively low
dissolved organics and solids
High dissolved and suspended organics, high
pH
High salt content, organic product loss, pH,
and alkalinity. High dissolved organics and
and dissolved solids.
Variable dissolved organics, High pH,
alkalinity, dissolved organics and dissolved
solids.
High soluble organics and by-product salts
Brine wastes. High dissolved solids and
organics. Variable pH, i.e., either very
high or low pH.
High dissolved organics and solids
High pH. High dissolved organics and
solids. High NH3-N
-------
TABLE V-5
Continued
Page 2 of 2 Pages
PROCESSING UNIT
Precipitator
Scrubber from cyanuric
chloride unit
Decanter
Nitrators
Incinerator exhaust
scrubbers
SOURCE
Aqueous wastes
Scrubber and filter water
Aqueous phase
Vent gas scrubbers
Scrubber water
NATURE OF WASTEWATER CONTAMINANTS
Dissolved solids and residual organics
High pH. Cyanide wastewater, low organics,
high dissolved solids
High dissolved organics, NH3_-N and TKN
High nitrates, dissolved solids and pH
Dissolved inorganics. High pH
-------
eight plants submitted data obtained during the manufacture
01 26 products. Parameters of significance in the oraano-
nitrogen subcategory are BOD, COD, TSS, ammonia nitrogen,
and pesticides.
Plant Cl presented data on seven products, with isopropalin
being the product with the strongest waste stream to
directly enter biological treatment. Benefin, trifluralin,
and ethalfluralin waste streams are treated in-plant by
activated carbon prior to biological treatment.
The data from Plant C2 is based on a limited number of
sample points from two combined waste streams. The toxicity
is high in both streams, and consequently the COD/BOD ratio
of the combined streams is quite high.
Plant C3 submitted data collected in-plant for two products:
metribuzin and benzazimide.
Plant CU submitted in-plant data representing ten products.
Plant C5 data is based on an estimated flow calculation.
Plant C6 submitted a thirty day sampling study for alachlor.
The daily variability of the raw waste load is described as
follows:
Minimum
Mean
Maximum
St. Dev.
BOD
77.1
87.9
110.5
13.3
COD
132.5
180
368.9
46.8
NH3-N
17.8
60.2
117.4
20.8
ALACHLOR
1.7
4.1
9.1
2.0
TSS
1.1
3.0
11.0
1.8
All units are in kg/kkg
In addition to the above, the plant estimated the combined
alachlor/propachlor raw waste load which served as the
design for a proposed waste treatment facility.
Plant C7 submitted a plant estimate for two products,
bromacil and diuron.
Plant C8, which produces aldicarb, has completely eliminated
its wastewater discharge due to the use of dedicated
vessels. Aldicarb has an LD-50 of 0.93 mg per Kg body
weight. Because of the occupational health aspect of this
98
-------
pesticide the plant has tightened. Consequently, Plant C8
has been excluded from cost calculations.
BOD concentrations of up to 1500 mg/1 are being treated,
while COD concentrations range as high as 3300 mg/1. Long
term TSS levels of more than 100 mg/1 are not usual. Total
nitrogen may run as high as 240 mg/1. Ammonia nitrogen, as
reported by Plant C6, is estimated to be 150 mg/1. Cyanide
can result from the production of some of the products in
this subcategory. Total pesticides as high as 90 mg/1 were
encountered.
Based on the data presented in Table V-6 and the followinq
discussion, the model plant for organo-nitrogen cost
calculations was determined to be represented by the
following data:
Production (Small Plant) = 9.43 kkg/day = 20,790 Lb/day
Production (Large Plant) = 116 kkg/day = 256,000 Lb/day
Flow = 35,400 L/kkg = 4240 Gal/1000 Lb
BOD =45.5 kg/kkg = 1,300 mg/1
COD =103 kg/kkg = 2900 mg/1
TSS = 2.50 kg/kkg = 70.7 mg/1
NH3-N =60.2 kg/kkg = 1700 mg/1
Total Pesticides =2.82 kg/kkg =80.0 mg/1
The model plant defined above does not represent any one
plant, nor does it represent merely the average of all data
presented. Additional factors which required consideration
for the model plant definition were reliability of data,
specific process influences (such as the production of
intermediates at any one plant), and relationship between
parameters (BOD/COD ratios, TKN/NH3-N comparisons, etc.).
The model plant does represent, then, the average of
available, reliable, and comparable data which may currently
be expected to exist in plants prior to necessary in-process
control and detoxification units and prior to biological
treatment expected in this subcategory. A detailed
discussion of each parameter so defined is as follows: The
rationale for not utilizing all reported data is explained
in the text for each parameter.
Flow — Wastewater from Plant Cl being recycled for product
recovery or incinerated was excluded from calculations. All
other plant data was considered valid. Data reported and
utilized are as follows:
FLOW FLOW
REPORTED UTILIZED
PLANT (Gal/1000 Lb) (Gal/1000 Lb)
99
-------
o
o
TABLE V-6
RAW WASTE LOADS
ORGANO-NITROGEN PESTICIDE PLANTS
SUBCATEGORY C
PLANT
Cl
C2
C3
C4
C5
C6
C7
C8
PRODUCT
1,2,3
4
5
6
7
8
9
10
11-20
11-20
21
22
22,23
24
25
26
L/Kkg
3,470
6,450
19,770
39,350
1,300
32,110
85,100
51 ,600
45,000
47,500
10,000
-
-
-
56,700
None
FLOW
gal/1000 Ib
416
774
2,370
4,718
156
3,850
10,200
5,180
5,400
5,700
1,200
_
-
_
6,800
None
BOD
kg/Kkg
-
-
-
-
3.73
_
-
37
40
24.5 2
87.9
48.1
58
23
-
mg/1
_
-
-
-
116
_
-
820
840
,450
_
-
_
405
-
COD
kg/Kkg
83*
154
4,562**
7 ,688**
1 ,582**
31.5
403
77
_
-
81.3
179.8
86.2
97
37
-
TOD
mg/1 kg/Kkg mg/1
23,900
23,900
230,802
195,380
1,216,000 -
981
4,740
1 ,480
— — _
-
8,120
•» — _
-
93.0
652
-
SOURCE OF
DATA
(a
(a
(a
(a)
(a)
(b)
(c)
(c)
(d)
(d)
(e)
(f)
(g)
(h)
(h)
(i)
* Portions recovered prior to wastewater treatment
** Portions incinerated prior to wastewater treatment
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MOD/1000 tb X 8.34)
-------
TABLE V-6
Continued
Page 2 of 4 Pages
PLANT
Cl
C2
C3
C4
C5
C6
C7
C8
TOC
PRODUCT kg/Kkg mg/1
1,2,3
4
5 -
6
7 -
8 15.0 467
9 -
10 -
11-20
11-20
21 -
22 54.4
22,23
24 -
25 -
26 - -
TSS TDS Total Phosphate
kg/Kkg mg/1 kg/Kkg mg/1 kg/Kkg mg/1
-
---___
------
---___
---___
4.1 128
3,770 44,300
333 6,400
897 19,900
1,760 36,700
1.81 181 - - .00901 0.9
3.0
1.1 - - - 0.418
----__
------
------
SOURCE OF
DATA
(a)
a)
(a)
(a)
(a)
(b)
(c)
(c)
(d)
(d)
(e)
(f)
(9)
(h)
(h)
(i)
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Ii> X 8.34)
-------
TABLE V-6
Continued
Page 3 of 4 Pages
PLANT
Cl
C2
C3
C4
C5
C6
C7
C8
TKN
PRODUCT kg/Kkg mgl
1,2,3
4
5
6
7
8 2.19 68
9
10
11 -20 8 1 78
11 -20 9 1 90
21 2.52 252
22
22,23
24
25
26
NH3-N
kg/Kkg mgl
_
-
-
-
-
-
27 318
-
_ _
-
-
60.2
5.2
_
-
-
CHLORIDE PESTICIDES*
kg/Kkg mgl kg/Kkg mgl
_
-
-
_
-
2.54 79
1,170 13,700
227 4,400
847 18,800
1,210 25,300
25.5 2,550
4.1
3,1
- — - _
- - _
N.D. N.D**
SOURCE OF
DATA
(a)
(a)
(a)
(a)
(a)
(b)
(c)
(c)
(d)
(d)
(e)
(f)
(g)
(h)
(h)
(i)
* Pesticide values represent the sum of products listed
** N.D. = Not Detectable
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34)
-------
o
CO
PRODUCT CODE:
1 - BENEFIN
2 = TRI PLURALIN
3 = ETHALFLURALIN
4 = ISOPROPALIN
5 = ORYZALIN
6 = PIPRON
7 = TEBUTHIORON
8 = ATRAZINE
9 - METRIBUZIN
10 - BENZAZIMIDE
11 - ATRAZINE
12 = SIMAZINE
13 = PROPAZINE
14 = AMETRYNE
15 = PROMETRYNE
16 = SIMETRYNE
17 = SUMITOL
18 = TERBUTRYNE
19 = PROMETONE
20 = CYBNAZINE
21 = DINOSEB
22 = ALACHLOR
23 = PROPOCHLOR
24 = BROMACIL
25 - DIURON
26 = ALDICARB
TABLE V-6
(Continued)
(pg 4 of 4)
SOURCE OF DATA CODE:
(a) - PLANT ESTIMATE.
(b) = 11 GRAB SAMPLES, 7/9/75 THROUGH 8/13/75.
(c) = PLANT ESTIMATE, 12/16/74.
(d) = PLANT ESTIMATE, 10/24/74.
(e) - VERIFICATION SAMPLING, 10/1/74.
(f) = DAILY COMPOSITE, 4/1/75 THROUGH 4/30/75.
(g) = PLANT ESTIMATE, 5/28/76.
(h) = PLANT ESTIMATE, 5/17/75.
(i) = PLANT ESTIMATE.
-------
Cl
C2
C3
C4
C5
C6
C7
416
774
2,370
1,718
156
3,850
10,200
5,180
5,400
5,700
1,200
4,300
6,020
1,210
6,800
Average
* Average of reported values
774
3,850
7,690*
5,550*
1,200
3,840*
6,800
4,240 Gal/1000 Lb
COD/BOD — Plants C5, C6, and C7 monitor both BOD and COD in
the raw waste. Based on the average of these plants a
COD:BOD ratio of 2.31:1 was used to complement existing
values. Although this average is suitable for cost-
calculations, it is noted that a high COD:BOD ratio may
result from specific products such as dinoseb which are low
in biodegradability. This fact reinforces the need for
monitoring both BOD and COD. Data reported and utilized are
as follows:
PLANT
Cl
BOD
REPORTED
(kg/kkg)
BOD
UTILIZED
(kg/kkg)
67.6
C2
C3
C4
C5
C6
C7
3.73
37
40
24.5
87.9
48.1
58
23
13.6
102
38.5*
24.5
48.1
23
COD
REPORTED
(kg/kkg)
83
154
4,562
7,688
1,582
31.5
403
77
81.3
179.8
86.2
97
37
COD
UTILIZED
(kg/kkg)
154
31.5
240
88.9
81.3
86.2
37
104
-------
Average
75.5 kg/kkg
103 kg/kkq
TSS — All TSS data was considered valid. Data reported and
utilized is as follows:
PLANT
C2
C5
C6
TSS
REPORTED
(kg/kkg)
U.I
1.81
3.0
1.1
TSS
UTILIZED
(kg/kkg)
U.I
1.81
3.0
1.1
Average
2.50 kg/kkg
NH3-N — The value of 60.2 kg/kkg ammonia at Plant C6 was
based on 30 days sampling of alachlor. This was considered
to be the most reliable data available. An additional value
of 5.2 kg/kkg was excluded since it represented the raw
waste load attainable after ammonia removal.
Pesticides — Few plants monitor pesticides in the raw
waste. Values for Plants C2 and C6, which resulted from
specific 30-day surveys, demonstrated that levels of
atrazine and propachlor/alachlor were similar. Data
reported and utilized are as follows:
PLANT
C2
C6
PESTICIDES
REPORTED
(kg/kkg)
2.54
U.I
3.1
PESTICIDES
UTILIZED
(kg/kkg)
2.5U
3.1
Average
Subcategory D - Metallo-Organic Pesticides
2.82 kg/kkg
In the manufacturing process for metallo-organic pesticides,
the principal sources of wastewater are: by product
stripping, product washing, caustic scrubbing, tank and
reactor clean-out and area washdowns. The wastewater
characteristics associated with these operations are
summarized in Table V-7.
A summary of raw waste load characteristics for this
subcategory is presented in Table V-8. A total of eleven
105
-------
TABLE V-7
SUMMARY OF POTENTIAL PROCESS - ASSOCIATED WASTEWATER SOURCES FROM
METALLO-ORGANIC PfGTICIDE PRODUCTION
o
en
PROCESSING UNI'f
Caustic scrubber
i;r,cnt caus:.-c solution
Intermediate recovery >„; .h wat<.=s~ ,/ashdown
Raw material drum
washer
Slurry wash
Multi-stage counter
current washer
By-product stripper
Tanks and reactors
iV -a was:', vvater, spills
(i»'i recovery)
Product rinse water
Water lost with scrubbed
salts, clean-out rinse
water
Air pollution control Scrubber water
Aqueous fraction
Clean-out rinse water
All processing areas Area washdowns
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-8
RAW WASTE LOADS
METALLO-ORGANIC PESTICIDE PLANTS
SUBCATEGORY D
FLOW BOD COD TSS METAL SOURCE
PLANT
D 1
D 2
D 3
D 4
D 5
D 6
D 7
D 8
D 9
D10
on
PRODUCT L/Kkg gal /1 000 15
1,2
1,2
2
3
3
4,5
4
4 26000 LPD
6
7,8,9 64,270
105 76,310
None
None
None
None
None
None
None
7000 GPD
None
8000
9150
kg/Kkg mg/1 kg/Kkg mg/1 kg/Kkg mg/1 kg/Kkg mg/1 OF DATA
-- -_ __
_________
-- __ __
_________
_________
_________
__ __ __
(a)
----_____
(TIN)
23.7 355 47.5 711 253 3800 4 60 (b)
(MANGANESE)
54 703 120 1572 132 1718 37 481 (c)
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34)
-------
PRODUCE CODE:
1 = DSMA
2 = MSMA
3 = PMA
4 = Copper 8 Quinolate
5 = CMP
6 = Zineb
7 = Tricyclohexyltin Hydroxide
8 = Triphenyltin Hydroxide
9 = Tributyl tin Oxide
10 = Maneb
o
00
TABLE V-8
Continued
Page 2 of 2 Pages
SOURCE OF DATA CODE:
(a) Plant estimate, 5/13/75
(b) Plant estimate, 5/23/75
(c) Plant estimate, 5/21/75
-------
plants submitted data on arsenic, mercury, copper, zinc,
tin, and manganese-based pesticides.
Three arsenic-based pesticide producers, Plants Dl, D2, and
D3, all have no discharge of wastewater due to a negative
process water balance.
Three mercury-based pesticide producers, Plants DU, D5, and
D6, all have no discharge of wastewater due to reuse and
recycle of all process wastewaters. Two copper-based
pesticide producers. Plants D6, and D7, report no discharge
of wastewater. One plant, D8, disposes of a small volume by
contract hauling to landfill.
One zinc-based pesticide producer. Plant D9, has a
wastewater discharge of evaporator condensate, but no
discharge of metals.
One tin-based pesticide producer, D10, submitted the data
shown in Table V-8. A considerable amount of this flow was
due to the use of barometric condensers, which will soon be
replaced with surface condensers.
One manganese-based pesticide producer, Dll, submitted data
shown in Table V-8.
A continuing effort is underway to better characterize the
waste streams resulting from the mamifacture of zinc,
manganese, and tin-based products in this subcategory.
Subcategory E - Formulators and Packagers
Washing and cleaning operations are the principal sources of
wastewater in formulating and packaging operations. Table
V-9 summarizes the wastewater characteristics for
formulation and packaging operations. A summary of raw
waste load characteristics for this subcategory is presented
in Table V-10. A total of 71 plants were contacted which
formulate wet, dry, or solvent based pesticides. Of these,
59 reported no generation of wastewater whatsoever. Of the
12 remaining plants, none discharged wastewater to navigable
streams.
Because the primary sources of wastewater 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 El. The
analyses available indicate that neither the rate of
109
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TABLE V-9
SUMMARY OF POTENTIAL PROCESS - ASSOCIATED WASTEWATER SOURCES FROM
PESTICIDE FORMULATORS AND PACKAGERS
PROCESSING UNITS
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
condensate from clean out
Area washdown and clean-up
water, spills, leaks
Spills, leaks, run-off
NATURE OF WASTEWATER 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 suspended and
dissolved solids. A major potential
source of wastewater.
Dissolved organics, suspended and dissolved
solids and intermittent low flow.
Dissolved organics, suspended and dissolved
solids and intermittent low flow.
-------
TABLE V-10
RAW WASTE LOADS
PESTICIDE FORMULATORS AND PACKAGERS
SUBCATEGORY E
Plant
El
E2
E3
E4
E5 - E15
E16 - E75
Product
Type
D,S
W,D,S
W,D,S
W,D,S
S
Report
Flow COD
(L/day) (mg/1)
15,519 1,700
*
*
*
**
no generation of wastewater
Total
Pesticide
(mg/1 )
38.7
*Less than 22,000 L/day (5,800 gal/day)
**Ranging from 20 to 4,000 L/day (5 to 1,000 gal/day)
NOTE: W = WET
D = DRY
S = SOLVENT
111
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production nor the type of product formulated has a direct
bearing on the quality or quantity of wastewater generated.
Plants E2, E3, and E4, the three largest plants of a major
pesticide formulator, each generate less than 22,000 I/day
(5800 Gal/day) .
Plants E5 through E15 all estimate wastewater generation to
range from 20 to 4000 I/day (5 to 1000 Gal/day).
Multi-Category Producers
In the preceeding sections raw waste load data has been
presented from plants which produce pesticides from a single
subcategory or whose sairpling was restricted to a single
process line. A substantial amount of data was collected,
however, from multi-category pesticide producers. Raw waste
loads from these plants have been compared to their
respective model plant values for verification and further
interpretation.
Table V-ll presents daily data collected over a six month
period at Plant Ml. Production mix was 63 percent to 83
percent organo-phosphorus and the remainder organo-nitrogen.
It can be seen that COD and BOD values fall well within the
range projected for the model plants; whereas, total
pesticides were somewhat lower. Suspended solids of 34.7
kg/kkg were considerably higher than the model plant, and
also much higher than previously reported levels from the
same plant. A statistical analysis of the data for COD
shows that one standard deviation above the mean represented
an increase in pounds of 42.6 percent, and that the maximum
daily COD value over six months was an increase of 108
percent over the mean. It is evident, therefore, that the
wide single product ranges illustrated in Table V-U are
dampened to a considerable degree, independent of type of
product being produced. With proper equalization, the
variability would be expected to more closely represent the
maximum variability over a one month period, or in this case
1.21:1.
Table V-12 presents monthly averages of Plant M2, which
produces halogenated organic, organo-phosphorus, and organo-
nitrogen pesticides in the approximate proportions of 3, 18,
and 79 percent, respectively. In addition, the treatment
system receives non-pesticide wastes. Due to the production
of intermediates and non-pesticide products, the BOD average
of 119 kg/kkg is not considered atypical in relation to the
model plant values.
112
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CO
TABLE V-ll
RAW WASTE LOAD
MULTI-CATEGORY PESTICIDE PRODUCER
PLANT Ml
Flow BOD COD TSS
L/Kkg
22,200
39,900
40,500
49,300
50,100
45,400
Mean 41,200
gal/1000 Lb
2,660
4,780
4,850
5,910
6,000
5,450
4,940
kg/Kkg
43.0
46.6
76.0
76.1
53.3
35.1
55.0
mg/1
1,940
1,170
1,880
1,540
1,060
770
1,330
kg/Kkg
134
173
203
191
239
239
197
mg/1
6,030
4,350
5,010
3,870
4,770
5,260
4,780
kg/ Kkg
6.87
13.1
44.3
52.0
27.8
64.2
34.7
mg/1
310
329
1,090
1,050
556
1,410
842
* Monthly averages of daily data from October 1975 through March 1976. Mean concentrations are
calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLE V-ll
RAW WASTE LOAD
MULTI-CATEGORY PESTICIDE PRODUCER
PLANT Ml
Continued
Page 2 of 2 Pages
NH3-N Phenol Total Pesticides
kg/Kkg
39.1
54.8
46.4
21.4
26.4
16.0
Mean 45.1
mg/1
1,760
1,370
1,150
434
527
352
1,090
kg/Kkg
0.14
0.26
0.35
0.25
0.14
0.21
0.23
mg/1
6.35
6.61
8.64
4.99
2.70
4.69
5.58
kg/Kkg
0.25
0.48
0.30
0.34
0.15
0,17
0.28
mg/1
11.1
11.9
7.52
6.88
3.03
3.72
6.80
* Monthly averages of daily data from October 1975 through March 1976. Mean concentrations are
calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLt V-12
RAW WASTE LOAD
MULTI-CATEGORY PESTICIDE PRODUCER
PLANT >I2
Flow BOD TSS TKN
L/Kkg
91,500
80,900
66,200
69,300
78,400
60,400
108,900
88,600
71 ,900
64,300
53,000
Mean 75,800
gal/1000 Lb
11,000
9,700
7,932
8,300
9,390
7,240
13,000
10,600
8,620
7,700
6,350
9,080
kg/Kkg
146
152
79.5
103
90.3
68.3
105
103
154
197
109
119
mg/1 kg/Kkg mg/1
1,590 4.43 48.4
1 ,880
1 ,200
1 ,490
1,150
1,130
964
1,160
2,140
3,060
2,060
1,570 4.43 48.4
kg/Kkg
40.8
29.3
28.1
39.2
26.2
18.5
27.5
18.4
20.2
27.7
17.8
26.7
mg/1
446
362
424
567
334
307
253
207
280
431
335
352
* Monthly averages from daily monitoring, April 1975 through March 1976. Mean concentrations are
calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLE V-12
RAW WASTE LOAD
MULTI-CATEGORY PESTICIDE PRODUCER
PLANT M2
Continued
Page 2 of 2 Pages
NH3-N Total Cyanide Total Chloride
kg/Kkg
15.6
10.5
8.80
10.1
9.36
6.00
8.50
5.10
6.48
8.80
4.98
Mean 8.57
mg/1
170
130
133
146
119
99.3
78.1
57.6
90.2
137
94.0
113
kg/Kkg
0.112
0.0800
0.020
0.0708
0.0981
0.0235
0.035
0.0837
0.083
0.110
0.036
0.068
mg/1
1.22
0.989
0.31
1.02
1.25
0.39
0.32
0.945
1.16
1.71
0.67
0.902
kg/Kkg
1,460
1,480
1,100
1,580
1,240
1,030
1,430
891
1,110
1 ,530
902
1,250
rng/1
15,900
18,300
16,600
22,700
15,800
17,000
13,100
10,100
15,490
23,800
17,000
16,500
. .v . . v. . . ^ M * *.• ** 3 w*s i i win «v* i i jr IM\SI i i vwi 111^3 npi II \ -/1 *J UIUVU^II I IU I V* I I I -7 / U * 1*1 C<
calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The pollutant parameters considered, as a result of this
study, to be of primary significance for the pesticide
chemicals industry are as follows:
Organic Pollutants Pesticides
Suspended Solids Metals
pH Phenol
Nutrients Cyanide
Measurement of these parameters will provide much of the
information necessary to assess the potential adverse
effects of a wastewater on a receiving stream or body of
water. Adverse effects of primary concern with respect to
the pesticide chemicals wastewaters are as follows:
a. the oxygen demanding capacity of organic materials
which will depress dissolved oxygen (DO) levels of
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.
These pollutants of primary significance are not all likely
to be present at concentrations of concern in any one
pesticide plant's wastewater. Organic wastes, suspended
solids, pHr and nutrients are potential pollutants for any
of the subcategories. Pesticides are, of course, specific
to the product manufactured or used in compounding. Metals
may be present in wastewaters at those facilities where
metallo-organic pesticides are produced or where metals are
employed in the production process. Phenol and cyanide may
117
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be present in wastewaters emanating from certain process
streams.
Pollutants considered to be of secondary significance for
the pesticide chemicals industry include the following:
Settleable solids Acidity
Dissolved solids Chloride
Alkalinity Sulfide
Oil and Grease
These measures of pollution may be of concern in a
particular location, but they are of less importance than
the pollutants of primary significance or they can be
indirectly assessed by measurement of pollutants of primary
significance.
The rationale and justification for pollutant categorization
within the foregoing groupings, as discussed herein, will
indicate the basis for selection of the parameters upon
which the actual effluent limitations guidelines werp
postulated for each industrial category. In addition,
particular parameters have been discussed in terms of their
validity as measures of environmental impact and as sources
of analytical insight, in the light of current knowledge.
RATIONALE FOR THE SELECTION OF POLLUTANT PARAMETERS
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 a constituent that, in appropriate concentrations, is
essential not only to keep organisms living but also 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 population through delayed
hatching of eggs, reduced size and vigor of embryos,
production of 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
118
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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 wastewaters are the Biochemical Oxygen Demand
(BOD) analysis, the Chemical Oxygen Demand (COD) analysis,
and the Total Organic Carbon (TOC) analysis. Each of these
methods have certain advantages and disadvantages when
applied to industrial wastewaters.
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 wastewater 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 wastewater treatment
facilities and to establish effluent limitation values.
Some limitations to the use of the BOD test to control or
monitor effluent guality are:
a. The standard BOD test takes five days before the
results are available, which tends to decrease its
usefullness as an operational control monitor.
b. At the start of the BOD test, a seed culture of
microorganisms is added to the BOD bottle. Tf the
seed culture is not acclimated (i.e., exposed to a
similar wastewater in the past), then it may not
readily biologically degrade the waste, and a low
BOD value may be reported. This situations is not
unlikely to occur when dealing with complex
industrial wastes for which acclimation is
desirable in most cases. The necessity of
using acclimated seed often contributes to the
difficulty of different analysts obtaining
duplicate values of BOD on industrial wastes.
c. The BOD test is sensitive to toxic materials,
as are all biological processes. Therefore,
if toxic materials are present in a particular
wastewater, the reported BOD value may very
well be erroneous. This situation can be remedied
by conducting a microorganism toxicity test,
i.e., serially diluting the sample until the
BOD value reaches a plateau indicating that the
material is at a concentration which no longer
119
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inhibit biological oxidation.
When properly performed, however, the BOD test measures the
actual amount of oxygen consumed by microorganisms in
metabolizing the organic matter present in the wastewater.
It is important to note that most of the 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.
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 oxidation
by a strong chemical oxidant. It is an important and
rapidly measured parameter. The method fails to include
some organic compounds (such as acetic acid) which are
biologically available to the stream organisms, while
including some biologic compounds (such as cellulose) which
are not a part of the immediate biochemical load on the
oxygen assets of the receiving water. The carbonaceous
portion of nitrogenous compounds can be determined, but
there is no reduction of the dichromate by ammonia in a
waste or by any ammonia liberated from the proteinaceous
matter. With certain wastes containing tO'xic substances,
this test or a total organic carbon 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 definitely
related to the BOD of a wastewater. 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.
The relationship of BOD to COD is an important indicator of
detoxification control and biodegradability. For example,
if the ratio of COD and BOD in the effluent from a treatment
system increases, the cause might be increased levels of
pesticide. Also, a high COD and BOD ratio (e.g., 10 as
compared to 2) might indicate relatively low
biodegradability.
The TOC analysis offers a third option for measurement of
organic pollutants in wastewaters. The method measures the
total organic carbon content of the wastewater by a
combustion method. The results may be used to assess the
ultimate potential oxygen-demanding load exterted by the
carbonaecous portion of a waste on a receiving stream.
There is little inherent correlation among TOC and BOD or
COD. A correlation must be determined for each wastewater
120
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by comparison of analytical results. TOC analysis is rapid
and generally more accurate and reproducible than either BOD
or CODr but it requires analytical instrumentation which may
be relatively expensive if not utilized fully. It is
therefore concluded that effluent limitations for organic
pollutants in terms of both BOD and COD are necessary for
all subcategories of the pesticide chemicals manufacturing
point source category.
Total Suspended Solids (TSS)
Suspended soldis may be (and usually are) 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 are 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 may be aesthetically displeasing. Also
disregarding any toxic effect attributable to substances
leached out by water, suspended solids may kill fish and
shellfish by causing abrasive injuries and by clogging the
gills and respiratory passages of various aquatic fauna.
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 th°
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 all subcategories
of the pesticide industry.
EH
Although not a specific pollutant, pH is related to the
acidity or alkalinity of a wastewater stream. It is not a
linear or direct measure of either; however, 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.
Technically, pH is the hydrogen ion concentration or
activity present in a given solution. pH numbers are 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 wastewater 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
"taste" of water and, at a low pH, water tastes "sour".
Extremes of pH or rapid pH changes can exert stress
conditions or kill aquatic 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 water 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 in most cases is
less as the pH increases. It is economically advantageous
to keep the pH close to 7.
122
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It is therefore concluded that pH is a significant parameter
requiring control in the pesticide industry.
Nutrients
Aquatic nutrients in this context are considered to be 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.
Increasing standing crops of aquatic plant growths, which
often interfere with water uses and are nuisances to man,
are thought to be frequently caused by increasing the supply
of phosphorus. 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
substantiate that it is frequently the key element required
by fresh water plants and is generally present in the least
amount relative to need. 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."
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 of vegetation physically impedes
such activities. Dense plant populations have been
associated with causing 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.
Phosphorus concentrations in wastewaters are measured by a
colorimetric procedure. Pretreatment of the sample before
analysis allows the measurement of various forms of
phosphorous including orthophosphate, organic phosphates,
complex phosphates and total phosphorus. In thoroughly
assessing the potential of a wastewater to contribute to
eutrophication, all these measurements should be made.
However, soluble orthophosphate concentrations are
considered to be the single most important parameter to
123
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measure. 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 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" wastewaters 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
wastewaters containing ammonia will contribute to
eutrophication of the receiving water and consequent
nuisance aquatic plant growth. Ammonia can also be toxic to
aquatic animals.
The toxicity of ammonia solutions is dependent upon the
amount of unionized 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 unionized ammonia
increase the toxicity of ammonia solutions. EPA has
recommended a maximum acceptable concentration of unionized
ammonia of 0.02 mg/1 in waters suitable for aquatic life.
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 a large quantity when depressed oxygen
conditions permit. Both nitrate and nitrite are aquatic
plant nutrients but they are not as readily assimilated as
ammonia.
In water supplies, nitrate nitrogen in excessive
concentrations can cause methemoglobinemia in human infants.
For this reason, nitrate has been limited by the United
States Public Health Service to ten mg/1 as nitrogen in
public water supplies.
Ammonia concentrations in wastewater 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.
124
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In this procedure, organic bound nitrogen is reduced
chemically to ammonia which is determined colorimetrically.
In the pesticide industry, as shown in Section V, ammonia
nitrogen may be a significant pollutant in the wastewaters
from certain plants in Subcategories B and Cf and phosphorus
may be a problem at individual plants. There is a need to
control discharges of nutrients in those cases where a
problem exists.
Pesticides
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 concentrations. 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 and some to harmless
products. 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.
The chlorinated hydrocarbons are among the most important
groups of synthetic organic pesticides because of their
sizeable number, wide use, stability in the environment,
toxicity to wildlife and nontarget organisms, and 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 but which 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.
The organo-phosphorous pesticides typically hydrolyze or
break down into less toxic products more rapidly than the
halogenated compounds. Practically all persist for less
than a year, while some last for only a few days in the
environment. They exhibit a wide range of toxicity, both
125
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more and less damaging to aquatic fauna than the chlorinated
hydrocarbons. Some exhibit a high mammalian toxicity.
Accumulation 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.
The organo-nitrogen pesticides, 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
halogenated organic pesticides. Metallo-organic pesticides
include the arsenicals, the mercury compounds, and those
containing zinc, manganese, tin, cadmium, lead, and other
metals. The toxicity of these compounds are highly
variable.
Arsenic is notorious for its toxicity to humans. Ingestion
of as little as 100 mg usually results in severe poisoning
and as little as 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 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.
Analyses of pesticides in wastewater are generally
accomplished by either colorimetric or gas chromatographic
methods. In some cases, such as toxaphene gas chromatograph
- mass specto analysis (Gas Chrom/Mass Spec) 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. Gas Chrom./Mass Spec is
even more costly and difficult to run.
The pesticides considred in this document are organic
compounds; however, they are not adequately measured by the
BOD, COD, or TOC methods of analysis. They are often toxic
to organisms used in the BOD analysis. The determination of
small quantities of organic materials, the pesticides, in
the presence of large quantities of materials normally
measured by COD and TOC analyses is an unreliable measure of
pesticide concentrations. The levels of pesticide pollution
that are normally of concern are well below the detection
limits of these methods.
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Metals
Metals may enter wastewaters of the pesticide industry when
they are used as a principal constituent of metallo-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 industry are the following:
Arsenic Lead Nickel
Cadmium Manganese Tin
Chromium Mercury Zinc
Copper
Arsenic is normally present in sea water at concentrations
of 2 to 3 ug/1 and tends to be accumulated by oysters and
other shellfish. Concentrations of 100 mg/kg have been
reported in certain shellfish. 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 AsH3. Surface water criteria for public water
supplies have set a permissible level of arsenic in those
waters at 0.05 mg/1.
Cadmium in drinking water supplies is extremely hazardous to
humans. Cadmium is cumulative in the liver, kidney,
pancreas, and 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 also.
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.
The toxic effects of cadmium on man have caused a limitation
of the amount of this metal allowed in water supplies. The
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maximum acceptable cadmium concentration in drinking water
is set at 0.01 mg/1 in the United States.
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.
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 ingested is known to cause chronic
zinc deficiency. The most important factor in domestic
water supplies is taste. 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.
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.
Copper concentrations less than 1 mg/1 have been reported to
be toxic (particularly in soft water) to many kinds of fish,
crustaceans, molluscs, insects, phytoplantkon, and
zooplankton. Concentrations of copper, for example, are
detrimental to some oysters above 0.1 ppm. Oysters cultured
in sea water containing 0.13 to 0.5 ppm of copper deposited
the metal in their bodies and became unfit as food.
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.
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
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aquatic life are extremely sensitive. Chromium also
inhibits the growth of algae.
Foreign to the human body, lead tends to be deposited in
bone as a cumulative poison. The intake that can be
regarded as safe for everyone cannot be stated definitely,
because the sensitivity of individuals to lead differs
considerably. Lead poisoning usually results from the
cumulative toxic effects of lead after continuous
consumption over a long period of time, rather than from
occasional small doses. Lead is not among the metals
considered essential to the nutrition of animals or human
beings. The maximum allowable limit for lead in the USPHS
Drinking Water Standards is 0.05 mg/1. It is not unusual
for cattle to be poisoned by lead in their water; the lead
need not necessarily be in solution, 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. In soft water, lead may be very toxic;
in hard water equivalent concentrations of lead are less
toxic. 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.
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.
The presence of manganese may interfere with water usage,
since manganese stains materials, especially when the pH _is
raised as in laundering, scouring, or other washina
operations. These stains, if not masked by iron, may be
dirty brown, gray or black in color, and usually occur in
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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
ppm manganese cannot be tolerated except for low-grade
products. Very small amounts of manganese--0.2 to 0.3 ppm--
may form heavy encrustations in piping, while even smaller
amounts may form noticable black deposits.
Mercuric salts are highly toxic to humans and can be readily
absorbed through the gastointestinal tracts, and fatal doses
can vary from 3 to 30 grams. The drinking water criteria
for mercury is 2 mg/1.
Mercuric salts are also extremely toxic to fish and oth=>r
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
concentrates the mercury, and predators that eat the fish in
turn concentrate the mercury even further. The criteria for
mercury in freshwater is 0.05 ug/1 for protection of aquatic
life. For marine life, the criteria is 0.1 ug/1.
Nickel and tin do not pose as serious threats to receivina
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.
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. 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
acclimatization 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 U 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.
The metals listed above can be analyzed in wastewaters by
either wet chemical or atomic absorption methods of
analysis.
Phenols
Phenols and phenolic compounds are a potential wastewater
constituent in the pesticide industry, particularly being
associated with the manufacture of halogenated organic
pesticides.
Many phenolic compounds such as TCDD 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 in fresh water for phenol.
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.
Disinfection of drinking water with chlorine when phenol is
present even at very low concentrations, forms
chlorophenols, producing taste and odor problems.
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 wastewaters 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, there is less than 1 percent of the cyanide
molecules in the form of the CN ion and the rest is present
131
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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 tensions. A temperature rise of 10°C produced a two-
to threefold increase in the rate of the lethal action of
cyanide.
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.
The level of cyanide which can be safely ingested has been
estimated at something less than 18 ing/day,, part of which
comes from normal environmental and industrial exposure.
The average fatal dose of HCN by ingestion by man is 50 to
60 mg. it has been recommended that a limit of 0.2 mg/1
cyanide not be exceeded in public water supply sources.
The harmful effects of the cyanides on aquatic life is
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 degrees C, while the
toxicity of HCN is increased at higher temperatures.
with lower forms of life and organisms, cyanide does not
seem to be as toxic as it is toward fish. The organisms
that digest BOD were found to be inhibited at 1.0 mg/1 and
at 60 mg/1 although the effect is more one of delay in
exertion of BOD than total reduction.
Certain metals such as nickeL may complex with cyanide to
reduce lethality, especially at higher pH values. On the
other hand, zinc and cadmium cyanide complexes may be
exceedingly toxic.
Pollutants of Secondary Significance
Settleable solids can be harmful to the aquatic environment
in the same manner as suspended solids. Separate
measurement of suspended solids and settleable solids is
not, however, considered necessary.
The quantity of total dissolved solids in wastewater 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
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recommend limits for total dissolved solids since they are
limited by other parameters.
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 wastewater should take
into account chloride concentrations.
Extremely high chloride concentrations can cause difficulty
in biological treatment. However, the successful
acclimation of activated sludge organisms to high chloride
concentrations has been documented by several pesticide
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. High chloride concentrations
are especially found in the effluents of Subcategory A
plants.
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. Fven 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 industry in those cases where
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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 odorr 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.
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
This section identifies the range of control and treatment
technologies currently available for the subcategories
identified in Section TV.
In general, the selection of a control and treatment
technology for a particular plant depends on economics, the
magnitudes of the pollutant concentrations, and the
wastewater flows in the final effluent. Therefore, each
facility must make the decision as to which specific control
measures are best suited to its own situation and needs. No
industrial wastewater treatment facility should be designed
without treatability studies to determine the optimum
design, nor should monies be budgeted without individual
cost analyses. Without ignoring these fundamental aspects,
but in order to allow an assessment of the economic impact
of the proposed effluent limitations guidelines, model
treatment systems have been proposed. These models are not
intended to be used as a design basis by individual plants.
It must be emphasized that the particular treatment systems
chosen are for use in the economic analysis and are not the
only systems capable of attaining the specific effluent
limitations. It is judged that plants having similar loads
and production in the same subcategories could attain the
limitations using these unit operations.
In some cases, data trends may imply higher waste loads,
particularly flows, per product unit for smaller plants.
There are several factors which may contribute to this.
Larger, more complex operations may offer mere opportunity
for recycle of wastewater, and in some cases may have the
resources for better water management. Washing of equipment
at smaller plants may involve proportionately larger surface
areas. In any event, the designs developed and costed
herein would appear to be generous in some cases for larger
plants and somewhat less generous for smaller plants.
For the sake of an orderly discussion, treatment technology
has been divided into: (1) in-plant control technology, and
(2) end-of-pipe technology. Tn-plant control technology
includes process modifications and/or pesticide
detoxification whether by hydrolysis, carbon adsorption, or
other means. End-of-line technology is represented by
equalization and biological treatment.
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IN-PLANT CONTROL TECHNOLOGY
Tn-plant control technology includes steps to reduce
wastewater strength and/or volume. The following discussion
addresses techniques which have general application in most
instances where a particular unit process or waste type is
encountered.
Waste segregation is an important and fundamental step in
meeting the needs of proposed standards of treatment. The
following factors generally form the primary basis for wast«=
segregation:
1. Wastes with high organic loadings may he
economically treated or disposed of separately from
the main process wastewater. As discussed in mor^
detail below, segregation for detoxification and
specific parameter control can be both effective
and economical.
2. Highly acidic or caustic wastewaters can usually be
more effectively adjusted for pH prior to being
mixed with other process wastewaters. If both
acidic and caustic streams are being generated,
combining these streams can reduce chemical
requirements.
3. Process wastewaters with high levels of settleable
solids can be clarified separately,.
4. Separate equalization for streams of hiahly
variable characteristics can be effective and
improve overall treatment efficiency. This hiahly
effective technique is installed currently in the
industry as common practice.
Tn some cases, wastewater 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.
Wastewater 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
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contamination in plant effluents and cause a particularly
difficult problem by producing a high volume, dilute waste
stream.
Many of the halogenated organic pesticides are manufactured
by a direct chlorination process in which residual chlorine
and by-product hydrogen chloride gases are frequently
vented. The common technique of control involves water or
caustic scrubbing and results in a wastewater discharge. An
alternative approach currently in practice is recycle of the
vented gas and recovery of hydrogen chloride as dry gas or
muriatic acid.
Solvent extraction of process wastes with recycle of the
solvent to the process is practiced on some production lines
in the pesticide industry.
Organo-phosphorus and organo-nitrogen compounds can be
detoxified by acid or alkaline hydrolysis to acceptable
levels depending on the type of compound, detention time,
pH, and temperature of the hydrolysis operation.
Comma, et. al. (1969), studied the hydrolysis rates of
diazinon and diazoxon and concluded that either acid or
alkaline hydrolysis of these compounds (pH less than 3.1 or
greater than 10.U) speeds the degradation process
appreciably. It was also shown that in the pH range of
natural waters diazinon will have appreciably long residual
lives. Cowart, et. al. (1971), studied the hydrolysis rates
of seven organo-phosphorus pesticides under slightly acidic
conditions and concluded that even though they were all
eventually hydrolyzed, they all exhibit residual lives much
greater than would be expected under normal environmental
conditions. It was also pointed out that the hydrolysis
products can be potentially highly toxic (e.g. parathion
hydrolyzes to p-nitrophenol). Investigations of the
hydrolysis rates of 2,U-D, picloram, atrazine, diuron,
trifluralin, bromocil, DSMA, DNBP, dicamba, dalaphon,
paraquat, vernolate, PMA, zineb, and nemagon by Kennedy, et.
al. (1969)r showed that eight of these compounds exhibited
partial decomposition when subjected to treatment with
strong base or strong acid. However, complete hydrolysis
was not obtained for any compound during the time period
they were studied.
Half lives and hydrolysis rate constants for diazinon at
20°C as shown by Faust and Comma are presented below. As
would be expected, the half life is drastically reduced at
pH values below 5 and above 9.
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Log k Half Life
PH Observed (days)
3.1 -4.8 0.49
5.0 -6.6 31
7.5 -7.3 185
9.0 -7.2 136
10.4 -5.9 6.0
Wolfe, et. al. (1967) in extensive studies at the EPA Athens
Laboratory investigated the chemical transformation of 10
selected materials: methoxychlor, toxaphene, and butoxyethyl
ester of 2,4-D (halogenated pesticides); malathion, diazinon
and parathion (organo-phosphorous pesticides); and
polychlorinated biphenyls. Their results regarding the
hydrolysis of these pesticides are summarized below.
1. Halogenated Pesticides - Hydrolysis of methoxychlor
is quite slow and is pH independent under normal
conSitions in aquatic environment; its half-life is
greater than 200 days at 25°C. The hydrolysis of
toxphene is extremely slow in water, even at high
temperatures. Hydrolysis of 2,4-D esters to 2,4-D
is slow in acidic water but rapid in basic water.
2. Organo-phosphorus Pesticides - Chemical hydrolysis
of malathion is likely to be the major pathway for
its transformation in basic waters (pH greater than
7). The hydrolysis rate of malathion depends upon
pH and temperature. Figure VII-1 (from Wolfe, et.
al.) shows, the pH and temperature effect of
malathion degradation.
Hydrolysis treatability studies at Plant B1
indicate rapid degradation of parathion at high pH
values (Figure VII-2) .
3. Organo-nitrogen Pesticides - Hydrolysis of carbaryl
is rapid in basic waters and slow in acidic waters.
Hydrolysis half-lives range from 3.2 hours at pH 9
to 4.4 months at pH 6.
Captan hydrolyzes rapidly in water with a maximum
half-life of one-half day. Wolfe, et. al. (1967)
have shown a pH-half-life profile somewhat similar
to Figure VII-3.
Atrazine is relatively stable to hydrolysis in
aquatic systems. Armstrong (1967) indicated that
half-lives at pH 2 and 13 (25°C) are 18 days and 13
138
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TO6
in
J-
3
O
102
pH
FIGURE VII-1
EFFECT OF pH AND TEMPERATURE
ON MALATHION DEGRADATION
10
139
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PARATHION CONCENTRATIONS, mg/1
N>
cn
o
CD o
o o
"O O i—i i—i
O 3» I— 73
-H -< m
:c co
i—11—i <
oco »-.
^y HH
O I
ro
01
o
o
o
c:
73
CO
ro
-------
Q Q Q
500
tt!
100
50
10
PH
FIGURE VII-3
pH-HALF-LIFE PROFILE FOR CAPTAN HYDROLYSIS
IN WATER AT 28°C
141
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days, respectively. Additional data from th^ EPA
Athens Laboratory indicates that the half-life of
Atrazine at UO°C and pH 0.5 (through the addition
of sulfuric acid) is approximately 200 minutes.
The fact that hydrolysis is commonly used for detoxification
in a highly effective manner is documented in discussions of
case studies later in this section.
The technical and economic advantages of applying hydrolysis
to segregated waste streams are as follows::
1. Detoxification is more cost effective on a
concentrated, segregated waste system than on a
dilute, combined effluent.
2. The size of detoxification equipment can be
minimized.
3. High temperatures necessary in some cases for rapid
detoxification can be maintained more readily.
4. Lime addition, lime solids disposal, and
neutralization requirements are less for a
concentrated waste stream.
Detoxification can also be accomplished by carbon
adsorption, particularly in the case of halogenated
organics, as cited by a number of references listed in the
bibliography of this document. Goodrich, et. al. (1970),
used activated carbon to remove up to 99 percent of minute
quantities of dieldrin in water solution. Aly, et. al.
(1965), showed that activated carbon treatment was effective
in the removal of 2,4-D, formulation solvents, and 2,4-D
DPC. Cohen, et. al. (1960), found that not only does
activated carbon remove toxaphene from water, but it also
removes the solvents and emulsifiers present in commercial
formulations and thereby removes odor problems as well.
Bernadin and Froelich (1975) reported that activated carbon
in laboratory tests had been demonstrated to be able to
achieve levels of less than 1.0 ug/1 of the following
materials: aldrin, dieldrin, endrin, DDE, DDTr DDD,
toxaphene, and arochlor 12U2 and 1254. Eichelberger and
Lichtenberg (1971) studied the efficiency of the standard
carbon adsorption method for recovery of eleven oraano-
chlorine and ten organo-phosphorus pesticides from water.
They concluded that the method is a useful procedure for the
isolation and measurement of following organo-chlorine
pesticides: methoxychlor, lindane, endrin, dieldrin, and
heptachlor epoxide. It may be used, although not as
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efficiently, for recovery of chlorodane, DDT, and
endosulphan. The method was reported as not suitable for
recovery of six of the organo-phosphorus pesticides studied:
fenthion, methyl parathion, malathion, ethion, trithion, and
methyl trithion.
Plant B8 has conducted carbon isotherm studies to determine
optimum conditions for the removal of sodium nitrophenol
from its methyl parathion production. At a flow rate of
0.68 1/min/sq m (1 qpm/sq ft) and a carbon requirement of
0.12 kg carbon per kg sodium nitro parathion, removal
exceeded 99.99 percent.
The plant has also conducted carbon isotherm studies for the
removal of dinitro butyl phenol (DNBP) from wastewater. At
pH values less than 1.0 and at a loading rate of 0.68
1/min/sq m (1 gpm/sq ft), more than 99 percent of the DNBP
was removed, producing an effluent ranging in DNBP
concentrations from 0.1 to 5 mg/1.
The fact that activated carbon detoxification is commonly
used in the industry is documented by discussion of case
histories later in this section.
Various other methods of pesticide detoxification are
reported in the literature. A large segment of the
available literature has been devoted to halogenated
organics, presumably because of the emphasis which has been
placed in recent years on halogenated organic compounds such
as DDT and 2,4 dichlorophenoxyacetic acid (2,4-D).
Roebeck, et. al. (1965), treated wastewaters containing
chlorinated hydrocarbons with ozone and showed that some
reduction in the concentration of halogenated organics could
be obtained with large and impractical concentrations of
ozone. It was also shown that by-products of unknown
toxicity were formed.
Aly, et. al. (1965), showed that although 2,4-D herbicides
could not be removed by potassium permanganate oxidation;
2,4-DPC could be effectively removed. Potassium
permanganate was shown by Leigh (1969) to be ineffective in
removing Lindane from wastewaters. Other studies by Leigh
indicated the effectiveness of potassium permanganate in
removing heptachlor and its relative ineffectiveness in
removing DDT from wastewaters. Studies by Roebeck, et. al.
(1965), indicate that not only is potassium permanganate
ineffective in removing chlorinated hydrocarbons from
wastewaters, but also that parathion was converted to a
different, more toxic compound.
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The studies of Alyr et. al. (1965), indicated that chlorine
treatment did not effect the removal of 2,4-D herbicides
from wastewaters. Leigh (1969) showed that (1) chlorine was
ineffective in removing Lindane from wastewaters; and (2)
chlorine was much less effective in the removal of
heptachlor than permanganate oxidation. Roebeck, et. al.
(1965), showed that chlorination did not affect the
concentrations of DDT, Lindane, or parathion in wastewaters.
Research by Aly, et. al. (1965), indicates that strongly
basic anion exchange resins may be successfully used to
remove high concentrations of 2,4-D and 2,4-DPC from
industrial wastewaters.
Kennedy (1973) studied the removal of chlorinated
hydrocarbons from wastewaters using XAD-U resins and
compared the results to carbon adsorption. It was concluded
that the XAD-U resin was as effective in removing the
pesticides as carbon and had an economical advantage in that
the resin could be regenerated more economically than the
carbon.
Treatability studies at Plant Bl have shown removal of
phenol to less than 1 mg/1 from concentrations up to 50,000
mg/1 by polymeric adsorption. Regeneration of the polymeric
adsorbent was reported to be easier than for activated
carbon due to lower binding energies.
Roebeck, et. al. (1965), have shown that DDT is easily
removed by settling and coagulation followed by filtration.
Cohen, et. al. (1960), have shown that alum coagulation is
effective in removing pesticides as toxaphene which are
extremely toxic to fish from water.
Huang, et. al. (1970)r have shown that clay minerals such as
illite, kaolinite, and montmorillonite are effective in
removing pesticides such as DDT from water.
Incineration of particularly strong wastes is commonly
practiced in the industry. From the results of incineration
studies, Carries, et. al. (1976), made the following
conclusions:
1. most organic pesticides 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 in which the greatest removal of
the active ingredient is effected;
144
-------
3. the most important incineration factors are the
temperature and the dwell time in the combustion
chamber ;
4. conventional waste incinerators are potentially
adequate facilities for pesticide incineration;
5.
6.
organo-nitrogen pesticides can generate cyanide gas
if the incineration temperatures and percent excess
air are not adequate;
incinerators burning pesticides
emission control devices;
will require
residues from the incineration of pesticides
formulations generally contain low levels of
pesticides; and
odor can be a problem, especially in
incineration of organo-sulfur compounds.
the
Kennedy, et. al. (1969)r in an investigation of the
incineration possibilities for the destruction of some
twenty pesticides, have concluded that incineration is
superior to chemical methods for the destruction of waste
pesticide chemicals.
High ammonia levels are a problem in some sectors of the
pesticide industry. Ammonia stripping of those streams with
high ammonia loads is applicable to the industry and
transferable from the fertilizer industry. In most cases it
is necessary to recover the stripped ammonia in order to
avoid creating air pollution problems. Extensive ammonia
removal by steam stripping has been designed at Plant M8 and
is planned to be in use in stages by 1977 and 1978.
Potentially, some sectors of the organo-nitrogen pesticide
chemicals manufacture can produce cyanide laden waste
streams. In such cases, these waste streams should pass
through a cyanide removal unit where the toxic cyanide group
is oxidized with chlorine in an alkaline medium to the
significantly less toxic cyanates.
END-OF-PIPE TREATMENT TECHNOLOGY
A biological treatment process not only accomplishes removal
of pollutants but also serves as an efficient monitor of in-
plant detoxification processes.
145
-------
A study by Ingols, et. al. (1966), concluded that
halophenols can be successfully biologically degraded when
they are present in low concentrations in wastewater.
Leigh (169) concluded that Lindane is not subject to
biodegradation nor does it adversely affect microbial
communities,
Hemmett, et. al. (1969), have shown that 2,4-D can be
successfully biodegraded.
A study by the Environmental Protection Agency (12130 EGK
06/71, June 1971) of the biological treatment of
chlorophenolic wastes indicates that these wastes can be
successfully biodegraded if aerated lagoons and
stabilization ponds are provided to avoid hydraulic
overloading and reduce BOD loading entering the biological
system. If these conditions are met, the treatment of these
wastes does not differ significantly from the treatment of
municipal sewage.
There is some evidence that the hydrolysis derivatives of
triazine are biodegradable (Kaufman and Kearney, 1970).
Mills (1959) described the criteria used in the development
of a biological treatment system for wastewaters resulting
in part from 2,U-D production. He reported that among the
various types of organic wastes produced, the most
troublesome and costly to treat was the 2,4-D waste. An
alkaline chlorination process achieved 95 to 98 percent
destruction of the dichlorophenol content of the waste, but
the waste still contained 20 to 30 mg/1 dichlorophenol.
Therefore, it was decided to investigate the bio-oxidation
process. Laboratory studies showed that dichlorophenol and
2rU-D acid could be oxidized by bacterial action.
Subsequent trickling filter pilot plant work on 2,4-D
wastewater indicated that dichlorophenol could be reduced by
86 percent (205 to 30 mg/1) and COD by 70 percent (585 to
170 mg/1). An activated sludge (complete mix) pilot plant
was used for 2,U-D wastewater combined with wastewaters from
other chemical processing. The proportion of 2,U-D
wastewater in the feed was gradually increased until it
constituted 40 percent of the total. It was found that the
daily addition of settled sewage was necessary to maintain a
viable floe.
It was concluded that an activated sludge system could
successfully treat the combined waste streams.
146
-------
It was noted that the 2,U-D waste resulted in a more dense
and more rapidly settling sludge, and that a dilution factor
of 3.4 was necessary. It was estimated that phenol removal
would be more than 99 percent and BOD removal from 90 to 95
percent.
Measurements at Plant Ml have shown a biological oxygen
uptake for 2,U-D acid of 0.72 mg/mg as compared to a
theoretical uptake of 1.15r and an oxygen uptake of 1.28
mg/mg for 2rU-D butylester as compared to a theoretical
value of 1.62. Both of these comparisons indicate good
biodegradability.
The concentration of halogenated organic pesticides in
activated sludge has been demonstrated by several studies.
Investigations in England by Holdenf et. al. (1966-1967),
have shown that pesticides tend to concentrate in primary
sludge, i. e. the final effluent contains a small fraction
of the influent pesticides while the sludge contains "orders
of magnitude" increases over the influent.
Unpublished data at the National Environmental Research
Center have indicated that activated sludge treatment
achieves as much as 90 percent removal of chlordane. The
data also indicate the removal of dieldrin, ODD, DDT, and
PCB by sewage sludge.
Boyle (1971) found concentrations in municipal sludges
ranging from 25 to 30 mg/1 for DDE, 20 to 30 mg/1 for ODD,
and 3 to 13 mg/1 for DDT, as compared to values several
thousand times lower in the liquid effluent.
Saleh (1973) investigated the effects of physical-chemical
treatment in combination with activated sludge on pesticide
reduction. He reported that multimedia filtration combined
with activated sludge reduced aldrin, ODD, and DDT by 100
percent, dieldrin by 72 percent, and DDE by 39 percent.
There was no removal of Lindane. When solids contact and
carbon adsorption were added to the system, the removal for
all of the above pesticides was essentially 100 percent.
Roebeck (1965) applied various physical-chemical processes
to the removal of pesticides with the following results:
147
-------
Percent Pesticide Removed (at 10 mq/1 level)
PPT Lindane Parathion Dieldrin Endrin
Chlorination
5 ing/1
10* 10*
99** 99**
10*
55
75
80
99**
99**
99**
99**
99**
10*
55
75
85
92
99**
15
50
10*
35
80
90
94
99**
Coagulation
and Filtration 98 10*
(alum)
Carbon Slurry
5 mg/1 - 30
10 mg/1 - 55
15 mg/1 - 80
Carbon Bed
0.5 gpm/ft2
Ozone
11 mg/1 10*
36 mg/1 30
* Less than
** More than
Control and Treatment Technology-Case Studies
The following discussions are of actual control and
treatment technologies existing in the pesticide chemicals
industry. Since, as previously stated, few pesticide plants
produce only one subcategory of pesticides, a separate
discussion is provided for "multi-category" plants. These
plants apply techniques in some cases to specific pesticide
wastewaters and in other cases to more than one. In
general, the treatment systems at multi-category plants tend
to be more complex, but greater in operational flexibility
and opportunities for recycle and reuse are usually
available.
Multi-Category Plants
Plant Ml, which manufactures halogenated organics, organo-
phosphorus, and organo-nitrogen compounds, collects all
pesticide wastewaters in separate surge tanks at each
processing area. Wash water and scrubber effluent are both
recycled to the process. Wastewaters from phenolic
processes are collected in a 12-acre equalization pond
before being blended with approximately three times their
volume of cooling water, clarified, and applied to rock-type
trickling filters. The trickling filters reportedly remove
148
-------
approximately 75 percent of the phenol and 60 percent of the
COD.
From the trickling filters the waste flows to an activated
sludge process which removes more than 98 percent of the
remaining phenol.
A different biological treatment system is used for general
organic wastes. Such wastes are collected in separate sewer
systems which discharge into an open channel leading to the
general treatment plant. After pH adjustment with limef the
waste flow is directed into two primary clarifiers. From
the clarifiers the waste passes to three activated sludge
aeration basins in which it is aerated for five hours.
The activated sludge units of the general treatment plant
are also used for final treatment of effluent from the
phenolic treatment plant after the phenol has been removed.
A biological solids concentration of about 2000 mg/1 is
maintained in the aeration basins.
The general treatment plant accomplishes 95 percent removal
of BOD and suspended solids.
Solids from the primary clarifiers of the general treatment
plant are dewatered in two HO x 60-inch solid bowl
horizontal centrifuges. A flocculant is added to the feed
to facilitate separation of solids. The dewatered material
(30 percent solids) is ultimately sent to a landfill.
Some brine wastes which cannot be handled effectively by
conventional biological treatment also require special
disposal. After being pumped to a large settling pond, they
are passed through sand filters and then pumped back to the
underground formation from which the brine was originally
drawn. The plant has invested more than five million
dollars in an incineration complex which includes burning
facilities for both liquid and solid waste materials. These
incinerators reportedly destroy all burnable wastes
generated in the plant.
Each month more than 650,000 gallons of liquid waste tars
and more than 700 drums of burnable waste chemicals are fed
to the incinerators. Among the waste tars are still
residues, waste solvents, chemical by-products, and other
hydrocarbons.
Plant M2, which manufactures halogenated organics, orcrano-
nitrogen, and organo-phosphorus pesticides, has selected
149
-------
processing steps that minimize usage of process water.
Resulting process streams are segregated, and the plant
provides emergency storage facilities, uses special pump
seals to reduce leakage, and recycles cooling water. Plant
M2 provides hydrolysis to detoxify pesticides, followed by
pH adjustment and biological treatment to reduce BOD. Final
holding in a one-acre pond is provided prior to discharge to
receiving waters.
The hydrolysis rates for pesticides produced at Plant M2 are
reported as follows:
Product
Rabon
Vapona
Dibrom
Phosdrin
Type
Organo-
Phosphate
Aldicarb Organo-
Nitrogen
Nemagon
Halogenated-
Organic
Temperature
50°C
50°C
27°C
23°C
38°C
38°C
38°C
38°C
23°C
23°C
23°C
43<>c
25°C
43°C
80°C
80°C
80°C
100°C
100°C
100°C
23°C
23°C
23°C
43°c
12.0
11.6
11.6
5-6
1.1
9.1
1.1
9.1
7.0
10.0
11.0
11.5
7.0
12.0
6.0
7.0
8.0
6.0
7. 0
8.0
7.0
9. 2
12.0
11.5
Half-Life
8 min
24 min
110 min
792 hrs
60 hrs
4.5 hrs
60 hrs
ca. 1 hr
30 days
8 hrs
1.4 hrs
6 min
7 days
8 min
19 hrs
205 min
49 min
115 min
54 min
7 min
Less than
175 days
85 days
4 hrs
40 min
Hydrolyis at elevated temperature and pH during the period
November 1975 through March 1976 resulted in no detectable
pesticides in the effluent (See Table VIT-1). Detection
limits for the analyses were as follows:
150
-------
Vapona: 0.100 mg/1
Dibrom: 0.100 mg/1
Rabon: 0.010 mg/1
Phosdrin: 0.100 mg/1
Aldicarb: 0.010 mg/1
A proposed upgrading of the entire treatment system includes
a 12 hour detention time hydrolysis basin to accomodate a
7.60 I/sec (120 gpm) effluent.
Non-aqueous streams at plant M2 are either trucked to off-
site contract disposal or sent to a liquid/gas incinerator.
As a result, the primary 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 pH adjusted to
10 with caustic. The combined waste is further combined
with other neutralized process wastes in a settler and phase
separator, and additional caustic is added before
discharging to an API separator to remove insoluble
organics. Skimmed oil is burned in the incinerator. The
separator effluent is further treated with 20 percent
caustic and sent to a treatment basin, and there combined
with sanitary package plant effluent. Steam is added to
bring the temperature to U3°C and the final alkaline
hydrolysis step occurs before discharge to the final holding
pond.
Table VII-1 presents the monthly mean values of five months
daily sampling at the holding pond (final effluent)
discharge of Plant M2. Parameters monitored include flow,
COD, TOC, TSS, oil and grease, total chlorides, and total
pesticides. BOD is not routinely monitored.
A 90-day detention, aerated lagoon with a volume of 6,800 cu
m (18 million gal) and 140 kw (190 hp) of aeration is
currently under construction. Pilot plant work at the plant
has indicated that the biological system can be properly
acclimated to the wastewater, which contains chloride
concentrations of approximately 30,000 mg/1. Organic
reductions in the 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.
Plant M3, which produces halogenated organics and orcrano-
nitrogen compounds, employs granular activated carbon
treatment consisting of two units in series preceded by
settling and filtration to treat combined process wastes,
rainfall runoff, floor wash, and tank farm drainage from the
151
-------
en
ro
TABLE VII-1
HOLDING POND (FINAL) EFFLUENT*
PLANT M2
Flow COD TOC
L/Kkg
47,514
19,673
17,949
29,867
51,697
Mean 33,340
gal /1 000 Ib
5,696
2,358
2,152
3,580
6,197
3,997
kg/Kkg
12.35
7.16
6.83
11.98
11.61
9.99
mg/1
251
364
256
401
225
377
kg/Kkg
6.85
4.59
4.60
7.14
7.23
6.08
mg/1
139
230
256
242
140
229
kg/Kkg
0.419
0.1716
0.1714
0.3439
0.5074
0.3228
mg/1
264
9
10
12
10
12
-------
en
CO
TABLE VII-1
Continued
Pg 2 of 2
HOLDING POND (FINAL) EFFLUENT
PLANT M2
OIL AND GREASE TOTAL CHLORIDE TOTAL PESTICIDES**
kg/Kkg
0.8175
0.3742
0.2214
0.6839
0.8821
Mean 0.5958
mg/1
17
19
12
23
17
22
kg/Kkg
1,335
593
565
1,118
576
837
mg/1
28,087
30,156
31,472
37,435
11,137
31,575
kg/Kkg
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
mg/1
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
* Monthly averages of daily sampling November, 1975 through March, 1976. Ratios calculated using
average monthly technical production. Mean concentration are calculated by the equation: mg/1 =
kg/Kkg divided by (MGD/1000 X 8.34).
** N.D. = Not Detectable
-------
concreted operations area. Concentrated organic wastes and
some filter backwash is contract hauled to incineration. A
pond with 4.3 days detention is used for equalization and pH
adjustment to 6 or 8. The carbon column effluent is aerated
in another pond to raise the dissolved oxygen concentration,
and then combined with cooling water before discharge to
receiving waters. Estimates (as made by plant personnel) of
final effluent quality of the carbon columns are as follows:
BOD 25- 50 mg/1
TOC 100-400 mg/1
SS 0-5 mg/1
COD 75-100 mg/1
The carbon is replaced on a monthly basis. Plant personnel
have observed a drop in efficiency toward the end of each
month. Whereas toward the beginning of the month the
efficiency is perhaps 99 percent, the overall efficiency for
the month is about 75 percent.
Plant MU, which manufactures halogenated organics, organo-
nitrogen products, and also formulates these products,
combines a small amount of cooling water, caustic scrubber
effluent, and process wastewater before discharge to a
municipal treatment system. Spillage and bad products are
removed off-site for incineration or burial at an approved
site. Dry clean-up is used for spills.
Plant M5, which manufactures halogenated organics and
organo-nitrogen products, processes all wastewaters in a 16-
day lime neutralization basin. The neutralized effluent
passes through a skimmer pond to an aeration pond and then
through a trickling filter. Phenol concentrations greater
than U50 mg/1 in the aeration pond lead to intermittent
operation of the trickling filter and inefficient treatment.
Plant M7, which manufactures halogenated organics, organo-
nitrogen, and organo-metallic compounds, provides carbon
treatment for one of its organo-nitroaen wastewaters. The
granular activated carbon system reduces the concentration
of the pesticide in the wastewater from more than 100 mg/1
to less than 25 mg/1 and often to about 1 mg/1. Washwater
is segregated for reuse.
The wastewaters from the total carbamate process are
currently being discharged, but it is planned to install an
evaporation-crystalization system to eliminate the
discharge. However, a discharge from the evaporator over-
head of 100,000 gpd with an ammonia concentration of about
154
-------
100 mg/1 and a BOD of 100 to 200 mg/1 (as estimated by
company personnel) will be discharged to a city sewer.
A treatment system to receive all surface runoff plus the
carbon column discharge is planned to be in operation during
1977. The system will consist of equalization, filtration,
activated carbon, cationic ion exchange, chemical
precipitation, and lime neutralization.
Plant M8, which produces organo-phosphorus, and organo-
nitrogen, compounds and also formulates, provides biological
treatment in a pure oxygen system after pesticide
destruction at each process line. The pure oxygen system
was chosen in preference to an air system because of reduced
odor problems. Waste gases from the pure oxygen system are
piped to a thermal oxidation system. The plant also
practices segregation, phenol recovery and reuse, and
employs surface condensers.
In order to reduce the impact of high salinity of the raw
wastewater (2,000 to 3,000 mg/1 chloride) on the treatment-
plant, the process water is diluted approximately 150
percent prior to activated sludge treatment.
The mixed liquor suspended solids concentration is
maintained at a fairly high concentration (6,000 to 8,000
mg/1) and the plant reportedly has a problem of relatively
high suspended solids in its final effluent.
A first-phase ammonia stripping facility is planned to be in
operation by 1977 and a second by 1978.
The final effluent is discharged to a receiving stream while
sludge, following thickening and vacuum filtration, is
hauled to landfill.
Table VII-2 presents the monthly mean effluent values for
six months as reported by Plant M8. Parameters monitored
include BOD, COD, TSS, phenols, total pesticides, and
ammonia nitrogen. Total pesticides monthly average
concentrations ranged from 3.04 to 7.85 mg/1 and averaged
U.U6 mg/1. Ammonia nitrogen monthly average concentrations
ranged from 252 to 658 mg/1 and averaged 408 mg/1 for the
six month period.
Plant M9, which manufactures halogenated organic, organo-
phosphorus and organo-nitrogen products, provides hydrolysis
of specific pesticide streams and biological treatment of
all pesticide wastewaters. A stripper is used to recover
solvent for reuse in the process.
155
-------
en
cr>
TABLE VII-2
OXYGEN ACTIVATED SLUDGE FINAL EFFLUENT*
PLANT M8
Flow BOD COD
L/Kkg
44,700
99,200
103,000
163,000
124,000
117,000
Mean 109,000
gal/1000 Ib
5,360
11,900
12,400
19,600
14,900
14,100
13,000
kg/Kkg
12.3
5.37
8.37
26.0
10.2
10.2
12.0
mg/1
275
54.1
79.6
159
82.1
86.7
no
kg/Kkg
72.6
109
117
170
164
187
137
mg/1
1,620
1,100
1,130
1,040
1,320
1,590
1,260
kg/Kkg
2.55
7.92
7.28
16.7
9.99
8.18
8.77
mg/1
57.0
79.8
70.4
102
80.4
69.6
80.9
* Monthly averages from daily monitoring, October 1975 through March 1976. Ratios calculated using
average monthly technical production reported by plant. Mean concentrations are calculated by
the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLE VII-2
Continued
Pg 2 of 2
OXYGEN ACTIVATED SLUDGE FINAL EFFLUENT*
PLANT M8
NH3-N PHENOL TOTAL PESTICIDES
en
kg/Kkg
29.4
41.2
46.5
60.0
59.2
29.7
Mean 44.3
rng/1
658
415
449
367
476
252
408
kg/Kkg
0.176
0.306
0.217
0.189
0.0889
0.190
0.194
mg/1
3.94
3.08
2.10
1.16
0.715
1.62
1.79
kg/Kkg
0.351
0.703
0.399
0.618
0.475
0.358
0.484
mg/1
7.85
7.08
3.86
3.78
3.82
3.04
4.46
* Monthly averages from daily monitoring, October 1975 through March 1976. Ratios calculated using
average monthly technical production reported by plant. Mean concentrations are calculated by
the equation: mg/1 = kg/ Kkg divided by (MGD/1000 Lb X 8.34).
-------
During a representative 30-day period in May 1975 thf
reduction of diazinon by hydrolysis averaged 99.9% resulting
in an effluent of 0.01 kg/day (0.03 Ib/day) prior to
biological treatment. The basin is maintained at a pH less
than 1 at ambient temperature during 8 to 15 days detention
time.
The biological system has been acclimated to a chlorides
concentration up to 20,000 mg/1 and is designed to handle up
to 30,000 mg/1.
Table VII-3 presents the monthly mean values from daily
sampling for one year of the final effluent at plant M9 for
one year. Parameters monitored include BOD, TSS, total
cyanide, diazinon, TKN, and ammonia nitrogen. The treatment
system achieves consistent removal of the above parameters.
The facility treats wastewater consisting of 66 to 85
percent pesticide wastes.
Plant M10, which produces halogenated organics and organo-
nitrogen pesticides, provides solids settling and filtration
of all process wastes.
Plant Mil, which produces organo-nitrogen and organo-
phosphorous pesticides, employs caustic hydrolysis, acid
hydrolysis, and chlorine oxidation to destroy toxic material
in the agueous process waste before discharging to a
holding/evaporation pond.
Plant M12 produces halogenated organics and organo-nitrogen
pesticides. Combined plant wastes, including sanitary
sewage and storm run-off, are treated in a biological system
operated jointly with a nearby chemicals supplier. Solids
residues are landfilled on plant property.
Plant M13 produces halogenated organics, metallo-organics,
and organo-nitrogen based pesticides. Combined plant wastes
are discharged to a municipal treatment system after mercury
recovery.
Treatment Technology Specific to Subcategory A
Plant Al hydrolyzes its pesticide waste to pH 10 by caustic
soda addition. After 16 hours of holding the wastewater it
is sent to an aeration pond which provides approximately 25
days retention. About 200,000 cu cm/sec (400 cfm) of air
accomplishes approximately 50 percent COD reduction. The
final effluent is discharged to a municipal sewer system.
Non-contact cooling water is discharged to a river.
158
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TABLE VI1-3
BIOLOGICAL TREATMENT SYSTEM CLARIFIER OVERFLOW*
PLANT M9
en
10
FLOW
BOD
TSS
Total Cyanide
L/Kkg
91,500
80,900
66,200
69,300
78,400
60,400
109,000
88,600
71,900
64,300
53,000
Mean 75,800
gal /1 000 Ib
11,000
9,700
7,930
8,300
9,390
7,240
13,000
10,600
8,620
7,700
6,350
9,080
kg/Kkg
3.68
2.91
1.65
1.85
1.82
1.99
1.95
5.68
13.7
8.99
4.49
4.43
mg/1
40.3
35.9
24.9
26.7
23.3
33.0
17.9
64.1
191.0
140.0
84.6
58.5
kg/Kkg
4.92
6.02
2.96
2.67
3.31
1.88
3.32
9.58
12.0
8.54
4.89
5.46
mg/1
53.8
74.4
44.7
38.6
42.3
31.1
30.0
108.0
162.0
133.0
92.3
72.1
kg/Kkg
0.054
0.031
0.015
0.017
0.047
0.026
0.023
0.044
0.104
0.074
0.035
0.043
mg/1
0.586
0.387
0.218
0.244
0.606
0.436
0.209
0.498
1.450
1.150
0.651
0.562
*Daily data for April 1975 through February 1976 averaged by month.Mean concentrations are
calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLE VI1-3
BIOLOGICAL TREATMENT SYSTEM CLARIFIER OVERFLOW*
PLANT M9
Continued
Page 2 of 2
DIAZINON
TKN
NH3
mg/1
.00013
.00012
. 00007
. 00009
.00012
.00005
.00016
.00018
.00018
. 00029
.00017
Mean .00014
kg/Kkg
.0016
.0016
.0011
.0014
.0016
.0012
.0015
.0020
.0027
.0045
.0032
.0018
mg/1
42.9
26.7
22.7
32.0
25.6
18.8
27.0
20.6
14.9
16.7
13.5
23.8
kg/Kkg
463
328
347
470
329
315
245
238
197
245
254
. 314
mg/1
16.7
12.7
10.2
11.4
9.87
8.56
11.5
6.24
2.92
3.49
3.49
8.81
kg/Kkg
180
157
155
167
127
143
104
72.0
38.5
51.2
65.8
116
a-. ——„ ...- _._._-,— __, Mean concentrations are
calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
A chronic operational problem with the treatment system is
inadequate equalization of the surge loads from the batch
operation. Occasional spills of surfactants cause foamina
which results in poor oxygen transfer. An emergency holdincr
tank is used to divert unusually high strength wastes for
later treatment.
Plant A2 has been involved in an extensive effort to reduce
water usage and segregate non-contact flows. Barometric
condensers are being replaced with vacuum pumps. Alcohol is
recovered by distillation and reused.
The plant provides lime for pH adjustment, sedimentation,
and filtration with utlimate discharge to a municipal sewer.
The filtration, system consists of both a sand-diluted,
copper catalyzed iron powder reduction bed filter, and a
stainless steel, 2 micron mesh filter, both of which are
periodically backwashed into a 9,000 cu ft acid brick sump.
The sump is equipped with a skimming bar and a sludge
collecting system. Both skimmings and sludge are
incinerated on-site. Acid water from the incinerator
scrubber goes to a final neutralization pit prior to
discharge to a municipal sewer. A pilot resin adsorption
system has been tested to determine optimum operating
conditions prior to construction of a full-scale system.
The filter and resin systems combined are expected by plant
personnel to remove an average of 99.9 percent of the
pesticides.
Plant A3 has its production area diked in order that all
leaks or spills may be contained. 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 ^ear with washings 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
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.
The plant mixes process waste neutralized by caustic soda
and limestone with clarified storm water and provides
further clarification. This effluent is then combined with
cooling water prior to final discharge to a stream. Sludgp
from the drying beds is disposed of in a landfill.
16]
-------
The system was designed to remove 90 percent of the
toxaphene concentration in the influent (2 mg/1 to 0.2
mg/1); according to plant personnel, the system actually
achieves greater than 95 percent removal.
Table VTI-4 presents the monthly mean values for effluent
daily sampling for suspended solids and toxaphene. Monthly
mean suspended solids averaged 58.1 mg/1 over an eleven
month period and ranged from between a minimum of 18 mg/1
and a maximum of 95.1 mg/1. Toxaphene concentrations
averaged slightly more than 0.1 mg/1.
Plant AH has eliminated wastewater discharge from its
toxaphene production 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 A5 segregates specific waste streams, uses surfacp
condensers, provides countercurrent use of chemicals and
washwater, employs special seals to minimize overflows, and
recycles and reuses wastewater. The plant has also
instituted design changes which allow chemical (including
phenol) recovery and regeneration, with reuse and sale of
waste materials as raw materials. The final discharge is to
a municipal system.
Plant A6 practices alcohol extraction of a segregated
process waste stream and converts the spent solvent to a by-
product. Another waste stream is steam stripped for raw
material recovery and reuse with recycle of*wastewater to
the feed. A brine recovery operation is proposed that would
concentrate the brine for chloride regeneration at a nearby
plant. Through by-product recovery and reuse the plant
hopes to achieve zero discharge. Currently the wastewater
is passed through two carbon columns then neutralized.
Table VII-5 represents eight months monitoring of the
activated carbon effluent at Plant A6, which reports BOD,
COD, TSS, phenols, TDS, and chlorinated hydrocarbon
concentrations. Phenol monthly average concentrations
ranged from 0.45 to 3.0 mg/1 and the mean value for the
eight month period was 1.58 mg/1.
Plant A7 deactivates its wastewater with caustic, dilutes it
with cooling water, and discharges it to a municipal system.
Following recovery of scrubber condensate for process reuse
and hydrolyzation. Plant A8 uses carbon adsorption at the
rate of 18,000 kg carbon per month (40,000 Ib/month) to
-------
cr>
oo
TABLE VII-4
SETTLING POND FINAL EFFLUENT*
PLANT A3
Flow TSS Toxaphene
L/Kkg
8,889
9,127
10,592
9,696
9,673
8,992
8,528
7,688
7,733
7,442
8,581
Mean 8,815
gal/1000 Ib
1,066
1,094
1,270
1,162
1,160
1,078
1,022
921
927
892
1,028
1,057
kg/Kkg
—
—
--
—
0.920
0.627
0.697
0.577
0.369
0.240
0.154
0.512
mg/1
--
—
—
—
95.1
69.7
81.8
75.1
47.7
32.3
18.0
58.1
gm/Kkg
0.735
0.758
1.820
1.560
1.170
0.874
0.930
0.785
0.715
0.421
0.433
0.927
mg/1
0.0827
0.0831
0.1720
0.1610
0.1210
0.0972
0.1090
0.1020
0.0925
0.0566
0.0505
0.1050
* Monthly averages of daily sampling, May 1974 through March 1975. Mean concentrations
calculated by the equation: mg/1 = (kg/Kkg)/(MGD/l000 Ib X 8.34).
-------
CT>
TABLE VII-5
NEUTRALIZED ACTIVATED CARBON (FINAL) EFFLUENT*
PLANT A6
Flow BOD COD TSS
L/Kkg
6,770
6,710
8,020
5,510
11,200
11,100
9,640
Mean 8,420
gal /1 000 Ib
812
804
961
661
1,340
1,330
1,160
1,010
kg/Kkg
12.8
16.2
17.6
10.3
31.8
31.5
24.5
20.7
mg/1
1,890
2,410
2,200
1,870
2,840
2,840
2,540
2,460
kg/Kkg
28.2
23.0
52.7
22.2
49.4
46.9
44.3
38.1
mg/1
4,160
3,430
6,570
4,020
4,410
4,230
4,600
4,520
kg/Kkg
3.0
1.9
31.7
24.5
23.3
17.7
9.0
15.9
mg/1
443
283
3,950
4,440
2,080
1,600
933
1,890
..._.__ MIVII V.H i j UT^IIA^V..;, UUIJT i j i s/ oin uuyii i cui uui j i _// u , CAi^cp l, r\uyu3 \. i 3 / j. r\a I I Uo l~d I UU I a LcU
from monthly technical production reported by plant. Mean concentrations are calculated by the
equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLE VII 5
Continued
Pg 2 of 2
NEUTRALIZED ACTIVATED CARBON (FINAL) EFFLUENT*
PLANT A6
Phenol
TDS
Chlorinated
Hydrocarbons
kg/Kkg
0.0206
0.012
0.0011
0.0025
0.033
0.01
0.014
Mean 0.013
mg/1
3.0
1.8
1.4
0.45
2.9
0.9
1.5
1.58
kg/Kkg
404
469
525
364
719
813
786
583
mg/1
59,600
69,900
65,500
65,900
64,200
73,300
81 ,500
69,200
kg/Kkg
0.003
0.0048
0.019
0.0139
0.088
0.13
0.392
0.09
mg/1
0.4
0.71
2.4
2.51
7.9
11.0
40.7
11.0
*NPDES monthly averages, July 1975 through February 1976, except August 1975.Ratios calculated
from monthly technical production reported by plant. Mean concentrations are calculated by the
equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
treat combined process wastes. The system is reported to
achieve 89 percent removal of TOC.
Table VII-6 presents the results of more than four months
effluent sampling at Plant A8 for TOC, COD, TSS, and TCL.
Effluent TOC, reported as a monthly mean value, ranged from
55 to 122 mg/1 and averaged 85.7 mg/1.
Plant A9 employs no wastewater treatment. The plant is
meeting its toxaphene discharge limitation of O.OU Ib/day
through in-plant control. An official of the plant has
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 be inevitably required.
Plant A10 has selected process steps which result in a
minimal use of process water. A solvent stripper recycled
raw materials to the reactors. The solvent used in
equipment cleanup is recycled as a raw material. The
wastewater is discharged to a 100-acre evaporation basin
which has no overflow. A small amount of solid waste is
handled by an on-site incinerator.
Plant All segregates brine from other process wastes for
separate disposal to a deep well. Combined process wastes
and cooling water are released
Plant A12 disposes of all contaminated and non-reusable
process wastewater and wet scrubber effluent to a sanitary
landfill without pretreatment.
Plant A13 treats process wastes using a settling pond with
two day detention, two aeration ponds with seven day
detention each, and a final settling pond. Final discharge
is to a municipal treatment system.
Plant A1U discharges only a small amount of non-reusable
process waste to an on-site evaporation ditch.
Plant A15 segregates and recycles mercury cell wastewater.
Trace organics are recovered from waste acid gases using
refrigerated condensers and then thermally destroyed. The
wastewater is neutralized and passed through a settling pond
before being discharged to a municipal sewer.
Plant A16 practices deep well injection of all process and
cooling water.
166
-------
cr>
TABLE VI1-6
ACTIVATED CARBON (FINAL) EFFLUENT*
PLANT A8
L/Kkg
3550
3180
2760
3210
Mean 3180
Flow
gal /1 000 Ib
426
381
331
385
381
TOC
kg/Kkg
0.240
0.425
0.152
--
0.272
mg/1
67.7
122
55.0
—
85.7
COD
kg/Kkg
--
1.35
0.684
--
1.02
mg/1
—
425
215
—
320
JSS TOTAL CHLUKlUt
kg/Kkg
--
1.33
0.995
0.112
0.814
mg/1
--
420
313
35
255
kg/Kkg
—
0.779
0.434
—
0.607
mg/1
—
248
135
—
191
*Daily effluent composites October 1975 through December 1975 and February 1976. Ratios calculated
using monthly average technical production and average flow reported by plant. Mean concentrations
are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
Plant A18 segregates and recycles cooling water. The entire
production area is built on a concrete pad and diked to
contain spills and rainfall runoff. Process waste streams
are segregated for separate primary treatment.
The only discharge from the toxaphene process at Plant AIR
is spent caustic which is generated at a rate of about 10
gpm. A company official has stated that independent
analyses have detected no toxaphene concentrations in this
stream.
Following pH adjustment and settling, the wastewater is
discharged to a municipal treatment system.
Plant A19 segregates high strength wastes for deep well
disposal and currently uses only a holding pond for other
wastewater before discharge. However, treatability studies
at the plant have shown that with proper pretreatment the
wastewater can be biologically treated.
A new waste treatment facility is under construction which
will consist of pH adjustment, dechlorination with sodium
hydrosulfide, presettling, equalization, clarification,
mixed media filtration, activated carbon dechlorination,
extended aeration, and final clarification. The expected
effluent concentration of BOD is 10 mg/1.
Table VII-7 presents the monthly mean values for BOD, COD,
TOC and TSS in the effluent of Plant A19. The BOD averaged
99 mg/1, TOC 78 mg/1, and suspended solids 36 mg/1.
Table VTI-8 shows the treated effluent averaged for five
plants treating halogenated organic waste. Two plants, Afi
and A8, both employ pH adjustment and activated carbon
adsorption in order to reduce the level of pesticides and
phenols in the waste. As demonstrated by Plant A6, an
average effluent phenol concentration of 1.58 mg/1 is
achievable, based on approximately 99 percent removal. An
average effluent pesticide concentration of 11.0 mg/1 was
reported. The degree of removal that this represents is
unknown due to lack of raw waste load monitoring. Reduction
of organics through activated carbon is not well documented,
although as noted previously, Plant A8 has demonstrated an
88 percent removal of TOC resulting in an effluent
concentration of 85.7 mg/1. The COD effluent of 320 mq/1
would represent approximately 94 percent removal; however,
this is based on a limited number of data points. Plant A6
operates carbon columns at an abnormally high suspended
solids level, and Plant A8, which achieves a suspended
solids removal of 83 percent, still discharges approximately
168
-------
TABLE VII-7
HOLDING POND (FINAL) EFFLUENT*
PLANT AT 9
L/Kkg
91 ,700
91 ,700
97,600
103,000
103,000
94,200
95,900
113,000
83,600
102,000
119,000
114,000
122,000
Mean 102,000
Flow
gal/1000 Ib
11,000
11,000
11,700
12,300
12,300
11,300
11,500
13,600
10,300
12,200
14,300
13,700
14,600
12,300
BOD
kg/Kkg
15.8
6.06
7.25
10.2
10.2
7.11
10.2
12.8
14.0
11.5
7.49
6.92
11.9
10.1
mg/1
172
66
74
100
100
75
107
113
163
113
63
60
97
99
COD TOC
kg/Kkg mg/1 kg/Kkg
30.6 333
17.6 192
16.4 168
8.80 86
22.4 219
10.7
2.96
6.90
7.94
12.0
8.73
5.67
5.45
19.2 197 8.29
mg/1
--
--
--
--
--
116
74
66
84
143
66
50
45
78
TSS
kg/Kkg
1.19
2.39
3.04
10.2
10.2
1.42
1.13
2.77
1.10
1.07
1.29
1.57
10.4
3.72
mg/1
13
26
31
100
100
20
12
24
13
11
11
14
85
36
*Monthly NPDES data from 24 hour composites taken twice per month except TOC (EPA grab samples).
Ratios calculated using monthly average technical production. Mean concentrations are calculated
by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
TABLE VI1-8
TREATED EFFLUENT SUMMARY
HALOGENATED ORGANIC PESTICIDE PLANTS
SUBCATEGORY A
FLOW
BOD
COD
TOC
PLANT
A3
A4
A6
A8
A9
A12
A18
AT 9
M9
L/Kkg
8,760
252
8,420
3,180
2,550
1,060
3,810
102,000
75,700
Gal /1 000 Lb kg/Kkg mg/1
1 ,050
3
1,010 20.7 2,460
382
306
127
457
12,300 10.1 99
9,080 4.43 58.5
kg/Kkg mg/1 kg/Kkg mg/1
-
-
38.1 4,520
1.02 320 0.272 " 85.7
-
-
-
19.2 197
-
Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34)
-------
TABLE VI1-8
Continued
Page 2 of 2 Pages
TSS PHENOL PESTICIDES
PLANT kg/Kkg mg/1 kg/Kkg
A3 0.52 60
A4
A6 15.9 1890 0.013
A8 0.814 255
A9
A12
A18 -
A19 3.7 36
M9 5.46 72.1
mg/1 kg/Kkg
0.001
N.D.
1.58 0.09
-
0.001
0.504
N.D.
-
0.210
mg/1
0.11
N.D.
11.0
-
0.4
0.423
N.D.
-
0.109
Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34)
Note: N.D. = Not Detectable
-------
255 mg/1. Both .JJsets of data indicate that treatment by
filtration may considerably improve operating efficiencies.
There is no one plant that utilizes biological treatment for
halogenated organic pesticide wastes exclusively. Plant
A19f which currently discharges 99 mg/1 BOD by utilizing
gravity separation, intends to achieve 10 mg/1 (1.01 kg/kkg)
by upgrading the present system. Plant M9, which treats
wastewater from a halogenated organic pesticide in
combination with other pesticide wastes, is achieving 58.5
mg/1 BOD. Plant A3, which operates a physical-chemical
treatment system, does not monitor organics but reports
greater than 90 percent pesticide removal.
Treatment Technology Specific to Subcategory B
Plant Bl detoxifies its two primary waste streams at an
elevated temperature and a pH greater than 11 achieved with
caustic soda. The detoxified wastes are combined with
wastewaters from non-pesticide production lines in a 25-acre
anaerobic settling pond. The clarified overflow passes to a
shallow aerobic pond which, during summer months, achieves a
COD reduction of 50 percent; however, during the winter COD
removal is negligible. The discharge from the aerobic pond
is combined with cooling water in a third pond before
further impondage for final clarification of oxidized iron.
Investigations of biological treatment, which to date is
reported to be the only viable alternative for meeting NPDES
permit requirements, are being continued by the plant.
Plant B2 flows its acidic process waste through a limestone
pit which increases its pH from a range of 1-2.5 to 4- 5.
The discharge from the limestone pit is combined with
alkaline waste and the total stream is passed into two
agitated hold tanks which have caustic addition when
necessary. Analyses of samples from the hold tank for
parathion, paranitro phenol, pH, and COD determine the feed
rate to the subsequent aeration basins and final clarifiers.
The centrifuged sludge from the activated sludge system is
disposed of on land; the liquid effluent 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 2 mg/1 of pesticides.
The solvent used in production is distilled off and
recycled. Incinerator scrubber water and acidic wastes are
segregated. Highly concentrated organic wastes are
incinerated.
172
-------
Incineration scrubber effluent is passed directly through
limestone neutralization beds before discharge to surface
waters. Table VII-9 is a tabulation of average monthly
values for BOD, COD, and pesticides. Daily maximum values
for COD and parathion are also reported by the plant. Table
VIT-10 is a listing of COD and pesticide ratios
demonstrating the daily variability of the effluent over a
typical 30-day operating period. The effluent COD ratio
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.
Table VII-11 presents the results of daily composited
samples taken on seven different days indicating the
effluent concentrations fcr some other parameters, including
TOC, TSS, phenols, total chlorides, total ortho-phosphate,
total phosphorus, and TKN.
Plant B3 disposes approximately 190,000 I/day (50,000
gal/day) to deep well injection. Floor drain water is
combined with cooling water and storm water, neutralization
with sodium hydroxide, and sent to a lagoon. The lagoon
effluent is filtered through rotary drum precoated filters
to remove settleable solids and the filtrate is discharged
to a stream. Solids are contract hauled to disposal off-
site. Washwater and distillation condensate are reused.
Solvent is stripped and stored for reuse.
Plant B4 recovers hydrogen sulfide and recycles distillation
overheads. The plant also utilizes emergency storage
facilities, special pump seals, and surface condensers.
Segregation and collection of specific wastes are employed
in conjunction with solvent extraction and materials
recovery and reuse. Detoxififcation is accomplished for
each individual process. Final disposal is ocean dumping.
Plant B5 discharges combined process and non-contact
wastewater to navigable waters from egualization and pF
adjustment. Some process wastes and residues are contract
hauled to off-site disposal.
Plant B6 recycles wash water and scrubber effluent to the
process.
Plant B7 which normally produces both organo-nitrogen and
organophosphorous, has operated its pretreatment system for
a period of two months when only organo-phosphorous products
were being manufactured. Table VIT-12 presents the monthly
average effluent BOD, COD, TSS, TP, phenol, total chloride,
173
-------
TABLE VII-9
MONTHLY ACTIVATED SLUDGE EFFLUENT SUMMARY*
PLANT B2
BOD
kg/Kkg
COD
kg/Kkg
Parathion
kg/Kkg
Monthly Average
0.659
0.938
0.214
0.417
0.385
0.520
0.688
0.104
0.275
0.409
0.296
0.456
0.829
0.512
0.413
Monthly Average
9.343
10.613
4.886
-
5.029
5.368
6.332
6.506
8.472
5.413
4.523
6.457
7.067
6.852
6.078
Daily Maximum
16.958
14.741
9.472
12.189
10.828
9.352
10.807
11.269
16.387
12.806
8.594
11.992
16.061
11.203
13.720
Monthly Average
0.0012
0.0005
0.0004
0.0005
0.0005
0.0008
0.0011
0.0006
0.0009
0.0007
0.0004
0.0005
0.0013
0.0006
0.0005
Daily Maximum
0.0058
0.0029
0.0011
0.0015
0.0005
0.0050
0.0098
0.0012
0.0009
0.0059
0.0029
0.0098
0.0058
0.0060
0.0038
Mean
0.474
6.64
0.0007
*Monthly averages of daily sampling January 1974 through March, 1975 reported as ratios by plant,
-------
TABLE VII-10
EFFLUENT DAILY VARIABILITY*
PLANT B2
COD
kg/Kkg
8.868
6.105
8.251
5.246
3.487
12.252
3.387
7.593
3.721
4.100
8.864
8.392
2.456
6.250
2.225
7.865
6.956
7.000
2.442
4.003
7.397
4.744
11.962
6.642
4.605
4.762
3.098
7.079
6.405
7.945
Parathion
gm/Kkg
**1.578
**0.476
**0.476
0.476
0.896
**0.652
0.048
0.555
0.471
1.414
0.471
0.456
1.250
**0.050
**0.050
1.359
**0.455
0.455
1.200
0.833
0.411
0.485
**0.548
**0.548
**0.548
**0.652
**0.500
**0.492
**0.682
**0.479
Mean 6.137 **0.647
* Daily composite samples, February 7, through March 8, 1976
** Less than
175
-------
TABLE VII-11
SELECTED DAILY ACTIVATED SLUDGE EFFLUENT*
PLANT B2
Flow COD TOC TSS
Mean
Mean
L/Kkg
48,500
67,600
67,600
67,600
67,600
71,800
71,800
66,100
gal/1000 Lb
5,820
8,110
8,110
8,110
8,110
8,610
8,610
7,930
kg/Kkg
12.5
23.3
14.5
19.8
35.7
24.0
21.0
21.5
mg/1
257
345
214
293
527
335
292
326
kg/Kkg
9.96
11.8
12.2
12.9
8.94
4.81
8.47
9.87
mg/1
205
175
180
140
132
67
118
149
kg/Kkg
3.86
1.22
1.13
1.48
--
5.69
0.697
2.35
mg/1
79
18
17
22
--
79
10
36
* Seven daily composites collected March through May, 1974. Ratios calculated from monthly
average technical production supplied by plant. Mean concentrations are calculated by the
equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
Phenol
TABLE VII-11
SELECTED DAILY ACTIVATED SLUDGE EFFLUENT*
PLANT B2
Continued
Page 2 of 2 Pages
TOTAL CHLORIDE ORTHO-PHOSPHATE TOTAL PHOSPHORUS
TKN
Mean kg/Kkg mg/1 kg/Kkg mg/1 kg/Kkg
0.00034 0.005 316 6,500 1.25
0.00034 0.005 399 5,900 1.31
1.02
0.00034 0.005 413 6,100 1.02
2.37
338 4,700 2.44
2.64
Mean 0.00034 0.005 366 5,730 1.72
* Seven dailv composites collected March through May,
mg/1
25.8
19.4
15.0
15.0
35.0
34.0
36.8
26.0
1974.
kg/Kkg
1.20
—
1.48
0.928
3.79
2.79
3.68
2.31
Ratios cal
mg/1
24.8
--
21.9
13.7
56.0
38.8
51.2
35.1
cuated from
kg/Kkg
0.054
0.038
0.019
0.019
0.019
0.020
0.040
0.0299
monthly ;
mg/1
1.12
0.56
0.28
0.28
0.28
0.28
0.56
0.45
weragi
technical production supplied by plant. Mean concentrations are calculated by the equation:
mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
—i
I CO
TABLE VII-12
PRIMARY TREATMENT EFFLUENT*
PLANT B7
Flow BOD COD TSS
L/Kkg
58,865
44,888
Mean 51 ,876
gal/1000 Ib
7,056
5,381
6,219
kg/Kkg
91.3
126
109
mg/1
1,550
2,800
2,180
kg/Kkg
241
333
337
mg/1
5,940
7,420
6,550
kg/Kkg
2.0
3.0
2.5
mg/1
34
67
49
^Monthly NPDES mean values. Ratios calculated from monthly average technical production supplied
by the plant during period of primary treatment.
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MOD/1000 Lb X 8.34)
-------
10
TABLE VII-12
Continued
P9 2 of 2
PRIMARY TREATMENT EFFLUENT*
PLANT B7
Phenol
kg/Kkg
0.225
0.197
Mean 0.212
mg/1
3.8
16
4.1
TOTAL
kg/Kkg
387
370
379
CHLORIDE
mg/1
6,580
8,240
7,360
NH3
kg/Kkg
78
70
74
mg/1
1,320
1,560
1,440
TOTAL
kg/Kkg
50.8
34.5
42.7
PHOSPHORUS
mg/1
862
769
830
*Monthly NPDES mean values. Ratios calculated from monthly average production supplied by the
plant during period of primary treatment.
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Ib X 8.34)
-------
and ammonia nitrogen for the two month period. This primary
settling removes 70 to 87 percent of the suspended solids.
The plant provides incineration of particularly strong waste
streams. It also employs special pump seals.
Table VIl-13 presents the average final effluent for four
plants which produce organo-phosphorus pesticides. The
reduction of COD at Plant B2, which produces only parathion,
is approximately 96 percent. BODr not monitored in the raw
waste, has an average effluent concentration of 9.5 mg/1.
Plant M2, which produces primarily organo-phosphorus but
also organo-nitrogen compounds, has demonstrated removals of
approximately 87.5 percent BOD and 65.4 percent COD. The
larger pollutant ratio for BOD for Plant M8 (12.0 kg/kkg) as
compared to Plant B2 (0.474 kg/kkg) is due to the larger
flow ratio and larger ratio of intermediate to final product
at Plant M8.
Both Plants B2 and M8r as previously noted, operate aeration
basins at high levels of mixed liquor suspended solids.
Consequently, effluent suspended solids concentrations are
higher than might be expected. Removal rates for suspended
solids for Plants B2 and M8 are approximately 74.8 percent
and 50.3 percent, respectively. Plant M2, which is
primarily an organophosphorus pesticide producer, has a
holding pond effluent suspended solids concentration of 12
mg/1, equivalent to 0.32 kg/kkg.
The amount of nutrients in the final effluent varies
considerably, due to process differences between products.
Plant B2, which produces parathion, reduces TKN from 2.74 to
0.45 mg/1, or approximately 78 percent. Plant M8, which
produces predominantly organo-phosphorus pesticides, reduces
NH3-N by approximately 45 percent to 408 mg/1. Plant M9,
which produces diazinon and organo-nitrogen pesticides,
reduces TKN approximately 42 percent to 314 mq/1, and
reduces NH3-N to 116 mg/1. The only plant monitoring
phosphorus in the effluent (Plant B2) averaged 35.1 mg/1.
This amounted to an 80 percent reduction.
Plant B2 monitors one pesticide, parathion, and reports
average removals of 99.7 percent or greater. Plant M9
reduces diazinon more than 99.9 percent to 0.0018 mg/1.
Plant M8 averages 4.46 mg/1 total pesticide in its effluent.
Only one plant (M9) reported cyanide data. The
concentration averaged 0.562 mg/1, or 0.043 kg/kkg.
Daily values of treated effluent at Plant B-2 are indicated
for COD and parathion in Table VII-9. The ratios of daily
maximum to 30-day average are 1.907 for COD and 6.192 for
180
-------
TABLE VI1-13
TREATMENT EFFLUENT SUMMARY
ORGANO-PHOSPHORUS PESTICIDE PLANTS
SUBCATEGORY B
Flow (L/Kkg)
(gal/1000 Ib)
BOD (kg/Kkg)
(mg/1)
COD (kg/Kkg)
(mg/1)
SS (kg/Kkg)
(mg/D
TP (kg/Kkg)
(mg/1)
TKN (kg/Kkg)
(mg/1)
N-NH3 (kg/Kkg)
(mg/1)
Phenol (kg/Kkg)
(mg/1)
Cyanide (kg/Kkg)
(mg/D
Pesticide (kg/Kkg)
(mg/1)
PLANT
B2
50,000
6,000
0.474
9.5
6.64
133
2.35
36
2.31
35.1
0.03
0.45
--
0.00034
0.005
__
0.00070
0.014
PLANT
M2
33,340
3,997
1.77
67
9.99
377
0.32
12
--
--
--
--
--
N.D.
N.D.
PLANT
M8
109,000
13,000
12.0
110
137
1,260
8.77
80.9
--
--
44.3
408
0.194
1.79
--
0.484
4.46
PLANT
M9
75,700
9,080
4.43
58.5
--
5.46
72.1
--
23.8
314
8.81
116
__
0.043
0.562
0.00014
0.0018
Note: Mean concentration are calculated by the equation: mg/1 = kg/Kkg
divided by (MGD/1000 Lb X 8.34).
181
-------
parathion. Ratios of daily maximum to 30-day average for
Plant M8 are as follows:
COD = 2.110
BOD = 2.149
Total Pesticides = 1.535
SS = 2.912
NH3 = 1.392
Phenol = 2.871
Treatment Technology Specific to Subcategory C
Plant C1 reports that it has not found a practical way to
treat Atrazine filtrate. Waste acid is pumped directly to a
pH adjustment facility where it is treated in two stages
with lime. The lime treatment also provides
chloroalkylation with the resulting removal of HCN and
derivatives.
A 7.2 million gallon holding/settling pond receives the
Atrazine waste along with other wastewaters. Solids, mainly
calcium carbonate, are periodically removed for thickening
and burial in an industrial landfill. The pond effluent is
further neutralized before discharge.
Plant C2 converted from direct discharge to deep well
injection in 1975.
Plant C3, which manufactures various other chemicals besides
organo-nitrogens, produces a waste stream of which only a
small portion is from pesticide manufacture. After highly
concentrated wastes have been segregated and contract
hauled, the remaining wastewater is treated by equalization,
extended aeration, lime neutralization, and chlorination.
Plant C4 provides carbon adsorption, neutralization, and
biological treatment of organo-nitrogen wastes; however, the
biological system also receives wastewaters from other
chemical processing. Acid is recovered and incinerated.
The carbon columns attain an average COD reduction of 83.U
percent removal and have an effluent BOD concentration of
less than 100 mg/1. Table VII-14 itemizes the average
effluent achievable.
The system is reported to have numerous operational problems
such as degassing and corrosion. Pesticides remaining after
carbon treatment are discharged to the biological treatment
system.
182
-------
Plant C5 discharges all process wastewaters into an
evaporation pond.
Plant C6 manufactures several other chemicals in addition to
an organo-nitrogen compound. All the process wastes are
combined and subjected to oil skimming and a series of
settling ponds prior to discharge.
Plant C7 discharges combined process wastewater, cooling
water, and sanitary sewage to a municipal treatment system
after neutralization and chlorination using sodium
hypochlorite bleach.
Plant C8 has previously discharged all process wastewater to
a municipal sewer. Based on treatability studies the plant
has started construction of an activated sludge system, with
the predicted effluent characteristics indicated in Table
VII-14. The low concentrations reported are a function of
the high flow ratio which, due to sampling location,
includes uncontaminated cooling water.
Plant C9 provides chemical treatment, filtration, and
adsorption of all process wastewater before discharge.
Plant CIO provides one day detention before discharge to
POTW.
Plant Cll discharges combined cooling, sanitary, and a small
amount of process wastes to a municipal sewer.
Approximately 600 gal of process wastewater is discharged
per week after pH adjustment using caustic soda.
Plant C12 contains all operations within a concreted area
which is completely surrounded by a grated collection
channel. The channel receives all rainfall from the
operations area, all wash downs, and all spillages, and
directs them to the treatment plant.
Of the plants discussed above and shown in Table VII-14,
Plant C8 and M9 are the most applicable to the development
of effluent guidelines as they both employ, or intend to
employ, biological treatment. Approximate removal rates for
the two plants are as follows:
BOD COD Pesticide
Plant C8 94.4% 86.4% 68.5%
Plant M9 93.5%
183
-------
TABLE VII-14
TREATED EFFLUENT SUMMARY
ORGANO-NITROGEN PESTICIDE PLANTS
SUBCATEGORY C
PARAMETER
Flow (L/Kkg)
(Gal/1000 Ib)
BOD (kg/Kkg)
(mg/1)
COD (kg/Kkg)
(mg/1)
TOC (kg/Kkg)
(mg/1)
TSS (kg/Kkg)
(mg/1)
TKN (kg/Kkg)
(mg/1)
NH3-N (kg/Kkg)
(mg/1)
TP (kg/Kkg)
(mg/1 )
Cyanide (kg/Kkg)
(mg/1)
Total Pesticide
(kg/Kkg)
(mg/1)
PLANT
C4
1,790
214
0.17
88
2.4
1,280
1.2
642
--
150
0.14
76
--
—
Negligible
0.0002
PLANT PLANT
C8 M3
172,000
20,600
2.69
12.2 37.5
11.7
53 87.5
250
2.99
13.5 2.5
—
5.17
23.4
0.418
1.9
__
0.976
4.4
PLANT PLANT
M7 M9
75,700
9,080
4.43
58.5
__
__
5.46
72.1
23.8
314
8.81
116
— — — —
0.043
0.562
0.269
.1.0 3.55
Note: Mean concentrations are calculated by the equation: mgl = kg/Kkg
divided by (MGD/1000 Lb X 8.34).
184
-------
Good correlations exist between effluent ratios at Plants C8
and M9 for BOD, TSSr and NH3-N.
Data from Plant C4 documents the applicability of activated
carbon by indicating low levels of pesticides in the
effluent, as well as good reduction of organics.
Treatment Technology Specific to Subcategory D
Plant D5 recycles all process water to the process.
Condenser cooling water and storm water are discharged to a
series of four evaporation ponds. The plant reports
sampling revealed approximately 1 mg/1 arsenic in the ponds.
Plant D6 also recycles all process wastewater resulting from
the manufacture of arsenate herbicides. Only non-contact
cooling water and contaminated storm runoff are discharged.
Acid waters are truck hauled to recovery, and some solids
are truck hauled to a landfill.
Plant D8, which produces halogenated organics, organo-
nitrogen, and metallo-organic pesticides, recycles mercury
wastes into the process.
Plant D9 practices complete reuse of all process wastewater.
The process actually has a negative water balance in that
all process and even storm water can be reused.
Also see above discussion for Plants M2, M6, M7, and M8.
Treatment Technology Specific to Subcategory E
Formulation and blending operations are generally conducted
on a batch basis and eguipment is multi-product in nature.
Vessels are cleaned between batches to avoid cross-
contamination. Many plants employ storage tanks to hold
wash liquids in order that they can be used for makeup
purposes at the next formulation of the same product. This
procedure reduces the total quantity of washwater discharged
and minimizes product losses. It can be applied in plants
where both water and solvent-based products are
manufactured. For example. Plant E50 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 wastewater generated is from equipment and
floor cleanup. Nearly all formulators use dry floor and
spill cleanup techniques and solvent recovery (for example,
Plants El - E38, and E50).
185
-------
Evaporation is the predominant disposal technique employed
by formulators. This method can be identified for Plant El
through E38 throughout 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 wastewater to landfill or by contract operators
is also employed by formulators, as exemplified by Plants
E39 through E42.
Spray irrigation following treatment is practiced by Plant
E50. The treatment includes oil skimming, chemical
coagulation, vacuum filtration, and aeration. During three
to four months of each 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 judged (and has been confirmed by
plant personnel) that with additional effort all wastewater
could be excluded from the municipal sewer.
Of the more than seventy-five plants contacted whosp
operations are devoted exclusively to formulation and
packaging, none were found who discharge wastewater to
navigable waters. In addition, 23 combined
manufacturing/formulation facilities who do discharge to
navigable waters report no significant wastewater generation
from formulation or packaging activities (see above
discussion of Plants Ml, M7 and M9). it is judged that a
facility generating wastewater from a formulation or
packaging operation could eliminate the wastewater by in-
plant controls, such as re-use or recycle, and/or
containment for evaporation, resulting in no discharge as
commonly achieved by many in this industry.
TREATMENT MODELS
In order to allow an assessment of the economic impact of
the proposed guidelines, model treatment systems have been
proposed. As previously emphasized, the particular systems
chosen are not the only systems capable of attaining the
specified pollutant reductions.
Since the purpose of this document is to develop effluent
limitations and guidelines for point source discharges into
navigable waters, municipal treatment is not directly
considered as a treatment alternative.
186
-------
Treatment systems considered herein are for subcategories
consisting of numerous plants located throughout the United
States, and therefore the systems are by necessity
generalized. The performances of the model treatment
systems discussed herein are based on the demonstrated
performances of existing facilities or a combination of
units operating at different facilities. The operating data
is buttressed by a considerable amount of laboratory data,
pilot plant operations, and treatability studies within the
industry. Nevertheless, the systems should not be blindly
implemented. Whenever a treatment plant is to be designed
for a particular industrial operation, the design should be
preceded by a characterization of the process wastewater of
the specific plant and by pilot plant studies in order to
provide an optimum treatment system for the given process.
The BPT model treatment systems developed for each
subcategory are illustrated in Figures VII-U through VII-6.
Design assumptions for each unit process are presented
below. In general, individual units within each plant have
been sized and arranged so that they may be taken out of
operation for maintenance without seriously disrupting the
operation of the plant.
The type and arrangement of in-process control required
varies from subcategory to subcategory and even from plant
to plant. In general, however, in-process control consists
of such facilities as neutralization, hydrolysis,
clarification, carbon adsorption, and resource recovery.
Since Subcategory A, B, and C wastewaters can contain
separable organics which would interfere with downstream
treatment processes, oil removal in an API type separator is
needed. The separator can be rectangular or circular
depending on land availability, flow, and other design
considerations. The skimmed organics cannot be reclaimed in
most cases and should be incinerated or containerized for
approved disposal. Subcategory C wastes contain high
suspended solids loadings in addition to oil and grease.
Removal of both pollutants can be accomplished in a
combination oil and solids separation. Skimmed oils or
organics should be incinerated or containerized for
disposal. Settled solids are held in a holding tank prior
to dewatering in combination with biological solids from the
treatment plant.
Waste streams which are not compatible with biological
treatment, such as distillation tower bottoms or tars, will
be generated by Subcategories A, B, and C. The most
applicable treatment for such wastes is incineration. The
187
-------
FIGURE VII-4
BPT COST MODEL
SUBCATEGORY A
00
CO
GENERAL
PROCESS -
WASTEWATER
STRONG
ORGANIC-
WASTES
EQUAL-
IZATION
BASIN.
WATER'
INCINERATOR
-VENT
SCRUBBER
-CAUSTIC
-ACID
NEUTRAL-
IZATION
TANK
API TYPE
SEPARATOR
OIL SKIMMINGS
FILTRATION
CARBON
ADSORPTION
RETURN SLUDGE
AERATION
BASIN
OVERFLOW
SLUDGE
THICKENER
AEROBIC
DIGESTOR
FINAL
CLARIFIER
FILTRATE
VACUUM
FILTER
SOLIDS TO
DISPOSAL
SLUDGE
MONITORING
STATION
T
FINAL
DISCHARGE
-------
FIGURE VII-5
BPT COST MODEL
SUBCATEGORY B
CO
HII
AMMI
WAST
STRONG T
nRRANir L
3H
">MT /\
EWATER
AMMONIA
STRIPPING
COLUMN BOTTOMS
BY-PRODUCT-*— 1
WATER 1 r-
T 1
INCINERATOF
WASTEWATER
OIL SKIMMINGS
GENERAL
PROCESS *• SEPA
1 1 ft OTPHA Trr> *>L.rr\
EQUAL I/A 1 ION *
(
,
M
SCRUBBER
— *-VENT
~| EFFLl
J
LIME
$ SLURRY
ftPI . LIME
RATOR SETTLING
SLUDGE RET
t
AERATION
HYDROLYSIS
t
I
MCIITDAI
JENT
IZATIO
FILTRATE
OVERFLOW
SOLIDS UNDERFLOW
"URN
FINAL
BASINS CLARIFIERS
>
IH
ICKENER
VACl
FIL1
N 1
1
JUM > TO
[ER DISPOSAL
t
FINAL
EFFLUENT
-------
FIGURE VI1-6
BPT COST MODEL
SUBCATEGORY C
10
o
HIGH
AMMONIA -
WASTEWATER
AMMONIA
STRIPPING
STRONG
ORGANIC—
WASTEWATER
GENERAL
PROCESS —
WASTEWATER
BY-PRODUCT-J
WATER—
COLUMN BOTTOMS
-VENT
INCINERATOR
SCRUBBER EFFLUENT-
SKIMMINGS
API
SEPARATOR
HYDROLYSIS
t
H
NEUTRALIZATION
FILTRATE
I OVERFLOW
SOLIDS UNDERFLOW
SLUDGE RETURN
AERATION
BASINS
FINAL
CLARIFIERS
THICKENER
AEROBIC
DIGESTOR
FINAL
EFFLUENT
EQUALIZATION
VACUUM
FILTER
SOLIDS
*- TO
DISPOSAL
-------
incinerator will burn principally liquid wastes, but it is
possible that provisions will be necessary to incinerate
toxic or polluting components from off-gases and vessel
vents. The incinerator should be equipped with air
pollution control devices, and the wastewater effluent from
these units should be discharged to the wastewater treatment
plant, specifically to the pH adjustment stage.
The pH of raw process wastewater flowing into the model
treatment system will probably deviate from neutral
conditions. In order to make the wastewater more amenable
to treatment, neutralization facilities are provided for all
subcategories.
Detoxification of wastewaters generated by the halogenated
organic model plant is accomplished by carbon adsorption,
while hydrolysis is employed for Subcategories B and C.
After in-process control the plant wastewaters require flow
equalization. Equalization is best carried out in a
concrete or concrete-lined basin. The size of the basin is
dependent on the flow and contaminant loading patterns
which, of course, are closely related to the production
processes with particular consideration given to the batch-
type operation.
Biological treatment consists of an activated sludge system.
The overall activated sludge process includes aeration
basins, final flocculator-clarifiers, and sludge handling
facilities.
Sludge handling facilities for Subcategory A and C plants
consists of sludge thickening, aerobic digestion, and vacuum
filtration. For Subcategory B, aerobic digestion will not
be required as the sludge produced will contain a large
amount of lime as a result of phosphate precipitation and
will be relatively stable without digestion.
No model waste treatment facility is provided for
Subcategory D wastewaters since no discharge of process
wastewater pollutants is recommended.
The model treatment system provided for the Subcategory E
model plant is total evaporation for the small volume of
wastewater expected following implementation of a suitable
process control system.
191
-------
Treatment System Design Basis
In addition to the wastewater loadings listed in Table VII-
15 the design configurations of the wastewater treatment
plant models are based on the criteria listed below.
API Separator
The API type operators are sized based on the following:
Temperature = UO°F
Rise rate of oil globules = 0.16 ft/min
Maximum allowable mean horizontal velocity = 2.U ft/min
Hydrolysis
Hydrolysis units for the purpose of detoxifying pesticide
wastes are designed for a detention time of 12 hours and a
length to width ratio of 5 to 1.
Carbon Adsorption
The carbon adsorption system for Subcategory A is a down-
flow, fixed bed type with a carbon contact time of 30 to UO
minutes depending on the characertistics of the influent.
The hydraulic loading on the system is assumed to be 160
1/min/sq m (4 gpm/sq ft) . For smaller plants the system is
assumed to be leased with carbon regeneration being provided
by the leaser. For larger plants, it is assumed that carbon
regeneration is accomplished on-site.
Incinerators
The design of the incinerator is based strictly on flow as
the heat release values of the waste are negliaible. Fuel
requirements are based on a heat requirement of 0.5 million
cal-gm/kg (1,000 BTU/lb) of waste.
Equalization Basin
Equalization basins are generally sized for a holding time
of 36 hours. The basin is equipped with a floating aerator
with the following energy requirements:
-------
TABLE VII-15
BPT TREATMENT SYSTEM DESIGN SUMMARY
Treatment System Hydraulic Loading
(Design Capacities)
Subcategory
A Small Plant
A Large Plant
B Small Plant
B Large Plant
C Small Plant
C Large Plant
E Small Plant
E Medium Plant
E Large Plant
Hydraulic Loading
(gpd)
151,000
798,000
76,100
835,000
88,000
1,080,000
10
500
5,000
(L/day)
572,000
3,020,000
288,000
3,160,000
333,000
4,100,000
37.5
1,890
18,900
193
-------
Influent Kilowatts Required
Suspended Solids Per Million Liters
Less than 500 mg/1 7.9
500 - 1000 mg/1 H.8
1000 - 2000 mg/1 15.8
More than 2000 mg/1 19.7
For flows less than 94,600 I/day the basin is constructed of
steel. For greater flows it is of reinforced concrete or a
lined earthen basin, whichever is more cost effective.
Neutralization
The two-stage neutralization basin is sized on the basis of
an average detention time of 10 minutes. The size of lime
and acid handling facilities is determined according to
acidity/alkalinity data collected during the survey. Bulk
lime-storage facilities (18 kkg) or bag storage is
provided, depending on plant size. Sulfuric acid storage is
either by 208 1 (55-gallon) drums or in carbon-steel tanks.
Line or acid addition is controlled by two pH probes, one in
each basin. The lime slurry is added to the neutralization
basin from a volumetric feeder. Acid is supplied by
positive displacement metering pumps. One kilowatt of
mixing is provided per 3,000 liters of capacity.
Ammonia Removal
Facilities are provided for steam stripping of ammonia from
selected waste streams for Subcategories B and C. While
this technology is not currently practiced in the pesticide
chemicals industry, one plant has plans to have such a
system on line by July 1977. Also, there are six ammonia
steam stripping units in operation in nitrogen fertilizer
plants and the operation is routinely performed in the
refining and organic chemicals industries. Concentrations
of ammonia in the condensate feed to these strippers varies
from 100 to 1300 mg/1 with the stripped effluent ranging
from 5 to 100 mg/1, thus providing reductions in some cases
of more than 95 percent. These systems, which are described
in the Development Document for Basic Fertilizer chemicals
(EPA 440/1-73/011), are considered to be applicable to the
pesticide chemicals industry and have been accepted by the
industry.
The model system included herein for cost purposes consists
of an equalization tank designed for 24-hour storage, a
pressure filter, a heat exchanger, steam stripping columns,
and ammonia storage facilities. All equipment is
194
-------
constructed of stainless steel or other corrosion resistant
material.
The wastewater feed is assumed to contain 3 percent ammonia
and the recovered ammonia solution to contain 22 percent
based on 95 percent ammonia removal.
The design assumptions were based in part on Guthrie (1969)
and the plans of the pesticide plant mentioned above.
Evaporation
The model treatment for Subcategory F consists of total
evaporation. The system consists of a concrete pit covered
with a transparent roof to prevent entrance of rainfall.
Evaporation is enhanced by a spray-recirculation systems.
As discussed earlier in this section, evaporation systems
are widely used by formulators at the present time.
Primary Flocculation Clarifiers
Primary flocculator clarifiers with surface areas less than
93 square meters (1,000 square feet) are rectangular units
with a length to width ratio of 1 to 4. The side water
depth varies from 1.8 to 2.4 meters (6 to 8 feet), dependina
on plant size, and the design overflow rate is 5 cu m/day/sq
m (400 gpd/sq. ft.) .
Clarifiers with surface areas greater than 93 square meters
(1,000 square feet) are circular units. The side water
depth varies from 2 to 4 meters (7 to 13 feet), depending on
plant size, and the design overflow rate is 5 cu m/day/sq m
(400 gpd/sq ft). Flocculent addition facilities are
provided.
Duplicate sludge pumps are provided to withdraw sludge at an
assumed 1.5 percent solids. A minimum freeboard of 0.46
meters (1.5 feet) is allowed. The rectangular units and the
circular ones of less than 150 meters (500 feet) diameter
are to be constructed of steel; the units with greater
diameters are to be of reinforced concrete.
Nutrient Addition
Facilities are provided for the addition of phosphoric acid
and anhydrous ammonia to the biological system in order to
maintain the ratio of BOD:N:P at 100:5:1.
Aeration Basin
195
-------
The size of aeration basins is based on detention times and
food to microorganism ratios commonly used within the
industry. Mechanical surface aerators are provided in the
aeration basin.
Aerators were selected on-the basis of the following:
Oxygen Utilization: Energy 0.8 kg/kg BOD removed
Endogenous 6 kg hr/1,000 kg MLVSS
Oxygen Utilization:
Oxygen Transfer
Motor Efficiency
Minimum Basin DO
Minimum Number of Aerators
3.5 Ib hr/shaft hp at
20°C in tap water
85 percent
2 mg/1
2
Oxygen is monitored in the basins using DO probes.
Sludge Thickener
The sludge thickener is designed on the basis of a solids
loading of 6 Ib/sq ft/day.
Aerobic Digestor
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 an oxygen requirement of 1.6 kg/kg VSS destroyed
and a mixing requirement of 120 hp per million gallons of
digester volume. A solids production of 0.6 kg VSS/kg BOD
removed and a VSS reduction of 50 percent were assumed.
Vacuum Filtration
The size of the vacuum filters is based on a cake yield of
10 kg/ sq m/hr for biological sludge, and 20 kg/sq m/hr for
combined primary and biological sludge. Maximum running
times of 16 hours for large plants and 8 hours for small
plants are used. The polymer system is sized to deliver 18
kg of polymer per ton of dry solids.
Final Sludge Disposal
For all plants, sludge is assumed to be disposed of at a
specially designated landfill.
196
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SUMMARY OF MODEL TREATMENT SYSTEMS
Table VII-16 lists the effluent flow and pollutant
concentrations expected to be achieved by each of the model
treatment systems discussed above. The process by which
these were derived is presented in Section IX, Summary of
Guidelines Development.
197
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00
TABLE VII-16
SUMMARY OF BPT
MODEL TREATMENT SYSTEM EFFLUENTS
SUBCATE60RY
A
B
C
E
MODEL PLANT
PRODUCTION FLOW
Kkg/day L/day
16.2 572,000
85.7 3,020,000
6.56 288,000
72.0 3,160,000
9.43 333,000
116 4,100,000
83
4,170
41,700
30-DAY MAXIMUM
EFFLUENT CONCENTRATIONS, mq/1
BOD COD NH3-N
246 601 NR
246 601 NR
34.6 271 101
34.6 271 101
244 597 138
244 597 138
__
__
--
TSS PHENOL
179 0.0482
179 0.0482
161 NR
161 NR
269 NR
269 NR
—
__
—
PESTICIDES
0.0866
0.0866
0.0397
0.0397
0.199
0.199
--
--
—
NR = Not Regulated
Note: Mean concentrations are calculated by the equation: mg/1 = kg/Kkg divided by (MGD/1000 Lb X 8.34).
-------
SECTION VIII
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
General
Cost information for the suggested end-of-pipe treatment
models is presented in the following discussion for the
purpose of assessing the economic impact of the proposed
effluent limitations and 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.
In order to evaluate the economic impact of treatment on a
uniform basis, treatment models which will provide the
desired level of treatment were proposed in Section VII for
each industrial subcategory. In-plant control measures,
other than incineration and pesticide detoxification, have
not been evaluated because the cost, energy, and non-water
quality aspects of in-plant controls are intimately related
to the specific processes for which they are developed.
Although there are general cost and energy requirements for
equipment items, these correlations are usually expressed in
terms of specific design parameters. Such parameters are
related to the production rate and other specific considera-
tions at a particular production site.
In the manufacture of a single product there is a wide
variety of process plant sizes and unit operations. Many
detailed designs might be required to develop a meaningful
understanding of the economic impact of process
modifications. The series of designs for end-of-pipe
treatment models can be related directly to the range of
influent hydraulic and organic loadings within each industry
and subcategory, and the costs associated with these systems
can be divided by the production rate for any given
subcategory to show the economic impact of the system in
terms of dollars per pound of product.
The major non-water quality consideration associated with
in-process control measures is the means of ultimate
disposal of wastes. As the volume of the process RWL is
reduced, alternative disposal techniques such as in-
cineration, pyrolysis, and evaporation become more feasible.
Recent regulations tend to limit the use of ocean discharge
and deep-well injection because of the potential long-term
detrimental effects associated with these disposal
procedures. Incineration and evaporation are viable
199
-------
alternatives for concentrated waste streams. Considerations
involving air pollution and auxiliary fuel requirements,
depending on the heating value of the waste, must be
evaluated individually for each situation.
Other non-water quality aspects such as noise levels will
not be perceptibly affected by the proposed wastewater
treatment systems. Most pesticide plants generate fairly
high noise levels because of equipment such as pumps,
compressors, steam jets, flare stacks, etc. Equipment
associated with in-process and end-of-pipe control systems
will not add significantly to these noise levels.
Annual and capital cost estimates have been prepared for
end-of-pipe treatment models for each subcategory to help
evaluate the economic impact of the proposed effluent
limitations guidelines. The capital costs were generated on
a unit process basis (e.g., equalization, neutralization,
etc.). The following percentage figures were added to the
total unit process costs:
Percent of Unit Process
Item Capital Cost
Electrical 14
Piping 20
Instrumentation 8
Site work 6
To this subtotal was added 15 percent for engineering design
and construction surveillance fees, and 15 percent for
contingencies.
Land costs were computed independently and added directly to
the total capital costs.
The basis for the computation of annual costs is presented
in Table VIIT-1.
The following is a discussion of the possible effects that
variations in treatment technology or design criteria could
have on the total capital costs and annual costs.
Capital
Technology or Design Criteria Cost Differential
1. Use aerated lagoons and 1. The cost reduction
sludge de-watering lagoons could be 20 to 40 per-
in place of the proposed cent of the proposed
treatment system. figures.
200
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TABLE VIII-1
BASIS FOR COMPUTATION OF ANNUAL COSTS
(AUGUST 1972 DOLLARS)
ANNUAL COST ITEM
Capital Recovery Plus Return
Operational Labor
Operational Supervision
Insurance and Taxes
Electrical Power
Furnace Oil (Grade 11)
Maintenance
Sludge Hauling and Disposal
Amhydrous Ammonia
Chlorine
Diammonium Phosphate
(18% N, 46% P)
Ferric Chloride
Ferric Sulfate
Hydrochloric Acid 18%
Phosphoric Acid, 75%
Soda Ash, 58%
Caustic Soda, 50%
Sulfuric Acid
Activated Carbon, Granular
BASIS OF COMPUTATION
Based on 10 years at 10
percent
$15,000 per man per year
including fringe benefits
$20,000 per man per year
including fringe benefits
Two percent of capital cost
$0.02 per Kw Hr.
$0.17 per gallon
Four percent of capital cost
$5.00/Cu.Yd.
$75/Ton
$0.11/Lb
$76/Ton
$0.05/Lb
$52/Ton
$43/Ton
$0.09/Lb
$0.03/Lb
$0.07/Gallon
$36/Ton
$0.04/Lb
201
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TABLE VIII-1
BASIS FOR COMPUTATION OF ANNUAL COSTS
(Continued)
ANNUAL COST ITEM
Calcium Hydroxide
Sodium Bisulfate
Sulfur Dioxide
Anionic Polymer
Cationic Polymer
Steam
Cooling Water
Ammonium Water, 29%
BASIS OF COMPUTATION
$25/Ton
$0.08/Lb
$0.17/Lb
$0.20/Lb
$0.125/Lb
$0.75/1000 Lb
$0.042/1000 Lb
$0.OS/Gallon
202
-------
2. Use earthen basins with 2. Cost reduction could
a plastic liner in place be 20 to 30 percent
of reinforced concrete con- of the total cost.
struction, and floating
aerators with permanent-
access walkways.
3. Place all treatment tankage 3. Cost savings would
above grade to minimize depend on the in-
excavation, especially if dividual situation.
a pumping station is re-
quired in any case. Use
all-steel tankage to
minimize capital cost.
4. Minimize flows and maximize 4. Cost differential would
concentrations through ex- depend on a number of
tensive in-plant recovery and items, e.g., age of
water conservation, so that plant, accessibility
other treatment technologies, to process piping,
e.g., incineration, may be local air pollution
economically competitive. standards, etc.
All cost data were computed in terms of August 1972 dollars,
which corresponds to an Fngineering News Records index (ENR)
value of 1980.
BPT COST MODELS
Based on the model treatment systems presented in Section
VII, capital and annual costs were developed for the purpose
of economic analysis. Itemizations of the capital costs for
the treatment models are listed in Tables VIIT-2 throuah
VIII-5 and summaries of the capital and annual costs are
presented in Tables VIII-6 through VIII-9.
NON-WATER QUALITY ASPECTS
The primary non-water quality aspects of the proposed
treatment systems involve the various alternatives to
treating and disposing of pesticide wastewaters into surface
waters.
Incineration is widely used 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 wastewater treatment
facility, air quality impact need not be significant.
203
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TABLE VIII-2
BPT CAPITAL COST ITEMIZATION
SUBCATE60RY A
ESTIMATED CAPITAL COST
TREATMENT UNIT
Influent pump station
Neutralization tank and mixer
API separator
Equalization basins (2)
Mixers
Pumps
Aeration basins
Aerators
Final Clarifiers (2)
Pumps
Thickeners
Overflow pumps
Digester
Aerator
Pumps
Vacuum filter and pumps
Acid Feed System
Caustic Feed System
Incinerator
Dual media filter
Backwash pumps
Decant basin
Pumps
Control building
Monitoring station
Carbon system
Carbon regeneration
Site work, electrical,
and instrumentation
SUBTOTAL
piping
SUBTOTAL
Engineering fees and contingency
TOTAL CAPITAL COST
SMALL PLANT
$ 45,000
9,000
40,000
60,000
30,000
11,000
160,000
60,000
80,000
11,000
24,000
7,000
60,000
20,000
7,000
54,000
20,000
42 ,000
50,000
77,000
13,000
45,000
7,000
60,000
15,000
*
*
1,007,000
483,000
$1,490,000
447,000
$1,937,000
LARGE PLANT
$ 70,000
23,000
86,000
85,000
40,000
13,000
245,000
144,000
350,000
13,000
47,000
7,000
90,000
20,000
7,000
72,000
75,000
137,000
130,000
190,000
30,000
80,000
11,000
70,000
15,000
300,000
350,000
2,700,000
1,296,000
$3,996,000
1,199,000
$5,195,000
* For the small plant, a leased carbon system is considered to be more
cost effective.
204
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TABLE VIII-3
BPT CAPITAL COST ITEMIZATION
SUBCATEGORY B
ESTIMATED CAPITAL COST
TREATMENT UNIT
Influent pump station
API separator
Lime mix tank and mixer
Lime feed system
Settling tank
Sludge pumps
Detoxifier
Pumps
Neutralization, tank and mixer
Acid feed system
Equalization basin
Mixer
Pumps
Aeration basins (2 with concrete liner)
Aerators
Thickener
Pumps
Vacuum filter
Clarifiers (2)
Pumps
Monitoring station
Control building
Incinerator
Ammonia steam stripping columns (2)
Equalization tank
Pressure filter
Heat exchangers (2)
Pumps
Ammonia absorber
Ammonia storage tank
Caustic storage tank
pH controller
Additional cost for corrosion resistant piping
SUBTOTAL $1,234,600
SMALL PLANT
$ 44,000
22,000
1,100
88,000
33,000
9,000
50,000
7,000
5,500
12,000
60,000
22,000
7,000
130,000
58,000
46,000
7,000
80,000
70,000
12,000
15,000
62,000
50,000
30,000
31,000
113,000
25,000
57,000
9,000
19,000
27,000
2,000
] 31,000
LARGE PLANT
$ 96,000
86,000
4,000
230,000
200,000
9,000
160,000
14,000
25,000
58,000
70,000
60,000
25,000
350,000
184,000
150,000
13,000
360,000
320,000
25,000
23,000
70,000
130,000
74,000
101 ,000
180,000
153,000
60,000
27,000
40,000
93,000
2,000
73,000
$3,465,000
205
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TABLE VIII-3
BPT CAPITAL COST ITEMIZATION
(Continued)
ESTIMATED CAPITAL COST
TREATMENT UNIT
Site work, electrical, piping, and
instrumentation
SUBTOTAL
Engineering and contingency
TOTAL
SMALL PLANT
$ 592,600
$1,827,200
548.200
$2,375,400
LARGE PLANT
$1,663,200
$5,128,200
1.538.500
$6,666,700
206
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TABLE VI11-4
BPT CAPITAL COST ITEMIZATION
SUBCATE60RY C
ESTIMATED CAPITAL COST
TREATMENT UNIT
Influent lift station
Detoxifier
Pumps
Neutralization tank and mixer
Solids and oil removal system
Equalization basin
Mixer
Aeration basins (2)
Aerators
Clarifiers (2)
Pumps
Thickener
Pumps
Digester
Aerators
Pumps
Primary solids thickener
Pumps
Vacuum filtration
Acid feed system
Caustic feed system
Monitoring station
Control building
Incinerator
Ammonia steam stripping columns (2)
Equalization tank
Pressure filter
Heat exchangers (2)
Pumps
Ammonia absorber
Ammonia storage tank
Caustic storage tank
pH controller
SMALL PLANT
$ 47,000
60,000
7,000
6,200
29,000
71,000
12,000
142,000
52,000
88,000
11,000
25,000
9,000
54,000
24,000
9,000
33,500
9,000
80,000
12,000
33,000
15,500
70,000
50,000
30,000
31,000
113,000
25,000
57,000
9,000
19,000
27,000
2,000
LARGE PLANT
$ 120,000
180,000
14,000
26,000
135,000
100,000
56,000
330,000
162,000
310,000
25,000
78,000
12,000
215,000
44,000
9,000
88,000
11,000
300,000
58,000
140,000
28,000
100,000
135,000
74,000
101,000
180,000
153,000
60,000
27,000
40,000
93,000
2,000
207
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TABLE VI11-4
CAPITAL COST ITEMIZATION
(Continued)
ESTIMATED CAPITAL COST
TREATMENT UNIT
Additional cost for corrosion resistant
piping
SUBTOTAL
Site work, electrical, piping, and
instrumentation
SUBTOTAL
Engineering and contingency
TOTAL
SMALL PLANT
$ 31,000
$1,293,200
$ 620,700
$1,913,900
$ 574,200
$2,488,100
LARGE PLANT
$ 73,000
$3,479,000
$1,669,900
$5,148,900
$1.544,700
$6,693,600
208
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TABLE VIII-5
BPT CAPITAL COST ITEMIZATION
SUBCATEGORY E
ESTIMATED CAPITAL COST
SMALL MEDIUM LARGE
TREATMENT UNIT PLANT PLANT PLANT
Evaporation Pond
Earth Work $ 50 $ 2,450 $ 24,500
Clearing and grubbing 20 1,010 10,150
Reinforced synthetic liner 180 8,820 88,500
Pumps 1,000 2,000 2,000
SUBTOTAL $1,250 $14,280 $125,150
Piping 250 2,860 25,030
Engineering fees and
contingency 188 2,140 18,800
TOTAL CAPITAL COST $1,688 $19,280 $168,980
209
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Equipment requirements for control of air pollutant
emissions vary for different applications, waste
characteristics, incinerator performance, and air pollutant
emission limitations. 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.
In all cases where incineration is used, provisions must be
made to ensure against entry of hazardous pollutants into
the atmosphere. Among other factors, 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.
The disposal of solid wastes generated by the proposed
treatment systems must be done with proper management. Lime
and biological sludges are generally compatible with
ultimate disposal in a specially designated landfill. The
following Table summarizes the sludge quantities generated
by the model plants:
PLANT SIZE DRY SOLIDS
SUBCATEGORY kl/day kkg/day
A 575 0.0866
3,030 0.456
B 288 1.10
3,156 7.55
C 333 0.328
4,090 4.02
If land disposal is to be used for materials considered to
be hazardous, the disposal sites must not allow movement of
pollutants to either grcund 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
210
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TABLE VIII-6
BPT COST SUMMARY
SUBCATEGORY A
SMALL PLANT
LARGE PLANT
Average Production KKG/Day
(Lb/Day)
Wastewater Flow Cu M/Day
(gpd)
TOTAL CAPITAL COST
Annual Cost:
Capital Recovery
Operating/Maintenance
Energy/Power
TOTAL ANNUAL COST
16.2
(35,900)
572
(151,000)
$1,937,000
316,000
405,550
30,450
$752,000
85.7
(189,000)
3,020
(798,000)
$5,195,000
847,000
561 ,600
128,000
$1,536,600
-------
TABLE VIII-7
BPT COST SUMMARY
SUBCATEGORY B
SMALL PLANT
LARGE PLANT
Average Production KKG/Day
(Lb/Day)
Wastewater Flow KL/Day
(gpd)
TOTAL CAPITAL COST
Annual Cost:
Capital Recovery
Operating/Maintenance*
Energy/Power
TOTAL ANNUAL COST
6.57
(11,900)
288
(76,100)
$2,375,400
$ 387,200
210,000
22,000
$ 619,200
72.0
(134,000)
3,160
(835,000)
$6,666,700
$1,086,700
850,000
180,000
$2,116,700
* The operating/maintenance cost gives credit for ammonia by-product recovery.
-------
TABLE VII1-8
BPT COST SUMMARY
SUBCATEGORY C
SMALL PLANT
LARGE PLANT
rv>
GO
Average Production KKG/Day
(Lb/Day)
Wastewater Flow KL/Day
(gpd)
TOTAL CAPITAL COST
Annual Cost:
Capital Recovery
Operating/Maintenance*
Energy/Power
TOTAL ANNUAL COST
9.43
(20,800)
333
(88,000)
$2,488,100
$ 405,600
215,000
21,000
$ 641,600
116
(256,000)
4,100
(1,080,000)
$6,693,600
$1,091,000
911,000
185,000
$2,187,000
* The operating/maintenance cost gives credit for ammonia by-product recovery.
-------
TABLE VIII-9
BPT COST SUMMARY
SUBCATEGORY E
Wastewater Flow Cu M/day
(gpd)
TOTAL CAPITAL COST
ANNUAL COST:
Capital Recovery
Operating/Maintenance
Energy/Power
TOTAL ANNUAL COST
SMALL
PLANT
0.038
(10)
MEDIUM
PLANT
1.90
(500)
LARGE
PLANT
18.9
(5000)
$1,688
$ 275
35
100
$ 410
$19,280
$ 3,140
390
200
$ 3,730
$168,980
$ 27,540
3,380
200
$ 31,120
214
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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 pretested 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 crganic 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. Monitorina
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).
Deep well injection has been considered economically
attractive by 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
215
-------
impermeable zones (aquicludes), and contain no natural
fractures or faults. The wastewater so disposed must he
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 samplina
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. Treatment
may be necessary to prevent odor development and air
pollution.
Off-site disposal is commonly practiced in the industry for
highly concentrated wastes. It is also common practice for
formulation plants with very low wastewater generation to
haul their wastewater 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 containerization.
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.
-------
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
The effluent limitations which must be achieved by July 1,
1977, are to specify the degree of effluent reduction
attainable through the application of the Best Practicable
Control Technology Currently Available (EPT). BPT ^is
generally based upon the average of best existina
performance by 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;
b. 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 wastewater
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 practice 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 use, there
must exist a high degree of confidence in the engineering
and economic practicability of the technology at the time of
construction or installation of the control facilities.
217
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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 reduction attainable through the application of
the best practicable control technology currently available
is as listed in Table IX-1.
It is further recommended that for all cases in which
discharge of wastewaters is allowed, the pH of the
wastewaters be in the range of 6.0 to 9.0; and that no
visible floating oil and grease be allowed.
DEVELOPMENT OF 30-DAY AND DAILY MAXIMUM VARIABILITY FACTORS
A 30-day maximum and a daily maximum factor were derived
which relate to the long term average for each plant. Tn
this manner the long term average effluents, as presented in
Section VII, can be combined and adjusted to yield 30-day
maximum and daily maximum limitations based on the
variability of discharges from plants within each
subcategory.
The variability factors were determined by statistical
analysis of the treated effluent data from each plant. Tn
this analysis, each plant's data were presumed to represent
a sample drawn from a three parameter log normal
distribution. The 30-day maximum factors were derived from
the observed monthly averages as follows:
Antilocr (X + 2.33Y1-T = 30-day maximum factor
z
Where: T = Constant term parameter added tc monthly
means.
X = Average of logarithms of T + monthly means.
Y = Standard deviation of logarithms of T +
monthly means.
1 = Long term average in pounds.
and, the initial data for calculations X, Y, and Z is
the daily effluent of each parameter in pounds.
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SUBCATEGORY
TABLE IX-1
BPT EFFLUENT LIMITATIONS GUIDELINES
EFFLUENT LIMITATIONS
EFFLUENT
CHARACTERISTICS
AVERAGE OF DAILY VALUES
FOR 30 CONSECUTIVE DAYS
DAILY
MAXIMUM
A
B
BOD
COD
TSS
Phenol
Total Pesticides
BOD
COD
TSS
NH3-N
Total Pesticides
BOD
COD
TSS
NH3-N
Total Pesticides
8.70
21.2
6.30
0.00170
0.00306
1.52
11.9
7.05
4.41
0.00175
8.64
21.1
9.51
4.88
0.00705
D
E
—NO DISCHARGE OF PROCESS WASTEWATER POLLUTANTS-
—NO DISCHARGE OF PROCESS WASTEWATER POLLUTANTS-
15.2
30.7
9.03
0.00480
0.00622
2.65
17.3
10.1
5.14
0.00392
15.1
30.4
13.6
5.69
0.0158
Note: All units are kg/Kkg
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The daily maximum factors were similarly developed as follows:
Antilog (X + 2.33YV-T = Daily maximum factor
Z
Where: T = Constant term parameter added to daily
values.
X = Average of logarithms of T + daily values.
Y = Standard deviation of logarithms of T +
daily values.
Z = Long term average in pounds.
and, the initial data for calculations X, Y, and z is
the daily effluent of each parameter in pounds.
In applying this factor a guideline based on plants with a
long term average of 2.0 kg/kkg BOD and a 30-day variability
of 2.0 would result in a 30-day maximum limitation of 4.0
kg/kkg. A plant averaging 2.0 kg/kkg would thus be
statistically projected to remain below 4.0 kg/kkg for 99
months out of 100 without any change or improvement to
current operating procedure.
It is expected, however, that good in-plant and waste
treatment management procedures combined with proper
equalization will preclude any excursions above the monthly
and daily maximum limitations. Effluent variability data
for each subcategory are outlined below.
Subcategory A--Halogenated Organics
Plant A6, which produces 2,UD and MCPA, employs activated
carbon and neutralization prior to discharge. Daily data
from July, 1975, through February, 1976, demonstrates that
the use of activated carbon has a considerable dampening
effect on BOD and COD in addition to removing phenols and
chlorinated hydrocarbons.
For purposes of variability analysis, only total pesticides
were considered. COD, BOD, and TSS variability are more a
function of biological treatment, which is a model
technology recommended after detoxification by activated
carbon. Long term averages and variability factors for
Plant A6 are as follows:
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30-Day Maximum* Daily Maximum*
Long Term Average* Variability Factor Variability Factor
Total
Pesticides: 0.017 kg/kkg 3.0 6.1
* Based on three of seven months data available due to
documented interference by non-pesticide products during
remainder of period.
Plant A3r which produces toxaphene, employs a physical-
chemical treatment system. Daily effluent data from May,
1974, through March, 1975, were analyzed for suspended
solids and toxaphene. Long term averages and variability
factors for Plant A3 are as follows:
30-Day Maximum Daily Maximum
Long Term Average Variability Factor Variability Factor
TSS: 0.512 kg/kkg 2.2 4.1
Toxaphene: .000927 kg/kkg 2.6 3.9
Plant M9, which produces chlorobenzilate in addition to
organo-phosphorus and organo-nitrogen pesticides, employs
biological treatment. The long term averages shown below
have been adjusted based on a final:technical product ratio
of 1.63:1. Daily clarifier overflow was analyzed for April,
1975, through March, 1976. Pertinent parameters for this
subcategory are BOD and suspended solids. Long term
averages and variability factors for Plant M9 are as
follows:
30-Day Maximum Daily Maximum
Long Term Average Variability Factor Variability Factor
BOD: 2.72 kg/kkg 4.3 6.3
TSS: 3.35 kg/kkg 3.6 4.9
Variability factors have been utilized to develop 30-day
maximum and daily maximum limitations. Variability factors
for total pesticides are 3.0 and 6.1, respectively, from
Plant A6. The factors for Phenol for Subcategory A have
been transferred from Plant M8, as described under
Subcategory B. 30-Day maximum and daily maximum for Phenol
are 1.7 and 4.8, respectively. Variability factors for BOD,
COD, and TSS are discussed under "Summary of Guidelines
Development."
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Subcategory B—Orqano-Phosphorus
Plant B2, which produces parathion, operates an activated
sludge treatment system. Daily effluent was analyzed for
January, June, and July, 1974. Monthly averages were
analyzed for a 15 month period. Based on these analyses,
long term averages and variability factors are as follows:
30-Day Maximum Daily Maximum
Long Term Average Variability Factor Variability Factor
COD: 6.64 kg/kkg 1.7 2.7
BOD 0.474 kg/kkg 2.4
Parathion: 0.0007 kg/kkg 2.3 5.6
Plant M8, which produces approximately 90 percent orqano-
phosphorus and 10 percent organo-nitrogen pesticides,
operates an activated sludge treatment system. The long
term averages shown below are adjusted based on a
final:technical product ratio of 2.61:1. Daily effluent was
analyzed for October 1975, through March, 1976. Long term
averages and variability factors are as follows:
30-Day Maximum Daily Maximum
Long Term Average Variability Factor Variability Factor
COD: 52.5 kg/kkg 2.0 2.6
BOD: 4.60 kg/kkg 3.0 4.9
TSS: 3.36 kg/kkg 2.4 3.8
NH3: 17.0 kg/kkg 1.6 2.0
Phenol: 0.0743 kg/kkg 1.7 U.8
Pesticides: 0.187 kg/kkg 1.4 2.3
Plant M9, which produces diazinon in addition to halogenated
organic and organo-nitrogen pesticides, operates an
activated sludge treatment system. Long term averages have
been adjusted by a final:technical product ratio of 1.63:1.
Daily data for an 11 month period were analyzed. Long term
averages and variability factors are as follows:
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30-Day Maximum Daily Maximum
Long Term Average Variability Factor Variability Factor
BOD: 2.72 kg/kkg 4.3 6.3
TSS 3.35 kg/kkg 3.6 4.9
NH3: 5.40 kg/kkg 2.0 2.2
Diazinon: 0.00014 kg/kkg 2.6 3.8
Based on the data presented above, 30-day maximum and daily
maximum variability^factors have been developed. Plants M8
and M9 both reported pesticide variabilities less than Plant
B2. However, since Plant B2 has-been defined as exemplary,
the corresponding 30-day maximum and daily maximum
variability factors of 2.5 to 5.6 have been utilized.
Variability factors for BOD, COD, NH3_, and TSS are
discussed under "Summary of Guidelines Development."
Subcategory C—Organo-Nitrogen
Total pesticides variability factors of l.U and 2.1 were
reported for Plant M8. Since the proposed guideline is
considerably lower than Plant M8«s long term average, due to
Plant M8«s lack of proper detoxification, it is anticipated
that variability will be greater than 1.4 and 2.1.
Therefore the variability factors of 2.5 and 5.6 have been
transferred from Plant B2r Subcategory B, which is operating
detoxification systems quite well. Variability factors for
BOD, COD, NH3, and TSS are discussed under "Summary of
Guidelines Development."
IDENTIFICATION OF BEST PRACTICAL CONTROL TECHNOLOGY
CURRENTLY AVAILABLE
The best practical control technology currently available
was described in Section VII. The recommended alternatives
for each subcategory are indicated in Table IX-2. BPT was
identified in Section VII as pesticide detoxification
followed by flow equalization and biological treatment.
SUMMARY OF GUIDELINES DEVELOPMENT
The development of Effluent Limitations Guidelines are based
on an analysis of the effluent data obtained from existing
treatment plants which correspond most closely to the
recommended treatment alternative. These effluent data,
expressed as long term averages in Section VII, were
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SUBCATEGORY A
SUBCATEGORY B
SUBCATEGORY C
SUBCATEGORY D
SUBCATEGORY E
TABLE IX-2
BPT TREATMENT TECHNOLOGY
Neutralization, API separation, equalization,
filtration, carbon adsorption, activated sludge,
and incineration of strong organic wastes.
API separation, hydrolysis, neutralization,
equalization, activated sludge, ammonia stripping
for segregated waste streams, and incineration
of strong organic wastes.
API separation, hydrolysis, neutralization,
equalization, activated sludge, ammonia stripping
for segregated waste streams, aerobic digestion,
and incineration of strong organic wastes.
In-plant control, water conservation, and water
reuse.
Recycle, containment and
Evaporation
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converted to 30 day maximum and daily maximum limitations by
applying the variability factors previously presented.
Since biological treatment was a common recommendation for
Subcategories A, B, and Cr and since those plants with long
term daily data were multicategory producers, variability
factors for biologically dependent parameters were assumed
to be the same, regardless of subcategory. The variability
for BOD, COD, TSS, and NH3 were therefore determined by
averaging the individual factors from Plants B2, M8, and M9.
30 day maximum and daily maximum factors for Subcategories
A, B, and C are as follows: BOD equal to 3.2 and 5.6; COD
equal to 1.8 and 2.6; TSS equal to 3.0 and U.3; NH3-N equal
to 1.8 and 2.1. Variability factors for Phenol and Total
Pesticides are dependent on different types and degrees of
detoxification, and thus are regulated separately for each
subcategory.
The specific manner in which individual plant long term
averages were combined for each subcategory is presented in
the following discussion. The final effluent limitations
are summarized in Table IX-1.
Subcategory A
The primary components of the model treatment system, i.e.
activated carbon detoxification, equalization, and
biological oxidation, are separately demonstrated at Plants
A2, A6, A8, A19, M2, and M9, as reported in Section VII. In
addition, plants AU, A7, A9, A10, A12, and A18 have either
completely or nearly eliminated wastewater discharges to
navigable waters through process modifications, in-plant
controls, or alternative disposal methods. Plant A3 has
demonstrated the ability to meet the recommended guidelines
via physical-chemical treatment. Demonstrated long term
averages for each parameter are identified below.
The reduction of phenol is based on removal in both the
carbon detoxification system and the biological system, as
demonstrated by the effluents of Plants A6 and B2 in Section
VII. Phenol reduction at Plant A6 averaged 98.9 percent
over a seven month period with individual months as high as
99.9 percent, equating to an effluent of 0.013 kg/kkg (1.58
mg/1) and 0.0025 kg/kkg (0.45 mg/1), respectively.
Plant B2, with activated sludge but no carbon treatment,
achieves 98.6 percent phenol reduction with an influent
concentration of 0.375 mg/1, i.e. a lower concentration than
the 1.58 mg/1 effluent of the activated'carbon at Plant A6.
If the results of the biological system of Plant B2 were to
-------
be applied to the activated carbon effluent of Plant A6, the
overall phenol removal would be 99.98 percent. However,
since the biological system at Plant B2 is designed for a
Subcategory B plant, it would not be cost effective to
directly transfer the design to a Subcategory A plant.
Therefore, it is judged that a cost effective biological
system combined with activated carbon treatment would
achieve a phenol reduction of 99.95 percent, via carbon
removal of 98.9 percent and biological removal of 95.4
percent, resulting in a long term effluent phenol load of
0.001 kg/kkg for the model plant. Using variability factors
of 1.7 and 4.8, 30 day maximum and daily maximum limitations
for phenol are 0.00170 kg/kkg and 0.00480 kg/kkg equating to
effluent concentrations of about 0.05 mg/1 and 0.14 mg/1,
respectively.
Pesticide limitations are based on reductions via activated
carbon and biological treatment as demonstrated by plants
A6, A8, A19r and M9. The activated carbon system of Plant
A6 has a highly variable total pesticide level in its
effluent due to documented interference by non-pesticide
organic chemicals. However, the system was free of such
interference for a period of nearly four months during which
time the average total pesticide loading in the effluent was
0.00710 kg/kkg, or 0.99 mg/1. Plant M9, which employs only
biological treatment, has an influent concentration (0.72
mg/1) comparable to the effluent concentration (0.99 mg/1)
at Plant A6, and achieves an 85.6 percent reduction of
chlorobenzilate. Plant A19 conducted biological oxidation
studies which showed an average 99 percent removal of
daconil. It is conservatively estimated, therefore, that
85.6 removal of the 0.00710 kg/kkg effluent from Plant A6
will yield a long term average of 0.00102 kg/kkg, or 0.0290
mg/1 for the model plant. Utilizing the variability factors
of 3.0 and 6.1, the 30 day maximum and daily maximum for
total pesticides become 0.00306 kg/kkg and 0.00622 kg/kka,
or 0.0866 mg/1 and 0.176 mg/1, respectively. As shown in
Table VII-4, the maximum 30 day value for Plant A3's
physical-chemical system was 0.00182 kg/kkg compared to
0.00306 kg/kkg for the recommended guideline. It is also
noted that Plants A4 and A18 report no detectable levels of
halogenated organics in their wastewater effluents. These
non-detectable levels are achieved by in-plant process
control.
The reduction of BOD, COD, and suspended solids for
Subcategory A plants is a function of solids separation,
activated carbon, and activated sludge, although the ^inal
effluent concentrations are heavily influenced by the nature
of the biological system. Plant M9, with only biological
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treatment, reduces BOD by 96.3 percent and generates an
effluent concentration of 58.5 mg/1. Therefore, on a
conservative basis, a facility using both carbon and
biological treatment can be expected to reach at least the
effluent BOD level achieved by Plant M9, i.e. 4.43 kg/kkg.
Since Plant M9 produces 1,63 kg of total product (including
intermediates) per kg of final technical product, an
effluent ratio of 2.72 kg/kkg is achievable. This value is
directly comparable to a level of 2.67 kg/kkg predicted by
Plant A19 based on the proposed treatment system described
in Section VII. Based on a long term average of 2.72 kg/kka
BOD, and using variability factors of 3.2 and 5.6, the 30
day maximum and daily maximum BOD limitations become 8.7
kg/kkg and 15.2 kg/kkg, or 246 mg/1 and 431 mg/1 for the
model plant, respectively.
Extensive studies conducted at Plant A19 have resulted in
the design of a combination activated carbon-activated
sludge treatment system which is currently under
construction. Based upon laboratory and pilot plant
studies, the projected COD effluent is 11.8 kg/kkg to
correspond with the above mentioned BOD effluent of 2.67
kg/kkg. Applying variability factors of 1.8 and 2.6 to the
long term average of 11.8 kg/kkg, the 30 day maximum and
daily maximum limitations become 21.2 kg/kkg and 30.7
kg/kkg, or 601 mg/1 and 870 mg/1 for the model plant,
respectively. An aerated lagoon added to the activated
carbon system at Plant A6 would therefore need to achieve a
44 percent removal to meet the 30 day limitations.
The following suspended solids effluents, from systems
similar to the model plant, were documented in Section VII:
Plant A3, 0.52 kg/kkg; Plant A8, 0.814 kg/kkg; Plant A19,
3.7 kg/kkg; and Plant M9, 3.35 kg/kkg (due to 1.63 total:
final product ratio). Based on the average of these four
plants, the long term effluent achievable is 2.10 kg/kka.
Applying the variability factors of 3.0 and 4.3, the 30 day
maximum and daily maximum limitations become 6.3 kg/kkg and
9.03 kg/kkg, equating to model plant concentrations of 178
mg/1 and 256 mg/1, respectively.
Subcategory B
Four major pesticide manufacturers operate full scale
treatment systems similar to that recommended for the model
plant. Treated effluent ratios for these plants vary
significantly for some parameters, due to differences in the
production of intermediates. In determining effluents
achievable these differences have been taken into
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consideration by adjusting the effluent value according to
the total product to final product ratio fer each plant.
In terms of detoxification, Plant B2, M2, and M9 exemplify
the best known operating systems. Collectively these plants
have submitted data representing more than three and one-
half years of daily monitoring showing total pesticide
effluent levels averaging between 1.8 and 11.0 ppb. Based
on these data, an effluent of 0.0007 kg/kkg, identical to
that generated by B2, is judged to be an achievable long
term average, since this plant most closely resembles the
model treatment system. Based on variability factors of 2.5
and 5.6 the 30-day maximum and daily maximum limitations for
total pesticides are 0.00175 kg/kkg and 0.00392 kg/kkg,
equivalent to concentrations of 0.0397 mg/1 and 0.0890 mg/1,
respectively.
Eighteen months of BOD data from Plant B2 demonstrates the
capability of an activated sludge plant to average less than
10 mg/1, or 0.174 kg/kkg. Similarly, Plant M2 has conducted
pilot scale studies, as part of a proposed upgrading, which
indicate a reduction to 8 mg/1 or 0.21 kg/kkg. Eleven
months of data at Plant M9 has shown a BOD effluent of 2.72
kg/kkg (using 1.63 total: final product ratio). Six months
of data from Plant M8, which is in a start-up mode, shows an
effluent BOD of 5.02 (total: final product ratio of 2.61).
The effluent from Plant B2 has been selected as the long
term average for BOD for Subcategory B. Applying
variability factors of 3.2 and 5.6. The 30 day maximum and
daily maximum become 1.52 kg/kkg and 2.65 kg/kkg. Equating
to model plant concentrations of 31.6 mg/1 and 60.1 mg/1,
respectively.
Three of the four major organo-phosphorus manufacturers
monitor COD. Plant B2 discharges 6.64 kg/kkg of COD with a
COD/BOD ratio of 14.0:1. Plant M2, which currently
discharges 9.99 kg/kkg COD, is projected to achieve 2.94
kg/kkg after addition of an aerated lagoon. Plant M9, which
does not monitor COD, is estimated to discharge 38.1 kg/kkg
based on the above-mentioned COD/BOD ratio of 14.0:1 Plant
M8 discharges 52.5 kg/kkg (using total: final product ratio
of 2.61). Based on the average of Plant B2, a long term
effluent of 6.64 kg/kkg has been demonstrated. Applying
variability factors of 1.8 and 2.6, the 30-day maximum and
daily maximum limitations for COD are 11.9 kg/kkg and 17.3
kg/kkg, equating to concentrations of 271 mg/1 and 393 mg/1,
respectively.
Suspended solids values for the three best plants are: Plant
B2, 2.35 kg/kkg. Plant M2, 0.32 kg/kkg; and Plant M9, 3.35
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kg/kkg (using 1.63 total: final product ratio). Based on
the average of Plant B2, an effluent of 2.35 kg/kkg is
achievable on a long term basis. Applying variability
factors of 3.0 and 4.3, the 30-day maximum and daily maximum
values becomes 7.05 kg/kkg and 10.1 kg/kkgr equating to
model plant concentrations of 161 mg/1 and 230 mg/lf
respectively.
As noted in Section VII, specific plants and/or products
have high ammonia levels whereas some plants are deficient
in nitrogen. The highest ammonia levels in the organo-
phosphorus subcategory were reported by Plant M8. A three
part plan for ammonia removal has been implemented which
will result in a 97.0 percent reduction. This is equivalent
to 2.45 kg/kkg for a long term average. Applying
variability factors of 1.8 and 2.1, the 30-day maximum and
daily maximum limitations are 4.41 kg/kkg and 5.14 kg/kkg.,
equating to model plant concentrations of 101 mg/1 and 117
mg/1, respectively.
Subcategory C
The major treatment components of detoxification,
equalization, and biological degradation are currently in
place at plants producing organo-nitrogen compounds.
Activated carbon is being utilized at Plants C4, C12T M3,
and M7. Hydrolysis has been employed at Plant M2, and a
great many other products have been successfully hydrolyzed
as documented in Section VII. Biological treatment systems
are in operation at Plants C4, Ml, M2, M8, M9, and D3.
Plant C8 has a full scale biological plant under
construction.
Based on the technology presented in Section VII, a
reduction of total pesticides by 99.9 percent by
detoxification can be expected. Applying this technology to
the raw waste loads identified in Section V produces an
effluent of 0.0103 mg/1 prior to biological treatment. Data
reported by Plant M9 covering ten triazine type pesticides
indicates essentially no removal through biological
treatment. Therefore by proper operation of detoxification
facilities an equivalent of 0.00282 kg/kkg pesticides can be
expected in the effluent. It is noted that this value is
being met by Plant C4, which employs activated carbon
treatment. Based on variability factors of 2.5 and 5.6, 30
day maximum and daily maxinum limitations are 0.00705 kg/kkg
and 0.0158 kg/kkg, equating to model plant concentrations of
0.199 mg/1 and 0.446 mg/1, respectively.
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BODr COD, and suspended solids long term averages achievable
are based on Plants C8 and M9, whose treatment systems most
closely represent the model plant, and whose waste results
primarily from organo-nitrogen pesticide production. Based
on the average of Plants C8 and M9, the long term BOD
average is 2.70 kg/kkg. Applying variability factors of 3.6
and 5.6 the 30 day maximum and daily maximum limitations are
8.64 kg/kkg and 15.1 kg/kkg, equating to model plant
concentrations of 244 mg/1 and 427 mg/1, respectively.
Based on Plant C8, the long term COD value is 11.7 kg/kkg.
Applying variability factors of 2.0 amd 2.6, the 30 day
maximum and daily maximum limitations are 21.1 kg/kkg and
30.4 kg/kkg, equating to model plant concentrations of 596
mg/1 and 860 mg/1, respectively.
Based on Plants C8 and M9, the long term suspended solids
level is 3.17 kg/kkg. Applying variability factors of 3.0
and 4.3, the 30 day maximum and daily maximum limitations
are 9.51 kg/kkg and 13.6 kg/kkg, equating to model plant
concentrations of 269 kg/kkg and 385 mg/1, respectively.
As in Subcategory B specific organo-nitroqen compounds can
produce high ammonia waste streams. Plant C8 has reported a
raw waste load of 60.2 kg/kkg, the highest in the
subcategory. Based on the technology presented in Section
VII, a 95.5 percent reduction is expected, producing an
effluent of 2.71 kg/kkg. Applying variability factors of
1.8 and 2.1, the 30 day maximum and daily maximum
limitations are 4.88 kg/kkg and 5.69 kg/kkg, equating to
model plant concentrations of 138 mg/1 and 161 mq/1,
respectively.
Subcategory D
Plants Dl through D8 demonstrate the existing practice of no
discharge of pollutants via in-process control and recycle
of wastewaters.
Subcategory E
Plants E2 through E75 demonstrate the existing practice of
no discharge of pollutants via in-process control and total
evaporation.
ENGINEERING ASPECTS OF CONTROL TECHNOLOGY
Since the wastewaters generated by the pesticide chemicals
industry are for the most part biodegradable, biological
treatment is the most applicable technology. As developed
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in Section VII, activated sludge and aerobic lagooning are
the most applicable types of biological treatment employed.
Commonly, high-strength industrial waste requires
modifications of the activated sludge design as applied to
treatment of municipal waste. These modifications include
longer detention times, completely mixed basins, and larcrer
secondary clarifiers. The complete-mix system is generally
preferred over other activated sludge systems because it i?
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.
A primary disadvantage of any activated sludge system is
operational difficulty. Operators must be well trained
specialists; the not uncommon industrial practice of
assigning personnel from the maintenance department or the
chemistry lab to "take care" of the wastewater treatment
plant has in many instances led to chronically poor
treatment efficiencies.
Perhaps the most common operational problem is "sludge
bulking" in which rising sludge in final clarifiers causes
floating matter to be discharged in the plant's effluent.
The floating material can considerably increase BOD and
suspended solids concentration in the effluent.
Sludge bulking can often result from poor operation allowing
inadequate aeration or nutrient levels, improper food to
microorganism ratio, or improper sludge age. It is
essential that operators maintain frequent (at least daily)
testing of the dissolved oxygen levels, suspended solids
concentrations, and nutrient concentrations in the effluent,
and, of course, the sludge volume index. If upsets still
occur even with the best operation and most constant
monitoring, it may be necessary to take additional measures
such as the addition of filtration, increased equalization,
or greater clarification.
Any biological treatment system requires a period of
stabilization before optimum efficiency can be expected.
This period may range from a few weeks up to a year of more,
with the longer period often resulting in part from the need
of operators (even those with previous experience) requirina
time to learn the eccentricities of a particular system.
The period of initial stabilization of a biological system
used for pesticide wastewaters can be lengthened by high
salt concentrations requiring special efforts in acclimating
a microbiological culture. As discussed in Section VII,
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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, be generated
at a rate of about 0.5 kg per kg of BOD.
The disposal of sludge can be a serious problem. Land
disposal (lagooning, land spreading, spray irrigation) is
the most common procedure. The feasibility of land disposal
of sludge (or wastewater for the matter) is essentially one
of economic and environmental impact - the availability of
suitable land reasonably close to the treatment plant. in
some cases sludge disposal may add increased costs to
control and treatment.
As discussed in Section VII, a variety of treatment modules
other than those discussed in this document may be employed
in the industry. For particular installations, other
modules could be more cost effective. This can only be
determined on a case by case basis.
Application of the best 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.
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 guestion.
However, up to two years may be required from design
initiation to plant start-up. The waste treatment
techniques are also broadly applied within many other
industries. The technology required may necessitate
improved monitoring of waste discharges and of 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 ether industries.
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SPECIFIC APPLICATIONS OF CONTROL AND TREATMENT TECHNOLOGY
It is recognized that a number of pesticide plants currently
operate treatment systems which in many cases differ in
detail from the technology recommended herein, and in some
cases do not meet the recommended guidelines. It is by no
means the intent of this document to suggest that these
functioning systems be deleted and replaced with the
respective model treatment plant. In all cases known, it is
within the boundaries of engineering feasibility for those
pesticide plants currently having treatment plants but not
achieving the effluent guidelines to do so by such
techniques as improving their treatment modules. Table IX-3
summarizes potential alternatives available to those plants
discussed in Section VII which do not currently meet the
guidelines and for which sufficient information is available
to permit engineering judgements to be made.
FACTORS TO BE CONSIDERED IN APPLYING EFFLEUNT GUIDELINES
The above assessment of what constitutes the Best
Practicable Control Technology Currently Available is
predicted 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
wastewater. 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 even 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.
In the case of multi-product plants, an important point to
consider is that the summation of the parts may not
necessarily make up the theoretical whole. A plant, for
example, that processes products covered under several of
the subcategories in this document could be theoretically
expected to meet a cumulative limitation; however, the
cumulative raw wastewater from such a plant may in some
cases exceed the calculated quantity; on the other hand, a
multi-product plant often has greater flexibility in
managing in-plant control techniques. The preceding factors
may affect costs of treatment technology to varying degrees.
There are several subcategories 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
233
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TABLE IX-3
POTENTIAL METHODS FOR
UPGRADING EXISTING SYSTEMS
PLANT
M2
M7
M8
M9
ro
CO
A2
A3
A6
A8
A9
PARAMETERS AND REDUCTION REQUIRED
All parameters NRR pending completion of
biological treatment.
All parameters NRR pending completion of
planned treatment.
Reduction required for BOD, COD, TSS,
total pesticides. Ammonia - NRR pending
completion of ammonia stripping facilities.
BOD - NRR; COD - Not monitored; TSS -
Requires reduction; Phenol - NRR; Ammonia -
NRR; Pesticides - reduction required
for halogenated and organo nitrogen.
All parameters NRR pending completion of
proposed treatment system.
Pesticides, TSS - NRR; BOD, COD, Phenol
not monitored.
Reduction required for BOD, COD, TSS,
Phenol, and Pesticides.
BOD - Not Monitored; COD - NRR; TSS -
NRR; Phenol - Not Monitored; Pesticides -
Not Monitored
All parameters - NRR
POTENTIAL REDUCTION METHODS
No further treatment required pending
completion of biological treatment.
No further treatment required pending
completion of planned treatment system.
Additional hydrolysis; dual media
filtration.
Dual media filtration.
No further treatment required pending
completion of proposed treatment system.
No further treatment required for
pesticides and TSS.
In-process treatment of organic chemi-
cal wastes to improve carbon column
operation; install biological treatment;
reduce solids from neutralization by
changing operation (e.g. use caustic
instead of lime) or by adding filtration.
Based on available data, no further
treatment required.
No further treatment required.
NRR - No reduction required
-------
no
GO
tn
PLANT
A12
A18
A19
B2
C4
C8
TABLE IX-3
POTENTIAL METHODS FOR
UPGRADING EXISTING SYSTEMS
Continued
Page 2 of 2 Pages
PARAMETERS AND REDUCTION REQUIRED
All parameters - NRR
Reduction required -
Pesticides - NRR.
All parameters - NRR
new treatment system
Reduction required -
parameters NRR.
AT 1 parameters - NRR
Reduction required -
other parameters NRR.
BOD, COD, TSS.
pending completion of
TSS; all other
NH3, Pesticides. All
POTENTIAL REDUCTION METHODS
No further treatment required
Equalization. Biological treatment.
No further treatment required pending
completion of new treatment system.
Improve or modify process or treatment
operation, e.g. reduce clarifier
overflow rate.
No further treatment required.
Modify process to generate less
ammonia or install steam stripping of
ammonia; install hydrolysis for
pesticides.
NRR - No reduction required.
-------
or to the cleanup periods. For example, while a formulation
plant is blending and packaging its products, virtually no
wastewater may be generated. During a subsequent period of
time, however, production operations may have completely
ceased but a considerable amount of wastewater 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.
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 wastewater and resulting in
intermediate products which are used in the subsequent
step), and ultimately produces final (technical) products.
The total wastewater 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 wastewater 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 wastewater
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 Bf but it purchases some of the intermediate products
and thereby eliminates certain processing steps and the
corresponding wastewater generation. In this case, the
wastewater loading per product unit could be substantially
lower than that of Plant A.
As discussed in Section III, this document has excluded
intermediates in calculating effluent ratios and instead
used the technical product as reported by industry in EPA
pesticide registration. Care must be exercised in the
application of guidelines to avoid unfair economic
constraints or advantages to various types of operations.
A factor to be considered for biological treatment is that
such a system requires a period of stabilization up to
several weeks or longer before optimum efficiency can be
expected. During this start-up period, large variations in
both BOD and suspended solids concentrations can be expected
in the discharge.
236
-------
The maximum daily limitations recommended herein allow for
compliance 99 percent of the time. In the event of non-
compliance, those parties responsible for treatment plant
operation should immediately report the occurence to the
appropriate authorities, take the necessary steps to correct
the situation, and report the probable cause of the non-
compliance.
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.
In all cases herein, including those for which no discharge
of polluted 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, hence runoff or leachate from that soil may exhibit
contamination, even in cases where there is no discharge of
process wastewater.
237
-------
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., halogenated organic, organo-phosphorus,
organo-nitrogen, and metallo-organic. In addition, some
compounds, listed as non-categorized pesticides in Table X-
1, are represented by common compounds whose active groups
do not allow classification in the above-mentioned four
subcategories and who consequently 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.
238
-------
TABLE X-l
INDEX OF PESTICIDE COMPOUNDS
BY SUBCATEGORY
SUBCATEGORY A - HALOGENATED ORGANIC PESTICIDES
Common Name
Aldrin
Benzoylprop Ethyl (Suffic)
BHC and Related Isomers
Bifenox (Modown)
Bromoxynil (Brominal)
Captafol (Difolatan)
Chloramben (Amiben)
Chloranil (Spergon)
Chlorodane (TECH.) and components
Chlordecone (Kepone)
Chlorobenzilate (Acaraben)
Chemical Name
1,2,3,4,10,10-Hexachloro-
l,4,4a,5,8,8a-hexahydro-
l,U-endo-exo-5,8-
dimethanonaphthalene
Ethyl N-benzoyl-N-(3,4-
dichlorophenyl)
-2-aminopropionate
Isomers of Hexachloro-
cyclohexane
Methyl 5- (2,4-dichloro-
phenoxy)-2-nitrobenzoate
3,5-Dibromo-4-hydroxy-
benzonitrile
cis-N-[ (1,1,2,2-Tetra-
chloroethyl) thio]-4-cyclo-
hexene-1,2-dicarboximide
3-Amino-2r 5-dichloro-
benzoic acid
2,3,5,6-Tetrachloro-l,4-
benzoqu inone
1,2,H,5,6,7,8,8-Octa-
chloro-2,3,3a,a,7,7a-hexa-
hydro-U,7-methanoindene
Decachloro-octahydro-1,3f
t»-metheno-2H-cyclobuta[ cd ]-
pentalen-2-one
Ethyl U,4«-dichloro-
benzilate
239
-------
TABLE X-1 (Con*-inu€'-M
SUBCATEGORY A - HALOGENATFD ORGANIC PFSTICIOEF - Cor,
Common Name
Chloroneb (Demosan)
Chlorothalonil (Daconil 2787)
Dalapon (Downpan)
DCPA (Dacthal)
DDD, Mixed, Tech. (TDE, Rhothane)
and Metabolites
DDTr Mixed (TECH.) and Metabolites
Dibromochloropropane (DBCP)
Dicamba (Banvel D)
Dichlobenil (Casoron)
Dichlone (Phygon XL)
Dichloran (Botran)
Dichlorobenzene, Ortho (ODB)
Dichlorobenzene, Para (PDB)
Dichlororopropene (Telone)
Chemical
l,U-Dichloro-2r 5-dimeth-
oxy benzene
2, 4,5, 6-Tetrachloroisopb-
thalonitrile
2r2-Dichloropropionic acid
Dimethyl 2, 3, 5, 6-tetra-
chloroterephthalate
2f 2-Bis (chloropheny) -1,
1-dichloroethane and
related compounds
Dichloro dipenyl tri-
chloroethane (mixt. of
metabolites of ca. 80%
£,£' and 20% orp_')
1, 2-Dibromo-3-chloropro-
pane and related halogen-
ated C3_ hydrocarbons
2-Methoxy-3f 6-dichloro-
benzoic acid
2 r 6-Dichlorobenzonitri le
2,3-Dichloro-lr 4-naphtho-
quinone
2r 6-Dichloro-4-nitroaniline
1 , 2-Dichlorobenzene
l,U-Dichlorobenzene
1 , 3-Dichloropropene
240
-------
TABLE X-1 (Continued)
SUBCATEGORY A - HALOGENATED ORGANIC PESTICIDES - Continued
Common Name Chemical Name
Dichlorprop (2,4-DP)
Dicofol (Kelthane)
Dieldrin (HEOD)
Diquat Dibromibe
2,4-D, Acid Esters and Salts
2,4-DB, Acid and Esters
Endosulfan (Thiodan) and Isomers
Endrin
Erbon (Baron)
Fenac
Heptachlor
2- (2,4-Dichlorophenoxy) -
propionic acid
1,1-Bis(p-chlorophenyl) -2,
2,2-trichloroethanol
1,2,3,4,10,10-Hexachloro-
exo-6,7-epoxy-l,4,4a,5,6,7,
8,8a-octahydro-l,4-endo,
exo-5,8-dimethanonaphthalene
6,7-Dihydrodipyrido[1,2-
a:2',1'-c ]pyrazidiinium
dibromide, monohydrate
2,4-Dichlorophenoxyacetic
acid, esters, and salts
4- (2,4-Dichlorophenoxy)
butyric acid, and esters
6,7,8,9,10,10-Hexachloro-
l,5,5a,6,9r9a-hexahydro-6,
9-methano-2,4,3-benzodi oxa-
thiepon 3-oxide
1,2,3,4,10,10-Hexachloro-
6,7-epoxy-l,4,4a,5,6,7,8f
8a-octahydro-l,4-endo,endo-5,
8-dimethanonaphthalene
2-(2,U,5-Trichlorophenoxy)
ethyl 2,2-dichloropropionate
2,3,6-Trichlorophenyl-
acetic acid
1,4,5,6,7,8,8-Heptachloro-
3a,4,7,7a-tetrahydro-4,
7-methanoindene
241
-------
TABLE X-1 (Continued)
SUBCATEGORY A - HALOGENATED ORGANIC PESTICIDES - Continued
Common Name
Hexachlorobenzene (HCB)
Hexachlorophene (Nabac)
1-Hyd roxych1ordene
loxynil (Actril)
Lamprecide (TFN)
MCPA, MCPB, MCPP, Acids and Esters
Methoxychlor (Marlate)
Mirex (Dechlorane)
Nitrapyrin (N-Serve TG)
Nitrofen (TOK)
Parinol (Parnon)
PCNB (Quintozene)
PCP (Pentachlorophenol)
Perthane
Chemical Name
Hexachlorobenzene
2,2«-Methylene bis(3,U,6-
trichlorophenol)
1-exo, Hydroxy-4,5,6,7,8,
8-hexachloro-3a,4,7,7a-
tetrahydro-4,7-methanoindene
4-Hydroxy-3,5-Diiodo-
benzonitrile
3-Trifluoromethyl-M-nitro-
phenol, sodium salt
(U-Chloro-2-methylpenoxy) -
acids and esters
2,2-Bis(p-methoxyphenyl) -
1,1,1-trichloroethane
Dodecachlorooctahydro-1,
3,U-metheno-2H-cyclo-
buta[ cd ]pentalene
2-Chloro-6-trichloro-
methylpyridine (and re-
lated chlorinated pyridines)
2,4-Dichloropheny1-p-
nitrophenyl ether
a,a-Bis(p-chlorophenyl) -
3-pyridine methanol
Pentachlor©nitrobenzene
2,3,U,5,6-Pentachlorophenol
1,l-Dichloro-2,2-bis(p-
ethylphenyl) ethane
242
-------
TABLE X-1 (Continued)
SUBCATEGORY A - HALOGENATED ORGANIC PESTICIDES - Continued
Common Name
Silvex, Acid [ 2-(2,4,5-TP) ]
Silvex, Isooctyl Esters
Silvex, Propylene Glycol Butyl
Ether Esters
Sodium Pentachlorophenate
(Dowicide G)
Strobane
Tecnazene (Fusarex)
Terrazole
Tetradifon (Tedion)
Tetrasul (Animert)
Toxaphene
2,4,5-Trichlorophenol (Dowcide 2)
2,4,5-T, Acid, Esters, and Salts
Chemical Name
2- (2,4,5-Trichlorophen-
oxy) propionic acid
2- (2,4,5-Trichlorophenoxy)
propionic acid, isooctyl
esters (mixed)
2-(2,4,5-Trichlorophenoxy)
propionic acid, propylene
glycol butyl ether esters
(C3H60 to C9H1J303)
2,3,4,5,6-Pentachloro-
phenol, sodium salt,
monohydrate
Polychlorinates of cam-
phene, pinene and related
terpenes
2,3,5,6-Tetrachloro-
nitrobenzene
5-Ethoxy-3-tri chlor o-
methyl-1,2,4-thiadiazole
4-Chloropheny1 2,4,4-
trichlorophenyl sulfone
S-p-Chlorophenyl 2,4,5-
trichlorophenyl sulfide
A mixture of chlorinated
camphene compounds of
uncertain identity (com-
bined chlorine 67-69%)
2,4,5-Trichlorophenol
2,4,5-Trichlorophenoxy-
acetic acid, esters,
and salts
243
-------
TABLE X-1 (Continued)
SUBCATEGORY B - ORGANQ-PHOSPHORUS PESTICIDES
Common Name
Acephate (Orthene)
Aspon
Azinphos Ethyl (Ethyl Guthion)
Azinphos Methyl (Guthion)
Bensulide (Prefar)
Bromophos (Brofene)
Bromophos Ethyl (Nexagan)
Carbophenothion (Trithion)
Chlorfenvinphos (Supona)
Chlormephos (MC 2188)
Chlorpyrifos (Dursban)
Chemical Name
O, S-Dimethyl acetylphos-
phoramidothioate
0,0,0,0-Tetrapropyl dithio-
pyrophosphate
OrO-Diethyl S-[4-oxo-l,2, 3-
benzotriazin-3 (4H) -ylmethyl ]-
phosphorodithioate
OrO-Dimethyl S-[U-oxo-1,2,3-
benzotriazin-3 (HE) -ylmethyl ]~
phosphorodith ioate
S- (O,O-Diisopropyl phosphoro-
dithioate) ester of N-(2-mer-
captoethyl) benzenesulfon-
amide
O- (4-Bromo-2,5-dichloro-
phenyl) 0,0-dimethyl phos-
phorothioate
O-(4-Bromo-2r5-dichloro-
phenyl)0,0-diethtl
phosphorothioate
S-[(p-Chlorophenylthio)-
methyl]0r 0-diethyl
phosphorodithioate
2-Chloro-l-(2,4-dichloro-
phenyl)vinyl diethyl
phosphate
S-Chloromethyl O,O-diethyl
phosphorothiolothionate
O r O-Diethyl O-(3 r 5, 6-tri-
chloro-2-pyridyl) phos-
phorothioate
244
-------
TABLE X-1 (Continued)
SUBCATEGORY B - ORGANQ-PHOSPHORUS PESTICIDES - Continued
Common Name
Chlorthiophos (CMS 2957)
Coumaphos (Co-Ral)
Crotoxyphos (Ciodrin)
Crufornate (Rue!ene)
Cythioate (Proban)
DBF
Demeton-O (Systox-O) (Thiono)
Demeton-S (Systox-S) (Thiolo)
Dialifor (Torak)
Diazinon (Spectracide)
Dichlofenthion (VC-13)
Dichlorvos (DDVP)
Chemical Name
OrO-Diethyl 0-2,4,5-
Dichloro- (methylthio)
phenyl thionophosphate
O- (3-Chloro-U-methyl-2-oxo-
2H-l-benzopyran-7-y )
0,0-diethyl phosphorothioate
a-Methylbenzyl 3-hydroxy-
crotonate dimethyl phosphate
O- (H-tert-Butyl-2-chloro-
phenyl) 0-methyl
N-methyl phosphoroamidate
O,0-Dimethyl O-p-sulfa-
moylphenyl phosphoro-
thioate
S,S,S-Tributyl phosphoro-
trithioate
0,0-Diethyl O-2-[(ethylthio) •
ethyl]phosphorothioate
0,O-Diethyl S-2-[(ethlythio) •
ethyljphosphorothioate
S-(2-Chloro-l-phthalind do-
ethyl) 0,0-diethyl
phosphorodithioate
O,O-Diethyl O-(2-isopropyl-
6-methyl-^-pyrimidinyl)
phosphorothioate
O-2,U-Dichlorophenyl 0,0-
diethyl phosphorothioate
2,2-Dichlorovinyl dimethyl
phosphate
245
-------
TABLE X-1 (Continued)
SUBCATEGORY B - ORGANQ-PHOSPHORUS PESTICIDES - Continued
Common Name
Dicrotophos (Bidrin)
Diethyl Phosphate (DEP)
Dimethoate (Cygon)
Dimethyl Phosphate (DMP)
Dioxathion (Delnav)
Disulfoton (Di-Syston)
Dursban
EPN
Ethephon (Cepha)
Ethion
Ethoprop (Mocap)
Famphur
Fenitrothion (Sumithion)
Chemical Name
3-Hyroxy-N,N-dimethyl-cis-
crotonamide dimethyl phosphate
O,O-Diethyl phosphate
0,0-Dimethyl S-(N-methyl-
carbamoyl methyl) phos-
phorodithioate
0,0-Dimethyl phosphate
S,S'-£-Dioxane-2r3-diyl
O,O-diethyl phosphorodi-
thioate (cis and trans isomers)
OrO-Diethyl S-[2-(ethylthio)-
ethyl ]phosphorodithioate
0,0-Diethyl O~(3,5,6-
Tri-chloro-2-pyridyl)
phosphorothioate
0-Ethyl O-p-nitrophenyl
phenylphosphoriothioate
(2-Chloroethyl)phosphonic acid
0,0,0',0-Tetraethyl SrS'-
methylene bisphosphorodi-
thioate
0-Ethyl S,Sr-dipropyl
phosphorodithioate
0-[p- (dimethylsuIfamoyl)
phenyl]0f 0-dimethyl
phosphorothioate
0,0-Dimethyl 0-(4-nitro-
m-tollyl)phosphorothioate
246
-------
TABLE X-1 (Continued)
SUBCATEGORY B - ORGANO-PHOSPHORUS PESTICIDES - Continued
Common Name
Fensulfothion (Dasanit)
Fenthion (Baytex)
Folex (Merphos)
Fonofos (Dyfonate)
Formothion (Anthio)
Glyphosate (Roundup)
IBP (Kitazin)
Leptophos (Phosvel)
Malathion
Mecarbam (MC-474)
Menazon (Azidithion)
Mephosfolan (Cytrolane)
Methamidophos (Monitor)
Chemical Name
OrO-Diethyl 0-[p-(methyl-
sulfinyl) phenyl]
phosphorothioate
0,0-Dimethyl 0-[4-(methyl-
thio)-m-tolyl]
phosphorothioate
Tributyl Phosphorotrithioite
0-Ethyl S-phenyl ethyl-
phosphonodithioate
OrO-Dimethyl S-(N-methyl-N-
formylcarbamoyl-methyl) -
phosphorodithioat e
N- (Phosphonomethyl) glycine
0,0-Diisopropyl S-benzyl
thiophosphate
0-(U-Bromo-2,5-dichloro-
phenyl) 0-methyl phenyl-
phosphonothioate
Diethyl mercaptosuccinate,
s-ester with 0,0-
dimethyl phosphorodithioate
S-[N-Ethoxycarbonyl-N-
methylcarbamoylmethyl] 0,0-
diethly phosphorodithioate
S-[(U,6-Diamino-l,3,5-
triazin-2-yl)methyl] 0,0-
dimethyl phosphorodithioate
P,P-Diethly cyclic propy-
lene ester of phosphonodi-
thioimidocarbonic acid
0-S-Dimethyl phosphor-
amidothioate
247
-------
TABLE X-1 (Continued)
SUBCATEGORY B - ORGANO-PHOSPHORUS PESTICIDES - Continued
Common Name
Methidathion (Supracide)
Mevinphos (Phosdrin)
Monocrotophos (Azodrin)
Morphothion (Ekatin M)
Naled (Dibrom)
Oxydemeton Methyl
Parathion Ethyl
Parathion Methyl
Pheneapton
Phorate (Thimet)
Phosalone (Zolone)
Chemical Name
S-[(2-methoxy-5-oxo-delta-
l,3,U-thiadiazolin-4-yl) -
methyl]0,0-dimethly phos-
phorodithioate
Methyl 3-hydroxy-alpha-
crotonate, dimethyl phosphate
Dimethyl phosphate of 3-
hydroxy-N-methyl-ci s-
crotonamide
0,0-Dimethly S-(morpholino-
carbonylmethyl) phos-
phorodithioate
1,2-Dibromo-2,2-dichloro-
ethyl dimethyl phosphate
S-[2-(ethylsulfinyl)ethyl-
0,0-dimethyl phos-
phorothioate
Or0-Diethyl-O-p-nitro-
phenyl phosphorothioate
0,0-Dimethyl 0-p-nitro-
phenyl phosphorothioate
Or 0-Diethyl-S-(2r 5-di-
chlorophenylthiomethyl)
phosphorothiolothionate
0,0-Diethyl S-[(ethylthio)-
methyl]phosphorodithioate
S-[(6-Chloro-2-oxo-3-
benzoxazolinyl) methyl ] 0 ,
0-diethyl phosphorodithioate
248
-------
TABLE X-1 (Continued)
SUBCATEGORY B - ORGANO-PHOSPHORUS PESTICIDES - Continued
Common Name Chemical Name
Phosfolan (Cyolane)
Phosmet (Imidan)
Phosphamidon (Dimecron)
Pirimiphos Ethyl (Primicid)
Pirimiphos-Methyl (Actellic)
Pyrazophos (Afugan)
Quninalphos (Ekalux)
Ronnel
Salithion
Stirofos (Gardona)
Surecide (SU087)
Temephos (Abate)
P,P-Diethyl cyclic ethylene
ester of phosphonodi-
thioimidocarbonic acid
0,0-Dimethyl-S-phthalimido-
methyl phosphorodithioate
2-Chloro-N,N-diethyl-3-
hydroxycrotonamide
dimethyl phosphate
0-[ 2- (Diethylamino) -6-
methyl-1-pyrimidinyl]
0,0-diethyl phosphorothioate
0-[ 2- (Diethylamino) -6-
methyl-4-pyrimidinyl1
0 r0-diemthyl phosphorothioate
2- (0,0-Diethyl thionophos-
phoryl)-5-methyl-6-carbe-
thoxy-pyrazolo(1,5a) -
pyrimidine
0,0-Diethyl 0-[quinoxa-
linyl-(2) ] thionophosphate
OrO-Dimethly 0-(2,4,5-tri-
chlorophenyl) phosphorothioate
2-Methoxy-UH-1,3,2-benzod i-
oxaphosphorin-2-sulfide
2-Chloro-l-(2,U,5-trichloro-
phenyl)vinyl dimethyl
phosphate
0- (p-Cyanophenyl) 0-ethyl
phenylphosphonothioate
0,0-Dimethyl phosphoro-
thioate 0,0-diester with
HrH•-thiodiphenol
249
-------
Tepp
TABLE X-1 (Continued)
Tetraethyl pyrophosphate
Thiometon (Ekatin)
Triazophos (Hostathion)
0,0-Dimethly S-[ 2-(ethylthio)
ethyl ] phosphorodithioate
OrO-Diethyl 0-(l-phenyl-
lH-l,2,U-triazol-3-
yl)phosphorothioate
SUBCATEGORY C - ORGANO-NITROGEN PESTICIDES
Common Name
Alachlor (Lasso)
Aldicarb (Temik)
Ametryn (Evik)
Aminocarb (Matacil)
Amitrole (Cytrol)
Amobam (Chemo-0-Bam)
Ancymidol (A-Rest)
Anilazine (Dyrene)
Antu
Asulam (Asulox)
Chemical Name
2-Chloro-2',6•-diethyl-N-
(methoxymethyl) acetanilide
2-Methyl-2-(methylthio)-
propionaldehyde-0-
(methylcarbomoyl)oxime
2- (Ethylamino) -4- (isopro-
pylamino)-6-(methyl-
thio) -a-triazine
U-Dimethylamino-m-tolyl
methylcarbamate
3-Amino-l,2fU-triazole
Diammonium ethylenebisdi-
thiocarbamate
a-Cyclopropyl-a-(p-methoxy-
phenyl)-5-pyrimidinemethanol
2,4-Dichloro-6-(o-chloroanil-
ino)-s-triazine
1 (1-Naphthyl) -2-thiourea
Methyl (4-amino benzene-
sulfonyl)carbamate
250
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANO-NITROGEN PESTICIDES - Continued
Common Name
Atraton (Gesatamin)
Atrazine (Aatrex)
Azobenzene
Barban (Carbyne)
Bentazon (Basagran)
Benefin (Balan)
Benomyl (Benlate)
Benthiocarb (Bolero)
Bantranil
Benzadox (Topcide)
Bromacil (Hyvar)
Butachlor (Machete)
Butralin (Amex 820)
Butylate (Sutan)
Chemical Name
2-(Ethylamino) -U-(isopropyl-
amino)-6-methoxy-s triazine
2-chloro-H- (ethylamino) -6-
(isopropylamino) -s-triazine
Diphenyl diimide
U-Chloro-2-Butynyl-m-chloro-
carbanilate
3-lsopropyl-lH~2,1,3-benzo-
thiadiazin- (i») 3H-one 2,
2-dioxide
N-Butyl-N-ethyl-a, a,a-tri-
f luoro-2r 6-dinitro-p-
toluidine
Methyl 1-(butylcarbamoyl) -
2-benzimidazolecarbamate
S-(U-Chlorobenzyl)N,N-diethyl-
thiolcarbamate
2-Phenyl-3,1-benzoxazinone- (4)
(Benzamidooxy)acetic acid
5-Bromo-3-s ec-butyl-6-
methyluracil
2-Chloro-2'r6«-diethyl-N-
(butoxymethyl) acetanilide
U- (lrl-Dimethylethyl) -N-
(1-methyl propyl)-2r
6-dinitronbenzeneamine
S-Ethyl N,N-diisobutyl-
thiocarbamate
25]
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANQ-NITROGEN PESTICIDES - Continued
Common Name Chemical Name
Captan N-[ (Trichloromethyl)thio]-U-
cyclohexene-1,2-dicarboximide
Carbaryl (Sevin) 1-Naphthyl N-methylcarbamate
Carbendazim (Derosal) 2-(Methoxycarbonylamino)-
benzimidazol
Carbetamide (Legurame) N-Phenyl-1-(ethylcarbamoyl) -
ethylcarbamate, D isomer
Carbofuran (Furadan) 2,3-Dihydro-2,2-dimethyl-7-
benzofuranyl methylcarbamate
Carboxin (Vitavax) 5,6-Dihydro-2-methyl-l,4-
oxathiin-3-carboxanilide
CDAA (Randox) NrN-Diallyl-2-chloroacetamide
CDEC (Sulfallate) 2-Chloroallyl diethyldithio-
carbamate
Chlordimeform (Chlorphenamidine) N«-(U-Chloro-o-tolyl)-N, N-
dimethylformamidine
Chlorpropham (CIPC) Isopropyl N-(3-chlorophenyl)
carbamate
Clonitralid (Bayluscide) 2«r5-Dichloro-4--nitrosali-
cylanilide ethanolamine
Cyanazine (Bladex) 2-[(4-chloro-6-(ethylamino)-
s-triazin-2-yl) amino]-
2-methlypropionitrite
252
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANQ-NITROGEN PESTICIDES - Continued
Common Name
Cycloate (Ro-Neet)
Cycloheximide (Actidione)
Cyprazine (Outfox)
Desmedipham (Betanex)
Diallate (Avadex)
Diaphene (Bromsalans)
Difenzoquat (Avenge)
Diflubenzuron (Th-6040,Dimilin)
Dimethirimol (Milcurb)
Dinitramine (Cobex)
Dinocap (Karathane)
Dinoseb (DNBP)
Chemical Name
S-Ethyl ethylcyclohexylthio-
carbamate
3[2-(3,5-Dimethyl-2-oxo-
cyclohexyl) -2-hydroxy-
ethyl]glutarimide
2-Chloro-4-(cyclopropylamino) -
6- (isopropylamino) -s-triazine
Ethyl m-hydroxycarbanilate
carbanilate (ester)
S- (2,3-Dichloroallyl) diiso-
propy1thiocarbamate
3 r4,5-Tribromosalicyanilide,4,5-
dibromosalicylanilide and other
brominated salicylanilides
1,2-Dimethyl-3,5-diphenyl-
IH-pyrazolium methyl sulfate
l-(4-Chloropheny)-3-(2,6-
difluorobenzoyl)urea
5-n-Butyl-2-dimethylamino-U-
hydroxy-6-methylpyrimidine
NU.,N^-Diethly-a,a,a-tri-
fluoro-3,5-dinitro-
toluene-2,U-diamine
2-(1-Methylheptyl)-4,6-
dinitrophenyl crotonate
2- (sec-Butyl) -4, 6-dinitrophenol
253
-------
TABLE X-1
SUBCATEGORY C - ORGANO-NITROC
Common Name
Dinoseb Acetate (Aretit)
Diphenamid (Enide)
Dithianon
Diuron
DNOC
Dodine (Carpene)
Drazoxolon (Ganocide)
EPTC (Eptam)
Ethiolate (Prefox)
Ethirimol (Milstem)
Fenaminosulf (Dexon)
Ferbam
Fluchloralin (Basalin)
Fluometuron (Cotoran)
Fluoridamid (Sustar 2-S)
Folpet (Phaltan)
(Continued)
EN PESTICIDES - Continued
Chemical Name
2-(sec-Butyl) -H,6-dinitro-
phenyl acetate
N,N-Dimethyl-2,2-diphenyl-
acetamide
2,3-Dicarbonitrile-l, H-
dithiaanthraquinone
3- (3,4-Dichlorophenyl)-1-
dimethylurea
4,6-Dinitro-o-cresol
n-Dodecylguanidine acetate
t*~ (2-Chlorophenylhydrazono) -
3-methyl-5-isoxazolone
S-Ethyl dipropylthiocarbamate
S-Ethyl diethylthiocarbamate
5-Butyl-2-(ethlyamino)-6-
hydroxy-U-methylpyrimidine
p-(Dimethylamino) benzenediazo
sodium sulfonate
Ferric dimethyldithiocarbamate
N-Propyl-N-(2-chloroethyl)-
a , a ra-trifluoro-2,6-
dinitro-p-toluidine
1,l-Dimethly-3-(ara,a-tri-
fluoro-m-tolyl)urea
N-U-Methyl-3-[[(1,1,1-tri-
f luoromethyl) sulf onyl ]
amino ]phenyl ]acetamide
N-(Trichloromethylthio)-
phthalimide
254
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANO-NITROGEN PESTICIDES - Continued
Common Name
Formetanate Hyrdochloride
(Carzol SP)
Isopropalin (Paarlan)
Karbutilate (Tandex)
Lenacil (Venzar)
Lethane 38U
Linuron (Lorox)
Meobal
Metalkamate (Bux)
Metham (SMDC)
Methazole (Probe)
Methiocarb (Mesurol)
Methomyl (Lannate)
Metoxuron (Dosanex)
Chemical Name
m[[ (Dimethlyamino) methylene]-
amino]phenyl methyl-
carbamate hydrochloride
2,6-Dinitro-N,N-dipropy-
loumidine
m- (3,3-dimethylureido)phenyl
tert-butylcarbamate
3-Cyclohexyl-6,7-dihydro-
iH-cyclopentapyrimidine-
2,i»(3H,5H) -dione
b-Butoxy-B1-thiocyanodiethyl
ether
3-(3,4-Dichlorophenyl) -1-
methoxy-1-methylurea
3,U-Xylyl methylcarbamate
Mixture of m-(1-ethylpropyl) -
phenyl methylcarbamate and m-
(1-methylbutyl) phenyl methyl-
carbamate (ratio of 1:3)
Sodium N-methyldithiocarbamate
2-(3,4-Dichloropheny) -4-
methyl-l,2f t»-oxadiazolidine-
3,5-dione
4- (Methylthio) -3,5-xylyl N-
methylcarbamate
S-Methyl N-[(methylcarbamoyl)-
oxy] thioacetimidate
3-(3-Chloro-U-methoxyphenyl) -
1,1-dimethylurea
255
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANO-NITROGEN PESTICIDES - Continued
Common Name
Mexacarbate (Zectran)
MH (Maleic Hydrazide)
Molinate (Ordram)
Monalide (Potablan)
Monolinuron (Aresin)
Monuron
Monuron-TCA (Urox)
Naphthalene Acetamide
Napropamide (Devrinbl)
Naptalam, Sodium Salt
Neburon
Nitralin (Planavin)
Norflurazon (Evital)
Oryzalin (Surflan)
Chemical Name
tJ-Dimethylamino-3, 5-xylyl
methylcarbamate
6-Hydroxy-3-(2H)-pyridazinone
S-Ethyl hexahydro-lH-azepine-
1-carbothiate
N- (U-Chlorophenyl) -2, 2-
dimethylpentanamide
3-(p-Chlorphenyl)-1-methoxy-
1-methylurea
3-(p-Chlorphenyl)-1,1-
diamethylurea
3-(p-Chlorophenyl)-1,1-di-
methylurea trichloroacetate
1-Naphthalene-acetamide
2-(a-Naphthoxy)-N,N-di-
ethylpropionamide
Sodium N-1-naphthylphthamate
l-(n-Butyl) -3- (3,4-dichloro-
phenyl)-1-methylurea
U-(Methylsulfonyl)-2,6-
dinitro-N,N-dipropylaniliane
a-Chloro-5- (methylamino) -2-
(a ta ra-trifluoro-m-
toyl) - (2H) -pyridazinone
3,5-Dinitro-N4.,N4-dipor-
pylsulfanilamide
f- JO
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANQ-NITROGEN PESTICIDES - Continued
Common Name
Oxadiazon (Ronstar)
Oxamyl (Vydate)
Oxythioquinox (Morestan)
Paraquat Bichloride (Gramoxone)
Pebulate (Tillam)
Perfluidone (Destun)
Phenmedipham (Betanal)
Phenothiazine
Pic lor am (Tordon)
Piperalin (Pipron)
Pirimicarb (Pirimor)
Potassium Azide (Kazoe)
Promecarb (Carbamult)
Chemical Name
2-tert-Butyl-U-(2,U-dichloro-
5-isopropoxyphenyl) delta-
1,3, U-oxadiazolin-5-one
Methyl N»,N'-dimethyl-N-
[ (methylcarbamoyl) oxy]-l
thiooxamimidate
6-Methyl-2,3-quinoxalinedi-
thiol cyclic-S, S-dithio-
carbonate
1,1'-Dimethyl-a , H'-bi-
pyridilium dichloride
S-Propyl butylethylthio-
carbamate
l,lrl-Trifluoro-N-[2-methyl-
U- (phenylsulf onyl) phenyl ]
methanesulfonamide
Methyl m-hydroxycarbanilate
m-methylcarbanilate
Dibenzo-1,4-thia zine
i»-Amino-3r5f 6-trichloro-
picolinic acid
3-(2-Methylpiperidino)propyl-
3 f4-dichlorobenzoate
2-(Dimethylamino) -5,6-
dimethyl-U-pyrimidinyl
dimethylcarbamate
Potassium azide
m-Cym-5ylmethylcarbamate
257
-------
TABLE X-1 (Continued)
SUBCATE6ORY C - ORGANO-NITROGEN PESTICIDES - Continued
Common Name
Prometon (Pramitol)
Prometryn (Caparol)
Pronamide (Kerb)
Propachlor (Ramrod)
Propanil (Rogue)
Propazine (Milogard)
Propham (IPC)
Propoxur (Baygon)
Pyracarbolid (Sicarol)
Pyrazon (Pyramin)
Siduron (Tupersan)
Simazine (Princep)
Sodium Azide (Smite)
Streptomycin Sulfate (Agri-
Strep)
Chemical Name
2,i»-Bis(isopropylamino) -
6-methoxy-s-triazine
2, 4-Bis (isopropylamino) -
6-(methylthio) -s-triazine
3,5-Dichloro-N-(lr1-dimethyl-
2-propynyl) benzamide
2-Chloro-N-isopropylacetani1ide
3,4-Dichloropropionanilide
2-Chloro-U,6-bis(isopro-
pylamino) -s-triazine
Isopropyl N-phenylcarbamate
o-lsopropoxyphenyl N-methyl-
carbamate
3,i»-Dihydro-6-methyl-N-phenyl-
2H-pyran-5-carboxamide
5-Amino-H-chloro-2-pheny1-
3(2H)-pyridazinone
1-(2-Methylcyclohexyl)-
3-phenylurea
2-Chloro-Ur 5,6-bis(ethyl-
amino) -s-triazine
Sodium Azide
D-Streptaminer 0-2-deoxy-
2- (methylamino) -a-1-gluco-
pyranosyl-(1-2)-0-5-deoxy-
3-C-formyl-a-l-lyxofuranosyl-
(1-U)-N-V-bis(aminoimmo-
methyl-, sulfate (2:3) (salt)
258
-------
TABLE X-1 (Continued)
SUBCATEGORY C - ORGANO-NITROGEN PESTICIDES - Continued
Common Name
Terbacil (Sinbar)
Terbutryn (Igran)
Thanite
Thiabendazole (Mertect)
Thiofanox (DS-156U7)
Thiophanate
Thiophanate Methyl
Thiram (Arasan)
Triallate
Tridemorph (Calixin)
Trifluralin (Treflan)
Triforine (Cela W524)
Vernolate (Vernam)
Chemical Name
3-(tert-Butyl) -5-chlor-6-
methyluracil
2-(tert-Butylamino)-4-(ethyl-
amino) -6- (methylthio) -s-
triazine
Isobornyl thiocyanoacetate
2- (U'-Thiazolyl) benzimidazole
3,3-Dimethyl-l-(methylthio) -
2-butamone 0-[(methylamino)-
carbonyl]oxime
l,2-Bis(3-ethoxycarbonyl-2-
thioureido)benzene
1,2-Bis(3-methoxycarbonyl-2-
thioureido) benzene
Tetramethylthiuram disulfide
S- (2r3f 3-Trichloroallyl) -
diisopropylthiocarbamate
N-Tridecyl-2,6-dimethyl-
morpholine
a,ara-Trifluoro-2,6-dinitro-
N,N-dipropyl-p-toluinin
NrN'-[1-4-Piperazinediyl-bis-
(2,2,2-trichloroethylene)]-
bis(formamide)
S-Propyl NrN-dipropylthio-
carbamate
259
-------
TABLE X-1 (Continued)
SUBCATEGORY D - METALLO-OBGANIC PESTICIDES
Common Name Chemical Name
Cacodylic Acid Dimethylarsinic acid
Calcium Arsenate Calcium arsenate
Cryolite (Kryocide) Sodium Fluoaluminate
Diphenyl Mercury Diphenyl mercury
DSMA Disodium methanearsenate,
hexahydrate
Ethylmercury Chloride (Ceresan) Ethylmercury Chloride
Fentin Acetate (Brestan)
Fentin Hydroxide (Outer)
Lead Arsenate
Maneb
Methanearsonic Acid (MAA)
Methylmercuric Chloride
Methylmercuric Iodide
MSMA (Bueno)
Nabam
Phenylmercuric Acetate
(Common name PMA)
Phenylmercuric Borate
Phenylmercuric Chloride
Triphenyltin acetate
Triphenyltin hydroxide
Acid lead arsenate
Manganous ehtylene-bis-
(dithiocarbamate)
Methly arsonic acid
Methylmercury chloride
Methylmercury ioidide
Monosodium acid methanearsonate
Disodium ethylene bis(dithio-
carbamate)
Phenylmercury acetate
Phenylmercury borate
Phenylmercury chloride
260
-------
TABLE X-1 (Continued)
SUBCATEGORY D - METALLO-ORGANIC PESTICIDES - Continued
Common Name
Phenylmercuric Hydroxide
Phenylmercuric Iodide
Vendex
Zineb
Ziram
NON-CATEGORIZED PESTICIDES
Common Name
Allethrin
Benzyl Benzoate
Biphenyl (Diphenyl)
Chlorophacinone (Rozol)
Coumafuryl (Fumarin)
Dimethyl Phthaiate
Diphacinone
Chemical Name
Phenylmercury hydroxide
Phenylmercury iodide
Hexakis (B,B-dimethyl-
ph en ethyl) -distannoxane
Zinc ethylenebisdithiocarbamate
Zinc dimethyldithiocarbamate
Chemical Name
2-Allyl-4-hydroxy-3-methyl-
2-cyclopenten-l-one ester of
2,2-dimethy1-3-(2-methyl-
propenyl)-cyclopropane-
carboxylic acid
Benzyl benzoate
Biphenyl
2-[(p-Chlorophenyl)phenyl-
acetyl]-l,3-indandione
3-(a-Acetonylfurfuryl)-
H-hydroxycoumarin
Dimethyl Phthalate
2-Diphenylacetyl-l,3-indandione
261
-------
TABLE X-1
NON-CATEGORIZED PESTICIDES -
Common Name
Endothall, Acid
EXD (Herbisan)
Gibberellic Acid
(Continued)
Continued
Methoprene (Altosid)
NAA (Naphthalene Acetic Acid)
Phenylphenol (Dowicide 1)
Piperonyl Butoxide
Propargite (Omite)
Protect
Pyrethrins
Resmethrin (SBP-1382)
Chemical Name
7-Oxabicyclo(2.2.1)heptane-
2,3-dicarboxylie acid
monohydrate
Diethyl dithiobis(thiono-
formate)
Gibb-3-ene-l,10-dicarboxylic
acid,2,Ha,7-trihydroxy-l-
methyl-8-methylene-l, 4a-
lactone
Isopropyl (2F,UE)-11-methoxy-
3,H,11-trimethyl-2,H-
dodecadienoate
1-Naphthalene acetic acid
o-Phenylphe nol
a-[2-(butoxyethoxy)ethoxy ]-
4,5-methylenedioxy-2-
propyltoluene
2-(p-tert-Butylphenoxy)cyclo-
hexy!2-propynyl sulfite
1,8-Naphthalic anhydride
Standarized mixture of
pyrethrins I and II (Mixed
esters of pyrethrolone)
(5-Benzyl-3-furyl)methyl-2,
2-dimethyl-3-(2-methl
propenyl) cyclopropane-
carboxylate (approx. 70%
trans, 30% cis isomers)
262
-------
TABLE X-1 (Continued)
NON-CATEGORIZED PESTICIDES - Continued
Common Name
Rotenone
sodium Phenylphenate (Dowicide
A)
Sulfoxide
Warfarin
Chemical Name
If2,12r12af Tetrahydro-
2-isopropenyl-8,9-dimethoxy-
[1] benzopyrano-[3,U-b]furo
[2r3-b][l] benzopyran-
6 (6aH)one
o-Phenylphenol, sodium salt,
monohydrate
l-Methyl-2-(3,4-methylane-
dioxyphenyl)ethyl
octyl sulfoxide
3-(a-Acetonylbenzyl)-U-
hydroxycoumari n
hydroxycoumarin
263
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SECTION XI
ACKNOWLEDGEMENTS
This report was prepared by the Environmental Protection
Agency on the basis of a comprehensive study of this
industry performed by Roy F. Weston, Inc., under contract
No. 68-01-2932. The original study was conducted and
prepared for the Environmental Protection Agency under the
direction of Project Director James H. Dougherty, P.E., and
Technical Project Manager Jitendra R. Ghia, P.E.
The RFW study was supplemented and updated by Environmental
Science and Engineering, Inc., under the direction of John
D. Crane, P. E.r and the management of Mr. James B. cowart.
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 and Ms. Elizabeth Brunetti.
The study was conducted under the supervision and guidance
of Mr. Joseph S. Vitalis and Mr. George Jett, Project
Officers. The supplemental follow on work was supervised by
Dr. W. Lamar Miller, Senior Technical Advisor.
EGDB project personnel also wish 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 of the EPA Office of General Counsel for his
invaluable input. A special thanks to Dr. Raymond Loehr for
his assistance. Dr. Donald Bloodgood, ES&WQIAC, made a
special effort to assist in the final revision and his
comments were especially valuable.
In addition Effluent Guidelines Development Branch would
like to extend its gratitude to the following individuals
for the input into the development of this document while
serving as members of the EPA working group/steerina
committe which provided detailed review, advice and
assistance:
W. Hunt, Chairman, Effluent Guidelines Division
L. Miller, Senior Technical Advisor, EGD
J. Vitalis, Project Officer, Effluent Guidelines Div.
G. Jett, Project Officer, Effluent Guidelines Div.
M. Strier, Office of Enforcement
D. Davis, Office of Planning and Evaluation
264
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P. Desrosiers, Office of Research and Development
R. Swank, SERL, Athens, GA
H. Trask, HWMD
C. Cook, Analysis and Evaluation
J. Rogers, Office of General Counsel
D. Oestreich, RTF
W. Garrison, SERL, Athens, GA
D. Becker, IERL, Cincinnati, OH
R. Holtje, Office of Toxic Substances
D. Lair, Region IV
P. Pan, Region V
P. Fahrenthold, Region VI
L. Reading, Region VII
L. DuPuis, Economic Analysis Section
G. Zweig, Ph.D., Office of Pesticides
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 Walt Sanders,
Lee Wolfe and Dale Denny, of EPA's Office of Research and
Development, for their technical assistance during this
study.
Acknowledgement and appreciation is extended to Ms. Kay
Starr and Ms. Nancy Zrubek for invaluable support in
coordinating the preparation and reproduction of this
report; to Mr. Norman Asher, Bruno Maier and Tom Tape
(federal interns) for proofreading, etc., to Mr. Eric
Yunker, Ms. Alice Thompson, Ms. Ernestine Christian, Ms.
Laura Cammarota and Ms. Carol Swann of the Effluent
Guidelines Division secretarial staff for their efforts in
the typing of drafts, necessary revision, and final
preparation of the revised Effluent Guidelines Division
development document. Last, but by no means least, many
thanks to the wives and sweethearts of the project personnel
for their patience and understanding during this study.
265
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SECTION XII
BIBLIOGRAPHY
Pesticide Chemicals Industry
Pesticide Handbook - Entoma, Entomological Society
of America, 24th Edition, 1974.
The Pollution Potential in Pesticide Manufacturing:
Pesticide Study Series - 5, Technical Studies
Report (TS-00-72-04), Environmental Protection
Agency, June 1972.
3. "Pesticides '72", Chemical Week, Part 1, June 21,
1972.
4. Pollution Control Technology for Pesticide
Formulators and Packagers, Grant No. R-8015777
Office of Research and Monitoring, Environmental
Protection Agency, 12 June 1974.
5- Development Document for Proposed Effluent
Limitations Guidelines and New Source Performance
Standards for the Ma-jor Organic Products, U.S.
Environmental Protection Agency, EPA 440/1-73/009,
December 1973.
6- "Pollution Control at the Source", Chemical
Engineering, August 6, 1973.
7- "Currents - Technology",Environmental Science and
Technology, Volume 8, No. 10, October 1974.
8. Development Document for Effluent Limitations
Guidelines and Standards of Performance, draft,
Organic Chemicals Industry Phase ii, Environmental
Protection Agency, under contract, number 68-01-
1509, February 1974.
9- The Pesticide Manufacturing Industry - Current
Waste Treatment and Disposal Practices, Water
Pollution Control Research Series (12020 FYE
01/72), U.S. Environmental Protection Agency,
January 1972.
10. Anon., "Activated - Sludge Process Solves Waste
Problem", Chemical Engineering, 68 (2), 1961.
266
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11. Biological Treatment of Chlorophenolic Wastes,
Water Pollution Control Research Series (12130 EGK
06/71), U.S. Environmental Protection Agency, June
1971.
12. Process Design Manual for Upgrading Existing
Wastewater Treatment Plants, EPA 1974.
13. EPA Internal Memorandum, "Variability in BOD
Concentration from Biological Treatment Plant", To:
Lilliam Regelson, From: Charles Cook, March 1974.
14. Production, Distribution, Use and Environmental
Impact Potential of Selected Pesticides, Midwest
Research Institute Report, Final Report, 25
February 1973, 15 March 1974, Contract No. EQ-311,
Council on Environmental Quality, 1974.
15. Pesticides :Ln the Aquatic Environment,
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16. Metabolism of Pesticides, U.S. Department of
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17. water Quality Criteria, 1972, f5501-00520 National
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18. Sittig, M., Pesticides Production Processes, Noyes
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1967.
19. "Pesticides and Pesticide Containers", Federal
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20. Chlorinated Insecticides, Volumes I and II,
Technology and Application, G.T. Brooks, The
University of Sussex, Brighton, Sussex, England,
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21. Guidelines For The Disposal of Small Quantities of
Unused Pesticides - Part A and Part B. Contract
68-01-0098, Project 15090 HGR, by Midwest Research
Institute, Kansas City, Mo. for EPA., Cincinnati,
Ohio, Published by Midwest Research Institute,
Kansas City, Mo. 64110.
267
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22. "Interaction of Heavy Metals and Biological Sewage
Treatment Process", Environmental Health Series,
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of Health, Education, and Welfare, May 1965.
23. Robeck, G. G. et al., "Effectiveness of Water
Treatment Process in Pesticide Removal," J. AWWA
57:181 (1965)
24. Cohen, J. M. et al., "Effect of Fish Poisons on
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25. Blecker, H. G. & T. M. Nichols, Capital and
Operating Costs of Pollution Control Eguipment
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26. Goodrich, P. R. & E. J. Monke, "Insecticide
Adsorption on Activated Carbon," Transactions of
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57. 60 (1970) .
27. Horsey, J., "Choosing a Solvent for Insecticide
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28. Winchester, J. M., and D. Yeo, "Future Development
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29. Sigworth, E. A., "Identification and Removal of
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30. Aly, O. M. & S. D. Faust, "Removal of 2.4-
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31. Coley, Gene and C. H. Stutz, "Treatment of
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32. Cristol, Stanley, "The Kinetics of the Alkaline
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268
-------
33. Eisenhauer, Hugh R., "Oxidation of Phenolic Wastes,
Part I: Oxidation with Hydrogen Peroxide and a
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34. Hill, D. W. and P. L. McCarthy, "Anaerobic
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35. Loos, et al., "Phenoxyacetate Herbicide
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36 Mills, R. E. "Development of Design Criteria for
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37 Smith, Robert, "Cost of Conventional and Advanced
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38. Faust, S. D. and Aly, O. M., "Water Pollution by
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39. Nicholson, H. P., "Insecticide Pollution of Water
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40. Huang, J. C.r "Organic Pesticides in the Aquatic
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41. Weibel, S. R. Wiedner, R. B. Cohen, J. M., and
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42. Kennedy, M. V., Stojanovic, B. J. and Shuman, F.
L. , "Chemical and Thermal Methods for Disposal of
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43. cowart, R. P., Boner, F. L. and Epps, E. A., Jr.,
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Pesticides," Bull, of Environ. Contarn. S Toxicol, 6
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44. von Rumker, R., Guest, H. R., and Upholt, W. M.,
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269
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45. Huang, J. c.r & Liao, C. S.r "Adsorption of
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46. Newland, Leo. W., Gordan Chester, and Garland B.
Lee, "Degradation of Gamma-BBC in Simulated Lake
Impoundments as Affected by Aeration," J WPCF 41
(5) , R-174-88 (1969) .
47. Working Group on Pesticides, Washington, D. c.,
"Ground Disposal of Pesticides: The Problem and
Criteria for Guidelines," March 1970.
48. Sweeny, K. H. et al.. Development of Field Applied
DDT, EPA-660/ 2-74-036, May 1974. "
49. Moore, F. L., Groenier, w. s., and Bayless, W. E.,
"Recovery of Toxic Metals from Industrial Effluent
Solutions by Solvent Extraction," Ecology and
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50. Posey, F. A., and Palko, A. A., "Electrochemical
Recovery of Reducible Inorganic Pollutants from
Aqueous Streams," Ecology and Analysis of Trace
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1973, Oak Ridge National Laboratory, ORNL-NSF-EAT-
6.
51. Carnes, R. A., and Oberacker, D. A., "Pesticides
Incineration," News of Environmental Research in
Cincinnati. April 5, 1976.U. s. EPA.
52. Farmer, W. J.r and Letey, j., "Volatilization
Losses of Pesticides from Soils," Environmental
Protection Technology Series. EPA 660/2-74-054
August 1974. '
53. Sanborn, J. R., "The Fate of Select Pesticides in
the Aquatic Environmental," Ecological Research
Series. EPA-660/3-74-025, December 19747"
54. Gomoa, H. M., and Faust, s. D., "Chemical
Hydrolysis and Oxidation of Parathion and Paraoxon
on Aquatic Environments," Fate of Organic
Pesticides in the Aguatic Environment. Advances in
Chemistry Series III. ACS, Washington, D. c.,
xy /o •
270
-------
55 Schacht, R. A., "Pesticides in the Illinois Waters
of Lake Michigan," Ecological Research Series, EPA-
660/3-74-002, January 1974.
56. Bunker, R. C., LeCroy, W. C., and Katchur, D.,
Plant Responses of Natural Vegetation to Selected
Herbicides at Aberdeen Proving Ground, Maryland,
Department of the Army, Fort Detrick, Frederick,
Maryland, September 1971.
57. Miranowski, J. A., Ernest U. F. W., and Cummings,
F. H., "Crop Insurance and Information Services to
Control Use of Pesticides," Socioeconomic
Environmental Studies Series, EPA-600/5-74-018,
September 1974.
58. MRI (Midwest Research Institute) Report, Wastewater
Treatment Technology Documentation for Endrin,
Manufacture and Formulation, Final Report Feb. 6,
1976; Contract No. 68-01-3521, MRI Project No.
4127-C.
59. MRI Report, Wastewater Treatment Technology
Documentation for Aldrin/Dieldrin, Manufacture and
Formulation, Final Report Feb. 6, 1976; Contract
No. 68-01-3524, MRI Project No. 4127-C.
60. MRI Report, Wastewater Treatment Technology
Documentation for DDT, Manufacture and Formulation;
Final Report Feb. 6, 1976; Contract No. 68-01-3524;
MRI Project No. 4127-C.
61. MRI Report, Wastewater Treatment Technology
Documentation For Toxaphene, Manufacture and
Formulation, Final Report Feb. 6, 1976; Contract
No. 68-01-3524, MRI Project No. 4127-C.
62. Pesticide Usage and its Impact on the Aguatic
Environmental in the Southeast. Environmental
Protection Agency, Office of water Programs,
Pesticides Study Series - 8 (September 1972)
EP2.25:8.
63. The Movement and Impact of Pesticides Used in
Forest Management on the Aquatic Environment in the
Northeast. EPA, Office of Water Programs, P. S.
Series - 9, (July 1972) EP2.25:8.
64. Patterns of Pesticides Use and Reduction in Use as
Related to Social and Economic Factors. EPA,
271
-------
Office of Water Programs, P. S. Series - 10, (Sept.
1972) - EP2.25:8.
65. Laws and Institutional Mechanisms Controlling
Release of Pesticides into the Environment. EPA,
Office of Water Programs, P._ S. Series - 11, (Sept.
1972) - EP2.25:8.
66. The Use of Pesticides in Suburban Homes and Gardens
and Their Impact on the Aguatic Environment. EPA,
Office of Water Programs, P. S^ Series - 2, (May
1972) EP2.25:8.
67. The Use of Pesticides for Rangeland and Sagebrush
Control. EPA, Office of Water Programs, P._ S^
Series - 3, (May 1972) EP2.25:8.
68. Development of a Case Study of the Total Effect of
Pesticides on the Environment, Non-Irrigated
Croplands of the Midwest. EPA, Office of Water
Programs, P^ S. Series - £, (June 1972) EP2.25:8.
69. The Effects of Agricultural Pesticides in the
Aguatic Environment, Irrigated Croplands, San
Joaguin Valley. EPA, Office of Water Programs, P_._
S._ Series - 6, (June 1972) EP2.25:8.
70. Van Valkenburg, J. W.r "The Physical and Colloidal
Chemical Aspects of Pesticidal Formulations
Research: A Challenge," Pesticidal Formulations
Research, Advances in Chemistry Series 86, ACS,
Washington, D. C. 1969.
71. Hemmett, R. B. Jr., 6 Faust, S. D., "Biodegradation
Kinetics of 2, H-dichlorophenoxyacetic Acid by
Aguatic Microorganism," Residue Review, 29, 1969.
72. Kennedy, D. C.r "Treatment of Effluent from
Manufacture of Chlorinated Pesticides with a
Synthetic, Polymeric Adsorbent, Amberlite XAD-U,"
Envir. Sci. & Tech., Vol. 7, No. 2V Feb. 1973.
73. Mackay, D., S Wolkoff, A. W., "Rate of Evaporation
of Low-Solubility Contaminants from Water Bodies to
Atmosphere", Envir. Sci. & Tech., Vol. 7, No. 7,
July 1973.
74. Ingols, R. S., Gaffney, P. E. 5 Stevenson, P. C.,
"Biological Activity of Halophenols," J. WPCF, 38,
No. 4, April 1966.
272
-------
75 Leigh, G. M.r "Degradation of Selected Chlorinated
Hydrocarbon Insecticides," J. WPCF, 41, 11, Part 2,
November 1969.
76. Gomma, H. M., Suffet, I. H., & Faus't, S. D.,
"Kinetics of Hydrolysis of Diazinon and Diazoxon,"
Residue Review 29, 1969.
77. "Pesticides '72", Part II, Chemical Week, July 26,
1972.
78 The Effects of Pesticides on Fish and Wildlife;
uTs.Department of the Interior, Fish and Wildlife
Service, Circular 226, Washington, D.C.; August
1965.
79 proceeding of the National Conference on Protective
Clothing and safety Equipment for Pesticide
Workers; Federal Working Group on Pesticide
Management, Washington, D.C.; June 1972.
80. "New Weapons Against Insects", Chemical and
Engineering News; July 28, 1975.
81. EPA Journal, June 1975, Vol I, No. VI, "Controlling
Pesticide Use Research Program Reorganized."
82. Farm Chemicals Handbook, 1973; Gorden L. Berg,
Editor!Meister Publishing Co., Willoughby, Ohxo
44094.
83 Guide to the Chemicals Used in Crop Protection,
Publication 1093, 4th Edition, by Hubert Martin,
Research Branch, Canada Department of Agriculture,
Ottawa, Canada; April 1961.
84. Acceptable Common Names and Chemical Names for the
Ingredient Statement on Pesticides Labels, 2nd
Edition; Pesticide Regulation Division, U.S.
Environmental Protection Agency, Washington, D.C.
20460; June 1972.
85. Pesticide Manual, 3rd Edition; Hubert Martin,
Editor;British Crop Protection council Worcester,
England, UK, November 1972.
86 Phenolic Waste Reuse by. Diatomite Filtration, Water
Pollution Control Research Series 12980 EZF 09/70,
U.S. Department of the Interior, Federal Water
273
-------
Quality Administration, Washington, D.C.; September
I -7 / \) •
87 * Investigation of Means for Controlled Self-
Destruction of Pesticides. Water Pollution Control
Research Series 88.89.90. ELO 06/70; U.S.
Environmental Protection Agency, Water Quality
Office, Washington, B.C. 20460; June 1970.
91• Chemistry and Toxicology of Agricultural Chemicals.
a Four-year Summary Report, 1965 through 1968; Food
Protection and Toxicology Center, University of
California, Davis; December 1968.
92. "Monitoring with Carbon Analyzers" Environmental
Science and Technology. Vol. 8, No. 10, October
1974, pp. 898 to 902.
93. "Initial Scientific and Minieconomic Review of
Aldicarb", Substitute Chemicals Program, U.S. EPA,
Office of Pesticide Programs, Washington, D.C.
20460; May 1975.
94. "Initial Scientific and Minieconomic Review of
Bromacil", Substitute Chemicals Program. U.S. EPA,
Office of Pesticide Programs, Washington, D.C.
20460; March 1975.
95. "Initial Scientific and Minieconomic Review of
Captan", Substitute chemicals Program, U.S. EPA,
Office of Pesticide Programs, Washington, D.C.
20460; April 1975.
96. "Intitial Scientific and Minieconomic Review of
Malathion", Substitute Chemicals Program, U.S. EPA,
Office of Pesticide Programs, Washington, D.C.
20460; March 1975.
97• "Initial Scientific and Minieconomic Review of
Methly Parathion", Substitute Chemicals Program:
U.S. EPA, Office of Pesticide Programs, Washington,
D.C. 10460; February 1975.
98. "Initital Scientific and Minieconomics Review of
Parathion", Substitute Chemicals Program, U.S. EPA,
Office of Pesticide Programs, Washington, D.C.
20460; January 1975.
99. "The Fate of Select Pesticides in the Aquatic
Environment", Ecological Research Series, EPA
274
-------
660/3-74-025; U.S. EPA, NERC, Office of Research
and Development, Corvallis, Oregon 97330; December
1974.
100. "Microbial Degradation and Accumulation of
Pesticides in Aquatic Systems", Ecological Research
Series, EPA 660/3-75-007; U.S. EPA, NERC,
Corvallis, Oregon 97330; March 1975.
101. "Toxicity of Selected Pesticides to the Bay Mussel
(Mytilus Edulis)", Ecological Research Series, EPA
660/3-75-016; U.S. EPA, NERC, Office of Research
and Development, Corvallis, Oregon 97330; May 1975.
102. "Methods for Acute Toxicity Tests with Fish, Macro-
invertebrates, and Amphibians", Ecological Research
Series, EPA-660/3-75-009; U.S. EPA, NERC, Office of
Research and Development, Corvallis, Oregon 97330;
April 1975.
103. "The Effect of Mirex and Carbofuram on Estuarine
Microorganisms", Ecological Research Series, EPA-
660/3-75-024, U.S. EPA, NERC, Office of Research
and Development, Corvallis, Oregon 97330; June
1975.
104. "Chlorinated Hydrocarbons in the Lake Ontario
Ecosystem (IFYGL)", Ecological Research Series,
EPA-660/3-75-022; U.S. EPA, NERC, Office of
Research and Development, Corvallis, Oregon 97330;
June 1975.
105. "A Conceptual Model for the Movement of Pesticides
Through the Environment", Ecological Research
Series, EPA-660/3-75-022, U.S. EPA, NERC, Office of
Research and Development, Corvallis, Oregon 97330;
June 1975.
106. "A Conceptual Model for the Movement of Pesticides
Through the Environment", Ecological Research
Series, EPA-660/3-74-024, U.S. EPA, NERC, Office of
Research and Development, Corvallis, Oregon 97330;
December 1974.
107. "An Analysis of the Dynamics of DDT in Marine
Sediments", Ecological Research Series, EPA-660/3-
75-013, U.S. EPA, NERC, Office of Research and
Development, Corvallis, Oregon 97330; May 1975.
275
-------
112.
108. "Rapid Detection System for Organophosphates and
Carbonate Insecticides in Water", Environmental
Protection Technology Series, EPA-R2-72-010,uTsT
EPA, Office of Research and Monitoring, Washington,
D.C. 20460, August 1972.
109. "Liquid Chromatography of Carbonate Pesticides",
Environmental Protection Technology Series, EPA-R-
2-72-079, U.S. EPA, NERC, Office of Research and
Monitoring, Corvallis, Oregon 97330; October 1972.
110. "Recondition and Reuse of Organically Contaminated
Waste Sodium Chloride Brines", Environmental
Protection Technology Series, EPA-R-2-73-200,uTsT
EPA, Office of Research and Monitoring, Washington,
D.C. 20460; May 1973.
111. "Current Practices in G.C.-M.S. Analysis of
Organics in Water", Environmental Protection
Technology Series, EPA-R2-73-277, U.S. EPA^NERC,
Office of Research and Development, Corvallis,
Oregon 97330; August 1973.
Environmental Applications of Advanced Instrumental
Analyses; Assistance Projects, FY'73, Environmental
Protection Technology Series, EPA-660/2-74-078,
U.S. EPA, NERC, Office of Research and Development,
Corvallis, Oregon 97330; August 1974.
"Promising Technologies for Treatment of Hazardous
Wastes", Environmental Protection Technology
Series, EPA-670/2-74-088, U.S. EPA, NERC, Office of
Research and Development, Corvallis, Oregon 97330;
November 1974.
114. "State-of-the-Art for the Inorganic Chemicals
Industry: Inorganic Pesticides"; Environmental
Protection Technology Series, EPA-600/2-74-099a,
U.S. EPA, Office of Research and Development,
Washington, D.C. 20460; March 1975.
115. "Use of Soil Parameters for Describing Pesticide
Movement Through Soils", Environmental Protection
Technology Series, EPA-660/2-75-009, U.S EPA, NERC,
Office of Research and Devleopment, Corvallis,
Oregon 97330; May 1975.
116. "Radiation Treatment of High Strength Chlorinated
Hydrocarbon Wastes", Environmental Protection
Technology Series, EPA-660/2-75-017; uTs^EPA7
113.
276
-------
NERC, Office of Research and Development,
Corvallis, Oregon 97330; June 1975.
117. "The Occurrence of Organohalides in Chlorinated
Drinking Waters", Environmental Monitoring Series,
EPA-670/4/-74-008; U.S. EPA, NERC, Office of
Research and Development, Cincinnati, Ohio 45268;
November 1974.
118. "Pesticide Transport and Runoff Model for
Agricultural Lands", Environmental Protection
Technology Series, EPA-660/2-74-013; U.S. EPA,
Office of Research and Development, Washington,
D.C., 20460; December 1973.
119. "Herbicide Runoff from Four Coastal Plain Soil
Types", Environmental Protection Technology Series,
EPA-660/2-74-017; U.S. EPA, NERC, Office of
Research and Development, corvallis, Oregon 97330;
April 1974.
120. "Pesticides Movement from Cropland Into Lake Erie",
Environmental Protection Technology Series, EPA-
660/2-74-032; U.S EPA, Office of Research and
Development, Washington, D.C. 20460; April 1974.
121. Report on Insecticides in Lake Michigan, Prepared
by the Pesticide Committee of the Lake Michigan
Enforcement Conference, U.S. Department of the
Interior, Great Lakes Region, Chicago, Illinois
60605; November 1968.
122. The Effects of Pesticides on Water Resource
Development, a Series of Papers Presented at the
Joint Meeting of the Arkansas - White Basins Inter-
Agency Committee and the Southeast Basins Inter-
Agency Committee, New Orleans, Louisiana; April 22,
1970.
123. Treatability of Wastewater From Organic Chemicals
and Plastics Manufacturing - Experience and
Concepts, by R.A. Conway, et.al., Research and
Development Department, Chemicals and Plastics,
Union Carbide Corporation, South Charleston, West
Virginia; September 1974.
124. water Pollution Control Program by Ciba-Geigy
Corporation, St. Gabriel, Louisana, Reguest for
Discharge Standards under Corps of Engineers
277
-------
Discharge Permit Application No. 172 D-000696, June
20/ 1973.
125. Environmental Impact of S-Triazine Compounds
Discharged to the Mississippi River bv Ciba-Geigy
Corporation, St. Gabriel, LouisHnU February 1,
•i. y I j •
126' Evaluation of Biological Treatment Feasibility for
a Wastewater from Herbicide Production for ciba^"
Geigy Corporation, St. Gabriel, ' Louisiana; AWARE,
Associated Water and Air Resources Engineers, Inc.-
Nashville, Tennessee; March 1973.
127. Effects of Toxaphene Contaminated on Estuarine
Ecology bY Robert J. Reimold, et.al.; University of
???5?lac *arine Institute, Sapelo Island, Georgia
31327; September 1973.
128. Toxaphene Interactions in Estuarine Ecosystems,
1973-1974 by Robert J. Reimold;University of
?????lao Marine Institute, Sapelo Island, Georgia
32327; September 1974.
129. Report to Hercules Incorporated on The Effects of
Toxaphene on Sewage Treatment, Project No. 70-OT^
75; Black, Crow and Eidsness, Inc., Houston, Texas;
September 1971.
130. Report on Evaluation of Industrial Waste Discharges
at VeIsicol Chemical Company, Memphis, Tennessee;
U.S EPA, NFIC, Denver, Colorado; April 1972~:
131. Potential Contamination of the Hydrologic
Environment From the Pesticide "Wa'ste Dumps in
Hardeman County, Tennessee^ U.S. GeoTHgTcar~S^Fvey~
Water Resources Division; August 1967.
132. "Biological Investigation of Stauffer Chemical
Company (Organic Plant)", by Bill Peltier, et.al •
Trip report on January 24-30, 1975 investigation,'
U.S. EPA, NERC, Athens, Georgia
133. Report of the Secretary's Commission on Pesticides
and Their Relationship to Environmental~He^Tth7
Part 1^ and II; U.S. Department of Health, Education
and Welfare, Washington, D.C.; December 1969.
134. Summation of Conditions and Investigations for the
Complete Combustion of Organic Pesticides,^PA NoT
278
-------
5-03-3516A, U.S. EPA, NERC, Office of Research and
Development, Cincinnati, Ohio 45268; February
1975.
115 Thermal Degradation of Military Standard Pesticj^e
135' JsSntiS^ TRW "Report NO. 24768-6018-RV-OO;
Department of the Army, U.S. Army Medical Research
and Development Command, Washington, B.C. 20;ns,
December 1974.
136. Incineration of DDT Solutions, Report S-1276, CGI
Environmental-systems Division, Prepared for the
Sierra Army Depot, Herlon, California 96113,
January 1974.
137 A Study of Pesticide Disposal in a Sewage Sludge
In^Jn^at£r7""by~"v^rsar Incorporated, Prepared by
U S. EPA, Contract No. 68-01-1587, Research and
Development Office, Washington, D.C. 20460.
138 Final Draft, Report on the Destruction of grange"
Herbicide by Incineration prepared by the Marquardt
Company for U.S. Air Force, Environmental Health
Laboratory, Kelly Air Force Base, Texas; February
1974.
139 incineration of Chlorinated Hydrocarbons with.
Recovery of ~HC1 at E.I. duPont deNeumours &
Company, Louisville, Kentucky; Reprint from
American Society of Mechanical Engineers, Research
Committee on Industrial Wastes.
1UO Recommended Methods of Reduction, Neutralization,
Recoverv7 or Disposal of Hazardous Waste, vol.. Vj_
National pliposal Site Candidate Waste Stream
constituent Profiel Reports - Pesticides |nd
Cvanide Compounds; by TRW Systems for U.S. EPA,
NERC,— office of Research and Development,
Cincinnati, Ohio 45268; August 1973.
iui "Specific ion Mass spectrometric Detection for Gas
Chromatographic Pesticides Analysis", ^nvironmental
Protection Technology series, EPA-660/2-74-004,
uTsT EPA, Office of Research and Development,
Washington, D.C. 20460; January 1974.
142 "A Tissue Enzyme Assey for Chlorinated Hydrocarbon
Insecticides", Environmental Protection Technology
Series, EPA-660/2-73-027; U.S. EPA, Office of
279
-------
Research and Development, Washington, D.C. 20460-
May 1974. *
1U3- Final Report of the Task Force on Excess Chemicals.
U.S. EPAr Washington, D.C. 20460; June 29, 1973~
144. Program For the Management of Hazardous Wastes by
Battelle for U.S. Environmental Protection Agency,
Office of Solid Waste Management Programs,
Washington, D.C. 20460; July 1973.
145> Catalytic Conversion of Hazardous and Toxic
Chemcials, Quarterly Reports by Alvin Weiss and
W.L. Kramich under EPA Grant R-802-857-01; January
I -7 / O •
146. "Development of Field Applied DDT", Water Pollution
Control Research Series, U.S. EPA, officeof
Research and Development, Washington, D.C. 20460-
May 1972.
147. "Development of Treatment Process for Chlorinated
Hydrocarbon Pesticide Manufacturing and Processing
Wastes", Water Pollution Control Research Series,
U.S. EPA, Office of Reserach and Development,
Washington, D.C. 20460; July 1973.
148. Program Report on Chemical Fixation of Hazardous
Waste and M£ Pollution-Abatement Sludges, J.L7
Mahlock for U.S. EPA, Washington, D.C. 20460-
January 1975. *
149. "Practical Removal of Toxicity by Adsorption" Paper
Presented at the 30th Annual Purdue Industrial
Wastewater Conference by F.E. Bernardin, Jr., and
E.M. Froelich, Calgon Corporation, Pittsburg,
Pennsylvania; May 8-9, 1975.
150. Effect of Pesticides in Water, A Report to the
States U.S. Environmental Protection Agency, Office
of Research and Development, Washington, D.C.
20460.
151• Inventory and Environmental Effects of Industrial
and Governmental Pesticide Uses, by Midwest
Research Institute for U.S. EPA, Office of Water
Programs, Washington, D.C. 20460; April 1972.
152. "Wastewater Treatment Technology Documentation for
Aldrin/Dieldrin, Endrin, DDT and Toxaphene", MRI
280
-------
Report for U.S. EPA, Office of Water Planning and
Standards, Washington, D.C. 20460; July 1975.
153 Wastewater Management Review No.I, MRI Report,
"Aldrin/Dieldrin", for U.S. EPA, Hazardous and
Toxic Substances Regulation Office, Washington,
D.C. 20460; May 1974.
154. Wastewater Management Review No. 2, MRI Report,
"Endrin", for U.S. EPA, Hazardous and Toxic
Substances Regulation Office, Washington, D.C.
20460; May 1974.
155. Wastewater Management Review No. 3, MRI Report,
"Toxaphene", for U.S. EPA, Hazardous and Toxic
Substances Regulation Office, Washington, D.C.
20460; May 1974.
156. Federal Register, "Proposed Toxic Pollutant
Effluent Standards", Vol. 38, No. 247, U.S.
Environmental Protection Agency, Washington, D.C.
20460; December 27, 1973.
157. Hager and Rizzo; Removal of Toxic Organics from
Wastewater by_ Adsorption with Granular Carbon, A
Paper Presented at EPA, Technical Transfer Session,
Athens, Georgia; April 19, 1974.
158. Pesticide Formulation, Edited by J. Wade Van
Walkenburg; Marcel Dekker, Inc., New York, N.Y.;
1973.
159. Kennedy, M.F.; "Chemical and Thermal Aspects of
Pesticides Disposal", Journal of Environmental
Quality, l(l):63-65; January 1972.
160. Robeck, G.G., et.al., "Effectiveness of Water
Treatment Processes in Pesticide Removal", Journal
of_ American Water Works Association, 57(2) :181-189;
February 1965.
161. Buescher, C.A., et.al., "Chemical Oxidation of
Selected Organic Pesticides", Journal of the Water
Pollution Control Federation, 36(8) :1, 005-1014;
August 1964.
162. Lambden, A.E. and D.H. Sharp; "Treatment of
Effluent from the Manufacture of Weedkillers and
Pesticides", Manufacturing Chemist, 31:198-201; May
1970.
281
-------
Proceedings; 23rd Industrial Waste Conference,
Purdue University, 1968; p. 1,166-1, 177^
176. Weiss, C.M., "Organic Pesticides and Water
Pollution", Public Works, 95 (12) : 84-87; December
1964.
177' Practical Removal of Toxicity by Adsorption by F E
Bernardin and E.M. Froelich for presentation 'at
30th Annual Purdue Industrial Conference, May 8-9,
-L _/ / 3 •
178> Degradation of_ Pesticides by_ Algae, EPA No 600/3-
76-022, U.S. EPA, Environmental Reserach
Laboratory, Athens, Georgia, March 1976.
179' Herbicide Toxicity in Mangroves, EPA No. 600/3-76-
004, U.S. Environmental Research Laboratory, Gulf
Breeze, Florida 32561.
180' £ Quantitative Method for Toxaphene by GC-C1-M
Specific Ion Monitoring, EPA No. 600/4-76-0107 U~~S~
EPA, Environmental Research Laboratory, Athens!
Georgia 30601.
181' Assessment of Industrial Hazardous Waste Practices-
Organic Chemicals^ Pesticides indExplosives
Industries, for EPA Solid Waste Management Program,
Washington, D.C. 20460, 1976.
182• N-Nitrosamine Formation from Atrazine, by N Lee
Wolfe ^et.al., for EPA, Bulletin of Environmental
Contamination and Toxicology, Vol. 15, No. 3
1976,p 342. '
183. Column Chromatographic Separation of
Polychlorinated Biphenyls fr^£Chlorinated
Hydrocarbon Pesticides, and thel? Subse^Iint—Ga~s
Chromatographic Quantisation iHTerms ~of
Derivatives. Bulletin of ~ EnvironmentaT
Contamination and Toxicology, Vol. 7, No. 6, 1972,
p. 338.
184. Radiation Treatment of High Strength Chlorinated
Hydrocarbon Wastes, EPA-660/2-75-017, Office—oT
Research and Development, Corvallis, Oregon 97330
June 1975.
-------
185. Comments on Development Document for Guidelines for
the Pesticides Industry, from A.W. Garrison, EPA,
Athens, Georgia 30601, August 2, 1976.
186. Matsumura, Fumio, et.al.; Environmental Technology
of Pesticides, Academic Press, New York, N.Y, 1972.
187. Hague, Rizwanul and V.H. Freed; Environmental
Dynamic of Pesticides, Plenum Press, New York,
N.Y., 1975.
188. Chemical Derivatization of Hydroxyatrazine for Gas
Chroma to'graphic Analysis, Journal of Agricultural
and Food Chemistry Vol. 23, No. 3, 1975, pp 430.
189. Chlorinated Hydrocarbon Pesticide Removal from
WastewaterT by D.R. Marks, Velsicol Chemical
Corporation Report No. MP-001-09, July 1976.
190. Sampling Program to Obtain Information on the
Treatability of_ Wastewaters by Activated Carbon
Adsorption Systems, for EPA, Effluent Guidelines
Development Branch, Washington, D.C. by Arthur D.
Little, Inc., Interim Report, May 1976.
191. Identification of: Organic Compounds in
Qrganophosphorus Pesticide Manufacturing
Wastewater, Quarterly Report No. 1, Midwest
Research Institute for Dr. Arthur W. Garrison,
January 5, 1976.
192. Identification of Organic Compounds in
Qrganophosphorus Pesticide Manufacturing
Wastewater, Quarterly Report No. 2, Midwest
Research Institute for Dr. Arthur W. Garrison, June
23, 1976.
193. Recondition and Reuse o_f Organically Contaminated
Waste Sodium Chloride Brines, EPA R2-73-200, Office
of Research and Monitoring, Washington, D.C.
20460, May 1973.
194. Federal Efforts to Protect the Public form Cancer-
Causing Chemicals are not very Effective, Report to
the Congress by the Comptroller General of the
United States, June 16.1976.
195. Chemical and Photochemical Transformation of
Selected Pesticides in Aquatic Systems, by N. Lee
283
-------
Wolfe, et.al., for EPA Environmental Research
Laboratory, Athens, Georgia 30601.
196. Burges, H.D. and Hussey, N.W.; Microbial Control of
Insects and Mites, Academic Press, New York, 1971.
197. Gunther, F.A., "Reported Solubilities of 738
Pesticide Chemicals in Water," Residue Review, Vol.
20; pp 1 - 148, Springer - Verlag, New York, N.Y.,
1968.
198. Bailey, G.W. and White, J.L., "Herbicides a
Compilation of their Physical, Chemcial and
Biological Properties," Residue Review, Vol. 1, pp
97 - 122, Springer - Verlag, New York, N.Y., 1965.
199. Leshendok, Thomas V.; Hazardous Waste Management
Facilities in the United States: EPA 530-SW-146.2;
U.S. Environmental Protection Agency, 401 M St.
S.W., Washington, D.C. 20460; February, 1976.
200' Preliminary Assessment of Suspected Carcinogens in
Drinking Water, Report to Congress; U.S.
Environmental Protection Agency, office of Toxic
Substances, 401 M St. S.W., Washington, D.C.
20460, December, 1975.
201• An Ecological Study of Hexachlorobenz ene (HCB),
U.S. Environmental Protection Agency, Office of
Toxic Substances, 401 M St. S.W., Washington, D.C.
20460; April, 1976.
202. Mason, Thomas J. Ph.D, et. al.; Atlas of Cancer
Mortality for U.S. Counties: 1950-1969; DREW Pub.
No. (NIH) 75-780; U.S. Department of Health,
Education and Welfare, National Institute of
Health, Bethesda, Maryland 20014.
203- Federal Register, "Pesticides - EPA Proposal on
Disposal and Storage", Part I, vol. 39, No. 200,
U.S. Environmental Protection Agency, Washington,
D.C. 20460; October 15, 1974.
Federal Register, "Effective Hazardous Waste
Management (Non-Radioactive)", Part II, Vol. 41,
No. 161, U.S. Environmental Protection Agency,
Washington, D.C. 20460; August 18, 1976, pp 35050-
jDU j1•
284
-------
205. Federal Register. "Pesticides and Pesticides
Container^ P^rt IV, Vol. 39, No. 85, U.S.
Environmental Protection Agency, Washington, D.c.
20460; May 1, 1974, pp 15236-15241.
206 The Federal Insecticide, Fungicide, and Rodenticide
Act,—as Amended", Public. Law 94_-140, U.S.
EnvTronmentalProtection Agency, Washington, D.C.
20460; November 28, 1975.
207 "Report of the Advisory Committee on 2, 4, 5-T to
the Administrator of the Environmental Protection
Agency", by Children's Hospital Medical Center, May
7, 1971.
208 "Report of the Mercury Advisory Committee of the
Environmental Protection Agency to the
Administrator", by Medical College of Ohio at
Toledo, July 6, 1971.
209. "Report of the Amitrole Advisory Committee", March
12, 1971.
210 "Report of the Mirex Advisory Committee", to
William D. Ruckelshaus, Administrator,
Environmental Protection Agency, Revised March 1,
1972.
211 "Information About Hazardous Waste Management
Facilities", EPA/530/SW-145, July 1975.
212 "Report of the Aldrin/Dieldrin Advisory Committee",
to William D. Ruckelshaus, Administrator,
Environmental Protection Agency, March 28, 1972.
213. "Substitute Chemical Program - Initial Scientific
Review of PCNB", Office of Pesticide Programs, U.S.
Environmental Protection Agency, EPA/540/1-75-016,
April 1976.
214. "Report of the Lindane Advisory Committee", July
12, 1970.
215. Substitute Chemical Program - "Initial Scientific
andMinieconomic Review of Carbofuran", Office of
Pesticide Programs, U.S. Environmental Protection
Agency, EPA/540/1-76-009; July, 1976.
216. Substitute Chemical Program - "Initial Scientific
Review of MSMA/DSMA", Office of Pesticide Programs,
285
-------
U.S. Environmental Protection Agency, EPA/540/1 -75-
020; December, 1975.
217. Substitute Chemical Program - "Initial Scientific
and Minieconomic Review of Monuron", Office of
Pesticide Programs, U.S. Environmental Protection
Agency, EPA/540/1-75-028; November, 1975,
218. Substitute Chemical Program - "Initial Scientific
Review of Cacodylic Acid", Office of Pesticide
Programs, U.S. Environmental Protection Aaenrv
EPA/540/1-75-021; December, 1975. ^C^°n A?ency'
219. "Chemical and Photochemical Transformation of
Selected Pesticides in Aquatic Systems", by N. Lee
Wolfe, et. al.r Environmental Process Branch, u S
Protection Agency, Athens, Georgia
J
220. federal Register, "Guidelines for Registering
Pesticides in United States", Part II, Vol. 40, No.
1^3, U.S. Environmental Protection Agency,
o?Songt°n' °-C* 20a6°; j™e 25, 1975, pp 26802-
26 928 .
221. Federal Register, Effluent Guidelines and
standards. General Provisions, Part II, Vol 39
No. 24, pp 4531 to 4533, February 4, 1974.
222. young, David R. , et.al.; "DDT in Sediments and
Organisms around Southern California Outfalls"-
journal-Water Pollution Control Federation. Vol '
48, No. 8, August, 1976. -
General References
GR-1 AICHE Environmental Division; "Industrial Process
Design for Pollution Control," Volume 4; October,
GR-2 Allen, E.E. ; "How to Combat Control Valve Noise »
Chemical Engineering Progress. Vol. 71 NO 8-
August, 1975; pp. 43-557 ' " '
GR-3 Jf J5^an ^*>lic Health Association; Standard
Metho.ds for Examination of Water and Waste Water'
13th Edition; APHA, Washington, D.c7 20036- 1971
286
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GR-4 Barnard, J.L.; "Treatment Cost Relationships for
Industrial Waste Treatment,« Ph.D. Dissertation,
Vanderbilt University; 1971.
GR-5 Bennett, H., editor; Concise chemical and Technical
Dictionary; F.A.I.C. Chemical Publishing Company,
Inc., New York, New York; 1962.
GR-6 Blecker, H.G., and Cadman, T.w.; Capital and
Operating Costs of Pollution Control Equipment
Modules, Volume I - User Guide; EPA-R5-73-023a; EPA
Office of Research and Development, Washington,
D.C. 20460; July 1973.
GR-7 Blecker, H.G., and Nichols, T.M.; Capital and
Operating Costs of Pollution Control Equipment
Modules, Volume II - Data Manual; EPA-R5-73-023b;
EPA Office of Research and Development, Washington,
D.C. 20U60; July, 1973.
GR-8 Bruce, R.D., and Werchan, R.E.; "Noise Control in
the Petroleum and Chemical Industries," Chemical
Engineering Progress, Vol. 71, No. 8; August, 1975;
pp. 56-59.
GR-9 Chaffin, C.M.; "Wastewater Stabilization Ponds at
Texas Eastman Company."
GR-10 Chemical Coagulation/Mixed Media Filtration of
Aerated Lagoon Effluent, EPA-660/2-75-025;
Environmental Protection Technology Series,
National Environmental Research Center, Office of
Research and Development, U.S. EPA, Corvallis,
Oregon 97330.
GR-11 Chemical Engineering, August 6, 1973; "Pollution
Control at the Source."
GR-12 Chemical Engineering, 68 (2), 1961; "Activated-
Sludge Process Solvents Waste Problem."
GR-13 Chemical Week, May 9, 1973; "Making Hard-to-treat
Chemical Wastes Evaporate."
GR-14 Cheremisinoff, P.N., and Feller, S.M.; "Wastewater
Solids Separation," Pollution Engineering.
GR-15 Control of Hazardous Material Spills, Proceedings
of the 1972 National Conference on Control of
Hazardous Material Spills, Sponsored by the U.S.
287
-------
Environmental Protection Agency at the Universitv
of Texas, March 1972.
GR-16 Cook, C.; "Variability in BOD Concentration from
Biological Treatment Plants," EPA internal
memorandum; March, 1974.
GR-17 Davis, K.E., and Funk, R.J.; "Deep Well Disposal of
Industrial Waste," Industrial Waste; January-
February, 1975. y
GR-18 Dean, J.A., editor; Lange's Handbook of Chemistry.
11th Edition; McGraw-Hill Book Company. New York,
New York; 1973.
GR-19 Eckenfelder, W.W., Jr.; Water Quality Engineering
for Practicing Engineers: Barnes and Noble, Inc.,
New York, New York; 1970.
GR-20 Eckenfelder, W.W., Jr.; "Development of Operator
Training Materials," Environmental Science Services
Corp., Stamford, Conn.; August, 1968.
GR~21 Environmental Science and Technology. Vol. 8, No.
10, October, 1974; "Currents-Technology."
GR-22 Fassell, W.M.; "Sludge Disposal at a Profit?", a
report presented at the National Conference on
Municipal Sludge Management, Pittsburgh
Pennsylvania; June, 1974.
GR~23 Guidelines for Chemical Plants in the Prevention
Control and Reporting of Spills; Manufacturing
Chemists Association, Inc., Washington, D.C. 1972.
GR-24 Hauser, E.A., Colloidal Phenomena. 1st Edition,
McGraw-Hill Book Company, New York, New York; 1939.
GR-25 Iowa State University Department of Industrial
Engineering and Engineering Research Institute,
"Estimating Staff and Cost Factors for Small
Wastewater Treatment Plants Less Than 1 MGDf» Parts
I and II; EPA Grant No. 5P2-WP-195-0452; June,
i y * 3 *
GR-26 Iowa State University Department of Industrial
Engineering and Engineering Research Institute,
"Staffing Guidelines for Conventional Wastewater
Treatment Plants Less Than 1 MGD," EPA Grant No
5P2-WP-195-0452; June, 1973.
-------
GR-27 Juddr S.H.; "Noise Abatement in Exisj:j-ncf
Refineries," Chemical Engineering Progress, Vol.
71, No. 8; August, 1975; pp. 31-42.
GR-28 Kent, J.A., editor; Reigells Industria-1 Chemistry,
7th Edition; Reinhold Publishing Corporation, New
York; 1974.
GR-29 Kirk-Othmer; Encyclopedia of Chemical Technology,
2nd Edition; Tnterscience Publishers Division, John
Wiley and Sons, Inc.
GR-30 Kozlorowski, B., and Kucharski, J. ; Industrial
Waste Disposal; Pergamon Press, New York; 1972.
GR-31 Lindner, G. and K. Nyberg; Environmental
Engineering, A Chemical Engineering Discipline; D.
Reidel Publishing Company, Boston, Massachusetts
02116, 1973.
GR-32 Liptak, B.G., editor; Environmental Engineers'
Handbook, Volume Ij_ Water Pollution; Chi 1 ton Book
Company, Radnor, Pa.; 1974.
GR-33 Marshall, G.R. and E.J. Middlebrook; Intermittent
Sand Filtration to Upgrade Existing Wastewater
Treatment Facilities, PR JEW 115-2; Utah Water
Research Laboratory, College of Engineering, Utah
State University, Logan, Utah 84322; February,
1974.
GR-34 Martin, J.D., Dutcher, V.D., Frieze, T.R., Tapp,
M., and Davis, E.M. ; "Waste Stabilization
Experiences at Union Carbide, Sea drift, Texas
Plant."
GR-35 McDermott, G.N. ; Industrial Spill Control and
Pollution Incident Prevention, J. Water Pollution
Control Federation, 43 (8) 1629 (1971).
GR-36 Minear, R.A., and Patterson, J.W.; Wastewater.
Treatment Technology, 2nd Edition; State ot
Illinois Institute for Environmental Quality;
January, 1973.
GR-37 National Environmental Research Center; "Evaluation
of Hazardous Waste Emplacement in Mined Openings;"
NERC Contract No. 68-03-0470; September, 1974.
289
-------
GR-38
Nemerow, N.L.; Liquid Waste of Industry - Theories
Practices and Treatment- Addition-Wesley PuTbishinq
Company, Reading, Massachusetts; 1971.
GR-39 Novak, S.M.; "Biological Waste Stabilization Ponds
at Exxon Company, U.S.A. Baytown Refinery and Exxon
Chemical Company, U.S.A. Chemical Plant (Divisions
of Exxon Corporation) Baytown, Texas."
GR-40 Oswald, W.J., and Ramani, R.; "The Fate of Algae in
Receiving Waters," a paper submitted to the
Conference on Ponds as a Wastewater Treatment
Alternative, University of Texas, Austin; July,
GR-41 Otakie, G.F.; A Guide to the Selection of Cost-
^fnnnly- ga-stewater Treatment Systems: FPA-43079-
75-002, Technical Report. U.S. EPA, Office of Water
Program Operations, Washington, B.C. 20460.
GR-42 Parker, C.L.; Estimating the Cost of Wastewater
Treatment Ponds; Pollution Engineering, November,
GR-43 Parker, D.S.; "Performance of Alternative Algae
Removal Systems," a report submitted to the
Conference on Ponds as a Wastewater Treatment
Alternative, University of Texas, Austin; July,
GR-44 Parker, W.P.; Wastewater Systems Engineering.
Prentice-Hall, inc., Englewood Cliffs, New Jersey,
GR-45 Perry,^J.H., et. al.; Chemical Engineers' Handbook.
5th Edition; McGraw-Hill Book Company,
New York: 1973.
GR-46 Public Law 92-500, 92nd Congress, S.2770; October
to, 1972.
GR-47 Quirk, T.P.; "Application of Computerized Analysis
to Comparative Costs of Sludge Dewatering by Vacuum
Filtration and Centrifugation," Proc. 23rd
^n?oStria- Wast-e Conference. Purdue University^"
1968; pp. 69-709.
GR-48 Riley, B.T., Jr.; The Relationship Between
Temperature and the Design and Operation of
290
-------
Biological Waste Treatment Plants, submitted to the
Effluent Guidelines Division, EPA; April, 1975.
GR-49 Rose, A., and Rose, E.; The Condensed Chemical
Dictionary, 6th Edition; Reinhold Publishina
Corporation, New York; 1961.
GR-50 Rudolfs, W.; Industrial Wastes, Their Disposal and
Treatment; Reinhold Publishing Corporation, New
York; 1953.
GR-51 Sax, N.I.; Dangerous Properties of Industrial
Material, 4th Edition; Van Nostrand Reinhold
Company, New York; 1975.
GR-52 seabrook, B.L.; Cost of Wastewater Treatment by.
Land Application?" EPA-430/9-75-003, Technical
P^rt; U.S. EPA, Office of Water Program
Operations, Washington, D.C. 20460.
GR-53 Shreve, R.N.; Chemical Process Industries, Third
Edition; McGraw-Hill, New York; 1967.
GR-54 spill Prevention Technigues for Hazardous Polluting
Substances,OHM 7102001; U.S. Environmental
Protection Agency, Washington, D.C. 20460;
February, 1971.
GR-55 Stecher, P.G., editor; The Merck Index, An
Encyclopedia of Chemicals and Drugs, 8th Edition;
Merck and Company, Inc., Rahway, New Jersey; 1968.
GR-56 Stevens, J.I., "The Roles of Spillage, Leakage and
Venting in Industrial Pollution Control", Presented
at Second Annual Environmental Engineering and
Science Conference, University of Louisville,
April, 1972.
GK-57 Supplement A 8. B - Detailed Record of Data Base for
"Draft Development Document for Interim Final
Effluent Limitations, Guidelines and Standards of
Performance for the Miscellaneous Chemicals
Manufacturing Point Source Category", U.S. EPA,
Washington, D.C. 20460, February, 1975.
GR-58 Swanson, C.L.; "Unit Process Operating and
Maintenance Costs for Conventional Waste Treatment
Plants;" FWQA, Cincinnati, Ohio; June, 1968.
291
-------
GR-59 U.S. Department of Health, Education, and welfare-
"Interaction of Heavy Metals and Biological Sewage
Treatment Processes," Environmental Health Series-
HEW Office of Water Supply and Pollution Control'
Washington, D.C. ; May, 1965.
GR-60 U.S. Department of the Interior; "Cost of Clean
Water," Industrial Waste Profile No. _3; Dept. of
Int. GWQA, Washington, D.C.; November, 1967.
GR-61 U.S. EPA; Process Design Manual for Upgrading
Existing Waste Water Treatment Plants. U.S EPA
Technology Transfer: EPA, Washington, D.C. 204 61F
October, 1974. '
GR-62 U.S. EPA; "Monitoring Industrial Waste Water," U.S.
|£A Technology Transfer: EPA, Washington, 57c7
20460; August, 1973.
GR-63 U.S. EPA; "Methods for Chemical Analysis of Water
and Wastes," U.S. EPA Technology Transfer: EPA
625/6-74-003; Washington, D.C. 20460; 1974.
GR-64 U.S. EPA; "Handbook for Analytical Quality Control
in Water and Waste Water Laboratories," U.S. EPA
Technology Transfer: EPA, Washington, D.C. 204607
June, 1972.
GR-65 U.S. EPA; "Process Design Manual for Phosphorus
Removal," U.S. EPA Technology Transfer; EPA,
Washington, D.C. 20460; October, 19777
GR-66 U.S. EPA; "Process Design Manual for Suspended
Solids Removal," U.S. EPfl Technology Transfer; EPA
' Washin
-------
GR-70 U.S. EPA; Effluent Limitations Guidelines and
Standards of Performance, Metal Finishing Industry,
Draft Development Document; EPA 440/1-75/040 and
EPA 440/1-75/040a; EPA Office of Air and Water
Programs, Effluent Guidelines Division, Washington,
D.C. 20460; April, 1975.
GR-71 U.S. EPA; Development Document for Effluent
Limitations Guidelines and Standards of Performance
-—organic Cheiricals Industry; EPA 440/1-74/009a;
EPA Office of Air and Water Programs, Effluent
Guidelines Division, Washington, D.C. 20460;
April, 1974.
GR-72 U.S. EPA; Draft Development Document for Effluent
Limitations Guidelines and Standards of Performance
-SteamSupply and Noncontact Cooling Water
Industries; EPA Office of Air and Water Programs,
Effluent Guidelines Division, Washington, D.C.
20460; October, 1974.
GR-73 U.S. EPA; Draft Development Document for Effluent
Limitations Guidelines and Standards of Performance
-Organic Chemicals Industry, Phase II Prepared by
Roy F. Weston, Inc. under EPA Contract No. 68-01-
1509; EPA Office of Air and Water Programs,
Effluent Guidelines Division, Washington, D.C.
20460; February, 1974.
GR-74 U.S. EPA; Evaluation of Land Application Systems,
Technical Bulletin; EPA 430/9-75-001; EPA,
Washington, D.C. 20460; March, 1975.
GR-75 U.S. EPA; "Projects in the Industrial Pollution
Control Division," Environmental Protection
Technology Series; EPA 600/2-75-001; EPA,
Washington, D.C. 20460; December, 1974.
GR-76 U.S. EPA; Wastewater sampling Methodologies and
Flow Measurement Techniques; EPA 907/9-74-005; EPA
Surveillance and Analysis, Region VII, Technical
Support Branch; June, 1974.
GR-77 U.S. EPA; A Primer on Waste Water Treatment; EPA
Water Quality office; 1971.
GR-78 U.S. EPA; Compilation of Municipal and Industrial
Injection Wells in the United States; EPA 520/9-74-
020; Vol. I and II; EPA, Washington, D.C. 20460;
1974.
293
-------
GR-79 U.S. EPA; "Upgrading Lagoons," U.S. EPA Technology
Transfer: EPA, Washington, D.C. 20460; August,
I y / j«
GR-80 U.S. EPA; "Nitrification and Denitrification
Facilities," U.S. EPA Technology Transfer: August,
1973.
GR-81 U.S. EPA; "Physical-chemical Nitrogen Removal,"
u"s» SPA Technology Transfer; EPA, Washington, D.C.
20460; July, 1974.
GR-82 U.S. EPA; "Physical-Chemical Wastewater Treatment
Plant Design," U.S. EPA Technology Transfer; EPA,
Washington, D.C. 20460; August, 1973.
GR-83 U.S. EPA; "Oxygen Activated Sludge Wastewater
Treatment Systems, Design Criteria and Operating
Experience," U.S. EPA Technology Transfer; EPA,
Washington, D.C. 20460; August, 1973.
GR-84 U.S. EPA; Wastewater Filtration Design
Considerations; U.S. EPA Technology Transfer; EPA,
Washington, D.C. 20460; July, 1974.
GR-85 U.S. EPA; "Flow Equalization," U.S. EPA Technology
Transfer; EPA, Washington, D.C. 20460; May, 1974.
GR-86 U.S. EPA; "Procedural Manual for Evaluating the
Performance of Wastewater Treatment Plants," u.s.
EPA Technology Transfer; EPA, Washington, D.C.
20460.
GR-87 U.S. EPA; Supplement to Development Document for
Effluent Limitations, Guidelines and New Source
Performance Standards for the Corn Milling
Subcategory, Grain Processing, EPA, office of Air
and Water Programs, Effluent Guidelines Division,
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GR-88 U.S. EPA; Pretreatment of Pollutants Introduced
Into Publicly Owned Treatment Works; EPA Office of
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GR-89 U.S. Government Printing Office; Standard
Industrial Classification Manual; Government
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294
-------
GR-90 U.S. EPA; Tertiary Treatment of Combined Domestic
and Industrial Wastes, EPA-R2-73-236, EPA,
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GR-91 Wang, Lawrence K.; Environmental Engineering
glossary (Draft) Calspan Corporation, Environmental
Systems Division, Buffalo, New York 14221, 1974.
GR-92 Water Quality Criteria 1972, EPA-R-73-033, National
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GR_93 weast, R.r editor; CRC Handbook of Chemistry and
Physics, 54th Edition; CRC Press, Cleveland, Ohio
44128; 1973-1974.
GR-94 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.
GR-95 APHA, ASCE, AWWA, and WPCF, Glossary of_ Water and
Wastewater Control Engineering, American Society of
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GR-96 organic Compounds, Identified in Drinking Water in
the United States; Health Effects Research
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Cincinnati, Ohio; April 1, 1976.
295
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SECTION XIII
GLOSSARY
C. Pesticide Chemicals Industry
Active Ingredient. The element or compound on which a
particular pesticide is based to perform its specified
function. The active ingredient makes up only a small
percentage of the final product which consists of binders,
fillers, diluents, etc.
Adjurant. A material which enhances the action of another
material.
Aerosols. Gaseous suspensions of minute particles of a
liquid or solid.
Algicide. Chemical agent used to destroy or control algae.
Alkaline Hydrolysis. A process whereby wastes are
detoxified by extended heat treatment in an alkaline medium.
Generally used in the organo-phosphorus pesticide industry.
Amination. The preparation of amines which are derived from
ammonia by replacement of one or more hydrogens or organic
radicals.
Attractants. Chemical agents which dry or attract insects
or other pests to them.
Boiler Blowdown. Wastewater resulting from purging of solid
and waste materials from the boiler system. A solids build
up in concentration as a result of water evaporation (steam
generation) in the boiler.
Broad Spectrum. A wide-range when referring to a pesticide;
it means the effectiveness covers a wide-range of pests.
Chlorination. A chemical proces where chlorine is
introduced into a chemical species by substitution or
addition.
Contact Insecticide. Insecticide which requires direct
contact with the insect to be affective.
Contract Disposal. Disposal of waste products through an
oustide party for a fee.
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Decanting Operations. Process whereby heavy (light) liquid
fractions are drained from a reactor or vessel allowing the
lighter (heavier) liquid layer to remain.
Defoliants. A category of chemical agents- which when
sprayed on plants causes the leaves to fall off prematurely.
Desiccants. Chemical used as a drying agent. Substances
which have such a great affinity for water that it will
abstract it from a great many fluid materials.
Detoxi f icati on. A process to remove or neutralize
components in a waste stream which inhibit or stop
biological growth.
Dust. Dry, solid powder. When applied to pesticide
production implies a dry, powder form product.
Emulsifiable Concentration. Pesticide in the concentrate
liquid form which when added to another liquid forms a
stable colloidal discharge form application.
Formulators. 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.
Fumigant. A chemical compound which acts in the gaseous
state to destroy insects and their larva and other pests.
Fungicides. A category of chemical agents used to destroy
fungi.
Granular. For a grainy texture or composition.
Halogenated-Organic Pesticides. A category of pesticides
which uses halogenated (primarily chlorine) organic
compounds as the active ingredients.
Herbicide. Category of chemical agents used to destroy or
control undesirable plant life such as weeds.
Insecticide, chemical agent used to destroy insects.
LD50. Abbreviation for lethal dose 50 - a dose of
substances which is fatal to 50% of the test animals.
Metallo-Organic Pesticides. A class of organic pesticides
containing one or more metal or metalloid atoms in the
structure.
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Nemataude. A chemical agent used to kill plant - parasitic
nematodes (i.e., unsegmented worms).
Noncontact Wastewater. Wastewater which does not come in
direct contact with process materials.
Non-Process Water. Waters which do not come in contact with
the product, or by-products such as cooling water, boiler
blowdown, etc.
Oleum. A mixture of 100 percent sulfuric acid and sulfur
trioxide.
Operations and Maintenance. Costs required to operate and
maintain pollution abatement equipment including labor,
material, insurance, taxes, solid waste disposal, etc.
Organic Pesticides. Carbon-containing substances used as
pesticides, excluding metallo-organic compounds.
Organo-Nitrogen Pesticides. A cateqory of pesticides which
uses nitrogenous compounds as the active ingredients.
Orqano-Phosphorus Pesticides. A category of pesticides
which uses phosphate or phosphorus compounds as the active
ingredients.
Packagers. 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. Pesticides includes
herbicides, insecticides, fungicides, etc., and each type of
pesticide is normally specific to the pest species it is
meant to control.
Plant Visitation. Part of data collection phase of the
study involving a visit to a pesticide production facility.
Prilled. To have been formed into pellet-sized crystals or
spherical particles.
Process Water. All waters that come in direct contact with
the raw materials and intermediate products.
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Rodenticides. Category of chemical agents which are used to
kill and destroy rodents, i.e., rats and mice.
Solution. A single phase, homogeneous liquid that is a
mixture in which the compounds are uniformly distributed.
Stripper. A device in which relatively volatile components
are removed from a mixture by distillation or by passage of
stream through the mixture.
Total Pesticides. The sum of all pesticides manufactured at
each facility covered in this development document,
including any pesticides registered with the Agency whether
or not those materials are intended for interstate commerce.
Wet Air Pollution Control. The technique of air pollution
abatement utilizing water as an absorptive media.
General Definitions
Abatement.
pollution.
The measures taken to reduce or eliminate
Absorption. A process in which one material (the absorbent)
takes up and retains another (the absorbate) with the
formation of a homogeneous mixture having the attributes of
a solution. Chemical reaction may accompany or follow
absorption.
Acclimation. The ability of an organism to adapt to changes
in its immediate environment.
Acid. A substance which dissolves in water with the
formation of hydrogen ions.
Acid Solution.
A solution with a pH of less than 7.00 in
which the activity of the hydrogen ion is greater than the
activity of the hydroxyl ion.
Acidity. The capacity of a wastewater for neutralizing a
base. It is normally associated with the presence of carbon
dioxide, mineral and organic acids and salts of strong acids
or weak bases. It is reported as equivalent of CaCO!3
because many times it is not known just what acids are
present.
Acidulate. To make somewhat acidic.
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Act. The Federal Water Pollution Control Act Amendments of
1972, Public Law 92-500.
Activated Carbon. Carbon which is treated by high-
temperature heating with steam or carbon dioxide producing
an internal porous particle structure.
Activated Sludge Process. A process which removes the
organic matter from sewage by saturating it with air and
biologically active sludge. The recycle "activated"
microoganisms are able to remove both the soluble and
colloidal organic material from the wastewater.
Adsorption. An advanced method of treating wastes in which
a material removes organic matter not necessarily responsive
to clarification or biological treatment by adherence on the
surface of solid bodies.
Adsorption Isotherm. A plot used in evaluating the
effectiveness of activated carbon treatment by showing the
amount of impurity adsorbed versus the amount remaining.
They are determined at a constant temperature by varying the
amount of carbon used or the concentration of the impurity
in contact with the carbon.
Advance Waste Treatment. Any treatment method or process
employed following biological treatment to increase the
removal of pollution load, to remove substances that may be
deleterious to receiving waters or the environment or to
produce a high-guality effluent suitable for reuse in any
specific manner or for discharge under critical conditions.
The term tertiary treatment is commonly used to denote
advanced waste treatment methods.
Aeration. (1) The bringing about of intimate contact
between air and a liquid by one of the following methods:
spraying the liquid in the air, bubbling air through the
liquid, or agitation of the liquid to promote surface
absorption of air. (2) The process or state of being
supplied or impregnated with air; in waste treatment, a
process in which liquid from the primary clarifier is mixed
with compressed air and with biologically active sludge.
Aeration Period. (1) The theoretical time, usually
expressed in hours, that the mixed liquor is subjected to
aeration in an aeration tank undergoing activated-sludge
treatment. It is equal to the volume of the tank divided by
the volumetric rate of flow of wastes and return sludge.
(2) The theoretical time that liquids are subjected to
aeration.
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Aeration Tank. A vessel for injecting air into the water.
Aerobic. Ability to live, grow, or take place only where
free oxygen is present.
Aerobic Biological Oxidation. Any waste treatment or
process utilizing aerobic organisms, in the presence of air
or oxygen, as agents for reducing the pollution load or
oxygen demand of organic substances in waste.
Aerobic Digestion. A process in which microorganisms obtain
energy by endogenous or auto-oxidation of their cellular
protoplasm. The biologically degradable constituents of
cellular material are slowly oxidized to carbon dioxide,
water and ammonia, with the ammonia being further converted
into nitrates during the process.
Algae. One-celled or many-celled plants which grow in
sunlit waters and which are capable of photosynthesis. They
are a food for fish and small aquatic animals and, like all
plants, put oxygen in the water.
Algae Bloom. Large masses of microscopic and macroscopic
plant life, such as green algae, occurring in bodies of
water.
Algicide. Chemical agent used to destroy or control algae.
Alkali. A water-soluble metallic hydroxide that ionizes
strongly.
Alkalinity. The presence of salts of alkali metals. The
hydroxides, carbonates and bicarbonates of calcium, sodium
and magnesium are common impurities that cause alkalinity.
A quantitative measure of the capacity of liquids or
suspensions to neutralize strong acids or to resist the
establishment of acidic conditions. Alkalinity results from
the presence of bicarbonates, carbonates, hydroxides,
volatile acids, salts and occasionally borates and is
usually expressed in terms of the concentration of calcium
carbonate that would have an equivalent capacity to
neutralize strong acids.
Alum. A hydrated aluminum sulfate or potassium aluminum
sulfate or ammonium aluminum sulfate which is used as a
settling agent. A coagulant.
Ammonia Nitrogen. A gas released by the microbiological
decay of plant and animal proteins. When ammonia nitrogen
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is found in waters, it is indicative of incomplete
treatment.
Ammonia Stripping. A modification of the aeration process
for removing gases in water. Ammonium ions in wastewater
exist in equilibrium with ammonia and hydrogen ions. As pH
increases, the equilibrium shifts to the right, and above pR
9 ammonia may be liberated as a gas by agitating the
wastewater in the presence of air. This is usually done in
a packed tower with an air blower.
Ammonification. The process in which ammonium is liberated
from organic compounds by microoganisms.
Anaerobic. Ability to live, grow, or take place where there
is no air or free oxygen present.
Anaerobic Biological Treatment. Any treatment method or
process utilizing anaerobic or facultative organisms, in the
absence of air, for the purpose of reducing the organic
matter in wastes or organic solids settled out from wastes.
Anaerobic Digestion. Biodegradable materials in primary and
excess activated sludge are stabilized by being oxidized to
carbon dioxide, methane and other inert products. The
primary digester serves mainly to reduce VSS, while the
secondary digester is mainly for solids-liquid separation,
sludge thickening and storage.
Anion. Ion with a negative charge.
Antagonistic Effect. The simultaneous action of separate
agents mutually opposing each other.
Antibiotic. A substance produced by a living organism which
has power to inhibit the multiplication of, or to destroy,
other organisms, especially bacteria.
Aqueous Solution. One containing water or watery in nature.
Aguifer. A geologic formation or stratum that contains
water and transmits it from one point to another in
quantities sufficient to permit economic development
(capable of yielding an appreciable supply of water).
Arithmetic Mean. The arithmetic mean of a number of items
is obtained by adding all the items together and dividing
the total by the number of items. It is frequently called
the average. It is greatly affected by extreme values.
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Autoclave. A heavy vessel with thick walls for conducting
chemical reactions under high pressure. Also an apparatus
using steam under pressure for sterilization.
Azeotrope. A liquid mixture that is characterized by a
constant minimum or maximum boiling point which is lower or
higher than that of any of the components and that distills
without change in composition.
Backwashing. The process of cleaning a rapid sand or
mechanical filter by reversing the flow of water.
Bacteria. Unicellular, plant-like microorganisms, lacking
chlorophyll. Any water supply contaminated by sewage is
certain to contain a bacterial group called "coliform".
Bateria, Coliform Group. A group of bacteria, predominantly
inhabitants of the intestine of man but also found on
vegetation, including all aerobic and facultative anaerobic
gram-negative, non-sporeforming bacilli that ferment lactose
with qas formation. This group includes five tribes of
which" the very great majority are Eschericheae. The
Eschericheae tribe comprises three genera and ten species,
of which Escherichia Coli and Aerobacter Aerogenes are
dominant. The Escherichia Coli are normal inhabitants of
the intestine of man and all vertbrates whereas Aerobacter
Aerogenes normally are found on grain and plants, and only
to a varying degree in the intestine of man and animals.
Formerly referred to as B. Coli, B. Coli group, and Coli-
Aerogenes Group.
Bacterial Growth. All bacteria require food for their
continued life and growth and all are affected by the
conditions of their environment. Like human beings, they
consume food, they respire, they need moisture, they require
heat, and they give off waste products. Their food
requirements are very definite and have been, in general,
already outlined. Without an adequate food supply of the
type the specific organism requires, bacteria will not grow
and multiply at their maximum rate and they will therefore,
not perform their full and complete functions.
NSPS Effluent Limitations. Limitations for new sources
which are based on the application of the Best Available
Demonstrated Control Technology.
Base. A substance that in aqueous solution turns red litmus
blue, furnishes hydroxyl ions and reacts with an acid to
form a salt and water only.
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Batch Process. A process which has an intermittent flow of
raw materials into the process and a resultant intermittent
flow of product from the process.
BAT Effluent Limitations. Limitations for point sources,
other than publicly owned treatment works, which are based
on the application of the Best Available Technoloay
Economically Achievable. These limitations must be achieved
by July 1, 1983.
Benthic. Attached to the bottom of a body of water.
Benthos. Organisms (fauna and flora) that live on the
bottoms of bodies of water.
Bioassay. An assessment which is made by using living
organisms as the sensors.
Biochemical Oxygen Demand (BOD). A measure of the oxygen
required to oxidize the organic material in a sample of
wastewater by natural biological processes under standard
conditions. This test is presently universally accepted as
the yardstick of pollution and is utilized as a means to
determine the degree of treatment in a waste treatment
process. Usually given in mg/1 (or ppm units), meaning
milligrams of oxygen required per liter of wastewater, it
can also be expressed in pounds of total oxygen required per
wastewater or sludge batch. The standard BOD is five days
at 20 degrees C.
Biota. The flora and fauna (plant and animal life) of a
stream or other water body.
Biological Treatment System. A system that uses
microorganisms to remove organic pollutant material from a
wastewater.
Slowdown. Water intentionally discharged from a cooling or
heating system to maintain the dissolved solids
concentration of the circulating water below a specific
critical level. The removal of a portion of any process
flow to maintain the constituents of the flow within desired
levels. Process may be intermittent or continuous. 2) The
water discharged from a boiler or cooling tower to dispose
of accumulated salts.
BOJD5. Biochemical Oxygen Demand (BOD) is the amount of
oxygen required by bacteria while stabilizing decomposable
organic matter under aerobic conditions. The BOD test has
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been developed on the basis of a 5-day incubation period
(i.e. BOD5) .
Boiler Slowdown. Wastewater resulting from purging of solid
^Tndwaste materials from the boiler system. A .solids build
up in concentration as a result of water evaporation (steam
generation) in the boiler.
BPT 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.
Break Point. The point at which impurities first appear in
the effluent of a granular carbon adsorption bed.
Break Point Chlorination. The addition of sufficient
chlorine to destroy or oxidize all substances that creates a
chlorine demand with an excess amount remaining in the free
residual state.
Brine. Water saturated with a salt.
Buffer. A solution containing either a weak acid and its
"salt or a weak base and its salt which thereby resists
changes in acidity or basicity, resists changes in pH.
Carbohydrate. A compound of carbon, hydrogen and oxygen,
usually having hydrogen and oxygen in the proportion of two
to one.
Carbonaceous. Containing or composed of carbon.
Catalyst. A substance which changes the rate of a chemical
reaction but undergoes no permanent chemical change itself.
Cation. The ion in an electrolyte which carries the
positive charge and which migrates toward the cathode under
the influence of a potential difference.
Caustic Soda. In its hydrated form it is called sodium
hydroxide. Soda ash is sodium carbonate.
Cellulose. The fibrous constituent of trees which is the
principal raw material of paper and paperboard. Commonly
thought of as a fibrous material of vegetable origin.
Centrate. The liquid fraction that is separated from the
solids fraction of a slurry through centrifugation.
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Centrifugation. The process of separating heavier materials
from lighter ones through the employment of centrifugal
force.
Centrifuge. An apparatus that rotates at high speed and by
centrifugal force separates substances of different
densities.
Chemical Oxygen Demand (COD) . A measure of oxygen-consumincr
capacity of organic and inorganic matter present in water or
wastewater. It is expressed as the amount of oxygen
consumed from a chemical oxidant in a specific test. It
does not differentiate between stable and unstable organic
matter and thus does not correlate with biochemical oxygen
demand.
Chemical Synthesis. The processes of chemically combining
two or more constituent substances into a single substance.
Chlorination. The application of chlorine to water, sewage
or industrial wastes, generally for the purpose of
disinfection but frequently for accomplishing other
biological or chemical results.
Clarification. Process of removing turbidity and suspended
solids by settling. Chemicals can be added to improve and
speed up the settling process through coagulation.
Clarifier. A basin or tank in which a portion of the
material suspended in a wastewater is settled.
Clays. Aluminum silicates less than 0.002mm (2.0 urn) in
size. Therefore, most clay types can go into colloidal
suspension.
Coagulation. The clumping together of solids to make them
settle out of the sewage faster. Coagulation of solids is
brought about with the use of certain chemicals, such as
lime, alum or polyelectrolytes.
Coagulation and Flocculation. Processes which follow
sequentially.
Coagulation Chemicals. Hydrolyzable divalent and trivalent
metallic ions of aluminum, magnesium, and iron salts. They
include alum (aluminum sulfate), quicklime (calcium oxide) ,
hydrated lime (calcium hydroxide), sulfuric acid, anhydrous
ferric chloride. Lime and acid affect only the solution pH
which in turn causes coagulant precipitation, such as that
of magnesium.
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Coliform. Those bacteria vhich are most abundant in sewage
and in streams containing feces and other bodily waste
discharges. See bacteria, coliform group.
Coliform Organisms. A group of bacteria recognized as
indicators of fecal pollution.
Colloid. A finely divided dispersion of one material (0.01-
10 micron-sized particles), called the "dispersed phase"
(solid), in another material, called the "dispersion medium"
(liquid) .
Color Bodies. Those complex molecules which impart color to
a solution.
Color Units. A solution with the color of unity contains a
mq/lofmetallic platinum (added as potassium
chloroplatinate to distilled water). Color units are
defined against a platinum-cobalt standard and are based, as
are all the other water quality criteria, upon those
analytical methods described in Standard Methods for the
Examination of Water and Vlastewater, 12 ed. , Amer. Public
Health Assoc., N.Y., 1967.
Combined Sewer. One which carries both sewage and storm
water run-off.
Composite Sample. A combination of individual samples of
wastes taken at selected intervals, generally hourly for 24
hours, to minimize the effect of the variations in
individual samples. Individual samples making up the
composite may be of equal volume or be roughly apportioned
to the volume of flow of liquid at the time of sampling.
Composting. The biochemical stabilization of solid wastes
into a humus-like substance by producing and controlling an
optimum environment for the process.
Concentration. The total mass of the suspended or dissolved
particlescontained in a unit volume at a given temperature
and pressure.
Conductivity. A reliable measurement of electrolyte
concentration in a water sample. The conductivity
measurement can be related to the concentration of dissolved
solids and is almost directly proportional to the ionic
concentration of the total electrolytes.
Contact Stabilization. Aerobic digestion.
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an
Contact Process Wastewaters. These are process-generated
wastewaters 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.
Continuous Process. A process which has a constant flow of
raw materials into the process and resultant constant flow
of product from the process.
Contract Disposal. Disposal of waste products through
outside party for a fee.
Crustaceae. These are small animals ranging in size from
0.2 to 0.3 millimeters long which move very rapidly through
the water in search of food. They have recognizable head
and posterior sections. They form a principal source of
food for small fish and are found largely in relativley
fresh natural water.
Cryogenic. Having to do with extremely low temperatures.
Crystallization. The formation of solid particles within a
homogeneous phase. Formation of crystals separates a solute
from a solution and generally leaves impurities behind in
the mother liquid.
Culture. A mass of microorganisms growing in a media.
Curie. 3.7 x 10»o disintegrations per second within a given
quantity of material.
Cyanide. Total cyanide as determined by the test procedure
specified in 40 CFR Part 136 (Federal Register, Vol. 38, no.
199, October 16, 1973).
Cyanide A._ Cyanides amendable to chlorination as described
in "1972 Annual Book of ASTM Standards" 1972: Standard D
2036-72, Method B, p. 553.
Cyclone. A conical shaped vessel for separating either
entrained solids or liquid materials from the carrying air
or vapor. The vessel has a tangential entry nozzle at or
near the largest diameter, with an overhead exit for air or
vapor and a lower exit for the more dense materials.
Decreasing. The process of removing greases and oils from
sewage, waste and sludge.
Demine ralization. The total removal of all ions.
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Denitrification. Bacterial mediated reduction of nitrate to
nitrite'Other bacteria may act on the nitrite reducing it
to ammonia and finally N2 gas. This reduction of nitrate
occurs under anaerobic conditions. The nitrate replaces
oxygen as an electron acceptor during the metabolism of
carbon compounds under anaerobic conditions. A biological
process in which gaseous nitrogen is produced from nitrite
and nitrate. The heterotrophic microogamsms which
participate in this process include pseudomonades,
achromobacters and bacilli.
Derivative. A substance extracted from another body or
substance.
Desorption. The opposite of adsorption. A phenomenon where
an adsorbed molecule leaves the surface of the adsorbent.
Development Document. Development document means the
document entitled "Development Document for Interim Final
Effluent Limitation and Guidelines for the Pesticide
Chemicals Manufacturing Point Source Category".
Diluent. A diluting agent.
Disinfection. The process of killing the larger portion
"(but not Necessarily all) of the harmful and objectionable
microorganisms in or on a medium.
Dissolved Air Flotation. The term "flotation" indicates
something floated on or at the surface of a liquid.
Dissolved air flotation thickening is a process that adds
energy in the form of air bubbles, which become attached to
suspended sludge particles, increasing the buoyancy of the
particles and producing more positive flotation.
Dissolved Oxygen (DO). The oxygen dissolved in sewage,
water or other liquids, usually expressed either in
milligrams per liter or percent of saturation. It is the
test used in BOD determination.
Distillation. The separation, by vaporization, of a liquid
mixtureof~miscible and volatile substances into individual
components, or, in some cases, into a group of components.
The process of raising the temperature of a liguid to the
boiling point and condensing the resultant vapor to liquid
form by cooling. It is used to remove substances from a
liquid or to obtain a pure liquid from one which contains
impurities or which is a mixture of several liquids having
different boiling temperatures. Used in the treatment of
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fermentation products, Yeastr etc., and other wastPS to
remove recoverable products.
Double-effect Evaporators. Double-effect evaporators are
two evaporators in series where the vapors from one are used
to boil liquid m the other.
Dg Units. The units of measurement used are milliarams per
liter (mg/1) and parts per million (ppm), where "mg/1 is
defined as the actual weight of oxygen per liter of water
and ppm is defined as the parts actual weight of oxygen
dissolved in a million parts weight of water, i.e., a pound
of oxygen in a million pounds of water is 1 ppm. For
practical purposes in pollution control work, these two are
used interchangeably; the density of water is so close to 1
g/cm3 that the error is negligible. Similarly, the changes
in volume of oxygen with changes in temperature are
insignificant. This, however, is not true if sensors are
calibrated in percent saturation rather than in mg/1 or ppm.
In that case, both temperature and barometric pressure must
be taken into consideration.
Drift. Entrained water carried from a cooling device bv the
exhaust air.
Dual—Media. A deep-bed filtration system utilizina two
separate and discrete layers of dissimilar media (e.g
anthracite and sand) placed one on top of the other to
perform the filtration function.
Ecology. Tne science of the interrelations between living
organisms and their environment.
Effluent. A liquid which leaves a unit operation or
£££?!+'i Sewage: ,Water °r °ther "^"8, partially or
completely treated or in their natural states, flowing out
of a reservoir basin, treatment plant or any other unit
operation. An influent is the incoming stream.
Elution. (1) The process of washing out, or removing with
the use of a solvent. (2) in an ion exchange process it is
defined as the stripping of adsorbed ions from an ion
exchange resin by passing through the resin solutions
containing other ions in relatively high concentrations.
Elutriation. A process of sludge conditioning whereby the
sludge is washed, either with fresh water or plant effluent
to reduce the sludge alkalinity and fine particles, thus
decreasing the amount of required coagulant in further
treatment steps, or in sludge dewatering.
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Emulsion. Emulsion is a suspension of fine droplets of one
liquid in another.
Entrapment Separator. A device to remove liquid and/or
solids from a gas stream. Energy source is usually derived
from pressure drop to create centrifugal force.
Environment. The sure of all external influences and
conditions affecting the life and the development of an
organism.
Equalization Basin. A holding basin in which variations in
flow and composition of a liquid are averaged Such basins
are used to provide a flow of reasonably uniform volume and
composition to a treatment unit.
Esterification. This generally involves the combination of
an alcohol and an organic acid to produce an ester and water
The reaction is carried out in the liquid phase, with
aqueous sulfuric acid as the catalyst. The use of sulfuric
acid has in the past caused this type of reaction to be
called sulfation.
Eutrophication. The process in which the life-sustaining
aualitv—ofa body of water is lost or diminished (e.g.,
aging or filling in of lakes) . A eutrophic condition is one
in which the water is rich in nutrients but has a seasonal
oxygen deficiency.
Evapotranspiration. The loss of water from the soil both by
evaporation and by transpiration from the plants growing
thereon.
Facultative. Having the power to live under different
conditons (either with or without oxygen).
Facultative Lagoon. A combination of the aerobic and
anaerobic lagoons. It is divided by loading and thermal
stratifications into an aerobic surface and an anaerobic
bottom, therefore the principles of both the aerobic and
anaerobic processes apply.
Fatty Acids. An organic acid obtained by the hydrolysis
T^SnifTcItion) of natural fats and oils, e.g., stearic and
palmitic acids. These acids are monobasic and may or may
not contain some double bonds. They usually contain sixteen
or more carbon atoms.
Fauna. The animal life adapted for living in a specified
environment.
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Fermentation. Oxidative decomposition of complex substances
through the action of enzymes or ferments produced bv
microorganisms. - y
Filter, Trickling. A filter consisting of an artificial bed
of coarse material, such as broken stone, clinkers, slate
slats or brush, over which sewage is distributed and applied
in drops, films for spray, from troughs, drippers, moving
distributors or fixed nozzles. The sewage trickles through
to the underdrains and has the opportunity to form zoogleal
slimes which clarify and oxidize the sewage.
Filter^—Vacuum. A filter consisting of a cylindrical drum
mounted on a horizontal axis and covered with a filter
cloth. The filter revolves with a partial submergence in
the liguid, and a vacuum is maintained under the cloth for
the larger part of each revolution to extract moisture. The
cake is scraped off continuously.
Filtrate. The liquid fraction that is separated from the
solids fraction of a slurry through filtration.
Filtration, Biological. The process of passing a liguid
through a biological filter containing media on the surfaces
of which zoogleal films develop that absorb and adsorb fine
suspended, colloidal and dissolved solids and that release
various biochemical end products.
Flocculants. Those water-soluble organic polyelectrolytes
that are used alone or in conjunction with inorganic
coagulants such as lime, alum or ferric chloride or
coagulant aids to agglomerate solids suspended in aqueous
systems or both, The large dense floes resulting from this
process permit more rapid and more efficient solids-liguid
separations.
Flocculation. The formation of floes. The process step
following the coagulation-precipitation reactions which
consists of bringing together the colloidal particles. it
is the agglomeration by organic polyelectroytes of the
small, slowly settling floes formed during coagulation into
large floes which settle rapidly.
Flora. The plant life characteristic of a region.
Flotation. A method of raising suspended matter to the
surface of the liquid in a tank as scum-by aeration, vacuum,
evolution of gas, chemicals, electrolysis, heat or bacterial
decomposition and the subsequent removal of the scum bv
skimming.
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wactionation (or Fractional Distillation). The separation
of constituents, or group of constituents, of a_liquid
mixture of miscible and volatile substances by vaporization
and recondensing at specific boiling point ranges.
Fungus. A vegetable cellular organism that subsists on
organic material, such as bacteria.
Gland. A device utilizing a soft wear-resistant material
used to minimize leakage between a rotating shaft and the
stationary portion of a vessel such as a pump.
Gland Water. Water used to lubricate a gland. Sometimes
called "packing water."
Grab sample. (1) Instantaneous sampling. (2) A sample
taken at a random place in space and time.
Grease. In sewage, grease includes fats, waxes, free fatty
acids, calcium and magnesium soaps, mineral oils and other
nonfatty materials. The type of solvent to be used for its
extraction should be stated.
Grit Chamber. A small detention chamber or an enlargement
of a sewer designed to reduce the velocity of flow of the
liquid and permit the separation of mineral from organic
solids by differential sedimentation.
Groundwater. The body of water that is retained in the
saturated zone which tends to move by hydraulic gradient to
lower levels.
Hardness. A measure of the capacity of water for
precipitating soap. It is reported as the hardness that
would be produced if a certain amount of CaCO3 were
dissolved in water. More than one ion contributes to water
hardness. The "Glossary of Water and Wastewater Control
Engineering" defines hardness as: A characteristic of water,
imparted by salts of calcium, magnesium, and ion, such as
bicarbonates, carbonates, sulfates, chlorides, and nitrates,
that causes curdling of soap, deposition of scale in
boilers, damage in some industrial processes, and sometimes
objectionable taste. Calcium and magnesium are the most
significant constituents.
Heavy Metals. A general name given for the ions of metallic
elements,such as copper, zinc, iron, chromium, and
aluminum. They are normally removed from a wastewater by
the formation of an insoluble precipitate (usually a
metallic hydroxide).
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A COmpound containing only carbon and
Hydrolysis. A chemical reaction in which water reacts with
another substance to form one or more new substances.
incineration. The combustion (by burning) of organic matter
in wastewater sludge.
Incubate. To maintain cultures, bacteria, or other
microorganisms at the most favorable temperature for
development.
Influent. Any sewage, water or other liquid, either raw or
partly treated, flowing into a reservoir, basin, treatment
plant, or any part thereof. The influent is the stream
entering a unit operation; the effluent is the stream
leaving it.
In-Plant Measures. Technology applied within the
manufacturing process to reduce or eliminate pollutants in
the raw waste water. Sometimes called "internal measures"
or "internal controls".
Ion. An atom or group of atoms possessing an electrical
charge.
Ion Exchange. A reversible interchange of ions between a
liquid and a solid involving no radical change in the
structure of the solid. The solid can be a natural zeolit-
or a synthetic resin, also called polyelectrolyte. Cation
exchange resins exchange their hydrogen ions for metal
cations in the liquid. Anion exchange resins exchange their
hydroxyl ions for anions such as nitrates in the liquid.
When the ion-retaining capacity of the resin is exhausted,
it must be regenerated. Cation resins are regenerated with
acids and anion resins with bases.
Lagoons. An oxidation pond that receives sewage which is
not settled or biologically treated.
L£—S-P-- A lethal concentration for 50% of test animals.
Numerically the same as TLm. A statistical estimate of the
toxicant, such as pesticide concentration, in water
necessary to kill 50% of the test organisms within a
specified time under standardized conditions (usually 24,48
Lfacji To dissolve out by the action of a percolating
liquid, such as water, seeping through a sanitary landfill.
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Lime. Limestone is an accumulation of organic remains
Consisting mostly of calcium carbonate. When burned, it
yields lime which is a solid. The hydrated form of a
chemical lime is calcium hydroxide.
Liquid-liquid-extraction. The process by which the
constituentsofasolution are separated by causing their
unequal distribution between two insoluble liquids.
Maximum Day Limitation. The effluent limitation value equal
to the maximum for one day and is the value to be published
by the EPA in the Federal Register.
Maximum Thirty Day Limitation. The effluent limitation
value for which the average of daily values for thirty
consecutive days shall not exceed and is the value to be
published by the EPA in the Federal Register.
Mean. The arithmetic average of the individual sample
values.
Median. In a statistical array, the value having as many
cases larger in value as cases smaller in value.
Median Lethal Dose (LD50). The dose lethal to 50 percent of
a group of test organisms for a specified period. The dose
material may be ingested or injected.
Median Tolerance Limit (TLm). In toxicological studies, the
concentrationof pollutants at which 50 percent of the test
animals can survive for a specified period of exposure.
Microbial. Of or pertaining to a pathogenic bacterium.
Molecular Weight. The relative weight of a molecule
compared to the weight of an atom of carbon taken as exactly
12.00; the sum of the atomic weights of the atoms in a
molecule.
Mollusk (mollusca). A large animal group including those
formspopularly called shellfish (but not including
crustaceans). All have a soft unsegmented body protected in
most instances by a calcareous shell. Examples are snails,
mussels, clams, and oysters.
Mycelium. The mass of filaments which constitutes the
vegetative body of fungi.
Navigable Waters. Includes all navigable waters of the
UnitedStates; tributaries of navigable waters; interstate
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intrastate lakes, rivers and streams which are
ized by interstate travellers for recreational or other
purposes; intrastate lakes, rivers and streams from which
an? ^ntrast't"13? ^ ^^ and S°ld ±n interSLt? coerce ;
and intrastate lakes, rivers and streams which are utilized
commerce PurPoses * industries in interstate
Neutralization. The restoration of the hydrogen or
hydroxyl ion balance in a solution so that the ionic
concentration of each are equal. Conventionally? ?he
notation »pH» (puissance d* hydrogen) is used to describe thl
hydrogen ion concentration or activity present in a given
solution. For dilute solutions of strong acids?^" acids
solution? C^!iderd t0 ?e «*"Pl«tely ^iLociate (Ionized in
solution) , activity equals concentration.
pw Source. Any facility from which there is or may be a
discharge of pollutants, the construction of which is
commenced after the publication of proposed regulations
S a Standard of Performance under section 306 of
Nitrate. Salt of nitric acid, e.g., sodium nitrate, NaNO3.
Nitrate Nitrogen. The final decomposition product of the
organic nitrogen compounds. Determination of this parameter
indicates the degree of waste treatment. parameter
Higification. Bacterial mediated oxidation of ammonia to
nitrite. Nitrite can be further oxidized to nitrate. These
bacterial8 a™obrUgh\v ab°Ut by °nly * few *Pecial?ze1
nv?rf * sPecies- Nitrosomonias sp. and ^itrococcus sp.
^ WhlCh ±S °xidized to nitrate by
to nitrites and nitrates
5actfria which causes the oxidation of ammonia
Str0cren'. An.inte^ediate stage in the decompo-
. . -
of organic nitrogen to the nitrate form. Tests for
is Sufficient °an determine whet^er the applied treatment
N^trpbacteria. Those bacteria (an autotrophic genus) that
oxidize nitrite nitrogen to nitrate nitrogen.
Nitrogen ^ Cycle. Organic nitrogen in waste is oxidized by
h^^1tnt° a^°ni^ ." °xygen is Prese"t, ammonia is
bacterially oxidized first into nitrite and then into
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nitrate If oxygen is not present, nitrite and nitrate are
bicSrially reduced to nitrogen gas. The second step is
called "denitrif ication."
Nitrogen Fixation. Biological nitrogen fixation is carried
on b?a selected group of bacteria which take up atmospheric
nitrogen and convert it to amine groups or for ammo acid
synthesis.
Nitrosomonas. Bacteria which oxidize ammonia nitrogen into
nitrite nitrogen; an aerobic autotrophic life form.
Non-contact Cooling Water. Water used for cooling that does
n^t come into direct contact with any raw material,
intermediate product, waste product or finished product.
r ------ +^+ PT™MB wastewaters.
manufacturing process which have not come in direct contact
w"h ?he re1c?ants used in the process, ^hese include such
streams as non-contact cooling water, cooling tower
blowdown, boiler blowdown, etc.
Monnutrescible. Incapable of organic decomposition or
decay.
Normal Solution. A solution that contains 1 gm molecular
weight of the dissolved substance divided by the hydrogen
equivalent of the substance (that is, one gram equivalent)
per liter of solution. Thus, a one normal solution of
slilfuric acid (H2SOU, mol. wt. 98) contains (98/2) U9qms of
H2S04 per liter.
NPDES. National Pollution Discharge Elimination System. A
federal program requiring industry to obtain permits to
discharge plant effluents to the nation's water courses.
NSPS. New source Performance Standards. See BADCT.
Nutrient. Any substance assimilated by an organism which
promotes growth and replacement of cellular constituents.
Oleum. A mixture of 100 percent sulfuric acid and sulfur
trioxide.
operations and Maintenance. Costs required to oper ate and
maintain pollution abatement equipment including labor,
material, insurance, taxes, solid waste disposal, etc.
nraanic Loading. In the activated sludge process, the food
toqmicoorganisml (F/M) ratio defined as the amount of
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biodegradable material available to a given amount of
microorganisms per unit of time. amount of
2|mosis. The diffusion of a solvent through a semi permeable
membrane into a more concentrated solution. niPerm .aoie
Oxidation. A process in which an atom or group of atoms
loses electrons; the combination of a substance with oxygen
accompanied with the release of energy. The oxidized alom
usually becomes a positive ion while the oxidizing agent
becomes a negative ion in (chlorination for example) ? g
Oxidation Pond. A man-made lake or body of water in which
^ C0nsumed bv bacteria. it receives an influent
while another species in thl reaction access
'to rl^' ' ^ ?*" time' the ^m oxidation was
to reactions involving hydrogen.
Reaction. Potential (ORP).. A measurement that
°f the oxid--g and reducing
diIso?vP/Vaila^e' The ^antitv of atmospheric oxygen
dissolved in the water of a stream; the" quantity of
gaVailable ^ ^ °M
svedn Designated as DO)
issolved in sewage, water or another liguid and usuallv
expressed in parts per million or percent of saturation"7
gzonation. A water or wastewater treatment process
involving the use of ozone as an oxidation agent? process
P^£ne. That molecular oxygen with three atoms of oxygen
forming each molecule. The third atom of oxygen in elch
o™ °f °ZTe 1S 10°Sely bound and easily released.
Ozone is used sometimes for the disinfection of water bui
more frequently for the oxidation of taste- producing
substances such as phenol, in water and Pfor the
neutralization of odors in gases or air
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Per Million (ppm).. Parts by weight in sewage
lr^ pSriSy^ wiiiht is equal to milligrams per liter
by ?he specif ic^ravity. It should be noted that in
is always understood to imply a
even though in practice a volume may be
measured instead of a weight.
Pathogenic. Disease producing.
Pavloader. A large piece of heavy equipment used for
transporting large volumes at a time.
Percolation. The movement of water benea th th e ground
surface both vertically and horizontally, but above tne
groundwater table.
T>^m^>-rM-ii-v The ability of a substance (soil) to allow
appreciable7' movement of water through it when saturated and
actuated by a hydrostatic pressure.
nH The negative logarithm of the hydrogen ion
concentration V activity in a solution The number 7
indicates neutrality, numbers less than 7 indicate
increasing acidity, and numbers greater than 7 indicate
increasing alkalinity.
Phenol. Class of cyclic organic derivatives with the
chemical formula C£H5OH.
Phosphate. Phosphate ions exist a* ™
phosphoric acid, such as calcium phosphate rock. in
municipal wastewater, it is most frequently present as
ortho phosphate.
Phosphorus Precipitation. The addition of the multivalent
metallic ions otcalcium, iron and aluminum to wastewater to
form insoluble precipitates with phosphorus.
Photosynthesis. The mechanism by which chlorophyll-bearing
plant uSlize light energy to produce carbohydrate and
oxygen from carbon dioxide and water (the reverse of
respiration) .
Physical/Chemical Treatment System. A system that utilizes
physical - (i.e., sedimentation, filtration, centnf ugation,
Sfivafed carbon, reverse osmosis, etc.) and/or chemical
means (i.e., coagulation, oxidation, precipitation, etc.) to
treat wastewaters.
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(1) Collective term for the plants and
PreS6nt in Plankton; contrasts with
Plankton. Collective term for the passively floating or
drifting flora and fauna of a body of water; consists
largely of microscopic organisms.
Point Source . Any discernible, confined and discrete
conveyance, including but not limited to any pipe ditch
channel, tunnel, conduit, well, discrete fissure, container,'
rolling stock, concentrated animal feeding operation, or
vessel or other floating craft, from which pollutants are or
may be discharged.
gollutional Load. A measure of the strength of a wastewater
in terms of its solids or oxygen-demanding characteristics
or other objectionable physical and chemical characteristics
or both or in terms of harm done to receiving waters. The
pollutional load imposed on sewage treatment works is
expressed as equivalent population.
Polvelectrolytes. Synthetic chemicals (polymers) used to
speed up the removal of solids from sewage. These chemicals
cause solids to coagulate or clump together more rapidly
than do chemicals such as alum or lime. They can be anionic
(-charge) , nonionic (+ and -charge) or cationic (^charge—
the most popular) . They are linear or branched organic
polymers. They have high molecular weights and are water-
soluble. Compounds similar to the polyelectrolvte
flocculants include surface-active agents and ion exchange
resins. The former are low molecular weight, water soluble
compounds used to disperse solids in aqueous systems. The
™Her4-are ^igh molecular weight, water-insoluble compounds
used to selectively replace certain ions already present in
water with more desirable or less noxious ions.
Population Equivalent (PE) . An expression of the relative
strength of a waste (usually industrial) in terms of its
equivalent in domestic waste, expressed as the population
that would produce the equivalent domestic waste. A
population equivalent of 160 million persons means the
pollutional effect equivalent to raw sewage from 160 million
persons; 0.17 pounds BOD (the oxygen demand of untreated
wastes from one person) = 1 PE.
Potable Water. Drinking water sufficiently pure for human
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Potash. Potassium compounds used in agriculture and
industry. Potassium carbonate can be obtained from wood
ashes. The mineral potash is usually a muriate. Caustic
potash is its hydrated form.
Preaeratipn . A preparatory treatment of sewage consisting
of aeration to remove gases and add oxygen or to promote the
flotation of grease and aid coagulation.
Precipitation. The phenomenon which occurs when a substance
held in solution passes out of that solution into solid
form. The adjustment of pH can reduce solubility and cause
precipitation. Alum and lime are frequently used chemicals
in sSch operations as water softening or alkalinity
reduction.
Pretreatment. Any wastewater treatment process used to
partially reduce the pollution load before the wastewater is
introduced into a main sewer system or delivered to a
treatment plant for substantial reduction of the pollution
load.
Primary Clarifier. The settling tank into which the
wastewater(sewage) first enters and from which the solids
are removed as raw sludge.
Primary Sludge. Sludge from primary clarifiers.
Primary Treatment. The removal of material that floats or
will settle in sewage by using screens to catch the floating
ob-jects and tanks for the heavy matter to settle in. The
first major treatment and sometimes the only treatment in a
waste-treatment works, usually sedimentation and/or
flocculation and digestion. The removal of a moderate
percentage of suspended matter but little or no colloidal or
dissolved matter. May effect the removal of 30 to 35
percent or more BOD.
Process Wastewater. Any water which, during manufacturing
or processing, comes into direct contact with or results
from the production or use of any raw material, intermediate
product, finished product, by-product, or waste product.
Process Water. Any water (solid, liquid or vapor) which,
during the manufacturing process, comes into direct contact
with any raw material, intermediate product, by-product,
waste product, or finished product.
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Putrefaction. Biological decomposition of organic matter
accompanied by the production of foul-smelling products
associated with anaerobic conditions.
Pyrolysis. The high temperature decomposition of complex
molecules that occurs in the presence of an inert atmosphere
(no oxygen present to support combustion).
Quench. A liquid used for cooling purposes.
Quiesance. Quiet, still, inactive.
Raw Waste Load (RWL) . The quantity (kg) of pollutant beina
discharged in a plant's wastewater. measured in terms of
some common denominator (i.e., kkg of production or m* of
floor area) .
Receiving^ Waters. Rivers, lakes, oceans or other courses
that receive treated or untreated wastewaters.
Recirculation. The refiltration of either all or a portion
of the effluent in a high-rate trickling filter for the
purpose of maintaining a uniform high rate through the
filter. (2) The return of effluent to the incoming flow to
reduce its strength.
Reduction. A process in which an atom (or group of atoms)
gain electrons. Such a process always requires the input of
energy.
Refractory Organics. Organic materials that are only
partially degraded or entirely nonbiodegradable in
biological waste treatment processes. Refractory organics
include detergents, pesticides, color- and odor-causing
agents, tannins, lignins, ethers, olefins, alcohols, amines,
aldehydes, ketones, etc.
Residual Chlorine. The amount of chlorine left in the
treated water that is available to oxidize contaminants if
they enter the stream. It is usually in the form of
hypochlorous acid of hypochlorite ion or of one of the
chloramines. Hypochlorite concentration alone is called
"free chlorine residual" while together with the chloramine
concentration their sum is called "combined chlorine
residual."
Respiration. Biological oxidation within a life form; the
most likely energy source for animals (the reverse of
photosynthesis) .
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Retention Time. Volume of the vessel divided by the flow
rate through the vessel.
Retort. A vessel, commonly a glass bulb with a long neck
bent downward, used for distilling or decomposing substances
by heat.
Reverse Osmosis. The process in which a solution is
pressurized to a degree greater than the osmotic pressure of
the solvent, causing it to pass through a membrane.
Salt. A compound made up of the positive ion of a base and
the negative ion of an acid.
sanitary Landfill. A sanitary landfill is a land disposal
site employing an engineered method of disposing of solid
wastes on land in a manner that minimizes environmental
hazards by spreading the wastes in thin layers, compacting
the solid wastes to the smallest practical volume, and
applying cover material at the end of each operating day.
There are two basic sanitary landfill methods; trench fill
and area or ramp fill. The method chosen is dependent on
many factors such as drainage and type of soil at the
proposed landfill site.
Sanitary Sewers. In a separate system, pipes in a city that
carry only domestic wastewater. The storm water runoff is
handled by a separate system of pipes.
Screening. The removal of relatively coarse, floating and
suspended solids by straining through racks or screens.
Secondary Treatment. The second step in most waste
treatment systems in which bacteria consume the organic part
of the wastes. This is accomplished by bringing the sewage
and bacteria together either in trickling filters or in the
activated sludge process.
Sedimentation, Final. The settling of partly settled,
flocculated or oxidized sewage in a final tank. (The term
settling is preferred).
Sedimentation, Plain. The sedimentation of suspended matter
in a liguid unaided by chemicals or other special means and
without any provision for the decomposition of the deposited
solids in contact with the sewage. (The term plain settling
is preferred).
Seed. To introduce microorganisms into a culture medium.
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Settleable Solids. Suspended solids which will settle out
01 a liquid waste in a given period of time.
+ht*li£q Vel^i^Y' The terminal rate of fall of a particle
as induced by gravity or other external
Sewage. Raw. Untreated sewage.
Sewage, Storm. The liquid flowing in sewers during or
therefrSm. * per±°* °f heavy rainfall and resulting
Sewerage. A comprehensive term which includes facilities
for collecting, pumping, treating, and disposing of sewage-
the sewerage system and the sewage treatment works.
T—T %Partffles with a size distribution of 0. 05mm-0. 002mm
(2.0mm). Silt is high in quartz and feldspar.
Skimming. Removing floating solids (scum) .
sludcfee — Activated. Sludge floe produced in raw or settled
sewage by the growth of zoogleal bacteria and other
organisms in the presence of dissolved oxygen and
accumulated in sufficient concentration by returning the
floe previously formed.
— Agje. The ratio of the weight of volatile solids in
the digester to the weight of volatile solids added per day.
There is a maximum sludge age beyond which no significant
reduction in the concentration of volatile solids will
OGCU1T •
Slu
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Sparger. An air diffuser designed to give large bubbles,
used singly or in combination with mechanical aeration
devices.
Sparging. Heating a liquid by means of live steam entering
through a perforated or nozzled pipe (used, for example, to
coagulate blood solids in meat processing) .
Standard Deviation. The square root of the variance which
describes the variability within the sampling data on the
basis of the deviation of individual sample values from the
mean.
Standard Raw Waste Load (SRWL). The raw waste load which
characterizes a specific subcategory. This is generally
computed by averaging the plant raw waste loads within a
subcategory.
Steam Distillation. Fractionation in which steam introduced
as one of the vapors or in which steam is injected to
provide the heat of the system.
Sterilization. The complete destuction of all living
organisms in or on a medium; heat to 121°C at 5 psig for 15
minutes.
Stillwell. A pipe, chamber, or compartment with
comparatively small inlet or inlets communicating with a
main body of water. Its purpose is to dampen waves or
surges while permitting the water level within the well to
rise and fall with the major fluctuations of the main body
of water. It is used with water-measuring devices to
improve accuracy of measurement.
Stoichiometric. Characterized by being a proportion of
substances exactly right for a specific chemical reaction
with no excess of any reactant or product.
Stripper. A device in which relatively volatile components
are removed from a mixture by distillation or by passage of
steam through the mixture.
Substrate. (1) Reactant portion of any biochemical
reaction, material transformed into a product. (2) Any
substance used as a nutrient by a microorganism. (3) The
liguor in which activated sludge or other material is kept
in suspension.
Sulfate. The final decomposition product of organic sulfur
compounds.
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Supernatant. Floating above or on the surface.
Surge tank. A tank for absorbing and dampening the wavelike
motion of a volume of liquid; an in-process storage tank
that acts as a flow buffer between process tanks.
Suspended Solids. The wastes that will riot sink or settle
in sewage. The quantity of material deposited on a filter
when a liquid is drawn through a Gooch crucible.
Synergistic. An effect which is more than the sum of the
individual contributors.
Synergistic Effect. The simultaneous action of separate
agents which, together, have greater total effect than the
sum of their individual effects.
Tablet. A small, disc-like mass of medicinal powder used as
a dosage form for administering medicine.
Tertiary Treatment. A process to remove practically all
solids and organic matter from wastewater. Granular
activated carbon filtration is a tertiary treatment process.
Phosphate removal by chemical coagulation is also regarded
as a step in tertiary treatment.
Thermal Oxidation. The wet combustion of organic materials
through the application of heat in the presence of oxygen.
TKN (Total K-jeldahl Nitrogen) . Includes ammonia and organic
nitrogen but does not include nitrite and nitrate nitrogen.
The sum of free nitrogen and organic nitrogen in a sample.
TLm'. The concentration that kills 50% of the test organisms
within a specified time span, usually in 96 hours or less.
Most of the available toxicity data are reported as the
median tolerance limit (TLm). This system of reporting has
been misapplied by some who have erroneously inferred that a
TLm value is a safe value, whereas it is merely the level at
which half of the test organisms are killed. In many cases,
the differences are great between TLm concentrations and
concentrations that are low enough to permit reproduction
and growth. LC50 has the same numerical value as TLm.
Total Organic Carbon (TOC). A measure of the amount of
carbon in a sample originating from organic matter only.
The test is run by burning the sample and measuring the
carbon dioxide produced.
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Total Solids. The total amount of solids in a wastewater
both in solution and suspension.
Total Volatile Solids (TVS). The quantity of residue lost
after the ignition of total solids.
Transport Water. Water used to carry insoluble solids.
Trickling Filter. A bed of rocks or stones. The sewage is
trickled over the bed so that bacteria can break down the
organic wastes. The bacteria collect on the stones through
repeated use of the filter.
Trypsinize. To treat with trypsin, a proteolytic enzyme of
the pancreatic juice, capable of converting proteins into
peptone.
Turbidity. A measure of the amount of solids in suspension.
The units of measurement are parts per million (ppm) of
suspended solids or Jackson Candle Units. The Jackson
Candle Unit (JCU) is defined as the turbidity resulting from
1 ppm of fuller's earth (and inert mineral) suspended in
water. The relationship between ppm and JCU depends on
particle size, color, index of refraction; the correlation
between the two is generally not possible. Turbidity
instruments utilize a light beam projected into the sample
fluid to effect a measurement. The light beam is scattered
by solids in suspension, and the degree of light attenuation
or the amount of scattered light can be related to
turbidity. The light scattered is called the Tyndall effect
and the scattered light the Tyndall light. An expression of
the optical property of a sample which causes light to be
scattered and absorbed rather than transmitted in straight
lines through the sample.
Viruses. (1) An obligate intracellular parasitic
microorganism smaller than bacteria. Most can pass through
filters that retain bacteria. (2) The smallest (10-300 urn
in diameter) form capable of producing infection and
diseases in man or other large species. Occurring in a
variety of shapes, viruses consist of a nucleic acid core
surrounded by an outer shell (capsid) which consists of
numerous protein subunits (capsomeres). Some of the larger
viruses contain additional chemical substances. The true
viruses are insensitive to antibiotics. They multiply only
in living cells where they are assembled as complex
macromolecules utilizing the cells' biochemical systems.
They do not multiply by division as do intracellular
bacteria.
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Volatile Suspended Solids (VSS) . The quantity of suspended
solids lost after the ignition of total suspended solids.
Waste Treatment Plant. A series of tanks, screens, filters,
pumps and other equipment by which pollutants are removed
from water.
Water Quality Criteria. Those specific values of water
quality associated with an identified beneficial use of the.
water under consideration.
Weir. A flow measuring device consisting of a barrier
across an open channel, causing the liquid to flow over its
crest. The height of the liquid above the crest varies with
the volume of liquid flow.
Wet Air Pollution Control. The technique of air pollution
abatement utilizing water as an absorptive media.
Oxidation . The direct oxidation of organic matter in
wastewater liquids in the presence of air under heat and
pressure; generally applied to organic matter oxidation in
sludge.
Zeolite. Various natural or synthesized silicates used in
water softening and as absorbents.
Zooplankton. (1) The aniinal portion of the plankton. (2)
Collective term for the nonphotosynthetic organisms present
in plankton; contrasts with phytoplankton.
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SECTION XIV
ABBREVIATIONS AND SYMBOLS
A.C. activated
ac ft acre-foot
Ag. silver
A.I. active ingredient
API American Petroleum Institute
atm atmosphere
ave average
B boron
Ba barium
bbl barrel
BOD5^ biochemical oxygen demand, five day
Btu British thermal unit
C centigrade degrees
C.A. carbon adsorption
cal calorie
cc cubic centimeter
cfm cubic foot per minute
cfs cubic foot per second
Cl. chloride
cm centimeter
CN cyanide
COD chemical oxygen demand
cone. concentration
cu cubic
db decibels
deg degree
DO dissolved oxygen
E. Coli Escherichia coli bacteria
Fq. equation
F Fahrenheit degrees
Fig. figure
F/M BOD (kg/day) kg/MLVSS in contractor
fpm foot per minute
fps foot per second
ft foot
gm gram
gal gallon
gpd gallon per day
gpm gallon per minute
Hg mercury
hp horsepower
hp-hr horsepower-hour
hr hour
in. inch
kg kilogram
kkg 1000 kilograms
kw kilowatt
kwhr kilowatt-hour
L(l) liter
L/kkg liters per 1000 kilograms
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Ib pound
m meter
M thousand
me milliequivalent
mg milligram
mgd million gallons daily
min minute
ml milliliter
MLSS mixed-liguor suspended solids
MLVSS mixed-liquor volatile suspended solids
mm millimeter
MM million
mole gram-molecular weight
mph mile per hour
MPN most probable number
mu millimicron
NO_3 nitrate
NH3-N ammonia nitrogen
O2 oxygen
POU phosphate
p. page
pH potential hydrogen or hydrogen-ion index (negative
logorithm of the hydrogen-ion concentration)
POTW public owned treatment works
pp. pages
ppb parts per billion
ppm parts per million
psf pound per square foot
psi pound per square inch
R.O. reverse osmosis
rpm revolution per minute
RWL raw waste load
sec second
Sec, Section
S.I.C. Standard Industrial Classification
SO^ sulfates
sq square
sq.ft. square foot
SS suspended solids
stp standard temperature and pressure
SRWL standard raw waste load
TDS total dissolved solids
TKN total Kjeldahl nitrogen
TLm median tolerance limit
TOC total organic carbon
TOD total oxygen demand
TP total phosphorus
TSS total suspended solids
u micron
ug microgram
vol volume
wt weight
yd yard
330
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TABLEXIII-1
METRIC TABLE
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) -by TO OBTAIN (ME'RIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
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/minute
horsepower
inches
inches of mercury
pounds
million gallons/day
nile
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 (°F-32)*
0.3048
5.755
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
i
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
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
331
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