£EPA
United States
Environmental Protection
Agency
Office Of Water
(WH-552)
EPA 821 R-92-005
April 1992
Development Document
For Best Available Technology,
Pretreatment Technology,
And New Source Performance
Technology For The
Pesticide Chemical Industry
Proposed
Printed on Recycled Paper
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PROPOSED
TECHNICAL DEVELOPMENT DOCUMENT
FOR THE
PESTICIDE CHEMICALS
MANUFACTURING CATEGORY
EFFLUENT LIMITATIONS GUIDELINES,
PRETREATMENT STANDARDS, AND
NEW SOURCE PERFORMANCE STANDARDS
William K. Reilly
Administrator
LaJuana S. Wilcher
Assistant Administrator, Office of Water
Thomas P. O'Farrell
Director, Engineering and Analysis Division
Marvin B. Rubin
Chief, Energy Branch
Thomas E. Fielding
Project Officer
March 31, 1992
Engineering and Analysis Division
Office of Science and Technology
U.S. Environmental Protection Agency
Washington, D.C. 20460
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TABLE OF CONTENTS
Page
SECTION 1 - INTRODUCTION
1.0 LEGAL AUTHORITY 1-1
1.1. BACKGROUND 1-1
1.1.1 Clean Water Act 1-1
1.1.2 Section 304(m) Requirements and Litigation 1-6
1.1.3 Pollution Prevention Act 1-7
1.1.4 Prior Regulation and Litigation for the Pesticide
Chemicals Category 1-7
1.2 SCOPE OF TODAY'S PROPOSED RULE 1-10
SECTION 2 SUMMARY
2.0 OVERVIEW OF THE INDUSTRY 2-1
2.1 SUMMARY OF THE PROPOSED REGULATIONS 2-3
2.1.1 Applicability of the Proposed Regulations 2-3
2.1.2 BPT 2-3
2.1.3 BCT 2-4
2.1.4 BAT 2-6
2.1.5 NSPS 2-9
2.1.6 PSES 2-19
2.1.7 PSNS 2-26
SECTION 3 INDUSTRY DESCRIPTION
3.0 INTRODUCTION 3-1
3.1 DATA COLLECTION METHODS 3-1
3.1.1 Pesticide Product Registration Process 3-2
3.1.2 Selection of PAIs for Study 3-3
3.1.3 Development of the "Pesticide Manufacturing
Facility Census of 1986" 3-5
3.1.4 EPA's 1988-1991 Sampling of Selected
Pesticide Manufacturers 3-29
3.1.5 Indus try-Supplied Data 3-33
3.1.6 EPA Bench-Scale Treatability Studies 3-34
3.1.7 Data transferred from the OCPSF Rulemaking 3-38
3.2 OVERVIEW OF THE INDUSTRY 3-41
3.2.1 Geographical Location of Manufacturing Facilities . . . 3-41
3.2.2 SIC Code Distribution 3-43
3.2.3 Age of Facilities 3-45
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TABLE OF CONTENTS (Continued)
3.2.4 Market Types 3-45
3.2.5 Type of Facilities 3-48
3.3 PESTICIDE PRODUCTION 3-49
3.3.1 Types of Pesticides 3-49
3.3.2 1986 Pesticide Active Ingredient Production 3-50
3.3.3 Distribution of PAI Production by Facility 3-51
3.3.4 Distribution of PAI Production During the Year .... 3-62
3.4 PESTICIDE MANUFACTURING PROCESSES 3-63
3.4.1 Batch vs. Continuous Processes 3-64
3.4.2 General Process Reactions 3-65
3.4.3 Intermediate/By-product Manufacture 3-77
3.5 CHANGES IN THE INDUSTRY 3-79
SECTION 4 - INDUSTRY SUBCATEGORIZATION
4.0 INTRODUCTION 4-1
4.1 BACKGROUND 4-2
4.1.1 November 1, 1976, Interim Final BPT Guidelines .... 4-3
4.1.2 April 25, 1978, Promulgated BPT Guidelines 4-4
4.1.3 November 30, 1982, Proposed BAT, BCT, NSPS, PSES,
PSNS Guidelines 4-5
4.1.4 June 13, 1984, Notice of Availability (NOA) 4-6
4.1.5 October 4, 1985, Promulgated BAT, NSPS, PSES, and
PSNS Guidelines 4-6
4.2 CURRENT SUBCATEGORIZATION BASIS 4-7
4.2.1 Product Type and Raw Materials 4-7
4.2.2 Manufacturing Process and Process Changes 4-7
4.2.3 Nature of Waste Generated 4-9
4.2.4 Dominant Product 4-10
4.2.5 Plant Size 4-10
4.2.6 Plant Age 4-10
4.2.7 Plant Location 4-11
4.2.8 Non-Water Quality Characteristics 4-12
4.2.9 Treatment Costs and Energy Requirements 4-13
4.3 PROPOSED SUBCATEGORIES 4-13
4.3.1 Organic Pesticide Chemicals Manufacturing 4-14
4.3.2 Metallo-Organic Pesticide Chemicals Manufacturing . . .4-15
11
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TABLE OF CONTENTS (Continued)
Page
SECTION 5 WATER USE AND WASTEWATER CHARACTERIZATION
5.0 INTRODUCTION 5-1
5.1 WATER USE AND SOURCES OF WASTEWATER 5-1
5.1.1 PAI Process Wastewater 5-4
5.1.2 Other Pesticide Wastewater Sources 5-6
5.1.3 Other Facility Wastewater Co-Treated with
Pesticide Wastewater 5-8
5.2 WASTEWATER VOLUME BY DISCHARGE MODE 5-12
5.2.1 Definitions 5-12
5.2.2 Discharge Status of Pesticide Manufacturing Facilities 5-13
5.2.3 Flow Rates by Discharge Status 5-13
5.3 WATER REUSE AND RECYCLE 5-15
5.4 RAW WASTEWATER DATA COLLECTION 5-20
5.4.1 Industry Supplied Self-Monitoring Data 5-20
5.4.2 EPA Pesticide Manufacturers Sampling Program 5-22
5.5 WASTEWATER CHARACTERIZATION 5-24
5.5.1 Conventional Pollutants 5-25
5.5.2 Priority Pollutants 5-32
5.5.3 Pesticide Active Ingredient Pollutants 5-40
5.5.4 Nonconventional Pollutants 5-41
5.6 WASTEWATER POLLUTANT DISCHARGES 5-43
SECTION 6 POLLUTANT PARAMETERS SELECTED FOR REGULATION
6.0 INTRODUCTION 6-1
6.1 CONVENTIONAL POLLUTANT PARAMETERS 6-1
6.2 PRIORITY POLLUTANT 6-3
6.3 NONCONVENTIONAL POLLUTANTS 6-9
SECTION 7 - TECHNOLOGY SELECTION AND LIMITS DEVELOPMENT
7.0 INTRODUCTION 7-1
7.1 TREATMENT PERFORMANCE DATABASES 7-2
ill
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TABLE OF CONTENTS (Continued)
7.1.1 Analytical Data Submitted with the Pesticide
Manufacturing Facility Census for 1986 and
Associated Data 7-3
7.1.2 Treatability Test Data 7-5
7.1.3 Existing Treatment Performance Databases 7-9
7.2 WASTEWATER TREATMENT IN THE PESTICIDE CHEMICALS MANUFACTURING
INDUSTRY 7-10
7.2.1 Carbon Adsorption 7-13
7.2.2 Hydrolysis 7-16
7.2.3 Chemical Oxidation/Ultraviolet Decomposition 7-19
7.2.4 Resin Adsorption 7-21
7.2.5 Solvent Extraction 7-23
7.2.6 Distillation 7-24
7.2.7 Membrane Filtration 7-25
7.2.8 Biological Treatment 7-29
7.2.9 Evaporation 7-31
7.2.10 Chemical Precipitation/Filtration 7-32
7.2.11 Chemical Reduction 7-34
7.2.12 Coagulation/Flocculation 7-35
7.2.13 Incineration 7-36
7.2.14 Stripping 7-37
7.2.15 Pre- or Post-Treatment 7-39
7.2.16 Disposal of Solid Residue from Treatment 7-41
7.3 TREATMENT PERFORMANCE DISCUSSION 7-43
7.3.1 Carbon Adsorption 7-44
7.3.2 Hydrolysis 7-48
7.3.3 Chemical Oxidation/Ultraviolet Decomposition 7-50
7.3.4 Resin Adsorption 7-51
7.3.5 Solvent Extraction 7-52
7.3.6 Distillation 7-54
7.3.7 Biological Treatment 7-55
7.3.8 Oxidation/Reduction and Physical Separation 7-56
7.3.9 Incineration 7-57
7.4 EFFLUENT LIMITATIONS DEVELOPMENT FOR PAIs 7-60
7.4.1 Statistical Analysis of Long-Term Self-Monitoring Data 7-60
7.4.2 Calculation of Effluent Limitations Guidelines
Under BAT 7-67
7.4.3 Calculation of Effluent Limitations Guidelines
Under NSPS 7-93
7.4.4 Analysis of POTW Pass-Through for PAIs 7-98
7.4.5 Calculation of Effluent Limitations Guidelines
Under PSES and PSNS 7-100
IV
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TABLE OF CONTENTS (Continued)
7.5 EFFLUENT LIMITATIONS DEVELOPMENT FOR PRIORITY POLLUTANTS . . .
7.5.1 Calculation of Effluent Limitations Guidelines
Under BAT 7-103
7.5.1.1 Volatile and Semi-Volatile Organic
Pollutants 7-104
7.5.1.2 Brominated Organic Pollutants 7-112
7.5.1.3 Lead 7-114
7.5.1.4 Cyanide 7-116
7.5.2 Calculation of Effluent Limitations
Guidelines Under NSPS 7-117
7.5.3 Calculation of Effluent Limitations
Guidelines Under PSES 7-117
7.5.4 Calculation of Effluent Limitations
Guidelines Under PSNS 7-120
7.6 EFFLUENT LIMITATIONS DEVELOPMENT FOR CONVENTIONAL POLLUTANTS
AND COD 7-121
SECTION 8 ENGINEERING COSTS
8.0 INTRODUCTION 8-1
8.1 ENGINEERING COSTING 8-1
8.1.1 Cost Methodologies 8-1
8.1.2 Cost Procedures 8-2
8.2 COST MODELING 8-6
8.2.1 Model Evaluation 8-6
8.2.2 CAPDET 8-15
8.2.3 Pesticide Industry Cost Model 8-28
8.3 TREATMENT TECHNOLOGIES 8-32
8.3.1 Activated Carbon 8-37
8.3.2 Biological Treatment 8-39
8.3.3 Chemical Oxidation 8-45
8.3.4 Off-Site Incineration 8-46
8.3.5 Distillation 8-50
8.3.6 Equalization 8-52
8.3.7 Filtration 8-52
8.3.8 Hydrolysis 8-54
8.3.9 Hydroxide Precipitation 8-57
8.3.10 Resin Adsorption 8-58
8.3.11 Steam Stripping 8-59
8.3.12 Monitoring for Compliance 8-68
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TABLE OF CONTENTS (Continued)
Page
SECTION 9 - BEST PRACTICABLE CONTROL TECHNOLOGY (BPT)
9.0 INTRODUCTION 9-1
9.1 BPT APPLICABILITY 9-1
SECTION 10 BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)
10.0 INTRODUCTION 10-1
10.1 SUMMARY OF BAT EFFLUENT LIMITATIONS GUIDELINES 10-2
10.2 IMPLEMENTATION OF THE BAT EFFLUENT LIMITATIONS GUIDELINES .... 10-3
10.2.1 National Pollutant Discharge Elimination System
(NPDES) Permit Limitations 10-3
10.2.2 NPDES Monitoring Requirements 10-5
10.3 BAT EFFLUENT LIMITATIONS GUIDELINES 10-6
SECTION 11 NEW SOURCE PERFORMANCE STANDARDS (NSPS)
11.0 INTRODUCTION 11-1
11.1 SUMMARY OF NSPS EFFLUENT LIMITATIONS GUIDELINE 11-1
11.2 IMPLEMENTATION OF THE NSPS EFFLUENT LIMITATIONS GUIDELINES . . . 11-2
11.2.1 National Pollutant Discharge Elimination System
(NPDES) Permit Limitations 11-2
11.2.2 Monitoring Requirements 11-3
11.3 NEW SOURCE PERFORMANCE STANDARDS (NSPS) 11-3
SECTION 12 PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES) AND
PRETREATMENT STANDARDS FOR NEW SOURCES (PSNS)
12.0 INTRODUCTION 12-1
12.1 SUMMARY OF PSES AND PSNS 12-3
12.2 PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS) . 12-4
SECTION 13 - BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY (BCT)
13.0 INTRODUCTION 13-1
VI
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TABLE OF CONTENTS (Continued)
Page
13.1 JULY 9, 1986 BCT METHODOLOGY 13-2
13.2 BCT TECHNOLOGY OPTIONS 13-4
13.3 BCT COST TEST ANALYSIS 13-6
13.3.1 The POTW Cost Test 13-6
13.3.2 Application to the Organic Pesticide Chemicals
Manufacturing Subcategory . 13-7
13.4 CONCLUSIONS 13-9
SECTION 14 METALLO-ORGANIC PESTICIDE CHEMICALS MANUFACTURING
SUBCATEGORY 14-1
SECTION 15 NON-WATER QUALITY ENVIRONMENTAL IMPACTS
15.0 INTRODUCTION 15-1
15.1 AIR POLLUTION 15-1
15.2 SOLID WASTE 15-5
15.3 ENERGY REQUIREMENTS 15-6
SECTION 16 ANALYTICAL METHODS
16.0 REGULATORY BACKGROUND AND REQUIREMENTS 16-1
16.1 CLEAN WATER ACT (CWA) 16-1
16.1.2 Safe Drinking Water Act (SDWA) 16-3
16.2 PROPOSED METHODS 16-9
16.2.1 Methods for PAI Pollutants 16-9
16.2.2 Methods for Metals 16-11
16.2.3 Development of Methods 16-11
16.2.4 Procedures for Development and
Modification of Methods 16-13
16.2.5 Method Writing and Modification 16-15
16.3 INVESTIGATION OF OTHER ANALYTICAL TECHNIQUES 16-16
SECTION 17 GLOSSARY
SECTION 18 REFERENCES
VI1
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LIST OF TABLES
Page
2-1 PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT 2-5
2-2 BCT EFFLUENT LIMITATIONS FOR THE ORGANIC PESTICIDE CHEMICALS
MANUFACTURING SUBCATEGORY 2-7
2-3 BAT AND PSES EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDE ACTIVE
INGREDIENTS (PAIS) 2-10
2-4 BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL
TREATMENT 2-15
2-5 BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
DIRECT DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE
BIOLOGICAL TREATMENT 2-17
2-6 NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD . 2-20
2-7 NSPS AND PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES
ACTIVE INGREDIENTS (PAIS) 2-21
2-8 EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS PRETREATMENT
STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS) 2-27
3-1 LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS) 3-7
3-2 TREATMENT UNIT OPERATIONS SAMPLED 3-31
3-3 COMPARISON OF THE GEOGRAPHIC DISTRIBUTION OF THE OCPSF vs.
PESTICIDE INDUSTRY BY REGION 3-44
3-4 DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES BY DECADE OF
OPERATION 3-46
3-5 PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS REPORTED TO
BE MANUFACTURED IN 1986 3-52
3-6 NUMBER OF PESTICIDE ACTIVE INGREDIENTS PRODUCED IN 1986 BY
NUMBER OF MANUFACTURING FACILITIES 3-60
3-7 NUMBER OF MANUFACTURING FACILITIES BY NUMBER OF PESTICIDE
ACTIVE INGREDIENTS PRODUCED 3-60
3-8 DISTRIBUTION OF FACILITIES BY QUANTITY OF PAI PRODUCTION .... 3-61
viii
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LIST OF TABLES (Continued)
Paee
5-1 PESTICIDE ACTIVE INGREDIENT PROCESS WASTEWATERS GENERATED IN
1986 BY EFFLUENT TYPE 5-7
5-2 WASTEWATER GENERATED FROM OTHER PESTICIDES WASTEWATER SOURCES . . 5-9
5-3 OTHER FACILITY WASTEWATER GENERATED FROM SOURCES OTHER THAN
PESTICIDE PRODUCTION AND CO-TREATED WITH PESTICIDE WASTEWATER . . 5-11
5-4 TOTAL PROCESS WASTEWATER FLOW BY TYPE OF DISCHARGE 5-14
5-5 PESTICIDE PROCESS WASTEWATER FLOW FOR THE ORGANIC PESTICIDE
SUBCATEGORY (SUBCATEGORY A) AND THE METALLO-ORGAN1C PESTICIDE
SUBCATEGORY (SUBCATEGORY B) 5-16
5-6 TYPES OF WASTEWATER RECYCLE OPERATIONS REPORTED 5-17
5-7 PRIORITY POLLUTANT DATA-FACILITY SELF MONITORING 5-35
5-8 PRIORITY POLLUTANT DATA EPA SAMPLING ORGANIC PESTICIDE
CHEMICALS MANUFACTURING 5-38
6-1 PRIORITY POLLUTANTS SELECTED FOR REGULATION 6-5
7-1 TREATMENT TECHNOLOGIES USED BY THE PESTICIDE CHEMICALS
MANUFACTURING INDUSTRY AS REPORTED IN THE 1986 FACILITY CENSUS . 7-12
7-2 PAI STRUCTURAL GROUPS 7-69
7-3 PAIs AND PAI STRUCTURAL GROUPS WITH PAI LIMIT DEVELOPMENT
METHODOLOGIES 7-80
8-1 CAPDET LARGE FACILITY UNIT PROCESSES 8-22
8-2 CAPDET SMALL FACILITY UNIT PROCESSES 8-25
8-3 WASTE INFLUENT CHARACTERISTICS 8-27
8-4 UNIT COST DATA 8-29
8-5 PROGRAM CONTROL/OUTPUT SELECTION 8-31
8-6 PESTICIDES OPTION 1 TOTAL COSTS BY PLANT 8-34
8-7 DESIGN PARAMETERS FOR THE BIOLOGICAL TREATMENT COST MODULE . . . 8-42
ix
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LIST OF TABLES (Continued)
Page
8-8 PRIORITY POLLUTANTS DIVIDED INTO GROUPS ACCORDING TO HENRY'S
LAW CONSTANT VALUES 8-63
8-9 STEAM STRIPPING DESIGN PARAMETERS FOR HENRY'S LAW CONSTANT
PARAMETERS 8-64
9-1 EXISTING BPT EFFLUENT LIMITATIONS FOR THE PESTICIDE CHEMICALS
POINT SOURCE CATEGORY (40 CFR PART 455) 9-2
9-2 ORGANIC PESTICIDE CHEMICALS EXCLUDED FROM THE 1978 BPT
SUBCATEGORY A GUIDELINES 9-3
9-3 PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT 9-5
10-1 BAT EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDE ACTIVE
INGREDIENTS (PAIS) 10-7
10-2 BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL
TREATMENT 10-12
10-3 BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
DIRECT DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE
BIOLOGICAL TREATMENT 10-14
11-1 NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD . . 11-5
11-2 PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES ACTIVE
INGREDIENTS (PAIS) 11-6
11-3 NSPS FOR PRIORITY POLLUTANTS FOR PLANTS WITH END-OF-PIPE
BIOLOGICAL TREATMENT 11-11
11-4 NSPS FOR PRIORITY POLLUTANTS FOR PLANTS THAT DO NOT HAVE
END-OF-PIPE BIOLOGICAL TREATMENT 11-13
12-1 PSES FOR ORGANIC PESTICIDE ACTIVE INGREDIENTS (PAIS) 12-5
12-2 PSES FOR PRIORITY POLLUTANTS 12-10
12-3 PSNS FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS) 12-12
12-4 PSNS EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS 12-17
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LIST OF TABLES (Continued)
Page
13-1 POTW COST TEST RESULTS FOR THE ORGANIC PESTICIDE CHEMICALS
MANUFACTURING SUBCATEGORY 13-10
16-1 TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS 16-4
XI
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LIST OF FIGURES
Page
3-1 FLOW CHART FOR DETERMINING INCLUSION OF PAI IN PESTICIDE
MANUFACTURING FACILITY CENSUS FOR 1986 3-6
3-2 DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES BY EPA
REGION 3-42
3-3 1986 PESTICIDE MARKET COMPOSITION 3-47
3-4 REACTION MECHANISMS FOR s-TRIAZINES AND ATRAZINE AND AMETRYN . . 3-66
3-5 REACTION MECHANISMS FOR CARBOFURAN AND NABAM 3-68
3-6 REACTION MECHANISMS FOR PROPANIL AND ALACHLOR 3-71
3-7 REACTION MECHANISMS FOR ISOPROPALIN 3-72
3-8 REACTION MECHANISMS FOR 2,4-D 3-74
3-9 REACTION MECHANISMS FOR PARATHION AND PHORATE 3-76
3-10 REACTION MECHANISM FOR GLYPHOSATE 3-78
5-1 EXAMPLE OF PESTICIDE ACTIVE INGREDIENT MANUFACTURING PROCESS . . 5-2
5-2 INDUSTRY SELF-MONITORING BOD LEVELS IN FINAL EFFLUENT DISCHARGE . 5-30
5-3 INDUSTRY SELF-MONITORING TSS LEVELS IN FINAL DISCHARGE 5-31
5-4 INDUSTRY SELF-MONITORING pH LEVELS IN FINAL DISCHARGE 5-33
5-5 INDUSTRY SELF-MONITORING COD LEVELS IN FINAL DISCHARGE 5-44
8-1 FLOWCHART USED TO DETERMINE TREATMENT COSTS FOR PAIS 8-3
8-2 FLOWCHART USED TO DETERMINE TREATMENT COSTS FOR PRIORITY
POLLUTANTS 8-4
xii
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SECTION 1
INTRODUCTION
1.0 LEGAL AUTHORITY
This regulation is being proposed under the authorities of
Sections 301, 304, 306, 307, and 501 of the Clean Water Act (the Federal Water
Pollution Control Act Amendments of 1972, 33 U.S.C. 1251 et seq., as amended
by the Clean Water Act of 1977, Pub. L. 95-217, and the Water Quality Act of
1987, Pub. L. 100-4), also referred to as "the Act."
1.1. BACKGROUND
1.1.1 Clean Water Act
The Federal Water Pollution Control Act Amendments of 1972
established a comprehensive program to "restore and maintain the chemical,
physical, and biological integrity of the Nation's waters," (Section 101(a)).
To implement the Act, EPA is to issue effluent limitations guidelines,
pretreatment standards and new source performance standards for industrial
dischargers.
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These guidelines and standards are summarized briefly below:
1. Best Practicable Control Technology Currently Available
(BPT) (Section 304(b)(l) of the Act).
BPT effluent limitations guidelines are generally based on the
average of the best existing performance by plants of various sizes, ages, and
unit processes within the category or subcategory for control of pollutants.
In establishing BPT effluent limitations guidelines, EPA considers
the total cost of achieving effluent reductions in relation to the effluent
reduction benefits, the age of equipment and facilities involved, the
processes employed, process changes required, engineering aspects of the
control technologies, non-water quality environmental impacts (including
energy requirements) and other factors as the EPA Administrator deems
appropriate (Section 304(b)(l)(B) of the Act). The Agency considers the
category or subcategory-wide cost of applying the technology in relation to
the effluent reduction benefits. Where existing performance is uniformly
inadequate, BPT may be transferred from a different subcategory or category.
2. Best Available Technology Economically Achievable (BAT^
(Sections 304(b)(2)(B) and 307(a)(2) of the Act).
In general, BAT effluent limitations represent the best existing
economically achievable performance of plants in the industrial subcategory or
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category. The Act establishes BAT as the principal national means of
controlling the direct discharge of priority pollutants and nonconventional
pollutants to navigable waters. The factors considered in assessing BAT
include the age of equipment and facilities involved, the process employed,
potential process changes, and non-water quality environmental Impacts
(including energy requirements, (Section 304(b)(2)(B)). The Agency retains
considerable discretion In assigning the weight to be accorded these factors.
As with BPT, where existing performance Is uniformly inadequate, BAT may be
transferred from a different subcategory or category. BAT may Include process
changes or internal controls, even when these technologies are not common
industry practice.
3. Best Conventional Pollutant Control Technology (BCT)
(Section 304(a)(4) of the Act).
The 1977 Amendments added Section 301(b)(2)(E) to the Act
establishing BCT for discharges of conventional pollutants from existing
industrial point sources. Section 304(a)(4) designated the following as
conventional pollutants: Biochemical oxygen demanding pollutants (BOD), total
suspended solids (TSS), fecal coliform, pH, and any additional pollutants
defined by the Administrator as conventional. The Administrator designated
oil and grease as an additional conventional pollutant on July 30, 1979 (44 FR
44501).
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BCT is not an additional limitation, but replaces BAT for the
control of conventional pollutants. In addition to other factors specified in
Section 304(b)(4)(B), the Act requires that BCT limitations be established in
light of a two part "cost-reasonableness" test. fAmerican Paper Institute v.
EPA, 660 F.2d 954 (4th Cir. 1981)]. EPA's current methodology for the general
development of BCT limitations was issued in 1986 (51 FR 24974; July 9, 1986).
4. New Source Performance Standards (NSPS) (Section 306 of the
Act).
NSPS are based on the best available demonstrated treatment
technology. New plants have the opportunity to install the best and most
efficient production processes and wastewater treatment technologies. As a
result, NSPS should represent the most stringent numerical values attainable
through the application of the best available control technology for all
pollutants (i.e., conventional, nonconventional, and priority pollutants). In
establishing NSPS, EPA is directed to take into consideration the cost of
achieving the effluent reduction and any non-water quality environmental
impacts and energy requirements.
5. Pretreatment Standards for Existing Sources (PSES) (Section
307(b) of the Act).
PSES are designed to prevent the discharge of pollutants that pass
through, interfere with, or are otherwise incompatible with the operation of
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publicly owned treatment works (POTWs). The Act requires pretreatment
standards for pollutants that pass through POTWs or interfere with POTWs'
treatment processes or sludge disposal methods. The legislative history of
the 1977 Act indicates that pretreatment standards are to be technology-based
and analogous to the BAT effluent limitations guidelines for removal of toxic
pollutants. For the purpose of determining whether to promulgate national
category-wide pretreatment standards, EPA generally determines that there is
pass-through of a pollutant and thus a need for categorical standards if the
nation-wide average percent of a pollutant removed by well-operated POTWs
achieving secondary treatment is less than the percent removed by the BAT
model treatment system.
The General Pretreatment Regulations, which set forth the
framework for the implementation of categorical pretreatment standards, are
found at 40 CFR Part 403. (Those regulations contain a definition of pass-
through that addresses localized rather than national instances of pass-
through and does not use the percent removal comparison test described above.
See 52 FR 1586, January 14, 1987.)
6. Pretreatment Standards for New Sources (PSNS) (Section
307(b) of the Act).
Like PSES, PSNS are designed to prevent the discharges of
pollutants that pass through, interfere with, or are otherwise incompatible
with the operation of POTWs. PSNS are to be issued at the same time as NSPS.
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New indirect dischargers, like the new direct dischargers, have the
opportunity to incorporate into their plants the best available demonstrated
technologies. The Agency considers the same factors in promulgating PSNS as
it considers in promulgating NSPS.
1.1.2 Section 304Cm) Requirements and Litigation
Section 304(m) of the Clean Water Act (33 U.S.C. 1314(m)), added
by the Water Quality Act of 1987, requires EPA to establish schedules for (i)
reviewing and revising existing effluent limitations guidelines and standards
("effluent guidelines"), and (ii) promulgating new effluent guidelines. On
January 2, 1990, EPA published an Effluent Guidelines Plan (55 FR 80), in
which schedules were established for developing new and revised effluent
guidelines for several industry categories. One of the industries for which
the Agency established a schedule was the Pesticide Chemicals ^category.
Natural Resources Defense Council, Inc. (NRDC) and Public Citizen,
Inc., challenged the Effluent Guidelines Plan in a suit filed in U.S. District
Court for the District of Columbia (NRDC et al. v. Reillv. Civ. No. 89-2980).
The plaintiffs charged that EPA's plan did not meet the requirements of
Section 304(m). A Consent Decree in this litigation was entered by the Court
on January 31, 1992. The Decree requires, among other things, that EPA
propose effluent guidelines for the manufacturing subcategories of the
Pesticide Chemicals category by March, 1992, and take final action by July,
1993.
1-6
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1.1.3 Pollution Prevention Act
In the Pollution Prevention Act of 1990 (42 U.S.C. 13101 et seq.,
Pub.L. 101-508, November 5, 1990), Congress declared pollution prevention the
national policy of the United States. The Act declares that pollution should
be prevented or reduced whenever feasible; pollution that cannot be prevented
should be recycled or reused in an environmentally safe manner wherever
feasible; pollution that cannot be recycled should be treated; and disposal or
release into the environment should be chosen only as a last resort.
1.1.4 Prior Regulation and Litigation for the Pesticide Chemicals
Category
EPA promulgated BPT for the Pesticides Chemicals Manufacturing
Category on April 25, 1978 (43 FR 17776; 40 CFR Part 455), and September
29, 1978 (43 FR 44846; 40 CFR Part 455, Subpart A). The BPT effluent
limitations guidelines established limitations for chemical oxygen-demand
(COD), BODj, TSS, and pH for wastewaters discharged by the organic pesticide
active ingredient (PAI) manufacturing subcategory (Subcategory A), except that
discharges of these pollutants resulting from the manufacture of 25 organic
PAIs and classes of PAIs were specifically excluded from the limitations. In
addition, BPT set a limitation for this subcategory on total pesticide
discharge which was applicable to the manufacture of 49 specifically listed
organic PAIs. BPT limitations requiring zero discharge of process wastewater
1-7
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pollutants were set for metallo-organic PAIs containing arsenic, mercury,
cadmium, or copper.
Several industry members challenged the BPT regulation on
April 26, 1978 and the U.S. Court of Appeals remanded them on two minor issues
[BASF Wyandotte Corp. v. Costie. 596 F.2d 637 (1st Cir. 1979), cert, denied.
Eli Lilly v. Costle. 444 U.S. 1096 (1980)]. The Agency subsequently addressed
the two issues on remand and the Court upheld the regulations in their
entirety [BASF Wyandotte Corp. v. Costle. 614 F.2d 21 (1st Cir. 1980)].
On November 30, 1982, EPA proposed additional regulations to
control the discharge of wastewater pollutants from pesticide chemical
operations to navigable waters and to POTWs (47 FR 53994). The proposed
regulations included effluent limitations guidelines based upon BPT, BAT, BCT,
NSPS, PSES, and PSNS. The proposed effluent limitations guidelines and
standards covered the organic pesticide chemicals manufacturing segment, the
metallo-organic chemicals manufacturing segment and the formulating/packaging
segment of the pesticide chemical industry. In addition, the Agency proposed
guidelines for test procedures to analyze the nonconventional pesticide
pollutants covered by these regulations on February 10, 1983 (48 FR 8250).
Based on the new information collected by EPA in response to the
comments on the November 30, 1982 proposal, on June 13, 1984, EPA published a
Notice of Availability (NOA) of new information (49 FR 24492). In this NOA,
the Agency indicated it was considering changing its approach to developing
1-8
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regulations for this industry. EPA requested comments on the data. EPA
published a second NOA of new information on January 24, 1985, which primarily
made available for public-review technical and economic data which had
previously been claimed confidential by industry.
EPA issued a final rule on October 4, 1985, that limited the
discharge of pollutants into navigable waters and into POTWs (50 FR 40672).
The regulation included effluent limitations guidelines and standards for the
BAT, NSPS, PSES, and PSNS levels of control for new and existing facilities
that were engaged in the manufacture and/or formulation and packaging of
pesticides. The regulation also established analytical methods for 61 PAIs
for which the Agency had not previously promulgated approved test procedures.
Several parties filed petitions in the Court of Appeals
challenging various aspects of the pesticide regulation fChemical Specialties
Manufacturers Association, et al.. v. EPA (86-8024)]. After a review of the
database supporting the regulation the Agency found flaws in the basis for
these effluent limitations guidelines and standards. Subsequently, the
Agency and the parties filed a joint motion for a voluntary remand of the
regulation in the Eleventh Circuit Court of Appeals. The Court dismissed the
case on July 25, 1986, in response to the Joint Motion. Upon consideration
of the parties' motion to modify the dismissal, on August 29, 1986, the Court
modified its order to clarify the terms of the dismissal. The Eleventh
Circuit Court of Appeals ordered that: (1) the effluent limitation guidelines
and standards for the pesticide chemicals industry be remanded to EPA for
1-9
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reconsideration and further rulemaking; and (2) EPA publish a FEDERAL REGISTER
notice removing the remanded pesticide regulation from the Code of Federal
Regulations.
EPA formally withdrew the regulations from the Code of Federal
Regulations on December 15, 1986 (51 FR 44911). Although no errors were found
in the analytical methods promulgated October 4, 1985, these methods were also
withdrawn to allow for further testing and possible revision. The BPT
limitations that were published on April 25, 1978 and September 29, 1978 were
not affected by the withdrawal notice and remain in effect. Those existing
regulations are not proposed to be changed in today's notice and EPA does not
request and will not evaluate public comments on them.
1.2 SCOPE OF TODAY'S PROPOSED RULE
The regulation proposed today covers two manufacturing
subcategories of the pesticide chemicals industry:
Subcategory A: Manufacturers of organic pesticide
chemicals; and
Subcategory B: Manufacturers of metallo-organic pesticide
chemicals.
EPA will address the Pesticide Chemicals Formulating and Packaging
subcategory at a later date.
1-10
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In today's notice, EPA is proposing to expand water pollution
control requirements for the organic pesticide chemicals manufacturing
subcategory by establishing effluent limitations guidelines and standards for
BAT, NSPS, PSES, and PSNS for new and existing facilities that are engaged in
the manufacture of organic pesticide chemicals. In addition, BCT for
conventional pollutants is proposed to be set equal to BPT for the organic
pesticide chemicals manufacturing subcategory.
For the metallo-organic pesticide chemicals manufacturing
subcategory, current BPT limitations require no discharge of process
wastewater pollutants. EPA is today proposing to reserve BCT, BAT, NSPS,
PSES, and PSNS effluent limitations for this subcategory.
The proposed effluent limitations guidelines and standards are
intended to cover discharges generated during the manufacture of PAIs from
chemical reactions. (For one PAI, the effluent guidelines apply only to
discharges of wastewater generated during the purification of that PAI to a
higher quality PAI product.) These guidelines do not apply to the production
of pesticide products through the physical mixing, blending, or dilution of
PAIs without an intended chemical reaction (except where dilution is a
necessary step following chemical reaction to stabilize the product), nor do
these regulations apply to packaging or repackaging of pesticide products.
These two types of operations are part of the Pesticide Chemicals Formulating
and Packaging Subcategory which will be covered under a separate rulemaking at
a later date. These regulations also do not apply to the manufacturer of
1-11
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chemicals ("intermediate") which are not pesticides but which subsequently are
converted by further chemical reactions to pesticide active ingredients. The
"intermediates" are covered by the Organic Chemicals, Plastics, and Synthetic
Fibers (OCPSF) effluent guidelines (40 CFR Parts 414 and 416).
1-12
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SECTION 2
SUMMARY
2.0 OVERVIEW OF THE INDUSTRY
According to 1986 data collected by EPA during the development of
this rule, the pesticide chemicals manufacturing industry includes 90
facilities whose production activities would be covered under the proposed
pesticide chemicals manufacturing regulation. Over half of the pesticide
manufacturing facilities also conduct pesticide formulating and/or packaging
(PFP) activities. In addition, more than half of the pesticide manufacturing
facilities generate wastewater discharges which are currently regulated under
the Organic Chemicals, Plastics, and Synthetic Fibers (OCPSF) Point Source
Category (see 40 CFR Part 414).
There are approximately 128 pesticide active ingredients (PAIs)
and classes of PAIs representing 186 individual active ingredients (Pyrethrin
I and Pyrethrin II are counted as one PAI because they are not separated in
the commerical product) manufactured by 225 separate pesticide production
processes. Of the reported 225 manufacturing processes used to produce
pesticides in 1986, 178 were batch processes. A "typical" facility
manufactures one active ingredient and is the only facility in the country
producing that PAI. "Typical" production is between 1,000,000 and 10,000,000
pounds of total PAI for the year.
2-1
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The technical study included all 90 facilities. Of the 90
facilities, 67 are dischargers: 32 facilities are direct dischargers, and 36
are indirect dischargers (one facility is both a direct and indirect
discharger). The remaining 23 facilities do not discharge pesticide
manufacturing process wastewater: 15 facilities dispose of their wastewater by
either on-site or off-site deepwell injection or incineration, and 8
facilities generate ho process wastewater because of recycle/reuse operations
or because they do not use water.
As a result of the wide variety of raw materials and processes
used and of products manufactured in the pesticide chemicals manufacturing
industry, a wide variety of pollutants are found in the wastewaters of this
industry. This includes conventional pollutants (pH, BOD, and TSS) , a variety
of toxic priority pollutants, and a large number of nonconventional pollutants
(i.e., COD and the PAIs) . The PAIs are organic and metallo-organic compounds
produced by the industry for sale.
Pesticide manufacturing plants use a broad range of in-plant and
end-of-pipe controls and treatment techniques to control and treat the wide
variety of pollutants. The treatment technologies used include physical
chemical treatment technologies to remove PAIs, followed by steam stripping to
remove volatile priority pollutants, followed by biological treatment to
remove non-volatile priority pollutants and other organic pollutants. The
major physical-chemical treatment technologies in use for PAI removal are
2-2
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activated carbon, chemical oxidation, and hydrolysis. More detail is provided
in Section 7.
2.1 SUMMARY OF THE PROPOSED REGULATIONS
2.1.1 Applicability of the Proposed Regulations
The proposed pesticide chemicals manufacturing regulations would
apply to process wastewater discharges from existing and new pesticide
chemicals manufacturing facilities. These regulations do not apply to
wastewaters from pesticide femulators and packagers, which will be addressed
in a separate rulemaking.
2.1.2 BPT
EPA promulgated BPT effluent limitations guidelines in 1978 (40 FR
17776; 43 FR 44846; 40 CFR Part 455) applicable to pesticide chemicals
manufacturing processes resulting from the manufacturing of: (1) All organic
PAIs (with some exceptions; see below), and (2) 'all metallo-organic PAIs
containing arsenic, mercury, cadmium, or copper. For plants manufacturing
organic PAIs, the regulations limited COD, BOD, TSS, and pH. The organic PAI
regulation also limited total pesticides in wastewaters resulting from the
manufacturing of 49 specific organics PAIs. For metallo-organic PAIs, the BPT
limitations require that there be no discharge of process wastewater
pollutants.
2-3
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The BPT limitations for organic pesticide chemical manufacturing
excluded from regulation 25 specific PAIs and classes of PAIs. In addition,
organo-tin pesticides were not covered by BPT. EPA proposes to expand the
coverage of BPT limitations (for BOD5, COD, TSS, and pH) to include
manufacture of 15 of the previously excluded organic PAIs and organo-tin PAIs.
Information demonstrates that all manufacturers of these PAIs are already
subject to permit limitations that are at least as stringent as the BPT
limitations. Table 2-1 presents these 15 organic PAIs and organo-tin PAIs.
The existing BPT limitations (i.e., those promulgated in 1978) are
not proposed to be changed. Additionally, no change is proposed to the
existing BPT effluent limitations guidelines for metallo-organic PAIs.
2.1.3 BCT
The Agency proposes in this regulation to set BCT equal to BPT for
conventional pollutants under the organic pesticide chemicals manufacturing
subcategory. The Agency proposes to reserve BCT for the metallo-organic
«
pesticide chemicals manufacturing subcategory.
The technology basis for BPT under the organic pesticide chemicals
manufacturing subcategory includes flow equalization and biological treatment
followed by clarification to remove BOD, COD, and TSS. Options for further
removal of TSS and/or BOD, initially considered for evaluation as BCT
candidate technologies, included multimedia filtration, carbon adsorption,
2-4
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Table 2-1
PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT
PAI Code
• • . . .
025
058
060
067
138
142
157
192
211
211.05
223
224
226
239
256
257
PAI
Cyanaz ine
Ametryn
Atrazine
Biphenyl
Glyphosate
Hexazinone
Methoprene
Organo-tin Pesticides
Phenylphenol
Sodium Phenylphenate
Prometon
Prometryn
Propazine
Simazine
Terbuthylaz ine
Terbutryn
2-5
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membrane filtration, incineration, evaporation, additional biological
oxidation (above the level required to meet BPT), and clarification through
the use of settling ponds. However, only multimedia filtration was deemed a
feasible option for BCT. Multimedia filtration was then evaluated by the BCT
cost test. This BCT technology, however, failed the BCT cost test and is
therefore not being proposed as BCT for the organic pesticide chemicals
manufacturing subcategory. Since no other technologies were identified that
would be expected to enhance conventional pollutant removal above that
provided by BPT technologies, the Agency is proposing to set BCT equal to BPT
limitations for conventional pollutants. Table 2-2 presents the BCT organic
pesticide chemicals manufacturing subcategory effluent limitations.
2.1.4 BAT
EPA based the proposed BAT limitations for PAIs under the organic
pesticide chemicals manufacturing subcategory on the use of the following
treatment technologies: hydrolysis, activated carbon, chemical oxidation,
resin adsorption, solvent extraction, distillation, and/or incineration.
Limitations for PAIs were derived on a mass basis, using long-term
data where available. Where long-term data were not available, limitations
were developed based on performance data from either industry or EPA
treatability studies. In these cases, in lieu of BAT performance data from
full scale operating systems, treatability studies were used to determine the
PAI concentration achievable through a specific treatment technology. These
2-6
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Table 2-2
BCT EFFLUENT LIMITATIONS FOR THE
ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY
Effluent
Character is tic
BODj
TSS
pH
Maximum for
Any Oneway*
7.4
6.1
**
Average of Daily Values for
30 Consecutive Days Shall
Not Exceed*
1.6
1.8
**
*Metric units: kilogram/1,000 kg of PAI produced; English units: pound/
1,000 Ibs of PAI produced; Established on the basis of pesticide production.
**Within the range of 6.0 to 9.0.
2-7
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concentration data were then applied to the total flow of PAI contaminated
streams and the reported PAI production data to calculate a mass based
limitation. In cases where treatability studies did not contain sufficient
information to determine process variability, daily and monthly variability
were based on the performance of operating BAT treatment systems. For some
PAIs for which there were no treatability data, limitations were developed
based on the treatment performance achieved for chemically and structurally
similar PAIs. This "technology transfer" was supplemented by treatability
studies.
BAT effluent limitations for 28 priority pollutants are proposed.
For 27 of the 28 priority pollutants limitations are based on the use of model
control technologies identified in the OCPSF rulemaking. Both the OCPSF end-
of-pipe biological treatment subcategory and the non-end-of-pipe biological
treatment subcategory limitations are being transferred for the priority
pollutants regulated under BAT in the organic pesticide chemicals
manufacturing subcategory.
Derivation of the proposed BAT limitations is detailed in
Section 7 of this document. "Daily Maximum" and "Monthly Average" production-
based limitations have been calculated for each regulated PAI pollutant.
"Maximum for any one day" and "Maximum for Monthly Average'1 concentration
limitations have been transferred from the OCPSF rulemaking for 23 of the 28
regulated priority pollutant. The proposed BAT effluent limitations for
organic PAIs and classes of PAIs and priority pollutants under the organic
2-8
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pesticide chemicals manufacturing subcategory are listed in Tables 2-3, 2-4,
and 2-5.
The Agency proposes to reserve BAT for the metallo-organic
pesticide chemicals manufacturing subcategory.
'Once a pollutant is regulated, it will also be limited in the
National Pollutant Discharge Elimination System (NPDES) permit issued to
direct dischargers. The limitations for pesticide chemicals manufacturing
plants include all priority pollutants regulated and those PAIs manufactured
at each plant.
2.1.5 NSPS
EPA proposes new source performance standards (NSPS) for the
organic pesticide chemicals manufacturing subcategory on the basis of the best
available demonstrated technologies and a 28% achievable flow reduction for
certain PAIs. NSPS are proposed for conventional pollutants (BOD, TSS, and
pH) and COD on the basis of BPT model treatment technologies and a 28%
achievable flow reduction. NSPS regulation of priority pollutants are based
on BAT model treatment technologies from the OCPSF rulemaking; because the
limitations for priority pollutants are concentration-based, the permit writer
would apply the 28% flow reduction when calculating NPDES permit effluent
limitations. The proposed NSPS limitations for conventional pollutants and
2-9
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concentration data were then applied to the total flow of PAI contaminated
streams and the reported PAI production data to calculate a mass based
limitation. In cases where treatability studies did not contain sufficient
information to determine process variability, daily and monthly variability
were based on the performance of operating BAT treatment systems. For some
PAIs for which there were no treatability data, limitations were developed
based on the treatment performance achieved for chemically and structurally
similar PAIs. This "technology transfer" was supplemented by treatability
studies.
BAT effluent limitations for 28 priority pollutants are proposed.
For 27 of the 28 priority pollutants limitations are based on the use of model
control technologies identified in the OCPSF rulemaking. Both the OCPSF end-
of-pipe biological treatment subcategory and the non-end-of-pipe biological
treatment subcategory limitations are being transferred for the priority
pollutants regulated under BAT in the organic pesticide chemicals
manufacturing subcategory.
Derivation of the proposed BAT limitations is detailed in
Section 7 of this document. "Daily Maximum" and "Monthly Average" production-
based limitations have been calculated for each regulated PAI pollutant.
"Maximum for any one day" and "Maximum for Monthly Average" concentration
limitations have been transferred from the OCPSF rulemaking for 23 of the 28
regulated priority pollutant. The proposed BAT effluent limitations for
organic PAIs and classes of PAIs and priority pollutants under the organic
2-8
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pesticide chemicals manufacturing subcategory are listed in Tables 2-3, 2-4,
and 2-5.
The Agency proposes to reserve BAT for the metallo-organic
pesticide chemicals manufacturing subcategory.
"Once a pollutant is regulated, it will also be limited in the
National Pollutant Discharge Elimination System (NPDES) permit issued to
direct dischargers. The limitations for pesticide chemicals manufacturing
plants include all priority pollutants regulated and those PAIs manufactured
at each plant.
2.1.5 NSPS
EPA proposes new source performance standards (NSPS) for the
organic pesticide chemicals manufacturing subcategory on the basis of the best
available demonstrated technologies and a 28% achievable flow reduction for
certain PAIs. NSPS are proposed for conventional pollutants (BOD, TSS, and
pH) and COD on the basis of BPT model treatment technologies and a 28%
achievable flow reduction. NSPS regulation of priority pollutants are based
on BAT model treatment technologies from the OCPSF rulemaking; because the
limitations for priority pollutants are concentration-based, the permit writer
would apply the 28% flow reduction when calculating NPDES permit effluent
limitations. The proposed NSPS limitations for conventional pollutants and
2-9
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Table 2-3
BAT AND PSES EFFLUENT LIMITATIONS FOR ORGANIC
PESTICIDE ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient C*AI)
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 403 [Potassium N-
hydr oxyme thy 1 - N -
methyldithiocarbamate ]
BAT/PSES effluent limitations
Dally Maximum Shall Hot Exceed li./l.OOO Ib. SAT
production
1.19 x 10-4
Monthly
Average Shall
not Exceed
U>./1,000 Ib.
FAX production
3.40 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.32 x 10-2
8.82 x 10-4
7.23 x 10-*
2.10 x 10-3
2.56 x 10-3
2.74 x 10-2
3.22 x W*
1.91 x 10-1
8.79 x lO'3
2.68 x 10"4
3.12 x 10"*
9.14 x 10-4
1.02 x 10-3
1.41 x lO'2
1.09 x 10-4
5.14 x 10-2
No discharge of process wastewater pollutants
1.69 x 10-2
8.72 x 10-3
No discharge of process wastewater pollutants
1.24 x 10-'
3.95 x lO'3
3.95 x lO'3
5.74 x 10-3
4.18 x 10-2
1.27 x 10-3
1.27 x 10-3
1.87 x 10-3
2-10
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Table 2-3
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Busan 853 [Potassium
dimethyldithiocarbamatej
Butachlor
Captafol
Carbarn S3 [Sodium
dimethyldithiocarbamate ]
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos'
Cyanazine
Dazomet3
DCPA
DEF
Diazinon1
Dichlorprop , salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
BAT/PSES effluent limitations
Daily Maximum Shall trot Exceed ib./l.OOO lit. PAI
production
5.74 x 10-3
3.53 x ID'3
Monthly
Average Shall
not Exceed
H>./1,000 Ib.
FAX production
1.87 x 10-3
1.09 x 10-3
No discharge of process wastewater pollutants
5.74 x 10-3
1.60 x 10-3
1.18 x W*
8.16 x 10-2
1.51 x lO'3
3.27 x W-4
1.63 x 10-3
5.74 x lO'3
7.79 x 10-2
1.15 x lO'2
2.82 x 10-3
1.87 x lO"3
7.30 x 10-*
2.80 x 10-5
3.31 x 10-2
4.57 x 10-"
9.96 x 10-3
8.11 x 10-4
1.87 x lO'3
2.64 x ID'2
5.58 x 10-3
1.12 x 10-3
No discharge of process wastewater pollutants
9.60 x 10-s
4.73
'3.40 x 10-2
7.33 x 10-3
3.15 x 10-2
2.95 x 10-3
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x lO'2
2-11
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Table 2-3
(Continued)
Organic Pesticide Active
Ingredient (PA!)
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Me thami dopho s
Methomyl1
Methoxychlor
Metribuzln
BAT/PSES effluent limitations
Daily Maximum Shall Sot Exceed It, /I, 000 Ib. FAX
product! on
Monttily
Average Shall
not Exceed
U>./1,ODO Ib.
PAI production
No discharge of process wastewater pollutants
2.20 x 10-2
3.22 x 10^
7.37 x HH
1.02 x 10-'
1.48 x 10-2
1.83 x 10-2
5.40 x 10-3
5.10 x 10-3
1.09 x 10-*
2.99 x 10-4
3.61 x 10-2
7.64 x 10-3
9.45 x 10-3
2.08 x 10-3
No discharge of process wastewater pollutants
8.80 x 10-3
7.06 x 10-3
5.74 x lO'3
2.69 x 10-3
2.35 x W^
2.90 x 10-3
2.49 x 10-3
1.87 x ID'3
1.94 x 10-3
9.55 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x lO'2
1.46 x 10-2
3.82 x lO'3
3.23 x 10-3
1.36 x lO'2
5.58 x lO'3
7.53 x 10-3
1.76 x lO'3
1.31 x 10-3
7.04 x lO'3
2-12
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Table 2-3
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Mevinphos
Nab am3
Nabonate3
Naled
Norflurazon
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendime thai in
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
BAT/PSES effluent limitations
Daily Maximum Shall Hot Exceed It. /1. 000 Ib. PAI
production
1.44 x 10-4
5.74 x 10-3
5.74 x lO'3
Monthly
Average Shall
not Exceed
Ib./ 1,000 It.
FAX production
5.10 x 10-3
1.87 x 10-3
1.87 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.72 x 10-2
7.72 x 10-4
7.72 x W*
5.75 x 10-*
3.21 x 10-3
2.32 x 10-*
2.51 x 10-*
7.42 x lO'3
3.43 x W-*
3.43 x W^
1.90 x 10-4
1.06 x 10-3
6.06 x 10-5
7.53 x 10-*
No discharge of process wastewater pollutants
2.10 x lO'3
2.10 x 10-3
2.00 x 10-*
5.34 x lO'3
1.06 x 10-3
2.10 x 10-3
9.14 x 10-*
9.14 x 10-*
6.90 x 10-5
1.66 x 10-3
4.84 x 10-*
9.14 x 10-*
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.10 x lO'3
9.14 x 10^
2-13
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Table 2-3
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [ Sodium
methyldithiocarbamate ]
Ziram3 [Zinc
dimethyldithiocarbamate ]
BAT/PSES effluent limitations
Dally Maximum Shall. Hok Ercoad li./l.OOO Ib. PAI
• • "'.'••' PJ*OwlofcApn ••..;' ''' '• ',.,;.'
. :•• ' • • ' •.
4.10 x 10-3
2.88 x 10-4
9.78 x lO'2
1.51 x 10-'
4.09 x W-*
2.10 x 10-3
2.10 x lO'3
1.02 x 10-2
6.52 x 10-2
3.22 x 10*
5.74 x ID'3
5.74 x 10-3
Monthly
•.-Average Shall. '••
•'• not Eroead
lb./l,000 Ib,
• )PAI production
1.35 x 10-3
8.96 x lO'5
3.40 x 10-2
5.12 x 10-2
1.06 x 10^
9.14 x KH
9.14 x 10^
3.71 x 10-3
3.41 x 10-2
1.09 x 10-4
1.87 x lO'3
1.87 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
wastewaters.
2 Monitor and report as total toluidine PAIs, as Trifluralin.
3 Monitor and report as total dithiocarbamates, as Ziram.
4 Monitor and report as total tin.
5 Applies to purification by recrystalization portion of the process.
2-14
-------
Table 2-4
BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS
FOR DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
2 - Chlorophenol
1 , 2 -Dichlorobenzene
1 , 4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
2 ,4-Dichlorophenol
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chi or ome thane
Bromome thane
Tr ib r omome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT/NSPS effluent limitations1
Maximum for
Any One Day
(pg/L)
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
25
59
89
211
59
26
Maximum for Monthly
Average
(M5/L)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
16
22
40
68
22
15
2-15
-------
Table 2-4
(Continued)
Priority Pollutant
BAT/NSPS effluent limitations1
Maximum for
Any One Day
C«5/U
Maximum for Monthly
Average
Cftg/L)
Tetrachloroethylene
Total Cyanide
Total Lead2
56
640
690
22
220
320
'All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
2-16
-------
Table 2-5
BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR DIRECT
DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
1 , 2 - Dichlorobenzene
1 , 4 -Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Ch 1 o r ome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
BAT/NSPS effluent limitations1
Msnri mum for
Any One Day
Oig/L)
134
380
380
574
59
46
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Ma-rimum for Monthly
Average
(pg/L)
57
142
142
180
22
21
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
2-17
-------
Table 2-5
(Continued)
Priority Pollutant
Total Cyanide
Total Lead2
BAT/NSPS effluent limitations1
Maximum for
Any One Day
<«5/D
640
690
Maximum for Monthly
Average
(MB/D
220
320
'All units are micrograms per liter.
Petals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
2-18
-------
COD are given in Table 2-6; for PAIs in Table 2-7; and for priority pollutants
in Tables 2-4 and 2-5.
The Agency proposes to reserve NSPS for the metallo-organic
pesticide chemicals manufacturing subcategory.
2.1.6 PSES
Pretreatment standards for existing sources which apply to
indirect dischargers are generally analogous to BAT limitations which apply to
direct dischargers. The Agency is proposing PSES for the same PAIs regulated
under BAT and for 26 priority pollutants of the 28 regulated under BAT (which
the Agency has determined pass through POTWs). The proposed standards would
apply to all existing indirect discharging organic pesticide chemicals
manufacturing plants.
EPA determines which pollutants to regulate in PSES on the basis
of whether or not they pass through, cause an upset, or otherwise interfere
with operation of a POTW (including interference with sludge practices). A
detailed discussion of the pass-through analysis conducted for priority
pollutants is presented in Section VI of the OCPSF Development Document. PAI
pass-through analysis is presented in Section 7.
2-19
-------
Table 2-6
NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD
Effluent
Characteristic
COD
BOD5
TSS
PH
Maximum for Any
1 Day
9.36
5.33
4.39
*
Average of Daily Values
Consecutive Days Shall Not
for 30
Exceed**
6.48
1.15
1.30
*
'These standards incorporate a 28 percent flow reduction achievable by new
sources.
*Within the range 6.0 to 9.0.
**Metric units: Kilogram/1,000 kg of PAI produced; English units:
Pound/1,000 Ib of PAI produced; established on the basis of pesticide
production.
2-20
-------
Table 2-7
NSPS AND PSNS EFFLUENT LIMITATIONS
FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen1
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 403
Bus an 853
Butachlor
Captafol
NSPS/PSNS Effluent Limitations
Dally MaziouB Shall Hot Exceed Ib./l.OOO
U>. PAI production
8.54 x 10-5
Monthly Average
Shall Hot Exceed
lb./l,000 li. PAI
production
2.45 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.67 x 10-2
6.35 x 10-*
5.21 x 10-"
1.51 x ID'3
1.85 x 10-3
1.97 x 10-2
2.32 x 10*
1.37 x 10-'
0
1.22 x 10-2
6.33 x lO'3
1.93 x 10-4
2.25 x 10-4
6.58 x 10-4
7.32 x 10-*
1.02 x 10-2
7.82 x 10-5
3.70 x lO'2
0
6.27 x 10-3
No discharge of process wastewater pollutants
3.89 x 10-2
2.84 x 10-3
2.84 x 10-3
4.14 x lO'3
4.14 x 10-3
2.54 x 10-3
3.01 x 10-2
9.14 x 10-*
9.11 x 10-4
1.35 x 10-3
1.35 x 10-3
7.87 x 10-4
No discharge of process wastewater pollutants
2-21
-------
Table 2-7
(Continued)
Organic Pesticide Active
Ingredient
Carbarn S3
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cy anaz ine
Dazomet
DCPA
DBF [S,S,S-Tributyl
phosphorotrithioate ]
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin'-2
Ethion
NSPS/PSNS Effluent Limitations
Daily Maximum Shall Hot Exceed li./ 1,000
Ib. FAX production
4.14 x 10-3
1.07 x 10-3
1.18 x 10-4
5.87 x 10-2
1.09 x ID'3
2.35 x 10^
1.18 x 10-3
4.14 x 10-3
5.61 x 10-2
1.15 x 10-2
2.05 x 10-3
Monthly Average
Shall Hot Exceed
Ih./l.OOO Ib. PAI
production
1.35 x 10-3
4.76 x W^
2.80 x lO'5
2.39 x 10-2
3.29 x 10"4
7.17 x 10-5
5.84 x W^
1.35 x lO'3
1.90 x lO'2
5.58 x 10-3
8.13 x 10*
No discharge of process wastewater pollutants
6.88 x ID*5
3.41
1.51 x 10-'
5.28 x 10-3
2.27 x 10-2
2.13 x 10-5
1.03
5.76 x lO-2
2.72 x 10-3
1.01 x 10-2
No discharge of process wastewater pollutants
1.77 x 10-2
2.32 x 10-*
5.31 x 10^
5.25 x 10-3
7.85 x 10-3
2.15 x 10-"
2-22
-------
Table 2-7
(Continued)
Organic Pesticide Active
Ingredient
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate , salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Me thoxy chl o r
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norflurazon
NSPS/PSNS Effluent Limitations
Daily Maximum Shall Not Exceed lb./ 1,000
li, PAI production
7.31 x lO'2
1.06 x 10-2
1.32 x 10-2
3.91 x 10-3
Monthly Average
Shall Hot Exceed
lb./l,000 It. PAI
production
2.60 x 10-2
5.50 x 10-3
6.79 x 10-3
1.50 x ID'3
No discharge of process wastewater pollutants
5.42 x 10-3
5.07 x 10-3
4.14 x 10-3
1.94 x 10-3
1.69 x 10"
1.73 x 10-3
1.82 x 10-3
1.35 x 10-3
1.40 x 10-3
6.88 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.05 x 10-2
2.75 x 10-3
2.34 x 10-3
9.80 x 10-3
1.03 x 10*
4.14 x 10-3
4.14 x 10-3
5.58 x lO'3
5.42 x 10-3
1.27 x 10-3
9.25 x 10"
5.06 x 10-3
3.69 x 10-5
1.35 x lO'3
1.35 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2-23
-------
Table 2-7
(Continued)
Organic Pesticide Active
Ingredient
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Pentachlorophenol , salts
and esters
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
S imaz ine
Stirofos
TCMTB
Tebuthiuron
Terbacil
NSPS/PSNS Effluent Limitations
Daily Hnriimm Shall Hot. Exceed Ib./l.OOO
Ib. PAI production
1.25 x lO'2
5.56 x W*
5.56 x 10-1
4.16 x 10^
8.81 x 1C'3
Monthly Average
Shall Hot Exceed
Ib./l.OOO Ib. PAI
production
5.36 x lO'3
2.45 x 1O4
2.45 x 10-4
1.38 x 10-4
2.79 x 10-3
No discharge of process wastewater pollutants
1.68 x 10-4
1.81 x 10"4
4.39 x 10-5
5.43 x 10-5
No discharge of process wastewater pollutants
1.51 x 10-3
1.51 x 10"3
1.28 x 10-4
3.84 x lO'3
7.63 x W-4
1.51 x 10-3
6.58 x 1O4
6.58 x 10-4
4.34 x lO'5
1.19 x 10-3
3.48 x W^
6.58 x 10"1
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.51 x 10-3
2.95 x ID'3
2.07 x W*
7.04 x 10-2
1.09 x 10-'
6.58 x 10*
9.72 x W*
6.45 x 10-5
2.45 x lO'2
3.69 x 10-2
2-24
-------
Table 2-7
(Continued)
Organic Pesticide Active
Ingredient
Terbufos
Terbuthylaz ine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [Sodium
methyldithiocarbaraate]
Ziram3 [Zinc
dimethyldithiocarbamate ]
NSPS/PSNS Effluent Limitations
Daily Maximum Shall Hot Exceed Lb./ 1,000
11). FAX production
2.95 x 10-*
1.51 x 10-3
1.51 x 1C'3
7.35 x lO'3
4.69 x lO'2
2.32 x 1C"4
3.86 x 10-3
4.14 x 10-3
Monthly Average
Shall Hot Exceed
U>./1,000 Ib. PAI
production
7.62 x 10-5
6.58 x 10"
6.58 x 10"
2.67 x ID'3
2.46 x 10-2
7.82 x 10-5
1.39 x 10-3
1.35 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
wastewaters.
2Monitor and report as total toluidine PAIs, as Trifluralin.
3Monitor and report as total dithiocarbamates, as Ziram.
4Monitor and report as total tin.
5Applies to purification by recrystallization portion of the process.
2-25
-------
Indirect dischargers generate wastewater with the same pollutant
characteristics as the direct dischargers; therefore, the same technologies
that were discussed for BAT are appropriate for application of PSES. For
priority pollutants, the Agency established PSES for all indirect dischargers
on the same technology basis as PSES in the OCPSF Development Document. PSES
for PAIs and priority pollutants in the organic pesticide chemicals
manufacturing subcategory are shown in Tables 2-3 and 2-8, respectively.
The Agency proposes to reserve PSES for the metallo-organic
pesticide chemical manufacturing subcategory.
2.1.7 PSNS
PSNS which apply to new facilities are generally analogous to PSES
which apply to existing facilities. The Agency is proposing PSNS for PAIs
under the organic pesticide chemicals manufacturing subcategory on the same
technology basis as PSES with a 28% achievable flow reduction for certain
PAIs. For priority pollutants, the Agency established PSNS for all indirect
dischargers on the same technology basis as PSNS in the OCPSF Development
Document. PSNS for PAIs and priority pollutants in the organic pesticide
chemicals manufacturing subcategory are shown in Tables 2-7 and 2-8,
respectively.
The Agency proposes to reserve PSNS for the metallo-organic
pesticide chemicals manufacturing subcategory.
2-26
-------
Table 2-8
EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
1 , 2 -Dichlorobenzene
1,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-Trans-Dichloroethylene
1, 2-DIchloropropane
1, 3-Dichloropropene
2 , 4 - D ime thy Ipheno 1
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
T r ib r omome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
PSES/PSNS Effluent Limitations
Maximum for Any One Day
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Maximum for Monthly
Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
2-27
-------
Table 2-8
(Continued)
Priority Pollutant
Total Cyanide
Total Lead2
PSES/PSNS Effluent Limitations
Maximum for Any One Day
640
690
Maximum for Monthly
Average
220
320
'All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead and zinc from complexed metal-bearing process wastewater
are not subject to these limitations.
2-28
-------
SECTION 3
INDUSTRY DESCRIPTION
3.0 INTRODUCTION
This section discusses characteristics of the Pesticide Chemicals
Manufacturing Industry and presents the following topics:
• Methods of data collection used by EPA;
• Overview of the industry;
• Pesticide production;
• Pesticide manufacturing processes; and
• Changes in the industry.
3.1 DATA COLLECTION METHODS
EPA has gathered and evaluated technical data from various sources
in the course of developing the effluent limitations guidelines and standards
for the Pesticide Chemicals Manufacturing Industry. These data sources
include:
Responses to EPA's Questionnaire entitled "Pesticide
Manufacturing Facility Census for 1986" (the "Facility
Census");
EPA's 1988-1990 sampling of selected pesticide
manufacturers;
Industry self-monitoring data;
Industry treatability studies;
3-1
-------
• EPA treatability studies;
• Previous EPA Office of Water studies of Pesticides Industry;
• Literature data;
• Toxic Release Inventory (TRI) database;
• Data transferred from the OCPSF Rulemaking;
• Office of Pesticide Programs (OPP) database; and
• Other EPA studies of Pesticides Industry.
EPA used data from these sources to profile the industry with respect to:
production; manufacturing processes; geographical distribution; and wastewater
generation, treatment, and disposal. EPA then characterized the wastewater
generated by pesticide manufacturing operations through an evaluation of water
use, type of discharge or disposal, and the occurrence of conventional, non-
conventional, and priority pollutants.
3.1.1 PesticideProduct Registration Process
A pesticide, as defined by the Federal Insecticide, Fungicide, and
Rodenticide Act (FIFRA), includes "any substance or mixture of substances
intended for preventing, destroying, repelling, or mitigating any pest, and
any substance or mixture of substances intended for use as a plant regulator,
defoliant, or desiccant." Under FIFRA all pesticides must be registered with
EPA prior to shipment, delivery, or sale in the United States. A pesticide
product is a formulated product; that is, it is a mixture of an "active
3-2
-------
ingredient" (the PAI) and "inert" diluents. Each formulation has a distinct
registration.
As part of its activities in regulating pesticides, EPA requires
all producers of pesticides (technical grade and formulated product) to report
annually the amount of pesticides produced by that facility each year. The
database containing these reports provides comprehensive data concerning the
PAIs produced in the United States and, therefore, is an excellent single
source of information on which PAIs are potentially manufactured in the United
States. This source is treated by EPA as Confidential Business Information
because it contains production information. Other sources, such as the
"Directory of Chemical Producers" published by SRI International, list
chemicals and the producer of each chemical, including chemicals typically
used as pesticides. This source does not include any production information
and is publicly available.
Although the data sources discussed above were very useful, the
most focused, comprehensive source of information on which facilities
manufactured PAIs was the administrative record for the remanded 1985
pesticide chemicals effluent limitations guidelines and standards.
3.1.2 Selection of PAIs for Study
For the Pesticide Chemicals Manufacturing Category, there are 270
PAIs or classes of PAIs that EPA considered for regulation. The initial basis
3-3
-------
for this list was the 284 PAIs and classes of PAIs presented in Appendix 2 of
the October 4. 1985 regulation (50 FR 40672). These 284 PAIs were originally
selected in 1977 on the basis of significant production and/or commercial use.
EPA then expanded this list to 835 PAIs by adding the following group of PAIs:
All salts and esters of listed organic acids (such as
2,4-D);
All metallo-organic PAIs (consisting of an organic portion
bonded to arsenic, cadmium, copper, or mercury);
All organo-tin PAIs;
All PAIs that appeared to be structurally similar to other
listed PAIs (such as organo-phosphorus pesticides); and
Any other PAIs with an analytical method previously
demonstrated to be applicable to wastewater.
EPA excluded from this list of 835 PAIs those PAIs already subject
to regulation under other effluent guidelines specifically, those regulated
by OCPSF (40 CFR Part 414), Inorganic Chemicals Manufacturing (40 CFR part
415), and Pharmaceuticals (40 CFR Part 439). Information provided to EPA
under FIFRA indicated that 335 of those 835 PAIs were produced in 1984-1985,
and the other 500 were not produced for domestic use in either 1984 or 1985.
An additional 15 (of the 835) were added to the 335 PAIs because those 15 PAIs
had been manufactured prior to 1984 and might still be manufactured for
export. The list of 350 PAIs and derivatives, such as salts and esters, was
then consolidated by putting salts and esters of a PAI into a PAI class, to
arrive at a total of 270 PAIs and classes of PAIs. Because the consolidated
3-4
-------
classes include all elements of the class, such as all salts and esters of
2,4-D (i.e., not just those in use in 1986), the 270 PAIs and classes of PAIs
actually include 606 of the 835 specific PAIs. Figure 3-1 presents a flow
chart of the methodology for determining which PAIs were included in the
Pesticide Manufacturing Facility Census of 1986. Table 3-1 lists the PAIs and
classes of PAIs considered for regulation.
3.1.3 Development of the "Pesticide Manufacturing Facility Census of
1986"
A major source of information and data used in developing effluent
limitations guidelines and standards is industry responses to questionnaires
distributed by EPA under the authority of Section 308 of the Clean Water Act.
These questionnaires typically request information concerning production
processes and pollutant generation, treatment, and disposal, as well as
wastewater treatment system performance data. Questionnaires also request
financial and economic data for use in assessing economic impacts and the
economic achievability of technology options.
EPA used its experience with previous questionnaires, including
the questionnaires distributed to the pesticides industry for the remanded
regulation, to develop a draft questionnaire for this study. EPA sent the
draft questionnaire to pesticide industry trade associations, pesticide
manufacturers and pesticide formulator/packagers who had expressed interest,
and to environmental groups for review and comment. Based on the comments
3-5
-------
Figure 3-1
FLOW CHART FOR DETERMINING INCLUSION OF PAI
IN PESTICIDE MANUFACTURING FACILITY CENSUS FOR 1986
284 PAIs
addressed in
1985 Rule
All salts or esters of PAIs addressed in 1985 Rule
(such as salts and esters of 2,4-D)
All specific examples of metallo-organic PAIs
( organic portion bonded to arsenic, cadmium, copper, or mercury)
All organo-tin PAIs
PAIs with structural similarity to PAIs included in 1985 Rule
(such as organo-phosphorus compounds)
PAIs known to have an analytical method promulgated or ready
to promulgate under §304(h) of the Clean Water Act
835 PAIs
Identified
as Potential
Candidates for
Regulation
WasPAl
Believed to
Be In
Production?
606 PAIs condensed into
272 PAIs or classes of PAI
Included in DCP
Was the
PAI a salt, aster,
or metallo-organic
of one of the
PAIs
3-6
-------
Table 3-1
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
10S01
51501
42002
82901
29001
12601
12602
17901
109901
44901
55004
55001
84001
102401
82601
**
82001
**
PAI
Coda
1
2
3
4
5
6
6
7
8
9
10
11
12
13
14
14
15
15
Chemical Hane
1 , 1-Bis ( chlorophenyl) -2 , 2 , 2-tr ichloroethanol [Dicof ol]
l,2-Dihydro-3,6-pyridazinedione [Maleic Hydrazide]
1,2-Ethylene dibromide [EDB]
1,3,5-Triethythexahydro-s-Triazine (Vancide TB]
1 , 3-Di chloropropene
Fhenarsazine Oxide
10 , 10 ' -Oxybisphenoxarsine
[l-(3-Ch.loroallyl)-3,5,7-triaza-l-azoniaadamantane chloride]
[Dowicil 75]
l-(4-Chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l-yl)
-2-butanone (Triadimefon)
2,2' -Methylenebis (3,4, 6-trichlorophenol ) [Bexachlorophene ]
2,2' -Methy lenebis ( 4 , 6-di chlorophenol ) [Tetr achlorophene ]
2,2'-Methylenebis(4-chlorophenol) tDichlorophene]
2,2-Dichlorovinyl dimethyl phosphate [Dichlorvos]
2,3,5-TrimethylphenyJjnethylcarbajnate [Landrin-2]
2,3,6-Irichlorophenylacetic acid [Fenac]
2,3,6-Trichlorophenylacetic acid, salts and esters
2,4,5-Trichlorophenoxyacetic acid [2,4,5-T]
2,4,5-Trichlorophenoxyacetic acid, salts and esters
eta *
00115-32-2
00123-33-1
00106-93-4
07779-27-3
00542-75-6
00058-36-6
04095-45-8
04080-31-3
43121-43-3
00070-30-4
01940-43-8
00097-23-4
00062-73-7
02686-99-9
00085-34-7
**
00093-76-5
**
Structural Group
DDT
Heterocyclic
EDB
s-Triazine
Alkyl halide
Organoarsenic
Organoarsenic
Anmonium
1,2,4-Pentacylcictriazine
Bis tri chlorophenol
Aryl halide
Axyl halide
Phosphate
Carbamate
Trichlorophenylacetic acid
Trichlorophenylacetic acid
Phenoxy acid
Phenoxy acid
Pesticida Type
Insecticide
Herbicide, growth regulator
Fumigant
Fungicide
Nematocide
Fungicide
Fungicide
Disinfectant
Fungicide
Disinfectant
Disinfectant
Disinfectant
Insecticide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
u>
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
LO
03
30001
**
30801
**
80811
36001
31301
8707
15801
39001
84101
100101
19101
30501
**
PAI
Coda
16
16
17
17
18
19
20
21
22
23
2k
25
26
27
27
Chemical Hame
2,4-Dichlorophenoxyacetic acid [2,4-D]
2,4-Dichlorophenoxyacetic acid, salts and esters
2,4-Dichlorophenoxybutyric acid [2,4-DB]
2,4-Dichlorophenoxybutyric acid, salts and esters
2, 4-Dichloro-6-(0-chloroanilino) -s-Triazine [Anilazine]
2,4-Dinitro-6-octylphenylcrotonate, 2,6-Dinitro-
4-octylphenylcrotonate, and Nitrooctylphenols [Dinocap]
(The octyl's are a mixture of 1-Methylheptyl, 1-Ethylhexyl,
and 1-Propylpentyl)
2, 6-Dichloro-4-nitroaniline [Dichloran]
2-Bromo-4-hydroxyacetophenone [Bus an 90]
2-Carbomethoxy-l-methylvinyl dimethyl phosphate, and related
compounds [Mevinphos]
2-Chloroallyl diethyldithiocarbamate [Sulfallate]
2-Chloro-l-(2,4-dichlorophenyl)vinyl diethyl phosphate
[Chlorfenvinphos]
2-Chloro-4-(l-cyano-l-methylethyl)amino)-6-ethylamino) -s-Triazine
[Cyanazine]
2-Chloro-N-isopropylacetanilide [Propachlor]
2-Methyl-4-chlorophenoxyacetic acid [MCPA]
2-Methyl-A-chlorophenoxyacetic acid, salts and esters
CAS #
00094-75-7
**
00094-82-6
**
00101-05-3
39300-45-3
00099-30-9
02491-38-5
07786-34-7
00095-06-7
00470-90-6
21725-46-2
01918-16-7
00094-74-6
**
Structural Group
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
s-Triazine
Phenylcrotonate
Haloaryl
Miscellaneous
Phosphate
Dithiocarbamate
Phosphate
s-Triazine
Acetanilide
Chlorophenoxy acid
Chlorophenoxy acid
Pesticide Type
Herbicide
Herbicide
Herbicide
Herbicide
Insecticide
Fungicide
Slimicide
Insecticide
Herbicide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
99901
67703
31401
**
31501
**
60101
80815
21201
**
35603
99001
67707
102401
101701
100501
28201
107801
Btt
Coda
28
29
30
30
31
31
32
33
3ino)-s-Triazine
2-(m-Chlorophenoxy)propionic acid fCloprop]
Z- (m-Chlorophenoxy Jpropionic acid, salts and esters
2-(Thiocyanomethylthio)benzothiazole [TCMTB)
2-((Hydroxymethyl)amino) ethanol [HAE]
2-((p-Chlorophenyl)phenylacetyl)-l,3-indandione [Chlorophacinone]
3,4,5-trimethylphanyl tnathylcarbamate [Landrin-1)
3,5-Dichloro-N-(l,l-ditnethyl-2-propynyl)benzamide [Pronamide]
3,5-Dimethyl-4-(methylthio)phenyl dimethylcarbaraate (Methiocarb]
3' ,4' -Dichloropropionanilide [Propanil]
3-Iodo-2-propynyl butylcarbamate [Polyphase antitnildaw)
CAS #
26530-20-1
00083-26-1
00120-36-5
**
00093-65-2
**
00148-79-8
22936-75-0
00101-10-0
**
21564-17-0
34375-28-5
03691-35-8
02655-15-4
23950-58-5
02032-65-7
00709-98-8
55406-53-6
Structural Group
Heterocyclic
Indandione
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
Heterocyclic
Triazine
Fhenoxyacetic acid
Phenoxyacetic acid
Heterocyclic
Alcohol
Indandione
Carbaraate
Chlorobenz amide
Carbamate
Chloropropionani lide
P«atiolde Type
Fungicide
Rodenticide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Herbicide
Herbicide
Herbicide
Fungicide
Bacteriostat
Rodenticide
Insecticide
Herbicide
Insecticide, Molluscide
Herbicide
Fungicide
OJ
VO
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
86001
**
37507
101101
19401
**
19201
**
44401
84701
55501
59804
103301
114401
**
90501
FAX
Code
43
44
45
46
46
47
47
48
49
50
51
52
53
53
54
Chemical Hame
3-(a-Acetonylfurfuryl)-4-hydroxycoumarin [Coumafuryl]
3-(a-Acetonylfur£uryl)-4-hydroxycoumarin, salts and esters
4,6-Dinitro-o-cresol [DNOC]
4-Amino-6-
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
98301
69105
**
80801
106201
80803
105201
99101
8901
9501
10101
104301
17002
12301
12302
35301
PAI
Coda
55
56
57
58
59
60
61
62
63
64
65
66
67
68
68
69
Cheaical Hana
Aldicarb (2-Methyl-2-(n>ethylthio)propionaldehyde
O- (me thy Icarbamoyl )oxime )
[ALkyl* dimethyl benzyl Anmonium chloride
* (50Z C14, 401 C12, 101 C16)]
Allethrin (all isomars and allethrin coil)
Ametryn (2-(Ethylan>ino)-4-(isopropylamino)-6-(methylthio)-
s-Triazine
Amitraz (N'-2.4-Dimethylphenyl)-H-( ( (2,4-diraethylphenyl)
imino)methyl)-N-methyln>ethanimidainide)
Atrazine (2-Chloro-4-(ethylamino) -6- (isopropylamino) -s-Triazine)
Bendiocarb (2,2-Dimethyl-l, 3-benzodioxol-4-yl methylcarbamate
Benomyl (Methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate)
Benzene Hexachloride
Benzyl benzoate
Beta-Thiocyanoethyl esters of mixed fatty acids containing from
10-18 carbons [Lethane 384)
Bifenox [Methyl-5-(2,4-dichlorophenoxy)-2-nitrobenzoateJ
Biphenyl
Bromacil (5-Bromo-3-sec-Butyl-6-raathyluracil]
Bromacil, lithium salt
Brotaoxynil [3, 5-Dibromo-4-hydroxybenzonitrile)
CAS #
00116-06-3
68424-85-1
**
00834-12-8
33089-61-1
01912-24-9
22781-23-3
17804-35-2
00608-73-1
00120-51-4
00112-56-1
42576-02-3
00092-52-4
00314-40-9
53404-19-6
01689-84-5
Structural Group
Carbamate
Ammonium
Cyclopropanecarboxylic acid
s-Triazine
s-Triazine
Carbamate
Carbamate
Arylhalide
Aryl
Thiocyanate
Nitrobenzoate
Aryl
Uracil
Uracil
Benzonitrile
Pesticide Type
Insecticide
Antimicrobial
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Fungicide - vegetables
Disinfectant
Repellant
Insecticide
Herbicide
Fungicide
Herbicide
Herbicide
Herbicide
co
I
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
35302
112301
101*01
12501
**
81701
81301
56801
90601
90602
29901
**
58201
27301
81501
81901
25501
FAX
Coda
69
70
71
72
72
73
74
75
76
77
78
78
79
80
81
82
83
Cb««loal Haoa
Bromoxynil octanoate
Butachlor (N-(Butoxymethyl)-2-chloro-2' , 6' -diethylacetanilide]
'-Bromo-'-nitrostyrane [Giv-gard]
Cacodylic acid [Dlmethylarsenic acid]
Cacodylic acid, salts and esters
Captafol [eis-N-< (1,1,2, 2-Tetrachloroethyl)thio)-4-cyclohexene-
1,2-dicarboximide]
Captan [H-Trichloromethylthio-4-cyclohexene-l,2-carboxiniidel
Carbaryl [ 1-Naphthylmethylcarbamate]
Carbofuran [2,3-Dihydro-2,2-dimethyl-7-benzofuranyl
methy Ic arbamate ]
CarbosuLf an [ 2 , 2-Dihydro-2 , 2-dimethyl-7-benzof ur anyl ( dibutylamino )
thio )methy Icarbamate ]
Chloramben [3-Amino-2, 5-dichlorobenzoic acid]
Chloramben, salts and esters
Chlordahe [Octachloro-4 , 7-methanotetrahydroindane]
Chloroneb [l,4-Dichloro-2, 5-dimethoxybenzene]
Chloropicrin [Trichloronitromethane]
Chlorothalonil [2,4 , 5, 6-Tetrachloro-l , 3-dicyanobenzene ]
Chloroxuron [3-(4-(4-Cb.lorophenoxy)phenyl)-l,l-dimethylurea]
CAS *
01689-99-2
23184-66-9
07166-19-0
00075-60-5
**
02425-06-1
00133-06-2
00063-25-2
01563-66-2
55285-14-8
00133-90-4
**
00057-74-9
02675-77-6
00076-06-2
01897-45-6
01982-47-4
Structural Group
Benzonitrile
Acetanilide
Mi Ecellaneous
Organoarsenic
Organoarsenic
Phthalimide
Fhthalimide
Carbamate
Carbamate
Carbamate
Haloaryl
Baloaryl
Multiring halide
Arylchloride
Alkyl halide
Fhthalonitrile
Urea
F«sticide Type
Herbicide
Herbicide
Slimicide
Herbicide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide
Insecticide
Herbicide
Herbicide
Insecticide
Fungicide
Fumigant
Fungicide
Herbicide
CO
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
83701
59102
59101
14504
24002
39105
109301
43401
28901
*«
27501
57601
104801
14502
11301
FAX
Cod*
84
85
86
87
88
89
90
91
92
92
93
94
95
96
97
Chemical Bane
Chloro-l-(2,4,5-trichlorophanyl)vinyl dimethylphosphate [Stirofos]
Chlorpyrifos methyl tO,0-Dimethyl 0-(3,5,6-trichloro-2-pyridyl)
phosphor othioate]
Chlorpyrifos [0,0-Diethyl 0-(3,5,6-trichloro-2-pyridyl)
[phosphorothioatej
Coordination product of Manganses 16Z, Zinc 21, and
Ethylenebisdithiocarbamate 622 [MancozebJ
Copper 8-hydroxyquinoLine
Copper ethylenediaminetetraacetate
Cyano(3-phonoxyphenyl)methyl 4-ehloro-a-(l-inethylethyl)
benzeneacetate (9CA) [Fenvalerate]
Cyclohaximide [3- (2- (3 , 5-0imethyl-2-oxocyclohexyl)-2-hydroxyethyl)
glutarimide]
Dalapon (2,2-dichloropropionic acid)
Dalapon, salts and esters
Decachloro-bis(2,4-cyclopentadiene-l-yl) [DienochlorJ
Demeton [0,O-Diethyl 0-(and S-)(2-ethylthio)ethyl)
phosphorothioate]
Desmedipham [Ethyl m-hydroxycarbanilate carbanilate]
DiAnnonium salt of ethylenebisdithiocarbamate
Dibromo-3-chloropropane [DBCP]
CAS #
00961-11-5
05598-13-0
02921-88-2
08018-01-7
10380-28-6
14951-91-8
51630-58-1
00066-81-9
00075-99-0
**
02227-17-0
08065-48-3
13684-56-5
03566-10-7
00096-12-8
Structural Group
Phosphate
Phosphorothioate
Phosphorothioate
Dithiocarbamate
Organocopper
Organo-copper
Benzeneacetic acid ester
Cyclic ketona
AUcylhalide
Alkylhalide
Arylchloride
Phosphor odithioate
Carbamate
Dithiocarbamate
EDB
PAatioide Type
Insecticide
Insecticide
Insecticide
Fungicide
Fungicide
Slimicide
Insecticide
Growth regulator
Herbicide
Herbicide
Miticide
Insecticide
Herbicide
Fungicide
Hematocide
CO
I-1
Ul
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
29801
**
29601
103401
32101
66501
57801
106201
69122
35001
53501
35201
58601
78701
57901
FAX
Ccxfo
98
98
99
100
101
102
103
104
105
106
107
108
109
110
111
' ' Chemical Bane
Dicamba [3,6-Dichloro-o-anisic acid]
Dicamba, salts and esters
Dichlone [2, 3-Dichloro-l, 4-naphthoquinone]
Diethyl 4,4'-o-phenylenebis(3-thioallophanate) [Thiophanata ethyl]
Di ethyl diphenyl dlchloroethane and related compounds [Per thane]
Diethyl dithiobis(thionoformate) [EXDJ
Diethyl 0-{2-isoprppryl-6-methyl-4-pyrimidinyl) phosphorothioate
[Diazinon]
Dif lubenzuron [H-{ ( (4-Chlorophenyl)amino)carbonyl)-
2 , 6-di f luor obenzami de ]
Diisobutylphenoxyethoxyethyl dimethl benzyl Ammonium chloride
[Benzethonium chloride]
Dimethoate [0,0-Dimethyl
[S- ( (methylcarbamoyl)methyl)phosphorothioate]
Dimethyl 0-p-nitrophenyl phosphorothioate [Parathion methyl]
Dimethyl phosphate ester of 3-hydroxy-N,N-dimethyl-cis-crotonate
[Dicrotophos]
Dimethyl phosphate ester of a-methylbenzyl 3-hydroxy-cis-crotonate
[Crotoxyphos]
Dimethyl 2,3,5,6-tetrachloroterephthalate [DCPA]
Dimethyul (2,2,2-trichloro-l-hydroxyethyl) phosphonate
[Trichlorofon]
CAS #
01918-00-9
**
00117-80-6
23564-06-9
00072-56-0
00502-55-6
00333-41-5
35367-38-5
00121-54-0
00060-51-5
00298-00-0
00141-66-2
07700-17-6
01861-32-1
00052-68-6
Structural Group
Aryl halide
Aryl halide
Aryl halide
Carbamate
DDT
Dithiocarbamate
Phosphorothioate
Benzamide
R4N
Phosphorodithioate
Phosphorothioate
Phosphate
Phosphate
Terephthalic acid ester
Phosphonate
Pastioide Typa
Herbicide
Herbicide
Fungicide
Fungicide
Insecticide
Herbicide
Insecticide
Insecticide
Disinfectant
Insecticide
Insecticide
Insecticide, Miticide
Insecticide
Herbicide
Insecticide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
37505
37801
67701
36601
38501
47201
63301
35505
44303
44301
79401
38901
** •
41601
113101
58401
41101
PAI
Code
112
113
114
115
116
117
118
119
120
121
122
123
123
124
125
126
127
Chemical Dane
Dinoseb [2-sec-Butyl-4,6-dinitrophenol]
Dioxathion [2,3-p-Dioxanedithiol S,S-bis(0,0-diethyl
[phosphorodithioate) ]
Diphacinone [2-(Diphenylacetyl)-l,3-indandione]
Diphenamid [N,N-Dimethyl-2,2-diphenylacetamide]
Diphenylamine
Dipropyl isocinchomeronate [MGK 326)
Disodium cyanodithioimidocarbonate [Nabonate]
Dluron (3-(3,4-Dichlorophenyl)-l, 1-dimethylurea]
Dodecylguanidine hydrochloride [Metasol DGH]
Dodine [Dodecylquanidine acetate]
Endosulfan [Hexachlorohexahydromethano-2,4, 3-benzodioxathiepin-
3-oxide]
Endothall [7-Oxabicyclo(2,2, l)heptane-2, 3-dicarboxylic acid]
Endothall, salts and esters
Endrin [Hexachloroepoxyoctahydro-endo , endo-diraethanonaphthalene ]
Ethalfluralin [N-Ethyl-N-(2-methyl-2-propenyl)-2,6-dinitro-
4- ( tr i fluoromethy 1 )benzeneamine ]
Ethion [0,0,0' ,0'-Tetraethyl S,S'-methylene bisphosphorodithioate]
Ethoprop [0-Ethyl S,S-dipropyl phosphorodithioate]
CAS t
00088-85-7
00078-34-2
00082-66-6
00957-51-7
00122-39-4
00113-48-4
00138-93-2
00330-54-1
13590-97-1
02439-10-3
00115-29-7
00145-73-3
**
00072-20-8
55283-68-6
00563-12-2
13194-48-4
Structural Group
Phenol
Phosphorodithioate
Indandione
Ac et amide
Arylamine
Aryl/aLkyl ester
Isocyanate
Urea
Ammonium
Ammonium
Multiring halide
Bicyclic
Bicyclic
Tricyclic
Toluidine
Phosphorodithioate
Phosphorodithioate
Pesticide Type
Herbicide
Insecticide
Rodenticide
Herbicide
Insecticide
Repellant
Slimicide
Herbicide
Fungicide
Fungicide
Insecticde
Herbicide
Herbicide
Insecticide
Herbicide
Insecticide
Insecticide
OJ
M
Ul
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
100601
28801
41405
59901
206600
53301
34801
35503
75002
81601
103601
**
103602
44801
115601
107201
PAI
Coda
128
129
130
131
132
133
134
135
136
137
138
138
139
140
141
142
Chemical Bane
Ethyl 3-methyl-4-(methylthio)phenyL l-(methylethyl)
phosphor amidate [Fenamiphos]
Ethyl 4,4'-dichlorob8nzilate [Chlorobenzilate]
Ethyl dlisobutylthiocarbamate [Butylate]
Famphur {0,O-Dimethyl 0-(p-(dimethylsul£amoyl)phenyl)
phosphorothioate]
Fenar imol [ a- ( 2-Chloropheny 1 ) - a- ( 4- chloropheny 1 )
-5-pyrimidinemethanol]
Fenthion [0.0-Diniethyl 0-(4-methylthio)-m-toluyl)phosphorothioate]
Ferbam [Ferric dimethyldithiocarbamate]
Fluometuron (1, l-Dimethyl-3-(a, a, a-trifluoro-m-tolyl)uraa]
Fluoroacetamide
Folpet [N-( (Trichloromethyl)thio)phthalimide)
GLyphosate [N- (Phosphonomethyl)glycine]
Glyphosate, salts and esters
Glyphosine [N,N-bis(Fhosphonomethyl)glycine]
Heptachlor [Beptachlorotetrahydro-4 , 7-methanoindene]
Hexadecyl cyclopropanecarboxylate [Cycloprate]
Hexazinone [ 3-Cyclohexyl-6-( dimethylami.no )- 1-methyl-
1.3,5-triazine-2,4-(lH,3H)-dione]
CAS t
22224-92-6
00510-15-6
02008-41-5
00052-85-7
60168-88-9
00055-38-9
14484-64-1
02164-17-2
00640-19-7
00133-07-3
01071-83-6
**
02439-99-8
00076-44-8
54460-46-7
51235-04-2
Structural Group
Fhosphoroamidate
Aryl halide
Carbamate
Fhosphorothioate
Pyrimidine
Fhosphorothioate
Dithiocarbamate
Urea
Amide
Fhthalimide
Phosphor amidate
Phosphor amidate
Phosphor amidate
Tricyclic
C-H-0
s-Triazine
Pactiolde Typ«
Nematocide
Miticide
Herbicide
Insecticide
Fungicide
Insecticide
Fungicide
Herbicide
Rodenticide
Fungicide
Herbicide
Herbicide
Herbicide
Insecticide
Herbicide
10
I
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
109401
100201
47601
97401
9001
35506
39504
57701
14505
34802
114001
**
101201
100301
90301
PAI
Cod*
143
144
145
146
147
148
149
150
151
152
153
153
154
155
156
Chemical State
Isofenphos t 1-Methylethyl 2-((ethoxy((l-methylethyl)amino)
phosphinothioyl)oxy)benzoate]
Isopropalln [2 , 6-Dinitro-H, N-dipropy Icumidine ]
Isopropyl N-phenyl carbamate [Propham]
Karbutllate [tert-Butylcarbamic acid ester of 3-(m-hydroxyphenyl)-
1, 1-dimethylurea]
Lindens [gamma isomer of Benzene hexachloride, 99Z pure]
Linuron [3-(3,4-Dichlorophenyl)-l-methoxy-l-methylurea]
Malachite green [Ammonium(4-(p-(dimethylamino)-alpha-
phenylbenzylidine ) -2 , 5-cyclohexadien- 1-ylidene ) -dimethyl
chloride]
Malathion [0,0-Dimethyl dithiophosphate of diethyl
[mere apt o sue c inate ]
Maneb [Manganese salt of ethylenebisdithiocarbamate]
Manganous dimethyldithiocarbamate
Mefluidide [N-(2,4-dimethyl-5-« (trifluoromethyl)sulfonyl)
amino)phenylacetamide]
Mefluidide, salts and esters
Methamidophos [0, S-Dimethyl phosphor amidothioate]
Methidathion [0,0-Dimethyl phosphorodithioate, S-ester of
4-(mercaptomethyl)-2-methoxy-delta 2-l,3,4-thiadiazolin-5-one]
Methomyl [S-Msthyl N-< (methylcarbamoyl)oxy)thioacetimidatej
CAS t
25311-71-1
33820-53-0
00122-42-9
04849-32-5
00058-89-9
00330-55-2
00569-64-2
00121-75-5
12427-38-2
15339-36-3
53780-34-0
**
10265-92-6
00950-37-8
16752-77-5
Structural Group
Phosphoroamidothioate
Toluidine
Carbamate
Carbamate ester
Arylhalide
Urea
R4N
Phosphorodithioate
Dithiocarbamate
Dithiocarbamate
Acetamide
Acetamide
Phosphoroamidothioate
Phosphorodithion
Carbamate
Pecticide Type
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Herbicide
Fungicide, Bactariostat
Insecticide
Fungicide
Fungicide
Defoliant
Defoliant
Insecticide
Insecticide, Miticida
Insecticide
CO
I
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
105401
34001
69134
53201
**
69129
68102
54101
108801
44201
14601
35502
35501
103001
80301
PAX
Coda
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
Chemical Kane
Methoprene [Isopropyl(E,E)-ll-methoxy-3,7, 11-trimethyl-
2,4-dodecadienoate]
Methoxychlor [2,2-bis(p-methoxyphenyl)-l, 1, 1-trichloroethane]
Mathylbenzethonium chloride
Methylbromide
Methylarsonic acid, salts and esters
MathyldodecyLbenzyl trinethyl Ammonium chloride 80Z and
methyldodecylxylylene bis(trimethylanmoniumchloride) 20Z
(HYAMINE 2389]
Methylene bisthiocyanate [Nalco 0-2303]
Methyl-2,3-quinoxalinedithiol cyclic S,S-dithiocarbamate
[Quinmethionate]
Metolachlor [2-Chloro-N-(2-ethyl-6-methylphenyl)-N-
(2-methoxy-l-a)ethylethyl)acetamide]
Mexacarbate [4-(Dimethylamino)-3,5-xylyl methylcarbamate]
Mixture of 83. 9Z Ethylenebis(dithiocarbamato) zinc and 16. 1Z
EthyLenebisdithiocarbamate, bimolecular and trimolecular cyclic
anhydrosulfides and disulfides [Metiram]
Monuron TCA = Monuron trichloroacetate
Monuron [3-(4-Chlorophenyl)-l, 1-dimethylurea]
N,N-Diethyl-2-(l-naphathalenyloxy)propionamide [Napropamide]
H.N-Diethyl-meta-toluaniide and other isotners [Deet]
CAS t
40596-69-8
00072-43-5
15716-02-6
00074-83-9
**
01399-80-0
06317-18-6
02439-01-2
51218-45-2
00315-18-4
09006-42-2
00140-41-0
00150-68-5
15299-99-7
00134-62-3
Structural Group
Estar
DDT
R4H
Alkyl halide
Organoarsenic
R4H
Thiocyanate
Heterocycle
Acetanilide
Carbamate
Dithiocarbamate
Urea
Urea
Amide
Toluamide
F«sticide Type
Regulator
Insecticide
Disinfectant
Fumigant
Herbicide
Disinfectant
Slimicide
Fungicide, Miticide
Herbicide
Insecticide
Fungicide
Herbicide
Herbicide
Herbicide
Repellant
t-1
03
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
CO
1
t-1
kO
14503
34401
35801
105801
30701
30702
**
57001
84301
79501
79101
36501
32701
32501
105901
59201
PAJ
Code
172
173
174
175
176
176
176
177
178
179
180
181
182
183
184
185
: Chemical Hone
Nab am (Disodium salt of ethyleneblsdithiocarbamate]
Naled [l,2-Dibromo-2,2-dichloroethyl dimethyl phosphate]
Norea [3-Hexahydro-4,7-methanoindan-5-yl-l, 1-dimethylurea]
Nor f lur azon [ 4 -Chloro-5- (methy lamino ) -2- ( a , a , a-tr if luoro-ro-toly 1 ) -
3 ( 2H ) -pyr idazinone ]
N- 1-Naphthylphthalimide
Naptalam (N-1-Naphthylphthalamic acid)
Naptalam, salts and esters
N-2-Ethylhexyl bicycloheptene dicarboximide [MGK 264]
N-Butyl-N-ethyl-a , a , a-trif luoro-2 , 6-dinitro-p-toluidine
[Benfluralin]
0,0,0,0-Tetraethyl dithiopyrophosphate [Sulfotepp]
0,0,0,0-Tetrapropyl dithiopyrophosphate [Aspon]
0, 0-Diethyl 0- ( 3-chloro-4 -methy l-2-oxo-2H- 1-benzopyran- 7-yl
[Coumaphos]
0, 0-Diethyl 0-(p- (methy IsulfinyDphenyDphosphorothioate
[Fensulfothion]
0 , 0-Di ethyl S- ( 2- ( ethy Ithio ) ethyl ) phosphorodi thioate [ Disulf oton ]
0,0-Dimethyl 0-(4-nitro-m-tolyl)phosphorothioate [Fenitrothion]
0,0-Dimethyl S-(phthalimidomethyl)phosphorodithioate [Phosraet]
CAS #
00142-59-6
00300-76-5
18530-56-8
27314-13-2
05333-99-3
00132-66-1
**
00136-45-8
01861-40-1
03689-24-5
03244-90-4
00056-72-4
00115-90-2
00298-04-4
00122-14-5
00732-11-6
Structural Group
Dithiocarbamate
Phosphate
Urea
Heterocyclic
Fhthalamide
Fhthalamide
Fhthalamide
Bicyclic
Toluidine
Dithiopyrophosphate
Dithiopyrophosphate
Phosphorothioate
Fhosphorothioate
Fhosphorodi thioate
Fhosphorothioate
Fhosphorodi thioate
Ea«tioide Type
Fungicide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Repellant
Herbicide
Insecticide
Insecticide, Miticide
Insecticide
Insecticide
Insecticide
Insecticide
Insecticide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
S8001
58702
**
**
**
**
**
59401
104201
103801
111601
111501
219900
41801
41701
FAX
Coda
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
: .. ' - .:•..• CbealctJ. Haoe
0,0-Dimethyl S-((4-oxo-l,2,3-benzotriazin-3(4H)-yl)methyl)
phosphorodithioate [Azlnphos Methyl]
0,0-Dimethyl S-( (ethylsulfiny 1) ethyl )phosphorothioate
[Oxyd erne ton methyl]
Organo-arsenic pesticides (not otherwise listed)
Organo-cadmium pesticides
Organo-copper pesticides
Organo-mercury pesticides
Organo-tin pesticides
ortho Dichlorobenzene1
Oryzalin [3,5-Dinitro-H4,H4-dipropylsulfanilanjide]
Oxamyl [Methyl N' ,N'-dimethyl-H-( (methylcarbamoyl)oxy)-
1-thiooxamidate]
Oxyfluorfen [2-Chloro-l-(3-ethoxy-4-nitrophenoxy)-
4- ( trif luoromethy 1 )benzene ]
0-Ethyl. 0-( 4- (methylthlo)phenyl) S-propyl phosphorodithioate
[Sulprofos]
0-Ethyl 0-(4-(methylthio)phenyl) S-propyl phosphorothioate {9CA}
[Sulprofos Oxon]
0-Ethyl 0-(p-nitrophenyl)phenylphosphonothioate [Santox]
0-Ethyl S-phenyl ethylphosphonodithioate [Fonofos]
CAS #
00086-50-0
00301-12-2
**
**
**
**
**
00095-50-1
19044-88-3
23135-22-0
42874-03-3
35400-43-2
38527-90-1
02104-64-5
00944-22-9
Structural Group
Fhosphorodithioate
Phosphorodithioate
Organoarsenic
Organocopper
Organ omercury
Tin alkyl
Aryl halide
Sulfanylimide
Carbamate
Miscellaneous
Fhosphorodithioate
Phosphorothioate
Fhosphonothioate
Fhosphonodithioate
Pmfciaide lypa
Insecticide
Insecticide
Coccidiostat
Fungicide
Disinfectant
Fungicide
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Insecticide
Insecticide, Miticide
Insecticide
CO
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
47802
61501
57501
108501
56502
63001
**
108001
109701
98701
64501
64103
57201
97701
18201
5101
PAI
Coda
201
202
203
204
205
206
206
207
208
209
210
211
212
213
214
215
Chemical Bane
o-Isoproxyphenyl methylcaxbamate [Propoxur]
para Dichlorobenzene1
Parathion [0,0-Diethyl 0-(p-nitrophenyl)phosphorothioate]
Fandimethalln
[N-(l-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine]
Pentachloronitrobenzene
Pentachlorophenol
Pentachlorophenol, salts and esters
Perfluidone (1, 1. l-Trifluoro-N-(2-methyl-4-(phenylsulfonyl)phenyl>
methanesulfonamide]
Pennethrin [ C3-Phenoxyphenyl)methyl 3-(2,2-dichlorethenyl)-
2 , 2-dimethy Icy c lopropanecarboxy late ]
Phenmadipham [Methyl m-hydroxycarbanilate m-methyl carbanilate)
Phenothiazine
Phony Iphenol
Phorate [O,0-Diethyl S-( (ethylthio)methyDphosphorodithioate]
Fhos alone [0,0-Diethyl S-( (6-chloro-2-oxobenzoxazolin-3-yl)cnethyl)
phos phoro th i oat e }
Phosphamidon [2-Chloro-H,N-diethyl-3-hydroxycrotonamide aster of
dimethylphosphate]
Picloram [4-Amino-3,5,6-trichloropicolinic acid)
CAS f
00114-26-1
00106-46-7
00056-38-2
40487-42-1
00082-68-8
00087-86-5
**
37924-13-3
52645-53-1
13684-63-4
00092-84-2
00090-43-7
00298-02-2
02310-17-0
13171-21-6
01918-02-1
Structural Group
Carbamate
Aryl halide
Phosphorothioate
Benzeneamine
Aryl chloride
Phenol
Phenol
Sulfonamide
Cyclopropanecarboxilic acid
Carbamate
Beterocyclic
Phenol
Phosphorodithioate
Fhosphorodithioate
Phosphorothioate
Pyridine
Pesticide Type
Insecticide
Mothballs
Insecticide
Herbicide
Herbicide
Preservative
Preservative
Herbicide
Insecticide
Herbicide
Insecticide
Bacteriostat
Insecticide
Insecticide, Miticide
Insecticide
Herbicide
N)
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
:••
**
67501
69183
34803
102901
39002
101301
111401
80804
80805
97601
80808
77702
119301
69004
69001
PAX
Code
215
216
217
218
219
220
221
222
223
224
22S
226
227
228
229
230
< • ' y" " ' ChaaioaJ. Horn s" • '
Picloram, salts and esters
Piperonyl butoxide [(Butylcarbityl)(6-propylpiperonyl)ether)
Poly (oxyethyLene(dimethylimino)ethylene (dime thylimino)ethylene
dichloride (FEED (Busan 77))
Potassium dimethyldithiocarbamate [Busan 85)
Potassium H-hydroxymethyl-N-methyldithiocarbamate [Busan 40]
KN Methyl [Potassium H-methyldithiocarbamate]
Potassium N-( alpha- (nitroethyDbenzyl)ethylenediamine
[Metasol J26]
Profenofos [0-(4-Bromo-2-chlorophenyl) 0-ethyl S-propyl
[phosphosothioate]
Prometon [2,4-bis(Isopropylamino)-6-methoxy-s-Triazine]
Prometryn [2 , 4-bis ( Isopropy lamino ) -6- (methylthio ) -s-Triazine]
Propargite [2-(p-tert-Butylphenoxy)cyclohexyl-2-propynyl sulfite]
Propazine [ 2-Chloro-4 , 6- ( isopropy lamino ) -s-Triazihe )
Propionic. acid
Propyl (3-dimethy lamino )propyl carbamate hydrochloride
[Propamocarb and Fropamocarb HC1]
Pyrethrin coils
Pyrethrin I
CAS #
**
00051-03-6
31512-74-0
00128-03-0
51026-28-9
00137-41-7
53404-62-9
41198-08-7
01610-18-0
07287-19-6
02312-35-8
00139-40-2
00079-09-4
25606-41-1
00121-21-1
Structural Group
Pyridine
Ester
R4H
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Miscellaneous
Fhosphorothioate
s-Triazine
s-Triazine
Sulfite
s-Triazine
Alkyl acid
Carbamate
Cyclopropanecarboxylic acid
Pesticide Typo
Herbicide
Synergist
Fungicide
Fungicide
Fungicide
Fungicide
Fungicide, Slimicide
Herbicide
Herbicide
Insecticide, Miticide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide
to
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
OJ
NO
OJ
69002
69006
97801
58301
71003
74801
35509
82501
**
80807
103901
34804
75003
39003
57101
41301
41401
PAX
Code
231
232
233
234
235
236
237
238
238
239
240
241
242
243
244
245
246
Chemical Hume
Pyrethrin II
Pyrethrum (synthetic pyrethrin)
Resmethrin [ (5-Phenylmethyl)-3-£uranyl)methyl 2,2-dimethyl-3-
( 2 -methyl- 1 -pr openy 1 ) cy c lopropan e c arboxy late ]
Ronnal [O,O-Dimethyl 0-(2,4,5-trichlorophenyl)phosphorothioate]
Rotenone
S,S,S-Tributyl phosphorotrithioate [DEF1
Siduron [l-(2-Methylcyclohexyl)-3-phenylurea]
Silvex [2-(2,4, 5-Trichlorophenoxypropionic acid)}
Silvex, salts and esters
Simazine (2-Chloro-4, 6-bis(ethylamino)-s-Triazine]
Sodium bentazon (3-Isopropyl-lB-2, 1,3-benzothiadiazin-
4(3H)-one-2,2-dioxide]
Sodium dimethyldithiocarbanate [Carbam-S]
Sodium monofluoroacetate
Sodium methyldithiocarbamate [Vapam]
Sulfoxide [l,2-Methylenedioxy-4-(2-(octylsulfidynyl)
ptopyl) benzene]
S-Ethyl cyclohexylethylthiocarbamate [Cycloate]
S-Ethyl dipropylthiocarbamate [EPTC]
CAS *
00121-29-9
08003-34-7
10453-86-8
00299-84-3
00083-79-4
00078-48-8
01982-49-6
00093-72-1
**
00122-34-9
25057-89-0
00128-04-1
00062-74-8
00137-42-8
00120-62-7
01134-23-2
00759-94-4
Structural Group
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Phosphorothioate
Bio extract
Phosphorotrithioate
Urea
Phenoxy acid
Phenoxy acid
s-Triazine
Heterocylic n,s
Dithiocarbamate
Acetate salt
Dithiocarbamate
Heterocyclic
Carbaroate
Carbamate
Pesticide Typo
Insecticide
Insecticide
Insecticide
Insecticide
Insecticide
Defoliant
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Rodenticide
Fungicide
Insecticide
Herbicide
Herbicide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
u>
N>
M
**
67501
69183
34803
102901
39002
101301
111401
80804
8C80S
97601
80808
77702
119301
69004
69001
PAI
Cod*
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
:;;: *: ':-....••••••'•••••• CbeaioaJ. Hone
Picloram, salts and asters
Piperonyl butoxide [(Butylcarbityl)(6-propylpiperonyl)ether]
Poly ( oxy ethy Lane ( dimethy limino ) athy lane ( dimethy limino ) a thy lane
dichloride [FEED (Bus an 77)]
Potassium dimethyldithiocarbamate (Bus an 85]
Potassium N-hydrojcymethyl-N-methyldithiocarbamate [Bus an 40]
KN Methyl [Potassium N-mathyldithiocarbamate]
Potassium H-( alpha- (nitroethyl)benzyl)ethylenediamine
[Metasol J26]
Profenofos [0-(4-Bromo-2-chlorophenyD 0-ethyl S-propyl
tphosphosothioate]
Prometon [2 , 4-bis ( Isopropylamino ) -6-methoxy-s-Triazine]
Prometryn [2,4-bis(Isopropylamino)-6-(methylthio)-s-Triazine]
Propargite [2-(p-tert-Butylphanoxy)cyclohexyl-2-propynyl sulfite]
Propazine [2-Chloro-4 , 6- ( isopropylamino ) -s-Triazihe]
Fropionic acid
Propyl (3-dimethylaniino)propyl carbaoate hydrochloride
[Propamocarb and Fropamocarb HC1]
Pyrethrin coils
Pyrethrin I
CAS #
**
00051-03-6
31512-74-0
00128-03-0
51026-28-9
00137-41-7
53404-62-9
41198-08-7
01610-18-0
07287-19-6
02312-35-8
00139-40-2
00079-09-4
25606-41-1
00121-21-1
Structural Group
Pyridina
Ester
R4N
Dithiocarbamate
Dithiocarbamata
Dithiocarbamate
Miscellaneous
Phosphorothioate
s-Triazine
s-Triazine
Sulfite
s-Triazine
Aliyl acid
Carbamate
Cyclopropanecarboxylic acid
P«8tiaide Tjpe
Herbicide
Synergist
Fungicide
Fungicide
Fungicide
Fungicide
Fungicide, Slimicide
Herbicide
Herbicide
Insecticide, Miticide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
69002
69006
97801
58301
71003
74801
35509
82501
**
80807
103901
34804
75003
39003
57101
41301
41401
PAI
Code
231
232
233
234
235
236
237
238
238
239
240
241
242
243
244
245
246
Chemical Hone
Pyrethrin II
Pyrethrum (synthetic pyrethrin)
Resmethrin E (5-Phenylmethyl)-3-furanyl)methyl 2,2-diniethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate)
Ronnel [0,0-Dimethyl 0-(2,4,5-trichlorophenyl)phosphorothioate]
Rotenone
S,S,S-Tributyl phosphorotrithioate [DBF]
Siduron [l-(2-Methylcyclohexyl)-3-phenylureal
Silvex [2-(2,4,5-Trichlorophenoxypropionic acid)]
Silvex, salts and esters
Simazine [2-Chloro-4 ,6-bis(ethylamino)-s-TriazineJ
Sodium bentazon J3-Isopropyl-lH-2, 1,3-benzothiadiazin-
4(3H)-one-2,2-dioxide]
Sodium dimethyldithiocarbanate [Carbam-S]
Sodium monofluoroac state
Sodium methyldithiocarbamate [Vapam]
Sulfoxide (l,2-Mathylenedioxy-4-(2-(octylsulfidynyl)
propyl) benzene]
S-Ethyl cyclohexylethylthiocarbamate [Cycloate]
S-Ethyl dipropylthiocarbamate [EPTC]
CAS f
00121-29-9
08003-34-7
10453-86-8
00299-84-3
00083-79-4
00078-48-8
01982-49-6
00093-72-1
**
00122-34-9
25057-89-0
00128-04-1
00062-74-8
00137-42-8
00120-62-7
01134-23-2
00759-94-4
Structural Group
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Phosphorothioate
Bio extract
Phosphorotrithioate
Urea
Phenoxy acid
Phenoxy acid
s-Triazine
Heterocylic n,s
Dithiocarbamate
Acetate salt
Dithiocarbamate
Heterocyclic
Carbamate
Carbamate
Pectlclde Type
Insecticide
Insecticide
Insecticide
Insecticide
Insecticide
Defoliant
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Rodenticide
Fungicide
Insecticide
Herbicide
Herbicide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
to
^
£»
41402
41403
41404
35604
9801
105501
59001
12701
105001
80814
80813
63004
**
35602
102001
PAX
Coda
247
248
249
250
251
252
253
254
255
256
257
258
258
259
260
Chemical Dante
S-Ethyl hexahydro-lH-azepine-1-carbothioate [Molinate]
S-Propyl butylethylthiocaxbamate [Pebulate]
S-Propyl dipropylthiocarbamate [Vernolate]
S- (2-Hydroxypropyl) thiomethanasulf onata [HPTMS J
S-(0,0-Diisopropyl) phosphorodithioate ester of
N- ( 2-mer captoathy 1 ) benzenesulf onamide [ BensuLide }
Tebuthluron [N-(5-(l,l-Dimethylethyl)-l,3,4-thiadiazol-2-yl)-
S , H ' -dimethylur ea]
temephos [0,0,0' ,O'-Tetramathy 1-0,0' -thiodi-p-
phenylenephosphorothioabe]
Terbacil [3-tert-Butyl-5-chloro-6-methyluracil]
Terbufos [S-( ( (1, l-Dimethylethyl)thio)methyl) 0,0-diethyl
phosphorodithioate]
Terbuthylazine [2-(tert-Butylamino)-4-chloro-6-(ethylamino)-
s-Triazlne]
Terbutryn [2-(tert-Butylamino)-4-(ethylainino)-6-(inethylthio)-
s-Triazinel
Tetrachlorophenol
Tetrachlorophenol salts and esters
Tetrahydro-3 , 5-dimethyl-2H-l, 3 , 5-thladiazine-2-thione [Dazomet]
Thiophanate methyl [Dimethyl 4 , 4 ' -o-phanylenebis
( 3-thioallophanate ) ]
CAS #
02212-67-1
01114-71-2
01929-77-7
29803-57-4
00741-58-2
34014-18-1
03383-96-8
05902-51-2
13071-79-9
05915-41-3
00886-50-0
25167-83-3
**
00533-74-4
23564-05-8
Structural Group
Carbamate
Carbamate
Carbamate
Thiosulphonate
Phosphorodithioate
Heterocyclic
Phosphorothioate
Uracil
Fhosphorodithioato
s-Triazine
s-Triazine
Phenol
Phenol
Heterocyclic
Carbamate
P«»tioide type
Herbicide
Herbicide
Herbicide
Fungicide
Herbicide
Herbicide
Insecticide
Herbicide
Insecticide
Herbicide
Herbicide
Preservative
Preservative
Fungicide
Insecticide
-------
Table 3-1 (Continued)
LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
u>
K)
en
79801
80501
74901
36101
86002
**
51705
14506
34805
78802
69005
69003
18301
PAJ
Code
261
262
263
264
265
265
266
267
268
269
270
271
272
Chemical lane
Thiraia [Tetramethylthiuram disulfide)
Toxaphene [technical chlorinated camphena (67-69Z chlorine)]
Tributyl phosphorotrithioate [Merphos]
Trif luralin [ a , a , a-Trif luoro-2, 6-dinitro-N , N-dipropyl-p-toluidine]
Warfarin [3-(a-Acetonylbenzyl)-4-hydroxycoumarin]
Warfarin salts and esters
Zinc 2-mercaptobenzothiazolate [Zinc MET)
Zineb [Zinc ethylenebisdithiocarbamate]
Ziram [Zinc dimethyldithiocarbamate]
S-(2,3,3-Trichloroallyl)diisopropylthiocarbamate
(3-Phenoxyphenyl)methyl d-cis and trans* 2,2-dimethyl-3-
(2-me thy IpropenyDcyclopropanecarboxy late
*(Max. d-cis 25Z; Min. trans 75Z) [Phenothrin]
(4-Cyclohexene-l,2-dicarboxiraido)methyl 2,2-dimethyl-3-
( 2-methylpropenyl ) eye lopropanecarboxy late [ Tetr amethr in ]
Isopropyl H-(3-chlorophenyl) carbamate [Chloropropham]
CAS t
00137-26-8
08001-35-2
00150-50-5
01582-09-8
00081-81-2
**
00155-04-4
12122-67-7
00137-30-4
02303-17-5
26002-80-2
07696-12-0
00101-21-3
Structural Group
Dithiocarbamate
Multiring halide
Fhosphorotrithioate
Toluidine
Hy dr oxy c oumar in
Hydroxycoumarin
Organozinc
Dithiocarbamate
Dithiocarbamate
s-Esterthiocarbamate
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Carbaraate
Pesticide Type
Fungicide
Insecticide
Defoliant
Herbicide
Rodenticide
Rodenticide
Fungicide
Fungicide
Fungicide
Herbicide
Insecticide
Insecticide
Herbicide plant growth
regulator
Deleted because the chemical is covered by OCPSF Effluent Limitations Guidelines and Standards
-------
from those reviewers, EPA determined that the draft questionnaire needed
extensive revision to better define and focus the questions and the pesticide
formulator/packager segment of the industry was significantly different from
the manufacturing segment and should be covered by a separate study.
As required by the Paperwork Reduction Act, 44 U.S.C. 3501 et
seq., EPA submitted the revised questionnaire to the Office of Management and
Budget for review, and published a notice in the Federal Register that the
questionnaire was available for review and comment. EPA also distributed the
revised questionnaire to the same industry trade associations, pesticide
industry facilities, and environmental groups that had provided comments on
the previous draft and to any others who requested a copy of the draft
questionnaire.
Based on additional comments received, EPA made changes to the
questionnaire to reduce the extent of production process information requested
and clarify certain other questions. EPA had included the request for
detailed production process information in part to have sufficient data to
adequately and rapidly respond to potential requests for variances from
effluent limitations and standards based on "fundamentally different factors."
However, the Water Quality Act of 1987 amended Section 301(n) of the Act,
superseding NPDES regulations at 40 CFR 122.21 regarding application for a
"fundamentally different factors" variance. Based on that amendment, EPA
determined that detailed production process information should not be
requested of all questionnaire recipients. OMB cleared the technical portion
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of the questionnaire (the Introduction and Part A) for distribution on April
8, 1988, but denied clearance to the economic portion (Part B). The economic
portion was subsequently revised, resubmitted and cleared. (See "Economic
Impact Analysis of Effluent Limitations and Standards for the Pesticide
Manufacturers" for information concerning the development of the economic
portion of the questionnaire.)
3.1.3.a Distribution of the Pesticide Manufacturing Facility Census for
1986
EPA's database for the remanded regulation identified 247
facilities that at one time had produced or manufactured pesticides. Other
sources cited above (see Section 3.1.1) identified only facilities that were
already part of the list of 247 facilities. Therefore, EPA believes that the
list covers all manufacturing facilities that were operating in 1986.
Under the authority of Section 308 of the Act, EPA distributed the
questionnaire entitled "Pesticide Manufacturing Facility Census for 1986"
(hereinafter, the "Facility Census") to all 247 facilities in EPA's database.
EPA received responses from all 247 facilities (a 100% response rate). The
responses in many cases indicated that the facility did not manufacture PAIs
anymore and in some cases indicated that the facility was closed. The
responses indicated that 90 facilities manufactured pesticides in 1986
compared to 120 facilities in 1985 (see Section 3.6 for a discussion on
changes in the industry).
3-27
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The questionnaire specifically requested information on: (1) the
PAI manufacturing processes used; (2) the quantity, treatment, and disposal of
wastewater generated during PAI manufacturing; (3) the analytical monitoring
data available for PAI manufacturing wastewaters; (4) the information on
treatability studies performed by or for facilities; (5) the degree of co-
treatment (treatment of PAI manufacturing wastewater mixed with wastewater
from other industrial manufacturing operations at the facility); and (6) the
extent of wastewater recycling and/or reuse at the facility. Information was
also obtained through follow-up telephone calls and written requests for
clarification of questionnaire responses.
EPA also requested that pesticide manufacturing facilities submit
wastewater self-monitoring data. Fifty-five facilities submitted some form of
self-monitoring data. One facility submitted data only for conventional
pollutants, while 37 of the 55 facilities submitted conventional pollutant
data along with priority pollutant and/or nonconventional pollutant data
(including the PAIs). Thirty-four of the 55 facilities submitted priority
pollutant data, and 49 facilities submitted data for PAIs. However, much of
these data were not useful in characterizing pesticide process wastewaters.
In many cases, only one detection was reported for a specific pollutant, or
the sampling locations represented commingled wastewaters containing pollutant
discharges from other industrial processes, such as OCPSF production. Often
the data represented sampling results only at the end-of-pipe plant discharge.
As will be discussed in Section 5, self-monitoring data from only six
facilities were useful in characterizing priority pollutant discharges in raw
3-28
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pesticide process wastewaters. However, industry-supplied data from 27
facilities covering 55 PAIs were sufficient in establishing effluent
limitations.
A summary of the information obtained from the "Facility Census"
is presented in this document and also reflects the additional data obtained
from follow-up telephone calls and written requests for clarification of the
information provided in responses to the questionnaire, as well as wastewater
concentration data submitted by facilities along with the Facility Census.
3.1.4 EPA's 1988-1991 Sampling of Selected Pesticide Manufacturers
Between 1988 and 1991, EPA visited 32 of the 90 manufacturing
facilities. During each visit, EPA gathered production process information
and information on waste and wastewater generation, treatment and disposal.
Based on these data and the responses to the Facility Census, EPA conducted
wastewater sampling at 20 of the 32 facilities in order to characterize
process discharges and treatment system performance. In addition, EPA
collected wastewaters for treatability studies at seven of the 32 facilities.
Four of these seven were among the 20 facilities sampled in order to
characterize process discharges and treatment system performance. That is,
EPA collected wastewater samples at 23 of the 32 facilities visited. The
other nine facilities visited were not sampled: two plants do not discharge
wastewater (they recycle/reuse their wastewater); two plants had no wastewater
treatment; three plants had pesticide manufacturing process wastewater so
3-29
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intimately commingled with wastewaters from other manufacturing processes that
sampling for characterization was not possible; one plant disposed of
wastewater by deep-well injection; and the ninth plant was not in production
during possible sampling times (however, the ninth plant did provide long-term
self-monitoring data).
During sampling activities, raw wastewaters from the manufacture
of 38 different PAIs were characterized. Samples were also collected to
assist in the evaluation of the performance of 62 specific treatment unit
operations. Table 3-2 presents a breakdown of the types of treatment units
sampled. Through the treatability studies, EPA analyzed the efficacy of
activated carbon adsorption, membrane filtration, hydrolysis and alkaline
chlorination for control of 76 PAIs. More detailed studies using actual
manufacturing process wastewater to develop additional treatment performance
data for activated carbon adsorption, hydrolysis, and alkaline chlorination
technologies were subsequently conducted. These more detailed studies
involved 13 specific PAIs included in today's proposed rule and are described
in more detail in Section 3.1.6. Facilities were selected for sampling after
an evaluation of existing data and responses to the Facility Census. The
facilities were selected for sampling if the data indicated that the
wastewater treatment system was effective in removing PAIs, and the PAIs
manufactured appeared to be representative of one or more PAI structural
categories, such as organo-phosphate PAIs. Wastewaters containing PAIs in 21
structural groups were analyzed during EPA sampling.
3-30
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Table 3-2
TREATMENT UNIT OPERATIONS SAMPLED
Treatment Unit Operation
Biological Oxidation
Flocculation
Activated Carbon
Aeration
Multimedia Filtration
Chemical Oxidation
Pressure Filtration
Hydrolysis
Evaporation Pond
Steam Stripping
Dechlorination
Resin Adsorption
Metal Separation
Solvent Extraction
Air Stripping
UV Decomposition
Land Application
Coagulation
Mechanical Evaporation
Cyanide Destruction
Total Number of Units
29
8
19
1
5
14
8
11
2
11
4
2
1
13
5
2
1
2
1
1
Total Number of Units
Units Sampled
7
1
11
0
1
7
3
7
0
4
1
1
1
3
1
1
0
2
0
1
Note: Plants operate more than one treatment unit.
3-31
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Prior to a sampling episode at a manufacturing facility,
representatives from the Agency conducted an engineering site visit. During
this visit, EPA gathered information about the manufacturing process(es),
treatment operation(s), and potential sample locations. Following the visit,
a draft sampling plan was prepared which provided the rationale for the
selection of sampling locations as well as the procedures to be followed
during sampling. A copy of this draft plan was provided to the plant for
comments prior to any wastewater sampling to ensure that the sample sites
selected would properly characterize the process wastewater and evaluate the
wastewater treatment system.
During the sampling episode, teams of EPA contractor engineers and
technicians collected and preserved samples and shipped them to EPA contract
laboratories for analysis. Levels of conventional pollutants, non-
conventional pollutants (including the pesticide active ingredients), and
priority pollutants were measured in raw wastewater and treated effluent. EPA
always offered to split the samples with the facility. In some cases, the
facility accepted the split samples provided by the EPA, while in some other
cases, plant personnel independently collected wastewater from the EPA
sampling sites. Following the sampling episode, a draft trip report was
prepared that included descriptions of the manufacturing and treatment
processes, sampling procedures, analytical results, QA/QC evaluation, and
discussion of the raw wastewater composition and treatment system performance.
The report was provided to the sampled facility for review and comment, and
any corrections were incorporated into the report. The facilities also
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identified any information in the draft report that the facility considered
confidential business information.
3.1.5 Industry-Supplied Data
All facilities which discharge wastewater directly to receiving
streams must have NPDES permits which establish effluent limitations and
monitoring requirements. Some POTWs also require indirect dischargers to
monitor their effluent. To make use of this self-monitoring data, the
Facility Census requested that each respondent provide all monitoring data
available for 1986 on raw waste loads, individual process stream measurements,
pollutant concentration profiles, or any other data on pollutants associated
with the manufacture of pesticide active ingredients. EPA later requested
selected plants to provide additional monitoring data for 1987-1989. Plants
selected to provide additional data were those with extensive self-monitoring
programs and wastewater treatment technologies that appeared to be exemplary.
EPA requested that all monitoring data be provided in the form of individual
data points rather than as monthly aggregates.
Under authority of Section 308 of the Act, EPA also requested two
facilities to conduct more extensive sampling of their wastewater treatment
systems. These two plants appeared to have exemplary PAI wastewater treatment
systems but the facilities had previously conducted no or only very limited
monitoring of their PAI wastewater. The sampling programs conducted by these
3-33
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two facilities at EPA's request provided needed long-term treatment system
performance data.
Pesticide wastewater treatability studies performed by or for the
facility were also requested by EPA. These additional data were also
considered in the development of effluent limitations guidelines. Because
treatability data were lacking for some PAIs, individual PAIs, which were
expected to be treatable with a specific technology, were targeted for
treatability studies. EPA collected samples of actual pesticide manufacturing
process wastewater at plants manufacturing those PAIs. Following sample
collection, the samples were transferred to an EPA contractor for bench scale
testing. The data were then used to develop limitations for these PAIs when
it was demonstrated that the technology was effective at PAI removal.
3.1.6 EPA Bench-Scale Treatability Studies
EPA conducted a number of bench-scale studies to evaluate the
treatability of PAIs by various wastewater treatment technologies. These
technologies included hydrolysis, membrane filtration, activated carbon
adsorption, chemical oxidation by alkaline chlorination and chemical oxidation
by ozone accompanied by irradiation with ultraviolet light. Treatability
studies were conducted both on clean water to which PAIs were added
("synthetic wastewaters") and on actual pesticide process wastewaters.
3-34
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The hydrolysis, membrane filtration, and activated carbon isotherm
treatability studies used synthetic wastewaters. General factors included in
the selection of specific PAIs for use in the synthetic wastewaters were the
availability of an analytical method for the specific PAI and the ready
availability of the PAI in a pure form from either government or commercial
sources. Another factor in selecting the PAIs was the hydrolysis rate of each
PAI: a too rapid hydrolysis rate could interfere in the chemical analysis of
the samples.
The hydrolysis studies used PAIs selected in part based on the
existence of hydrolysis data gathered from a literature survey (for comparison
with EPA treatability study results), and in part based on the lack of any
literature data, so as to fill in those data gaps. All of the PAIs selected
were expected to hydrolyze under some conditions.
In the hydrolysis treatability study, a series of bench-scale
tests were conducted to determine the hydrolysis rates of selected PAIs,
Thirty-eight PAIs were selected for testing and separated into four synthetic
test solutions. The hydrolysis treatability study was conducted at three
different pH levels (2, 7, and 12) and at two different temperatures (20°C and
60°C).
The activated carbon studies used PAIs selected from various
structural groups to determine which groups would be most amenable to
activated carbon technology. Carbon adsorption isotherms were developed for
3-35
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29 specific PAIs. Some manufacturers of some PAIs in a few of the PAI
structural groups were known to use activated carbon technology to treat their
wastewaters; in these cases, the purpose of the carbon isotherm study was to
establish benchmarks for determining the potential efficacy of activated
carbon technology to other structural groups or to other PAIs in the same
structural group. The results of the carbon isotherm tests were evaluated
using the Freundlich isotherm equation.
The membrane filtration studies used PAIs selected to span the
molecular weight range of the 270 PAIs under consideration for regulation,
because the effectiveness of membrane filtration tends to vary according to
molecular weight. In the membrane filtration treatability study, a series of
bench-scale tests were conducted to identify specific PAIs which could be
separated from water by various membrane materials. Synthetic test solutions
containing 19 PAIs were tested on 7 different types of membranes. The
membranes were manufactured from 3 types of materials (cellulose acetate,
thin-film composite, and Aramid) and were of various pore sizes, with nominal
molecular weight cut-offs ranging from 150 to 500.
The treatability studies using actual pesticide manufacturing
process wastewater were conducted to supplement full-scale treatment system
performance data. These studies helped to fill in gaps where little or no
treatability data were available for the PAI, and to help assess performance
of existing full-scale treatment systems where the performance of those
systems appeared to be inadequate compared to the performance of other
3-36
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facilities treating the same or similar PAIs. The PAIs selected for study
were the PAIs in production at the plants during the treatability study.
EPA collected actual process wastewaters to determine adsorption
properties of specific PAIs using accelerated column tests. Four PAIs were
evaluated as part of these tests which use bench scale results to estimate
full-scale carbon system performance, design and cost. Two of the PAIs
studied in these tests were also evaluated as part of the carbon isotherm
s tudy.
One series of chemical oxidation treatability studies was
conducted to determine the applicability of alkaline chlorination as a method
of treating pesticide manufacturing process wastewaters. In these bench-scale
tests, manufacturing wastewaters from six PAI processes were tested at
chlorine dosages equal to 50,100 and 125% of the chlorine demand for the
specific wastewater at pH 12 and ambient temperatures. Contact times of 0.5,
1.5 and 4.0 hours were examined.
Because alkaline chlorination of wastewater containing organic
matter may generate volatile organic toxic pollutants, which must subsequently
be controlled, EPA also conducted chemical oxidation treatability studies for
five of those same six PAIs using ozone rather than chlorine. The preliminary
results of those studies indicate that ozone can achieve about the same degree
of PAI reduction as chlorine. Chemical oxidation with ozone is usually more
expensive than chemical oxidation with chlorine. However, ozone oxidation
3-37
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does not produce volatile toxic pollutants. When the cost of controlling
those volatile toxic pollutants is added to the cost of alkaline chlorination,
the total cost for chlorination may exceed the cost of ozone oxidation.
3.1.7 Data transferred from the OCPSF Rulemaking
The Clean Water Act of 1977 stressed the control of toxic
pollutants, including 65 toxic pollutants and classes of pollutants. From
*
this list of 65, EPA has derived a subset of 126 individual "priority"
pollutants on which the Agency has focused (see, e.g., list of 126 priority
pollutants at 40 CFR Part 423, Appendix A). EPA has determined that 28 of the
126 priority pollutants may be present in pesticides manufacturing
waste-waters, and EPA is proposing today to set direct discharge limitations
and pretreatment standards for these 28 priority pollutants. For 23 of these
28 priority pollutants, EPA is relying on the OCPSF technical database to
propose limitations. Limitations for one priority pollutant, cyanide, are
proposed based on long-term data collected from the pesticide industry. The
other four priority pollutants being proposed for regulation today were not
regulated under OCPSF and there are no treatment performance data for these
four specific pollutants. EPA developed proposed limitations for these four
priority pollutants by transferring limitations from other structurally
similar priority pollutants. This is the same procedure that was used in
developing OCPSF limitations (40 CFR Part 414) when performance data was
lacking for certain priority pollutants.
3-38
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Limitations were developed under the OCPSF rulemaking for 23
priority pollutants that were also detected in pesticide manufacturers'
wastewaters during the EPA sampling and industry self-monitoring efforts.
Fifty-five of the 90 pesticide chemicals manufacturing facilities also
manufacture compounds regulated under the OCPSF category. Based on these
factors, EPA is proposing that technical data from the OCPSF category and
effluent limitations for priority pollutants based on that data be transferred
to the pesticide chemicals manufacturing category as supporting data for the
proposed limitations for the priority pollutants in this regulation.
EPA is relying on the OCPSF database to set BAT and NSPS
limitations for 23 priority pollutants. The OCPSF limitations for volatile
priority pollutants were based on data from plants that exhibited efficient
volatile pollutant reduction using either in-plant steam stripping
technologies alone or in-plant steam stripping followed by biological
treatment. OCPSF limitations were also based on activated carbon or in-plant
biological treatment for some semi-volatile organic priority pollutants. The
OCPSF guideline established limitations for lead based on performance data
obtained from EPA's study of the metal finishing industry.
EPA is also proposing to transfer PSES and PSNS and data
supporting those standards from the OCPSF category for the same 23 priority
pollutants. EPA is relying on an analysis originally done to support the
OCPSF regulations to determine pass-through for these pollutants. That
analysis demonstrates that 21 of the 23 priority pollutants do pass through a
3-39
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POTW. Therefore, EPA is proposing PSES and PSNS for 21 of those 23
pollutants. EPA's pass-through analysis is discussed in more detail in
Section 7.
Only technical data used to develop limitations are being
transferred from the OCPSF rulemaking for these 23 pollutants. The economic
analysis evaluating whether attainment of these limitations is economically
achievable by pesticides manufacturers has been performed independently as
part of today's proposed rulemaking.
EPA is also proposing BAT, NSPS, PSES, and PSNS limitations for
four brominated priority pollutants that are present in pesticides
manufacturers' wastewaters but which are not regulated under the OCPSF
guidelines. The proposed limitations were developed based on steam stripping,
using the same procedure followed in developing the OCPSF regulations for
volatile pollutants where treatment performed data were unavailable.
In the OCPSF regulation, EPA established effluent limitations for
28 priority pollutants based on steam stripping technology, but EPA had
performance data for only 15 of those 28 priority pollutants. To develop
limitations for the 13 priority pollutants with no performance data, EPA
divided the 15 priority pollutants with data into 2 subgroups, a high
stripability subgroup and a medium stripability subgroup, based on Henry's Law
Constants (a ratio of aqueous solubility, or tendency to stay in solution, to
vapor pressure, or tendency to volatize). Based on each pollutant's Henry's
3-40
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Law Constant, the 13 priority pollutants lacking performance data were
assigned to either the high or medium stripability subgroup, and the average
data for each subgroup was then transferred for limitations development. (For
more details, see 52 FR 42540-41, November 5, 1987.)
This same procedure was followed for each of the four brominated
volatile priority pollutants for which limitations are proposed today.
3.2 OVERVIEW OF THE INDUSTRY
This subsection provides an overview of the Pesticide Chemicals
Manufacturing Industry by presenting general information on the geographical
locations, SIC code distribution, age, typical markets, and types of
facilities.
3.2.1 Geographical Location of Manufacturing Facilities
In 1986, 90 manufacturing facilities, located in 29 states,
reported producing 1 or more of 178 PAIs from the list of 270 PAIs and classes
of PAIs. In addition, 8 other products were produced before and after 1986,
but not in 1986. The majority of pesticide manufacturing facilities are
located in the eastern half of the United States, with a large concentration
in the southeast corridor and Gulf Coast states. Approximately 50% of all
pesticide production occurs in these areas. The geographic distribution of
pesticide manufacturing facilities by EPA region is presented in Figure 3-2;
3-41
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Figure 3-2
U)
35n
0
DISTRIBUTION OF PESTICIDE MANUFACTURING
FACILITIES BY EPA REGION
Northeast Southeast Midwest
Region
West
# Manufacturers
% PAI Manufacture
70%
0%
-------
EPA Regions I, II, and III are included in the "Northeast" region on the
figure, EPA Region IV is included in the "Southeast1' region, EPA Regions V,
VI, and VII are included in the "Midwest" region, and EPA Regions VIII, IX,
and X are included in the "West11 region.
Table 3-3 presents the geographic distribution of OCPSF
manufacturing facilities by EPA Region as surveyed in 1983. The distribution
of OCPSF manufacturing facilities is similar to the distribution of the
pesticide chemicals manufacturing industry. Of the 90 pesticide chemicals
manufacturers, 55 also manufacture products covered under the OCPSF
guidelines.
3.2.2 SIC Code Distribution
Standard Industrial Classification (SIC) codes, established by the
U.S. Department of Commerce, are classifications of commercial and industrial
establishments by type of activity in which they are engaged. The primary
purpose of the SIC code is to classify the manufacturing industries for the
collection of economic data. An operating establishment is assigned an
industry code on the basis of its primary activity, which is determined by its
principal product or group of products. The primary product of a
manufacturing establishment is determined by the value of production.
3-43
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Table 3-3
COMPARISON OF THE GEOGRAPHIC DISTRIBUTION
OF THE OCPSF vs. PESTICIDE
INDUSTRY BY REGION
Region1
Northeast
Southeast
Midwest
West
TOTAL
No. of OGPSF
Manuf ac tur ing
Facilities
311
181
361
87
940
No. of
Pesticide
Manufacturing
Facilities
22
25
35
8
90
% of OCPSF
Manuf ac tur ing
Facilities
33.1
19.3
38.4
9.2
100
% of
Pesticides
Manuf ac tur ing
Facilities
24.4
27.8
38.9
8.9
100
'The "Northeast" region includes EPA Regions I, II, and III; the "Southeast"
region includes EPA Region IV; the "Midwest" region includes EPA Regions V,
VI, and VII; and the "West" region includes EPA Regions VIII, IX, and X.
3-44
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This industry is included within, but not limited to, SIC Major Group
28, Chemical and Allied products. More specifically, facilities manufacturing
PAls may be engaged in one or more of the following SIC groups: 2831; 2833; 2834;
2842; 2843; 2861; 2865; 2869; 2879; and 2899.
3.2.3 Age of Facilities
The majority of facilities which currently manufacture pesticide
active ingredients began manufacturing operations in the 1950s and 1960s. The
majority of pesticide manufacturing operations also began about this time and
pesticide operations start-ups continued into the 1970s. The oldest reported
pesticide operation began in 1909, while the most recent operation began in 1987.
Thirty-nine facilities reported that pesticide operations began at the same time
the facility operations began. Table 3-4 presents the distribution of pesticide
manufacturing facilities by decade of when operations began at the facility, when
pesticide operations began at the facility, and when the most recent major
expansion of pesticide operations occurred.
3.2.4 Market Types
Figure 3-3 presents the percent of PAI production by market type from
information reported on the 1986 questionnaire for 88 of the 90 pesticide
chemicals manufacturing facilities. Approximately 18% of 1986 pesticide active
ingredient production was delivered to industry, commerce, or U.S. government
3-45
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Table 3-4
DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES
BY DECADE OF OPERATION
Decade
Prior to 1930s
1930s
1940s
1950s
1960s
1970s
1980s
No Response
TOTAL
No. of Facilities Reporting
Facility
Operations Began
15
6
9
16
20
12
8
4
90
Pesticides
Operations Began
1
7
6
16
22
22
12
4
90
Last Major Expansion of
Pesticides Operations
0
1
0
0
5
18
53
13
90
3-46
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Figure 3-3
1986 PESTICIDE MARKET COMPOSITION
U.S. Home
and Garden
Other Markets
14%
Exports
14%
U.S. Industry, Commerce
and Government
18%
U.S. Agriculture
52%
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markets. Fifty-two percent of production was reported to be used in the
agricultural end use market and 14% was exported. The remaining PAI production
(-16%) was reported by other market types including OCPSF, Pharmaceuticals,
formulating/packaging operations and home and garden use.
3.2.5 Type of Facilities
Of the 90 pesticide manufacturing facilities, 55 generate wastewater
discharges which are currently regulated under the OCPSF Point Source Category.
Thirty-nine of these facilities co-treat OCPSF wastewater with pesticide
manufacturing wastewater.
Over half of the 90 pesticide manufacturing facilities also conduct
pesticide formulating and/or packaging (PFP) activities. Nineteen of these
facilities co-treat PFP wastewater with pesticide manufacturing wastewater.
The census data suggest that a "typical" facility reported
manufacturing one active ingredient in 1986, was the only facility in the country
producing that PAI, produced between 1,000,000 and 10,000,000 pounds total
pesticide active ingredient for the year, also manufactured OCPSF compounds, and
conducted PFP operations.
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3.3 PESTICIDE PRODUCTION
A wide variety of pesticide active ingredients (PAIs) or classes of
PAIs are produced by the pesticide chemicals manufacturing industry. A summary
of the 270 pesticide active ingredients considered for regulation, their
production levels, and production distribution is presented below.
3.3.1 Types of Pesticides
Pesticide active ingredients (PAIs) and classes of PAIs can be
categorized into the following nine types of pesticides:
• Herbicides: used for weed control;
• Insecticides: used for control of insects;
• Rodenticides: used for control of rodents;
• Fungicides: used for control of fungi;
• Nematocides: used for control of a particular class of worms,
which are often parasites of animals and plants;
• Miticides: used for control of mites, which are tiny
arachnids that often infest prepared food or act as parasites
on animals, plants, or insects;
• Disinfectants: used for control of bacteria and viruses;
• Defoliants: used to remove leaves from growing plants; and
• Synergists: used in conjunction with other substances to
enhance the effects of each.
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Table 3-1 presents the 270 PAIs or classes of PAIs considered for regulation by
pesticide type. One type of pesticide, the rodenticides, were not manufactured
in 1986.
The 270 PAIs or classes of PAIs may also be grouped into 67 groups,
based on their chemical structure (or arrangement of atoms in each molecule) as
shown in Table 3-1. Pesticide active ingredients or classes of PAIs which have
the same structure have similarities in physical properties, such as molecular
weight and solubility. These similarities may result in'similar amounts and
types of pollutants in the wastewater generated during the manufacture of the
pesticide. Pesticide chemicals with similar structures may also be controlled
or removed from wastewater by similar wastewater treatment technologies. These
topics will be discussed further in Section 7 (Treatment Technologies and
Performance Data).
3.3.2 1986 Pesticide Active Ingredient Production
Based on responses to the Facility Census, the pesticide chemicals
manufacturing industry in 1986 manufactured 130 of the 270 PAIs and classes of
PAIs and 48 salts and esters of these active ingredients (for a total of 178
active ingredients). These PAIs were manufactured by 224 separate pesticide
production processes. In addition, there were eight other PAIs which were
manufactured either before or after 1986, but not during 1986. A pesticide
production process involves the manufacture of one PAI or salt or ester at a
facility. One or more individual manufacturing processes may exist at an
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individual facility. In addition, a facility may use one set of unit operations
or one reactor to manufacture different PAI products at different times. For
example, a facility may manufacture two PAIs using the same equipment with one
PAI manufactured during the spring and the other manufactured during the fall.
Total 1986 industry production reported for the 178 active
ingredients was approximately 1.2 billion pounds with 55% of this total accounted
for by herbicides. Table 3-5 presents the list of individual PAIs manufactured
in 1986 and the 8 PAIs manufactured before or after 1986.
3.3.3 Distribution of PAI Production by Facility
Tables 3-6, 3-7, and 3-8 present different views of the distribution
of PAI production by facility. Table 3-6 presents the distribution of PAIs
produced by number of manufacturing facilities. Table 3-7 presents the
distribution of manufacturing facilities by number of PAIs produced. Table 3-8
presents the distribution of facilities by quantity of production. As shown in
Table 3-6, 144 of the 178 PAIs produced in 1986 were reported to be manufactured
by only one facility in the United States. As shown in Table 3-7, 47 of the 90
manufacturing facilities reported producing only one active ingredient. The
remaining facilities produced between 2 and 16 active ingredients each. Each of
the 7 largest pesticide active Ingredient manufacturing facilities produced more
than 45 million pounds of active ingredient in 1986 and together represented
almost half (47%) of all 1986 pesticide production for the 178 PAIs.
3-51
-------
Table 3-5
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986'
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
AI Code
3.00
4.00
5.00
7.00
8.00
11.00
12.00
16.00
16.09
16.12
16.13
16.17
16.27
16.29
16.31
16.32
16.50
16.52
17.03
17.06
20.00
21.00
22.00
25.00
26.00
27.05
Common Name
EDB
Vancide TH
Dichloropropene
Dowicil 75
Triadimefon
Dichlorophene
Dichlorvos
2,4-D
2,4-D; 2-Butoxylethyl ester
2,4-D; Butyl ester
2,4-D; Diethano lamine salt
2,4-D; Dime thy lamine salt
2,4-D; Isooctyl (2-ethylhexyl) ester
2,4-D; Isoctyl (2-octyl) ester
2,4-D; Isopropylamine salt
2,4-D; Isopropyl ester
2,4-D; Trithano lamine salt
2,4-D; Trlisopropanolamine salt
2,4-DB; Dimethylamine salt
2,4-DB; 2-Ethylhexyl ester
Dichloran or DCNA
Bus an 90
Mevinphos
Cyanazlne or Bladex
Propachlor
MCPA; Dimethylamine salt
3-52
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
AI Code
27.09
27.13
27.16
28.00
30.02
30.03
30.05
31.01
31.02
31.03
32.00
35.00
36.00
39.00
41.00
42.00
45.00
49.00
52.00
53.00
54.00
55.00
56.00
58.00
60.00
62.00
Common Name
MCPA; Isooctyl ester
MCPA; Sodium salt
MCPA; 2-Ethylhexyl ester
Octhilinone
2, 4 -DP; Dimethylamine salt
2,4-DP; Isooctyl ester
2,4-DP; 2-Ethylhexyl ester
MCPP; Diethanolamine salt
MCPP; Dimethylamine salt
MCPP; Isooctyl ester
Thiabendazole
TCMTB
HAE
Pronamide
Propanil
Polyphase antimildew or Guardsan 388
Metribuzin
Etridiazole
Acephate or Orthene
Acifluorfen
Alachlor
Aldicarb
Hyamine 3500
Ametryn
Atrazine
Benomyl
3-53
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
AI Code
66.00
67.00
68.00
68.02
69.00
69.03
70.00
71.00
73.00
74.00
75.00
76.00
80.00
81.00
82.00
*84.00
86.00
88.00
*90.00
91.00
98.00
103.00
*107.00
110.00
112.00
Common Name
Bifenox
Biphenyl
Bromacil
Bromacil; Lithium salt
Bromoxynil
Bromoxynil; Octanoic acid ester
Butachlor
Giv-gard
Captafol
Captan
Sevin (Carbaryl)
Carbofuran
Chloroneb
Chloropicrin
Chlorothalonil
Stirofos
Chlorpyrifos
Bioquin
Fenvalerate
Cycloheximide
Dicamba
Diazinon
Methyl Parathion
DCPA
Dinoseb
3-54
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
AI Code
113.00
115.00
117.00
118.00
*119.00
120.00
123.00
123.02
123.03
123.04
*124.00
125.00
126.00
127.00
129.00
130.00
132.00
133.00
135.00
138.00
138.01
140.00
142.00
144 . 00
*148.00
Common Name
Dioxathion
Diphenamid
MGK 326
Nabonate
Diuron
Metasol DGH
Endothall
Endothall; Salt
Endothall; Salt
Endothall; Salt
Endrin
Ethalfluralin
Ethion
Ethoprop
Chlorobenzilate or Acaraben
Butylate
Fenarimol
Fenthion or Baytex
Fluometuron
Glyphosate
Glyphosate; Isopropylamine salt
Heptachlor
Hexazinone
Isopropalin
Linuron
3-55
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
AI Code
150.00
154.00
156.00
157.00
158.00
160.00
161.01
163.00
170.00
171.00
172.00
173.00
175.00
176.00
177.00
178.00
182.00
183.00
185.00
186.00
190.01
190.02
190.03
191.01
191.02
Common Name
Malathion
Me thami dopho s
Me thorny 1
Methoprene
Methoxychlor
Methylbromi.de or Bromomethane
Monosodium methyl arsenate
Nalco D-2303
Napropamide
Deet
Nab am
Naled
Norflurazon
N - 1 - Naph thy Iph thai imide
MGK 264
Benfluralin
Fensul f o th i on
DIsulfoton
Phosmet
Azinphos Methyl
Copper naphthenate
Copper octoate
Copper salt of fatty & resin acids
Phenyl mercuric dodecyl succinate
Phenyl mercuric acetate
3-56
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
AI Code
191.03
191.05
192.01
192.02
192.03
192.04
192.05
192.06
192.07
192.08
196.00
197.00
200.00
203.00
204.00
*205.00
206.00
206.01
208.00
210.00
211.00
211.05
212.00
215.00
215.01
Common Name
Phenyl mercuric oxide
Chloromethoxy propyl mercuric acetate
Tributyltin neodecanoate
Tributyltin monopropylene glycol maleat
2- (Methyl- 2 -phenyolpropyl) distannoxane
Tricyclohexyl tin hydroxide
Tributyltin oxide
Triphenyl tin hydroxide
Tributyl tin fluoride
Tributyl tin benzoate
Oxyfluorfen
Bolstar (Sulprofos)
Fonofos
Parathion
Pendimethalin
PCNB
Pentachlorophenol (PGP)
Pentachlorophenol ; Sodium salt
Permethrin
Pheno th i az ine
Phenylphenol
Phenylphenol ; Sodium salt -
Phorate
Picloram
Picloram; Potassium salt
3-57
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
AI Code
215.03
216.00
218.00
219.00
220.00
221.00
223.00
224.00
226.00
227.00
230.00
232.00
236.00
239.00
241.00
243.00
245.00
246.00
247.00
249.00
250.00
251.00
252.00
253.00
254.00
Common Name
Picloram; Triisopropanolamine salt
Piperonyl butoxide
Bus an 85 Or Arylane
Bus an 40
KN Methyl
Metasol J26
Prometon or Caparol
Prometryn
Propazine or Milogard
Propanoic acid
Pyrethrin I
Pyrethrin II
DEF
S imaz ine
Carbarn- S or Sodam
Vapam
Cycloate or Ro-Neet
EPTC or Eptam
Molinate
Vernolate or Vernam
HPTMS
Bensulide or Betesan
Tebuthiuron
Temephos
Terbacil
3-58
-------
Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
REPORTED TO BE MANUFACTURED IN 1986
AI Code
178 255.00
179 256.00
180 257.00
181 259.00
182 *262.00
183 264.00
184 268.00
185 272.00
186 NA2
Common
Name
Terbufos or Counter
Terbuthylaz ine
Terbutryn
Dazomet
Toxaphene
Trifluralin or Treflan
Ziram
Chloropropham
Diphenyl antimony 2 -ethyl
hexoate
'This list also includes eight additional PAls manufactured between 1985 and 1990
(these PAIs are marked with an asterisk).
Voluntarily submitted data for PAI not originally on the list considered for
regulation.
3-59
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Table 3-6
NUMBER OF PESTICIDE ACTIVE INGREDIENTS PRODUCED IN 1986
BY NUMBER OF MANUFACTURING FACILITIES
AI Production At:
One Facility
Two Facilities
Three Facilities
Four Facilities
Five Facilities
Total
No. of PAIs
144
25
7
1
1
178
Table 3-7
NUMBER OF MANUFACTURING FACILITIES BY NUMBER OF
PESTICIDE ACTIVE INGREDIENTS PRODUCED
No . of PAIs Produced
One
Two
Three
Four
Five or More
Total
No. of Facilities
47
16
10
7
10
90
3-60
-------
Table 3-8
DISTRIBUTION OF FACILITIES BY QUANTITY OF PAI PRODUCTION
Number of Facilities
7
19
38
18
8
90
Range of PAI Production (Ibs)
>45,000,000
10,000,000-45,000,000
1,000,000-9,999,999
100,000-999,999
0-99,999
-1,150,108,000 (Ibs/yr)
3-61
-------
Approximately 42% of the facilities produced between 1 million and 10 million
pounds of active ingredient in 1986.
3.3.4 Distribution of PAI Production During the Year
The bulk of PAIs identified in the Facility Census are either
herbicides or insecticides. These PAIs are used during the growing season, or
in the case of preemergent PAIs, just before the growing season. Therefore, PAI
production is expected to be seasonal. PAIs must als.o be formulated into final
end use products prior to sale or use. Therefore, the manufacture of the PAIs
would be expected to precede the time of use. Herbicide production in 1986
increased rapidly through the fall and early winter and peaked in March of that
year, just prior to the growing season. However, the 1986 production data for
other pesticide types (e.g., disinfectants) indicated that production often
reflects individual facility manufacturing schedules rather than any seasonal
trends.
Most of the facilities indicated that pesticide production operations
were managed on a campaign basis and that production of a specific PAI occurred
as a short-term production run from a few days to a few months. For some other
PAIs, however, production often continued nearly year round.
3-62
-------
3.4 PESTICIDE MANUFACTURING PROCESSES
There are two stages in the production of pesticides: the manufacture
of a PAI, followed by the formulation and packaging of the PAI. A PAI is
manufactured by the chemical reaction of two or more raw materials often in the
presence of solvents, catalysts, and acidic or basic reagents. The raw materials
may include any of a large number of organic and inorganic compounds. Pesticide
active ingredients may also be used as raw materials in manufacturing derivative
PAIs typically through the formation of various salts and esters. The proposed
pesticide chemicals manufacturing effluent guidelines and standards are intended
to control the discharge of pollutants in wastewater generated during the
manufacture of PAIs from raw materials. (For one PAI, the effluent guidelines
apply only to the discharge of wastewater generated during the purification of
that PAI to a higher quality PAI product.) These regulations do not apply to the
manufacturer of chemicals ("intermediate") which are not pesticides but which
subsequently are converted by further chemical reactions to PAIs. The
"intermediates" are covered by the OCPSF effluent guidelines (40 CFR Parts 414
and 416).
The formulation of pesticides through the mixing, blending, or
dilution of one or more PAIs, without an intended chemical reaction is distinct
from pesticide manufacturing and will be covered under separate guidelines.
Therefore, formulation will not be discussed further in this section.
3-63
-------
The manufacturing processes used by facilities to produce pesticide
active ingredients are highly dependent upon the type of active ingredient(s)
being manufactured at that facility. The types of processes used (batch or
continuous), the process chemistry, and the intermediate/byproduct manufacture
are described in the next section.
3.4.1 Batch vs. Continuous Processes
Batch processes are those in which raw materials and reagents are
added to a reactor, a reaction occurs, and then product is removed from the
reactor. The composition of the reactor changes over time, but flow neither
enters nor leaves the reactor until the chemical reaction process is complete.
Of the 224 manufacturing processes used to produce pesticides in 1986, 178 were
batch processes. All salts and esters produced in 1986 were manufactured using
batch processes.
During continuous processes, raw materials and reagents flow
continuously into the reactor and are converted into product while they reside
in the reactor. Product also flows continuously out of the reactor. Continuous
processes may operate for days, weeks, or months at a time. Of the reported 224
manufacturing processes used to produce pesticides in 1986, 46 were continuous
processes.
The survey data showed no relationship between the magnitude of daily
or annual production and the use of batch or continuous processes. This result
3-64
-------
was as expected because a number of variations exist, such as multistage batch
operations, and combinations of batch and continuous stages in a single process.
3.4.2 General Process Reactions
The following paragraphs describe the generic reaction mechanisms for
several of the structural categories of pesticide active ingredients. The
mechanisms described are not directly applicable to every pesticide active
ingredient manufactured in each structural category. They do attempt to present
a general mechanism for the majority of pesticide active ingredients produced
within each category.
NITROGEN-CONTAINING PESTICIDES
a. s-Triazines
s-Triazines are produced by reacting hydrogen cyanide and chlorine
to form cyanuric chloride followed by substitution of one or more of the
chlorines with amines, mercaptans or alcohols to form the desired product.
Atrazine is produced by the reaction of ethylamine and cyanuric chloride followed
by the addition of isopropylamine. Atrazine can then be reacted with methyl
mercaptan to form ametryn. The general structure and reaction for the s-
triazines as well as the specific reactions for atrazine and ametryn are shown
in Figure 3-4.
3-65
-------
U)
Figure 3-4
REACTION MECHANISMS FOR s-TRIAZINES AND ATRAZINE AND AMETRYN
HCN + CI2
a
s-TRIAZINES
a
C.H.NH.
a
(CH,hCHNH,
a
ATRAZINE
CH,SH
AMETRYN
Marshall Sittlg, editor, Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Noyes Data
Corporation, Park Ridge, NJ , 1980; p. 51, 63.
-------
b. Carbamates
The fundamental building block of carbamate pesticides is carbamic
acid, the monoamide of carbonic acid:
0 O
II II
HO- C-OH HO- C-NH2
Carbonic acid Carbamic acid
Carbamates are made by the reaction of alkyl or aryl alcohols with isocyanate as
shown:
0
II
R-OH + R'-N=C=0 > R-0- C-NHR'
N-Methyl carbamates are produced when methyl isocyanate is used. The
aryl N-methylcarbamates are easily formed when phenol and methyl isocyanate are
reacted. The pesticide carbofuran can be synthesized by reacting 2,2-dimethyl-
2,3-dihydrobenzofuran with methyl isocyanate in the presence of triethylamine and
ether as shown in Figure 3-5. (Nabam, also shown in Figure 3-5, is discussed
later in this section). Other commercially feasible processes for carbamates
involve the reaction of the alcohol with phosgene followed by the appropriate
amine.
3-67
-------
U)
-------
Thiolcarbonic acid and diothiocarbonic acid are the sulfur analogs
of carbonic acid which can form thiolcarbamic acid and dithiocarbamic acid upon
the addition of an amide:
0 S
II II
HS C OH HS C OH
Thiolcarbonic acid Dithiocarbonic acid
0 S
II II
HS C NH2 HS C NH2
Thiolcarbamic acid Dithiocarbamic acid
Dithiocarbamates are produced by the reaction of an alkyl amine and carbon
disulfide with sodium hydroxide, as shown:
NaOH ||
RNH2 + CS2 > R-NH- C -SR
In like manner, the ethylene-bisdithiocarbamates are produced by the reaction of
a diamine with carbon disulfide. The reaction for Nabam using ethylenediamine
is shown in Figure 3-5.
3-69
-------
c. Amides and Anilides
Nitrogen containing pesticides that are not carbamic acid derivatives
can be made by reacting an amine with a carbonyl acid or carbonyl acid chloride.
At this stage the intermediate can then be further reacted with alcohols,
sulfonyl halides, or other reagents to synthesize the desired product. The
general reaction mechanism is shown below. The specific reactions for propanil
and alachlor are shown in Figure 3-6.
0
II
RNH2 + R'-C-OH > R'- C NHR
Other mechanisms for nitrogen-containing pesticides include the
reaction of an amine with chloro-alkyls or chloro-aryls, where, by simple
substitution, the desired pesticide can be formed. The reaction for isopropalin
are shown in Figure 3-7.
PHENOXYACETIC ACID HERBICIDES
d. 2.4-D
An alkyl substituted phenol or phenoxide is reacted with chlorine or
the alkyl substituted benzene or 2,4-dichlorophenol is reacted with carboxylic
acid and/or sodium hydroxide to produce 2,4-dichlorophenoxyacetate. The product
3-70
-------
u>
I
Figure 3-6
REACTION MECHANISMS FOR PROPANIL AND ALACHLOR
+ CH3CH2COOH
NHCC2H3
SOCI2
a
PROPANIL
C,H
2"5
H3COH2C
H5C2
CHjOH
NH3
ALACHLOR
Marshall Sittig, editor, Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Noyes Data
Corporation, Park Ridge, NJ, 1980; p. 32, 639.
-------
Figure 3-7
REACTION MECHANISMS FOR ISOPROPALIN
Cl
-vj
KJ
N(C3H7)2
+ (C3H7)2NH2
CH(CH3)2
CH(CH3)2
ISOPROPALIN
Marshall Sittig, editor, Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Noyes Data
Corporation, Park Ridge, NJ, 1980; p. 460.
-------
can then be reacted with an alcohol to produce 2,4-D esters, an amine to produce
2,4-D amine salts, or with sodium hydroxide to produce 2,4-D sodium salts. The
general reaction is shown in Figure 3-8.
ORGANOPHOSPHORUS PESTICIDES
e. Phosphorothioates and Phosphorodithioates
The fundamental building block of organophosphorus pesticides is
phosphoric acid having the chemical structure:
0
II
RO- P - OR
The phosphorothioates are derivatives of phosphorothioic acid, the sulfur analog
of phosphoric acid with the following structures:
0 S
II II
RO- P - SR and RO- P - OR
I I
OR OR
3-73
-------
Figure 3-8
REACTION MECHANISMS FOR 2,4-D
2,4-D ESTERS
ROH
CO
i
ONa
H
+ ClCH2COONa
OCHzCOONa
,R
(RNH3)OH
2,4-D AMINE SALTS
NaOH
2,4-D SODIUM SALTS
Marshall SIttig, editor, Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Noyes Data
Corporation, Park Ridge, NJ, 1980; p. 229.
-------
The phosphorodithioates are further sulfur-substituted as follows:
S 0
II II
RO- P - SR and RO- P - SR
OR SR
To synthesize these organophosphorus pesticides, phosphorus pentasulfide is
reacted with an alcohol to form the phosphorothioic acid. The acid can then be
chlorinated and further substituted with an alkyl or aryl group to produce the
desired product. To form the phosphorodithioates, the phosphorothioic acid is
reacted with formaldehyde or other appropriate reagents, and then further reacted
with mercaptan to form the desired phosphorordithioate. Example chemical
reactions for parathion, a phosphorothioate, and phorate, a phosphorodithioate
are shown in Figure 3-9.
f. Phosphoroamidates
Like the phosphorothioates, the phosphoroamidates are the nitrogen
analog of phosphoric acid having the chemical structure:
S
II
R-0 -P - NHR
OR
3-75
-------
CO
Figure 3-9
REACTION MECHANISMS FOR PARATHION AND PHORATE
PS
25
S
I
— SH
CI
S
ONa
Acetone
NOj
PARATHION
P2S3 + CH2H5OH
S
II
(C2H5O)2P —SH
CH2=0
S
H
C2H5SH
— SCH2SC2H5
PHORATE
Marshall Sittig, editor, Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Noyes Data
Corporation, Park Ridge, NJ, 1980; p. 584, 611.
-------
Again, the reaction involves substitution of the acid with the
appropriate akyl groups to form the desired product. The reaction for glyphosate
is shown in Figure 3-10.
3.4.3 Intermediate/By-product Manufacture
In the 1986 Pesticide Manufacturing Facility Census, the EPA
specifically asked for the identification of pesticide intermediates and the
amount of intermediate sold. An intermediate, as defined in the Pesticide
Manufacturing Facility Census for 1986, is any "specific precursor compound
formed in the process of manufacturing an active ingredient." For example, if
chemical A and chemical B are reacted to form chemical C, and then chemical C is
reacted further to produce a PAI, then chemical C is an intermediate. The
Facility Census did not require facilities to provide detailed process chemistry
because industry objected to providing sensitive CBI, and because the Agency
determined that its primary reason for requesting this information in preliminary
versions of the Census questionnaire (for use in fundamentally different factors
variance determinations) was no longer necessary. Fifteen intermediates at 11
facilities were reported to be produced and sold in 1986. These intermediates
are associated with 15 pesticide manufacturing processes. As discussed in
Section 3.4, the manufacturers of intermediates are not subject to this
regulation.
3-77
-------
Figure 3-10
REACTION MECHANISM FOR GLYPHOSATE
o o
II NaOH II
(HO)2PCH2C1 + NH2CH2COOH • (HO)2PCH2NHCH2COOH
oo then HL,I
GLYPHOSATE
Marshall Slttig, editor, Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Noyes Data
Corporation, Park Ridge, NJ, 1980; p. 441.
-------
A by-product is identified as a stream from the reaction process,
other than intermediates or active ingredients, which is sold. For example, if
chemical A and chemical B are reacted to form chemical C and chemical D, of which
chemical D.is the desired PAI, then chemical C is a by-product if sold. Fifteen
by-products at 17 facilities were reported to be produced and sold in 1986.
These by-products are associated with 30 pesticide manufacturing processes. The
manufacture of by-products are not subject to this regulation.
3.5 CHANGES IN THE INDUSTRY
The Facility Census of 1986 gives a snapshot of the pesticide
chemicals manufacturing industry as it was in 1986. However, the industry had
and has undergone changes prior to and since 1986. The nature and extent of
those changes are discussed below.
Since 1986, the Agency is aware of 10 facility closings and 1
facility opening. The 1986 Facility Census also identified eight metallo-organic
pesticide manufacturers and 86 organic pesticide manufacturers (four facilities
manufacture both metallo-organic and organic pesticides) . Since 1986, the Agency
is aware of no metallo-organic and 10 organic pesticide manufacturers shutting
down facility operations.
One hundred seventy-eight PAIs and salts and esters of PAIs were
identified in the 1986 Facility Census as being manufactured that year from 224
production processes. The Agency believes that 16 production processes have been
3-79
-------
closed since 1986 resulting in 14 organic chemical and 2 metallo-organic PAIs no
longer being produced; however, these PAIs are included in this regulation if
data were available to develop limitations. In addition, several facilities have
decreased production of PAIs due to economic factors or to restricted use of
their pesticide products.
The Agency has also compared the list of PAIs or classes of PAIs not
manufactured in 1986 with the OPP database of registered pesticides (FATES
Database) in order to identify if any of these PAIs were now being manufactured.
Of the 144 PAIs not manufactured in 1986, 97 PAIs were reported as being
formulated and packaged in 1986-1988 according to the FATES database. The
remaining 47 PAIs were not reported in FATES as being formulated or packaged.
3-80
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SECTION 4
INDUSTRY SUBCATEGORIZATION
4.0 INTRODUCTION
Division of a point source category into groupings entitled
"subcategories" provides a mechanism for addressing variations between
products, raw materials, processes, and other parameters which result in
distinctly different effluent characteristics. Regulation of a category by
subcategory provides that each subcategory has a uniform set of effluent
limitations which take into account technological achievability and economic
impacts unique to that subcategory.
The factors considered in the subcategorization of the pesticide
point source category include:
Product type;
Raw materials;
Manufacturing process and process changes;
Nature of waste generated;
Dominant product;
Plant size;
Plant age;
Plant location;
Non-water quality characteristics;
Treatment costs and energy requirements.
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EPA evaluated these factors and determined that subcategorization
is necessary. These evaluations are discussed in detail in the following
sections. The pesticide chemicals point source category was divided into
three subcategories:
A. Organic pesticide chemicals manufacturing;
B. Metallo-organic pesticide chemicals manufacturing; and
C. Pesticide Chemicals Formulating and Packaging.
Subcategory C, the pesticide chemicals formulating and packaging
industry, will be addressed separately at a later date.
4.1 BACKGROUND
In the November 1, 1976, Federal Register. EPA promulgated interim
final BPT guidelines for the pesticide point source category establishing a
subcategorization approach which included five subcategories. Comments
received on this notice were incorporated into the April 25, 1978 and
September 29, 1978 final rule which presented a revised subcategorization
approach including three subcategories.
In the November 30, 1982, Federal Register. EPA proposed
additional guidelines (including BAT, BCT, NSPS, PSNS, and PSES) for the
pesticide point source category which established 13 subcategories. A Notice
of Availability (NOA) appeared in the June 13, 1984, Federal Register, which
presented on alternative subcategorization approach of three subcategories.
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The October 4, 1985, Federal Register, which promulgated BAT, NSPS, PSNS, and
PSES guidelines for the pesticide point source category incorporated the
alternative subcategorization approach of the June 13, 1984, Federal Register.
Subsequent to the October 4, 1985 promulgated rule, EPA voluntarily withdrew
the BAT, NSPS, PSNS, and PSES guidelines pursuant to litigation brought by the
industry.
This section discusses the subcategorization methodologies for the
interim final and final BPT guidelines and the proposed and final BAT, NSPS,
PSNS, and PSES guidelines which were later remanded and presents the concerns
and issues raised during the public comment periods for each.
4.1.1 November 1. 1976. Interim Final BPT Guidelines
The interim final BPT effluent limitations guidelines promulgated
November 1, 1976 for the pesticide chemicals point source category established
five subcategories:
• The halogenated organic pesticides subcategory (Subpart A);
• The organo-phosphorous pesticides subcategory (Subpart B);
• The organo-nitrogen pesticides subcategory (Subpart C);
• The metallo-organic pesticides subcategory (Subpart D); and
• The pesticide formulating and packaging subcategory
(Subpart E).
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The subcategories chosen reflected differences in the character,
volume, and treatability of wastewater streams due to manufacturing process
variables related to each grouping of chemicals. EPA believed that the
differences in process wastewater characteristics were significant and
warranted the establishment of five separate subcategories.
4.1.2 April 25. 1978. Promulgated BPT Guidelines
On promulgating the interim final regulations, the Agency
recognized that certain ambiguities were present in its subcategorization
based on chemical structure. Many pesticides contain more than one functional
group, such as halogens, phosphorous, sulfur, nitrogen, etc. and do not fit
the former subcategorization scheme. Such compounds could not be readily
assigned to particular subcategories. In order to resolve these ambiguities
and also in response to industry comments, the Agency re-examined its data to
determine if there were reasons to provide different effluent limitations on
the basis of chemical structure and other potential differences among plants.
Review of raw waste load characteristics revealed no consistent pattern
between or within chemical family groupings that would provide a basis for
subcategorization. The Agency found that the quantities of pollutants in the
effluents of those plants with properly operated treatment technologies
installed were similar, regardless of the organic pesticide chemicals
manufactured. The Agency, therefore, concluded that the wastewaters of all
organic pesticide chemicals can be treated or controlled to similarly
documented levels in the Agency's treatability database. For the final BPT
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regulation, the Agency consolidated the halogenated organic, organo-
phosphorous, and organo-nitrogen pesticide subcategories into a single
subcategory, designated as the organic pesticide chemicals manufacturing
subcategory.
EPA retained distinct subcategories for the manufacture of
metallo-organic pesticide chemicals and formulating and packaging of pesticide
chemicals for the promulgated BPT effluent limitations guidelines.
4.1.3 November 30. 1982. Proposed BAT. BCT. NSPS. PSES. PSNS Guidelines
On November 30, 1982, EPA proposed additional regulations to
control the discharge of wastewater pollutants from pesticide chemicals
manufacturing and formulating/packaging operations to navigable waters and to
publicly owned treatment works (POTWs) (47 FR 53994).
EPA proposed to subdivide the Organic Pesticide Chemicals
Manufacturing Subcategory (Subpart A) into 11 subcategories. EPA proposed to
retain the Metallo-organic Pesticide Chemicals Manufacturing Subcategory and
the Pesticide Chemicals Formulating and Packaging Subcategory as the 12th and
13th subcategories. EPA based this proposed new subcategorization scheme on
the nature of the priority pollutants and groups of priority pollutants which
had been detected or were likely to be present in pesticide wastewaters, and
the treatment technologies to remove those priority pollutants from industry
wastewater prior to discharge.
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4.1.4 June 13. 1984. Notice of Availability (NOA)
Commenters criticized the proposed subcategorization scheme on the
grounds that (1) the priority pollutant PAI combination were often
inaccurate, (2) subcategorization by treatment technology assumed a technology
would be used when an alternative technology could be used, and (3) the
subcategorization scheme projected was overly complex and possibly unworkable.
Commenters recommended that EPA not change the subcategorization used for BPT.
The Agency in general agreed with these comments, and i-n the June 13, 1984
Notice of Availability (NOA) stated that it was considering reducing the
number of subcategories back to three:
Organic pesticide chemicals manufacturing;
Metallo-organic pesticide chemicals manufacturing; and
Pesticide chemicals formulating and packaging.
The NOA announced the availability of new information collected in response to
comments received on the November 30, 1982 proposal. -EPA then requested
comments on the new data and the new subcategorization.
4.1.5 October 4. 1985. Promulgated BAT. NSPS. PSES. and PSNS Guidelines
Commenters supported the revised subcategorization scheme
presented in the June 1984 NOA. Therefore, on October 4, 1985, the Agency
promulgated effluent limitations guidelines for BAT, NSPS, PSES, and PSNS
based on the three subcategories identified in the June 1984 Notice of New
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Information. The primary factors for subcategorizing plants in the industry
were dominant product type, manufacturing processes, and raw materials used.
As discussed in Section 1.2, the October, 1985 guidelines were voluntarily
withdrawn by EPA in 1986.
4.2 CURRENT SUBCATEGORIZATION BASIS
In the current study, the Agency has developed new data and has
evaluated these data to determine the appropriate subcategorization. Based on
this evaluation, the Agency believes the pesticides chemicals industry should
be subdivided into the same three subcategories established by BPT. These
are:
Subcategory A Organic Pesticide Chemicals Manufacturing
Subcategory B Metallo-organic Pesticide Chemicals
Manufac tur ing
Subcategory C Pesticide Chemicals Formulating and Packaging
The following paragraphs discuss EPA's consideration of the
factors listed previously (see Section 4.0) in determining appropriate
subcategories for the Pesticides Chemicals Category. The primary bases for
subcategorizing plants in this industry were found to be product type and raw
materials used.
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4.2.1 Product Type and Raw Materials
Metals or metallic compounds are generally not used as raw
materials in the manufacture of organic pesticide chemicals, but such
substances are used as raw materials for metallo-organic pesticide chemicals
manufacturing. For this reason, wastewaters from metallo-organic pesticide
chemicals manufacturing have a much higher concentration of metals and
metallo-organic compounds than wastewater from organic pesticide chemicals
manufacturing. The types of treatment technologies effective for treating
wastewater from metallo-organic wastewaters are different from those
technologies used to treat organic pesticide chemicals, due to the higher
concentrations of metals and metallo-organic compounds in wastewaters from
metallo-organic pesticide chemicals. Therefore, product type and raw
materials are appropriate bases for subcategorization of this industry.
4.2.2 Manufacturing Process and Process Changes
Facilities that manufacture pesticide active ingredients use a
variety of unit operations, including chemical synthesis, separation,
recovery, purification, and product finishing. The specific active ingredient
product dictates not only the raw materials that will be used but also the
sequence of unit operations and the quantity and quality of wastewater that is
generated. Some pesticide chemicals manufacturing facilities have introduced
process changes which affect wastewater characteristics and quality. In the
period from 1977 to 1986, a number of facilities eliminated the use of
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priority pollutants as solvents. Other facilities implemented solvent
extraction to recover raw materials, intermediates, or products from
wastewater streams for reuse within the process, and recycle of process
waters, in order to minimize the discharge of pollutants from the
manufacturing process. Given the wide range of process chemistry and unit
operations used in the manufacture of different pesticide active ingredients,
subcategorization based on the manufacturing process and process changes would
result in too many subcategories, thus are not appropriate for the purpose of
delineating subcategories.
4.2.3 Nature of Waste Generated
Based on an analysis of the data available to EPA, there are no
consistent differences in the amount and identity of pollutants (except for
the active ingredient itself) in waste loads from different organic pesticide
chemicals manufacturing facilities. However, manufacturers of metallo-organic
pesticide chemicals tend to generate smaller volumes of wastewater with higher
metal concentrations compared to manufacturers of organic pesticide chemicals
(see Section 5). Therefore, the nature of the waste generated from pesticide
manufacturing operations is also a good basis for subcategorization that
differentiates between organic PAIs and metallo-organic PAIs. This factor is
directly related to the product type and raw materials used, and therefore is
consistent with subcategorization based on product type and raw materials.
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4.2.4 Dominant Product
In the pesticide chemicals manufacturing category, there are a
large number of products produced. The category also includes a large variety
of manufacturing processes and wastewater characteristics. Subcategorization
based on dominant product manufactured would result in a large number of
subcategories and is therefore not appropriate for subcategorization for the
pesticide chemicals manufacturing industry.
4.2.5 Plant Size
Plant size and production capacity do not impact characteristics
of wastewater produced during the manufacture of pesticide chemicals based on
data available to EPA. The size of the plant will not affect the
effectiveness of treatment technologies (i.e., the pollutant concentration
levels in the effluent that can be achieved with treatment technologies),
although it can affect the cost of treatment facilities and the cost of
treatment per unit of production. Overall, EPA does not believe that plant
size is an appropriate method of subcategorization for the pesticide chemicals
manufacturing industry.
4.2.6 Plant Age
The age of a plant or a production process can sometimes have a
direct bearing on the volume of wastewater generated, how the wastewater is
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segregated, and the ability of the plant to implement new treatment
technologies. Compared to new plants, older facilities tend to have a greater
volume of wastewater and higher pollutant loadings, even though pollutant
concentrations may be lower due to water contributions from noncontact
sources. However, plants that began manufacturing one set of products may be
manufacturing entirely different products now. Also, older facilities that
have continued to manufacture the same product have often improved or modified
the process and treatment technologies over time. Therefore,
subcategorization on the basis of plant age is not appropriate.
4.2.7 Plant Location
As discussed in Section 3, the majority of pesticide chemicals
manufacturing facilities are located in the eastern half of the United States,
with a concentration in the southeast corridor and Gulf Coast states. Based
on analyses of existing data, plant location has little effect on wastewater
quality, although it may affect the cost of treatment and disposal of process
wastes.
Facilities located in urban areas have higher land costs for
treatment facilities. Distance from the plant to an off-site disposal
location may also increase costs of off-site disposal of solid or liquid
waste. Climatic conditions may affect the performance of some treatment
technologies and necessitate special provisions (e.g., heating of biological
oxidation units in colder climates or cooling requirements in warmer
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climates). However, for pesticide chemicals manufacturing there are no
consistent differences in wastewater treatment performance or cost due to
location. Therefore, geographical location is not an appropriate basis for
subcategorization.
4.2.8 Non-Water Quality Characteristics
Non-water quality characteristics from the pesticide chemicals
manufacturing industry include environmental impacts due to solid waste
disposal, transportation of wastes to an off-site location for treatment or
disposal, and emissions to the air. The impact from solid waste disposal is
dependent upon the treatment technology employed by a facility and the
quantity and quality of solid waste generated by that facility. Contract
hauling wastewater from pesticide chemicals manufacturing creates a hazard
through the transportation of potentially hazardous materials. However, both
of these impacts are a result of individual facility practices, rather than a
trend of different segments of the industry.
Air emissions from the pesticide chemicals manufacturing industry
are somewhat related to the active ingredient product(s) manufactured and/or
the raw materials used. However, most PAIs are very low in volatility
compared to the various solvents used in the manufacturing processes. Since
the same solvents are used in manufacturing many different PAIs, therefore,
air pollution control problems and equipment utilized are not generally unique
to different segments of this industry. For example, baghouses or wet
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scrubbing devices remove particulates and vapors and toxic gases are
frequently incinerated.
Based on these discussions, the Agency believes that
subcategorization on the basis of non-water quality characteristics is not
needed.
4.2.9 Treatment Costs and Energy Requirements
The same treatment unit operation could be utilized for different
wastewater sources, such as steam stripping to remove volatile priority
pollutants and hydrolysis to remove organo-phosphorus pesticides. However,
the cost of treatment and the energy required will vary depending on flow
rates, wastewater quality, and the amount and identity of pollutants in the
wastewater. Moreover, alternative technologies could be selected by
dischargers. Therefore, subcategorization based on treatment costs and energy
requirements is not appropriate.
4.3 PROPOSED SUBCATEGORIES
Based on product type, raw materials, and the nature of waste
generated, EPA has defined two subcategories for the pesticide chemicals
manufacturing industry. The two subcategories are the same as the
manufacturing subcategories contained in the existing 40 CFR Part 455
regulations.
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4.3.1 Organic Pesticide Chemicals Manufacturing
This subcategory applies to discharges resulting from the
production of carbon-containing PAIs, excluding metallo-organic active
ingredients containing arsenic, cadmium, copper, or mercury. Although organo-
tin pesticides fit the definition of a metallo-organic pesticide given in the
BPT regulation (see Section 455.32), organo-tin pesticides were not included
in the metallo-organic pesticide chemicals subcategory (see Section 455.31
(a)) during the 1978 rulemaking because wastewaters from their manufacture
have significantly different wastewater characteristics than wastewaters from
the manufacture of metallo-organic pesticides containing arsenic, cadmium,
copper, and mercury. EPA does not believe it is appropriate to include the
organo-tin pesticides in the metallo-organic subcategory because their
pollutants are different, and the organo-tin production has larger volumes of
wastewater. The amounts and types of pollutants from organo-tin pesticide
manufacture are closer to the amounts and types of pollutants from the
manufacture of the organic pesticide chemicals. Therefore, EPA has determined
that organo-tin pesticides should be included in the organic pesticide
chemicals manufacturing subcategory. EPA proposes to regulate the following
pollutants in this subcategory: conventional pollutants, nonconventional
pollutants (including COD and the PAIs), and priority pollutants.
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4.3.2 Metallo-Organic Pesticide Chemicals Manufacturing
This subcategory applies to discharges resulting from the
manufacture of metallo-organic pesticide active ingredients that contain
mercury, cadmium, arsenic, or copper (see Section 455.30 and Section 455.31
(a)). The three existing direct dischargers in this subcategory are currently
subject to BPT effluent limitations requiring zero discharge of process
wastewater pollutants. Currently there are only five existing indirect
dischargers in this subcategory.
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SECTION 5
WATER USE AND WASTEWATER CHARACTERIZATION
5.0 INTRODUCTION
In 1988, under the authority of Section 308 of the Clean Water
Act, the Environmental Protection Agency (EPA) distributed questionnaires
entitled, "Pesticide Manufacturing Facility Census for 1986," to 247
facilities that EPA had previously identified as possible pesticide active
ingredient manufacturers. Responses to the questionnaire by these 247
facilities indicated that 90 facilities manufactured pesticides in 1986. This
section presents information on water use at these 90 facilities. This
section also presents information on process wastewater characteristics for
those pesticide chemicals manufacturing processes that were sampled by EPA and
for those pesticide chemicals manufacturing facilities that provided
self-monitoring data.
5.1 WATER USE AND SOURCES OF WASTEWATER
As described in Section 3.5, pesticide active ingredient
manufacturing processes vary from facility to facility and from active
ingredient to active ingredient. A simplified flow diagram for pesticide
active ingredient manufacture is presented in Figure 5-1, showing typical
5-1
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Figure 5-1
EXAMPLE OF PESTICIDE ACTIVE INGREDIENT MANUFACTURING PROCESS
Raw Materials
Solvent
Water
1 Other Reactan
l
i
Reaction — »> Intermediate —
Water Water
ts 1 1
l i
i i
* t
*
fe Reaction ^ Purification
1 1
1 1 1 I
i 1 i '
t ] t t
Wastewater Wastewater Wastewater
(e.g., Carrier/Reaction Media) ' (e.g., Water of Reaction) (e-9- Process
| Stream Wash)
T
r ^
Further processing
and/or sales.
May also be a
source of wastewater.
i ^
Water
1
I
l
l
i
t
Wastewater
(e.g., Product Wash)
Tvpes of Process Watt
Carrier/Reaction Media
Water of Formation
Product Wash
Process Stream Wash
Product
Equipment Wash
Pump Seal Wash
Pump Seal Water
Steam Jets/Vacuum Pumps
Scrubber Water
-------
streams which enter and leave the manufacturing process. The manufacture of a
pesticide active ingredient requires several types of input streams. These
include raw materials, solvents, other reactants, and water. Raw materials
are those organic and inorganic compounds that chemically react with one
another to form the pesticide active ingredient. Solvents are organic or
inorganic compounds used as reaction or transport media, but which do not
participate in the chemical reaction. Other reactants include acidic or basic
compounds used to facilitate, catalyze, or participate in the chemical
reaction (for example, an acidic reaction medium may be required to ensure the
desired pesticide product). Water or steam may be added to the reaction
medium to act as a solvent or carrier, or water may be added during subsequent
separation or purification steps.
Streams leaving the process include the active ingredient
products, by-products, intermediates which are sold or used in other
manufacturing processes, and liquid and solid wastes. A by-product is a
compound formed during the reaction process other than the active ingredient
product which can be sold. A common by-product in the pesticide manufacturing
industry is hydrochloric acid. An intermediate is defined in the Facility
Census as "any specific precursor compound formed in the process of
manufacturing an active ingredient." An intermediate is not a PAI itself but
instead is an organic chemical compound. In some cases, part of the
intermediate is removed from the pesticide process for use in other
manufacturing processes or for sale. Liquid and solid wastes include
hazardous and nonhazardous organic and inorganic wastes as well as wastewater.
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In addition, some chemical compounds may leave the manufacturing process in
the form of air emissions.
Three sources of wastewater were reported at pesticide
manufacturing facilities in 1986. These include:
PAI process wastewater water leaving the manufacturing
process.
Other pesticide wastewater pesticide-containing wastewater
generated from sources not directly associated with the
manufacturing process, such as employee shower water or
contaminated storm water.
Other facility wastewater wastewater from other
manufacturing operations, such as organic chemicals
production, or other facility sources, such as sanitary
wastewater, which is typically commingled and treated with
pesticide-containing wastewater. Other types of liquid
wastes leaving the pesticide manufacturing process include
spent solvents, spent acids, and spent caustics. These
wastes can become process wastewaters when combined with
other sources of process wastewaters that are treated and/or
discharged.
These sources are described in more detail below.
5.1.1 PAI Process Wastewater
Process wastewater is defined by EPA regulations at 40 CFR 122.2
as "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."
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Specifically, PAI process wastewaters associated directly with the
production process are:
Water of reaction: water which is formed during the
chemical reaction, such as from the reaction of an acid with
an alcohol (see Section 3.5.2).
Process solvent: water used to transport or support the
chemicals involved in the reaction process; this water is
usually removed from the process through a separation stage,
such as centrifugation, decantation, drying, or stripping.
Process stream washes: water added to the carrier, spent
acid, or spent base which has been separated from the
reaction mixture, in order to purify the stream by washing
away the impurities.
Product washes: water added to the reaction medium in order
to purify an intermediate product or active ingredient by
washing away the impurities; this water is subsequently
removed through a separations stage; or water which is used
to wash the crude product after it has been removed from the
reaction medium.
Spent Acid/Caustic: Acid and basic reagents are used to
facilitate, catalyze, or participate in the reaction
process. Spent acid and caustic streams, which may be
primarily water, are discharged from the process during the
separation steps which follow the reaction step.
Most of the above sources are present in manufacturing almost all
PAIs. Other sources of process wastewater associated with pesticide
operations include:
Steam jets or vacuum pumps: water which contacts the
reaction mixture, or solvents or water stripped from the
reaction mixture, through the operation of a venturi or
vacuum pump.
Air pollution control scrubber blowdown: water or acidic or
basic compounds used in air emission control scrubbers to
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control fumes from reaction vessels, storage tanks, and
other process equipment.
Equipment washes: water used to clean process equipment
during unit shutdowns.
Pump seal water: water used to cool packing and lubricate
pumps which may contact pesticide-containing water through
leakage and may therefore become pesticide-containing
wastewater.
General/Uncategorized process wastewater: a combination of
sources or cases where total flow is greater than the sum of
individual identified parts.
These water uses could result in the water becoming contaminated with
pesticide active ingredient or other compounds used in the manufacturing
process. These sources may be intermittent or absent entirely. The water use
reported for each source is presented in Table 5-1. As shown in the table,
about 34% of the water use is for product wash.
5.1.2 Other Pesticide Wastewater Sources
In addition to process wastewater, other types of wastewater may
»
be generated during pesticide production from non-process sources which can
also contain pesticide pollutants and other pollutants. These include:
Showers used by pesticide production employees. Many
facilities provide shower facilities for employees coming
off shift so that any PAIs that the employee may
inadvertently have contacted can be washed away before the
employee leaves the facility. [Note: Safety showers, which
are used to deluge an employee, clothing and all, in the
event of an accident, are always located near production
equipment. Accidents are very infrequent and these showers
are therefore seldom used. When used, any water generated
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Table 5-1
PESTICIDE ACTIVE INGREDIENT PROCESS WASTEWATERS
GENERATED IN 1986 BY EFFLUENT TYPE
Effluent Type
Product Wash
Scrubber Slowdown
Process Stream Wash
Process Solvent
Spent Acid
General Process/
Unidentified Wastewater1
Contaminated Stormwater2
Steam Jet/Vacuum Pump
Equipment Wash
Spent Solvent
Spent Caustic
TOTAL
Waste Volume
(gal/yr)
487,669,000
207,232,000
201,058,000
196,042,000
178,212,000
58,894,000
43,810,000
28,255,000
22,492,000
15,001,000
6,890,000
1,445,554,000
Percent
33.7
14.3
13.9
13.6
12.3
4.1
3.0
2.0
1.6
1.0
0.5
100.0
# Facilities
40
33
35
29
7
17
4
7
18
15
4
'General process wastewater also includes water of reaction and pump seal
water.
Contaminated stormwater reported as a source of process wastewater is
presented here. See Table 5-2 for contaminated stormwater reported as another
pesticide wastewater source.
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is process wastewater and is included as a source of process
wastewater in Section 5.1.1. Because of the infrequent use,
the amount of water is minuscule compared to other sources
of process wastewater.];
Laundries used to wash clothing from pesticide production
employees. Many facilities provide on-site laundry
facilities to wash employee uniforms to remove any PAIs that
may inadvertently be on the uniform after the work shift.
Cleaning safety equipment used in pesticide production.
Equipment includes goggles, respirators, and boots. These
must be cleaned after every use so they will be
contamination-free when next needed. Cleaning is usually
done with solvents followed by a soap and water wash.
Contaminated stormwater. Accidents, leaks, spills, shipping
losses, and fugitive emissions can all lead to PAIs and
other pollutants coming into contact with stormwater. This
contaminated stormwater is process wastewater and should be
treated before discharge.
Not all plants have all of these sources, and none monitor the flows (except
for stormwater). The number of plants reporting these sources is presented in
Table 5-2, along with the average estimated flows reported. As shown in Table
5-2, the flows from employee showers, laundries, and safety equipment cleaning
are all very small compared to stormwater, which itself is a relatively small
portion of total industry wastewater generation (see Table 5-1).
5.1.3 Other Facility Wastewater Co-Treated with Pesticide Wastewater
Often, a facility which manufactures pesticides also manufactures
other products. Wastewaters generated from other operations may be co-treated
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Table 5-2
WASTEWATER GENERATED FROM OTHER PESTICIDES WASTEWATER SOURCES
Source
Showers
Laundry
Safety Equipment
Contaminated Stormwater1
# Facilities
(out of 90)
67
21
47
47
Average Wastewater
Generated (gal/day)
3,070
1,210
3,480
177,000
'Contaminated stormwater reported as another source of pesticide wastewater is
presented here. See Table 5-1 for contaminated stormwater reported as a
source of process wastewater.
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with wastewater associated with pesticide manufacture. Facilities reported
co-treating wastewater from the following production operations:
Pesticide Formulating/Packaging (PFP) of "in-scope" and
"out-of-scope" PAIs ("out of scope" PAIs are those PAIs not
included in the list of 270 PAIs and classes of PAIs
considered for regulation);
Organic Chemicals, Plastics, Synthetic Fibers (OCPSF);
Inorganic Chemicals;
Pharmaceuticals;
Other Manufacturing: including production of out-of-scope
PAIs or wastewater from manufacturing operations not listed
above; and
Other Wastewater: including sources such as sanitary
wastewater.
Table 5-3 presents the number of facilities co-treating wastewater from these
operations along with the average percent of total flow co-treated for each
wastewater source. On the average, when pesticide manufacturing wastewater is
co-treated with other wastewaters, the pesticide manufacturing wastewater
constitutes 38% of the total wastewater being treated. OCPSF operations
contributed the largest percent of wastewater co-treated with pesticide
wastewater at 39 manufacturing facilities. Typically, 50% of the total
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Table 5-3
OTHER FACILITY WASTEWATER GENERATED FROM SOURCES OTHER THAN PESTICIDE
PRODUCTION AND CO-TREATED WITH PESTICIDE WASTEWATER
Source
Pesticide Formulating/
Packaging
Organic Chemicals, Plastics,
and Synthetic Fibers
Inorganic Chemicals
Pharmaceuticals
Other Manufacturing
Wastewater
Other Wastewater2
#
Facilities1
19
39
14
9
17
27
Average % of Total
Flow Co-Treated
4
50
23
28
28
34
'A facility is double counted if it co-treated more than one source of water
with pesticide manufacturing wastewater.
20ther wastewater includes, for example, sanitary water.
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wastewater volume from treatment systems that co-treat pesticide manufacturing
water with OCPSF water is due to OCPSF processes. On the other hand, only 4%
of the total wastewater volume from treatment systems that co-treat pesticide
manufacturing water with PFP water is due to PFP processes. Other facility
wastewater, such as sanitary wastewater, is commingled with pesticide
wastewater at 27 manufacturing facilities.
5.2 WASTEWATER VOLUME BY DISCHARGE MODE
5.2.1 Definitions
Direct discharge refers to the discharge of a pollutant or
pollutants directly to waters of the United States (not to a publicly owned
treatment works). Facilities that directly discharge wastewaters do so under
the National Pollutant Discharge Elimination System (NPDES) permit program.
Indirect discharge refers to the discharge of pollutants
indirectly to waters of the United States, through publicly owned treatment
works (POTWs).
No discharge refers to facilities that do not discharge their
wastewaters to waters of the United States, as a result of either reuse of
process water back into the product, no water use, recycle off-site or within
the plant in other manufacturing processes, or disposal off-site or on-site
5-12
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that does not result in a discharge to waters of the United States (e.g., by
incineration, evaporation, or deep-well injection).
5.2.2 Discharge Status of Pesticide Manufacturing Facilities
Thirty-two of the 90 manufacturing facilities are direct
dischargers, while 36 are indirect dischargers. One facility discharges
wastewater both directly and indirectly; therefore, there are 67 dischargers.
Of the remaining 23 facilities, 15 facilities dispose of their wastewater by
on- or off-site deep well injection, incineration, or evaporation and 8
facilities generated no process wastewater by recycle/reuse or no water use.
5.2.3 Flow Rates by Discharge Status
The total amount of process wastewater discharged from pesticide
manufacturing processes to waters of the United States was approximately 1.30
billion gallons in 1986, compared to 1.45 billion gallons generated.
Eighty-two percent of all process wastewater generated was discharged directly
to a receiving stream while 8% was discharged indirectly. Most of the
remaining wastewater was disposed of by deep well injection (DWI). Table 5-4
presents the volumes of pesticide process wastewater discharged or disposed in
1986.
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Table 5-4
TOTAL PROCESS WASTEWATER FLOW BY TYPE OF DISCHARGE
(Gallons per Year)
Discharge
Status
Direct
Indirect
No Discharge1
TOTAL
Number of
Facilities
32
36
23
9 12
Percent of
Facilities
36
40
26
102
Total
Flow (gal)
1,179,246,000
117,938,000
148,370,000
1,445,554,000
111
No discharge" facilities dispose of their wastewater through deep well
injection (DWI), incineration (on or off-site), or evaporation.
2The number of facilities is greater than 90 and the percent is greater than
100 due to one facility that discharges both directly and indirectly.
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Table 5-5 summarizes process wastewater flows by discharge status
for organic pesticide chemicals manufacturing (Subcategory A) and metallo-
organic pesticide chemicals manufacturing (Subcategory B). Over 99% of the
wastewater generated and the wastewater discharged in the pesticide
manufacturing industry is due to manufacturing of organic pesticide
(Subcategory A) products.
5.3 WATER REUSE AND RECYCLE
Recycling or reuse of process wastewater during pesticide
production in 1986 was reported by 25 of the 90 manufacturing facilities.
Because of the diversity within the industry, it is difficult to summarize the
types of recycle operations which are currently available. Table 5-6,
therefore, presents general descriptions of current recycling operations.
One group of PAIs in Subcategory A was examined in more detail.
This group manufactures PAIs by reaction of phenoxy acids to form either salts
or esters. The manufacture of phenoxy esters generates "water of formation",
due to the chemistry of the esterification reaction, while the manufacture of
phenoxy salts does not generate any process waste streams but requires water
to be added to the reactor since the salts are sold in solution. Therefore,
use of the water of reaction from the formation of the ester as make-up water
for salt formation could eliminate a source of pollution.
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Table 5-5
PESTICIDE PROCESS WASTEWATER FLOW FOR THE
ORGANIC PESTICIDE SUBCATEGORY (SUBCATEGORY A) AND
THE METALLO-ORGANIC PESTICIDE SUBCATEGORY (SUBCATEGORY B)
Discharge Status
Direct
Indirect
No Discharge1
TOTAL
Total Subcategory A
Flow (gal)
1,179,246,000
117,317,000
146,318,000
1,442,881,000
Total Subcategory B
Flow (gal)
0
621,000
2,052,000
2,673,000
'"No discharge" facilities dispose of their wastewater 'through deep well
injection (DWI), incineration (on or off-site), or evaporation.
5-16
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Table 5-6
TYPES OF WASTEWATER RECYCLE OPERATIONS REPORTED
Recovery of process input or product
Reused in pesticide manufacturing process
Reused in formulating/packaging process
Reused in equipment washwater
Reused as cooling water or scrubber water
Reused contaminated stormwater in manufacturing
process
TOTAL
# Facilities
14
8
2
2
2
1
29i
'The number of facilities exceeds 25 due to multiple recycle operations at
some facilities.
5-17
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Reuse of reaction waters from the esterification processes as feed
water for phenoxy salt neutralization and formulation serves the dual purpose
of eliminating a contaminated wastewater discharge and recovering the phenoxy
acid active ingredient.
The ability of a facility to reuse waters as feed to the
neutralization reaction depends on:
1) The ratio of production between the esterification and
neutralization process; and
2) The quality of the water recovered from the esterification
process.
The production ratio is important because approximately 0.5 pounds of water
are normally added to make each pound of product during the manufacture and
formulation of phenoxy salts, while approximately 0.08 pounds of reaction
water are generated from the esterification of 1 pound of product. Given
these ratios, a facility will achieve a perfect water balance if 1 pound of
phenoxy salts are produced for every 6.25 pounds of phenoxy ester produced.
Therefore, if the quantity of phenoxy salts produced at a facility is more
than 16% of the quantity of phenoxy esters produced, there will be
insufficient esterification water generated to meet phenoxy salt formulation
requirements, and fresh make-up water or reactor vessel washwater must also be
used as formulation feedwater. Conversely, if phenoxy salt production is less
than 16% of phenoxy ester production, the facility will generate more
esterification reaction water than may be used in salt formulations, and water
will have to be disposed.
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In 1986, of the facilities which manufactured both phenoxy salts
and esters, phenoxy salt production was always much higher than 16% of phenoxy
ester manufacture, indicating that these facilities should have been able to
reuse all esterification water that year. However, three additional factors
affect the amounts of esterification water a facility may reuse. First,
purity requirements for waters used in the manufacturing of phenoxy salts have
an effect on the amount of esterification reaction water which may be reused
in this way. Secondly, while the amount of water generated by the
esterification reaction may be determined stoichiometrically, the water
requirements for phenoxy salt neutralization and formulation will vary based
on the specific product registrations being produced. Finally, phenoxy salts
and esters are often manufactured in short production runs throughout the
year, depending on immediate consumer demand, and a facility may not be able
to store these waters until they can be reused.
In general, reaction water from the esterification of a given
phenoxy acid active ingredient may only be used in the manufacture of salts of
the same active ingredient. The importance of this requirement varies
depending on the application and labeling of the phenoxy salt product, and too
high a contamination level may affect the final product registration. It is
also important that the water used in phenoxy salt formation have a low
alcohol content, because alcoho-1 can cause cloudiness within the phenoxy salt:
formulation product. An effective alcohol/water separation stage at the
esterification process is critical to the yield of a high quality water that
may be reused in phenoxy salt manufacturing.
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All but one of the U.S. facilities which convert phenoxy acids to
salts and esters reuse the waters generated by the esterification reaction as
make-up water for salt formation. When production schedules do not allow
immediate use of esterification process wastewater for salt formation, the
esterification process wastewater is typically stored until needed. When
demand for the phenoxy acid ester exceeds the demand for the phenoxy acid salt
so much that there is not enough storage capacity for the wastewater, the
excess wastewater is disposed of. All plants that recycle the esterification
process wastewater have had this wastewater incinerated when necessary,
although typically this has occurred only once in several years.
5.4 RAW WASTEWATER DATA COLLECTION
Section 3.1 of this document introduced the many wastewater data
collection efforts undertaken for development of these regulations. Studies
that produced data on raw wastewater characteristics include industry-supplied
self-monitoring data submitted as a follow-up to the Facility Census and data
obtained from EPA sampling at pesticide manufacturing facilities. Results of
these data gathering efforts are described in more detail below.
5.4.1 Industry Supplied Self-Monitoring Data
As part of the Facility Census, EPA requested that pesticide
manufacturing facilities submit any available wastewater monitoring data and
requested that these data be submitted as individual data points (as opposed
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to monthly averages, for example). In response, facilities submitted
monitoring data for conventional and priority pollutants, as well as for PAIs
and other non-conventional pollutants, such as COD. However, these monitoring
data usually represented pollutant concentrations in end-of-pipe wastewater
streams. Therefore, EPA made additional requests for data from sampling
locations that would characterize pesticide process wastewater discharges
prior to commingling with wastewaters from other industrial sources. Many
facilities were able to provide these types of monitoring data for raw
pesticide process wastewaters and also for sampling locations that allowed EPA
to evaluate certain treatment technologies.
The PAI analyses were often quite detailed and were provided for
raw and treated process wastewaters. Monitoring data submitted for 55 PAIs
from 27 facilities were of sufficient quality to develop BAT/PSES guidelines
based on plant performance.
Priority pollutant data submitted by facilities were not quite as
useful. In most cases, these priority pollutant data were collected at
sampling locations representing commingled wastewaters. For this reason, it
was difficult to attribute many of these pollutants to the pesticide
processes. In some cases, however, facilities had analyzed raw pesticide
process wastewaters for priority pollutants. These data usually matched well
with the facility's indication in the Facility Census that the pollutant was
known or believed present in their pesticide process wastewaters. Although
quantitative priority pollutant data were supplied by 43 facilities for a
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total of 49 priority pollutants, only 11 facilities reported these
concentration data for raw pesticide process wastewaters.
The conventional and nonconventional (other than the PAIs)
pollutant data were also submitted for both in-plant and end-of-pipe sampling
locations. At sampling points following commingling of other industry-related
wastewaters, however, it was not possible to attribute these pollutants solely
to the pesticide processes. These data were useful in evaluating the overall
performance of the end-of-pipe BPT treatment systems.
5.4.2 EPA Pesticide Manufacturers Sampling Program
As described above in Section 5.4.1, the wastewater self-
monitoring data submitted as a follow-up to the Facility Census were the
result of sampling and analyses conducted by individual plants and their
laboratories. To expand and augment these wastewater characterization data,
EPA conducted sampling episodes at 20 pesticide manufacturing facilities
between 1988 and 1990. Through this sampling effort, EPA verified the
presence of many of the priority pollutants that were indicated as known or
believed present according to responses to the Facility Census. In addition,
EPA verified the presence of certain priority pollutants that may not have
been reported by the facilities, but were expected to be present based on
EPA's process analysis.
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The sampling episodes also allowed EPA to test analytical methods
for the PAIs. Results of the PAI analyses obtained by EPA contract
laboratories were compared with results obtained by the facilities'
laboratories when the facilities chose to split samples with EPA. EPA also
requested and reviewed information on the analytical methods typically used by
the facilities to quantify the concentration of PAIs in their wastewaters.
Facilities were selected for sampling based on self-monitoring
data which indicated that the wastewater treatment system was effective in
removing PAIs, and the PAIs manufactured at the facility appeared to be
representative of one or more PAI structural groups. During the sampling
episodes, raw wastewaters from the manufacture of 38 different PAIs were
characterized. In addition, EPA sampled at various locations throughout the
treatment systems at these facilities to evaluate pollutant removal
performance.
The EPA sampling episodes were usually three days in duration.
Samples were collected to represent a "snapshot characterization" of the
wastewater stream at each sampling point. Automatic sampling devices were
used where possible to collect the daily composite samples. If an automatic
sampler could not be used, discrete equal volume grab samples, or aliquots,
were manually collected at equal time intervals and added to the compositing
container (a specially clean 10-liter glass jar). At the end of each daily
sampling period, each composite sample was poured into specially cleaned
individual fraction containers for shipment to the EPA contract laboratories.
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These fractions included analyses for: Group I (BOD5, TSS, total fluoride, and
pH); Group II (TOG, COD, ammonia nitrogen, and nitrate and nitrite nitrogen);
extractable (semi-volatile) organics; metals; and the pesticide active
ingredient(s). The fractions for volatile organics, cyanide, and oil and
grease analyses were not poured from the composite containers, but manually
collected as individual grab samples during each daily sampling period.
After the individual sample fraction containers were filled each
day, they were preserved according to EPA protocol. In addition, the samples
were maintained at 4°C (using ice) during storage and shipment, with the
exception of the metals fraction which does not need to be kept iced. The
purpose of this procedure was to minimize any potential degradation reactions,
including biological activity, that could occur in the samples prior to
analysis. It was not necessary to follow this procedure for the metals
fraction since these analyses are not specific to the compounds containing the
metal analyte but rather are reported as total metals contained in the sample
(such as total copper, total mercury, etc.).
5.5 WASTEWATER CHARACTERIZATION
The pesticide chemicals manufacturing industry generates process
wastewaters containing a variety of pollutants. Most of this process
wastewater receives some treatment, either in-plant at the process unit prior
to commingling with other facility wastewaters or in the end-of-pipe
wastewater treatment system. This section presents the Agency's database on
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the pollutant characterization of pesticide wastewaters generated by pesticide
chemicals manufacturing facilities. This database was compiled from the two
data gathering efforts previously described in Section 5.4. Wastewater
characterization data were used by EPA to evaluate which pollutants are
present in industry wastewaters at significant levels that merit regulation
and to determine which technologies are applicable for treatment of
wastewaters containing these pollutants. Wastewater characterization is
discussed separately below for conventional pollutants, priority pollutants,
PAIs, and other non-conventional pollutants. Treatment technologies are
discussed later in Section 7.
5.5.1 Conventional Pollutants
Conventional pollutants include:
• Biochemical Oxygen Demand (BOD5) ;
• Total Suspended Solids (TSS);
pH;
• Oil and Grease (O&G); and
• Fecal Coliform.
The most widely used measure of general organic pollution in
Wastewater is five-day biochemical oxygen demand (BOD5) . BOD5 is the quantity
of oxygen used in the aerobic stabilization of wastewater streams. This
analytical determination involves the measurement of dissolved oxygen used by
microorganisms to biodegrade organic matter and varies with the amount of
biodegradable matter that can be assimilated by biological organisms under
5-25
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aerobic conditions. The nature of specific chemicals discharged into
wastewater affects the BOD5 due to the differences in susceptibility of
different molecular structures to microbiological degradation. Compounds with
lower susceptibility to decomposition by microorganisms or that are more toxic
to microorganisms tend to exhibit lower BOD5 values, even though the total
amount of organic pollutant may be much higher than compounds exhibiting
substantially higher BOD5 values. Therefore, while BOD5 is a useful gross
measure of organic pollutant, it does not give a useful measure of specific
pollutants, particularly priority pollutants and PAIs.
Total solids in wastewater is defined as the residue remaining
upon evaporation at just above the boiling point. Total suspended solids
(TSS) is the portion of the total solids that can be filtered out of solution
using a 1 micron filter. Raw wastewater TSS content is a function of the
active ingredients manufactured and their processes, as well as the manner in
which fine solids may be removed during a processing step. It can also be a
function of a number of other external factors, including storm water runoff,
runoff from material storage areas, and landfill leachates that may be
diverted to the wastewater treatment system. Solids are frequently washed
into the plant sewer and removed at the wastewater treatment plant. The total
solids are composed of matter which is settleable, in suspension, or in
solution and can be organic, inorganic, or a mixture of both. Settleable
portions of the suspended solids are usually removed in a primary clarifier.
Finer materials are carried through the system, and in the case of an
activated sludge system, become enmeshed with the biomass where they are then
5-26
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removed with the sludge during secondary clarification. Some manufacturing
plants may show an increase in TSS in the effluent from the treatment plant.
This characteristic is usually associated with biological systems and
indicates an inefficiency of secondary clarification in removal of secondary
solids. Treatment systems that include polishing ponds or lagoons may also
exhibit this characteristic due to algae growth.
pH is a unitless measurement which represents the acidity or
alkalinity of a wastewater stream (or any aqueous solution), based on the
dissociation of the acid or base in the solution into hydrogen (H+) or
hydroxide (OH") ions, respectively.
Raw wastewater pH can be a function of the nature of the processes
contributing to the waste stream. This parameter can vary widely from plant
to plant and can also show extreme variations in a single plant's raw
wastewater, depending on such factors as waste concentration and the portion
of the process cycle discharging at the time of measurement. Fluctuations in
pH are readily reduced by equalization followed by a neutralization system, if
necessary. Control of pH is important regardless of the final disposition of
the wastewater stream (e.g., indirect discharge to a POTW or direct discharge)
to maintain favorable conditions for various treatment system unit operations,
as well as receiving streams.
Raw wastewater oil and grease (O&G) is an important parameter in
some wastewaters as it can interfere with the smooth operation of wastewater
5-27
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treatment plants and, if not removed prior to discharge, it can interfere with
the biological life in receiving streams and/or create films along surface
waters. However, oil and grease monitoring involves use of a solvent to
extract oil and grease from the sample. This solvent usually also extracts
organic materials other than petroleum oil, such as priority pollutants and
the PAIs. None of the pesticide plants sampled or visited have any petroleum
oil problems in wastewater; the oil and grease measurements reflect only gross
levels of organics and are poor measures of priority pollutants and PAIs
(because there are much more accurate pollutant-specific methods for these
parameters). Therefore, oil and grease is not an important parameter in
pesticide wastewaters.
The drinking water standard for microbial contamination is based
on coliform bacteria. The presence of coliform bacteria in wastewater, a
microorganism that resides in the human intestinal tract, indicates that the
wastewater has been contaminated with feces from humans or other warm-blooded
animals. The promulgated BPT limitations do not include a limit for coliform
bacteria, because very few pesticide manufacturing plants directly discharge
sanitary wastewater, and because coliform bacteria is not expected to be
present in the PAI contaminated wastewater streams generated by pesticide
manufacturing facilities. EPA did not pursue any further data collection
efforts characterizing fecal coliform in pesticide manufacturing plants for
this regulation.
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Self-monitoring data submitted by pesticide manufacturers included
substantial amounts of conventional pollutant analytical results. The data
indicate that conventional pollutant levels are widely scattered for in-plant
process streams. Analytical data developed through EPA's sampling program
show the same results. Industry data characterizing final effluent streams
show that, on average, plant wastewater treatment systems are removing
conventional pollutants to consistently low levels. For almost all (>99%)
BODj and TSS results reported for end-of-pipe discharge, the results were
below the industry-average concentration-based daily maximum BPT limit for the
respective pollutant. The average concentration-based BPT limit was
calculated based on the concentration-based BPT limits for each plant in EPA's
database. The individual plant concentration-based BPT limits were back
calculated from the mass-based BPT limit by factoring in each plant's flow
rate and production rate. For pH, most (>88%) of the results reported for
end-of-pipe discharge were within the BPT limits of between 6 to 9.
Analytical data developed through EPA's sampling program show the same results
for the conventional pollutants.
The industry-submitted BOD5 data characterizing end-of-pipe
discharge are summarized in Figure 5-2. The table displays the number of BOD5
results reported in ranges of 100 mg/L, and compares the results with the
industry average daily maximum BPT limit of 582 mg/L. The table shows that
the BODj levels in end-of-pipe discharges are typically under 100 mg/L. The
industry-submitted TSS data characterizing end-of-pipe discharge are
summarized in Figure 5-3, along with the industry average daily maximum BPT
5-29
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en
I
CO
O
3000n
Figure 5-2
INDUSTRY SELF-MONITORING BOD LEVELS IN FINAL EFFLUENT DISCHARGE
Average BP " Limit
582mg/L
0-100
100-200 200-300 300-400 400-500 500-600
BOD Concentration (mg/L)
>600
-------
Ul
U)
5000-f
-8 1000
0
Figure 5-3
INDUSTRY SELF-MONITORING TSS LEVELS IN FINAL EFFLUENT DISCHARGE
493$
Average BPT Limit
480mg/L
0-100
100-200 200-300 300-400 400-500
TSS Concentration (mg/L)
>500
-------
limit of 480 mg/L. Similar to BOD5, the table shows that the .TSS levels in
end-of-pipe discharges are typically under 100 mg/L. The industry-submitted
pH data characterizing end-of-pipe discharge are summarized in Figure 5-4,
along with the BPT limit range of between 6 and 9. The figure shows that the
majority of the results were within the BPT range.
5.5.2 Priority Pollutants
Data characterizing the pesticide manufacturing process wastewater
with respect to priority pollutants have been gathered by EPA qualitatively
from industry responses to the Facility Census and quantitatively from
industry supplied self-monitoring data and EPA sampling and analysis episodes.
In addition, the EPA Toxic Release Inventory System (TRIS) was used to confirm
the presence of priority pollutants in pesticide manufacturing wastewaters at
some facilities. Due to the aggregated nature of the reporting in TRIS,
however, it was not useful for quantifying priority pollutant discharges in
pesticide wastewaters. Many of the plants with priority pollutant emissions
exceeding the TRIS reporting thresholds manufacture pesticide and non-
pesticide chemicals. For this reason, these priority pollutant emissions
could not be attributed solely to the pesticide processes.
In- the Facility Census, respondents were asked to identify all
priority pollutants that were known or believed to be present in wastewaters
from each pesticide manufacturing process or indicate if those priority
pollutants were known to be absent. They were also asked to indicate the
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en
I
Co
3000-r
0
Figure 5-4
INDUSTRY SELF-MONITORING pH LEVELS IN FINAL EFFLUENT DISCHARGE
BP" Limit Range
6-9
« 1500-
0-2 2-4 4-6 6-7 7-8 8-9 9-10 10-11 11-12 12-13 13-14
pH Ranges
-------
source of the priority pollutant (i.e., raw material, reaction by-product,
solvent, catalyst, or contaminant). Priority pollutants were reported by 47
pesticide manufacturing facilities in their responses to the Facility Census.
A total of 60 unique priority pollutants were known or believed present in
wastewaters associated with the production of 83 PAIs at these 47 facilities.
Twenty-two facilities reported that no priority pollutants would be expected
in their pesticide manufacturing process wastewaters, and the other 21
facilities did not know whether priority pollutants would be present.
In addition to reporting priority pollutants in the Facility
Census, some facilities also submitted priority pollutant data obtained during
self-monitoring sampling. As discussed earlier in this section, most of these
data were not generally useful since they represented end-of-pipe sampling
locations at facilities that also manufacture non-pesticide chemicals.
However, six facilities submitted priority pollutant concentrations for raw
process wastewaters where multiple detections were reported. Table 5-7
summarizes the priority pollutant data submitted by these organic pesticide
chemical (Subcategory A) manufacturing facilities (no Subcategory B facilities
submitted priority pollutant data for raw process wastewaters). Table 5-7
shows the minimum and maximum concentrations reported for each priority
pollutant as well as the total number of samples analyzed for each pollutant
and the number of these samples with detectable concentrations. These data
are aggregated for all facilities, so the maximum and minimum concentrations
may represent samples collected at different facilities. Table 5-7 also shows
whether or not at least one of the facilities submitting data for each
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Table 5-7
PRIORITY POLLUTANT DATA-FACILITY SELF MONITORING
Pollutant
Tetrachlorome thane
Hexachloroe thane
2,4, 6-Trichlorophenol
Chloroform
2-Chlorophenol
2 ,4-Dichlorophenol
2 ,4-Dimethylphenol
Methylene Chloride
Chlorome thane
Phenol
Toluene
Cyanide
Number of
Samples
Analyzed
21
2
10
32
12
6
5
30
8
5
6
235
Number of
Reported
Detections
11
2
10
28
12
6
2
24
4
4
6
235
Reported Concentrations (/jg/L)
Minimum
0.5
260
590
0.5
7
13,350
2,300
0.5
3
100
2,200
180
Maximum
3,100
1,300
15,700
110,000
24,320
108,000
2,600
7,400,000
50
690
400,000
7,625,000
Known or
Believed
Present
Known
-
Known
Known
Believed
Known
-
Known
Known
Known
Known
Ul
LJ
-------
priority pollutant had indicated in the Facility Census that the pollutant was
known or believed present in their process wastewaters. Nine of the 12
priority pollutants shown in the table were reported as known or believed
present in pesticide process wastewaters.
To verify the presence of priority pollutants reported as known or
believed present by facilities and to augment the limited priority pollutant
data submitted by facilities, EPA conducted sampling episodes at 20 pesticide
manufacturing facilities. As discussed in Section 5.4, in each episode
samples were collected for three days at locations throughout the wastewater
generation, treatment, and discharge path. A report that there was detection
of a priority pollutant in at least two daily samples at the same location
would indicate high probability that the priority pollutant was in fact
present. Reported detection of a priority pollutant in only one sample would
cast doubt on the presence of that pollutant.
Where priority pollutants were reported detected in only one
sample at any sample site, EPA used the following procedure to evaluate the
report. First, EPA examined samples collected at other sites during the
episode for reported detections for that same pollutant in pesticide
manufacturing process wastewaters. Second, EPA examined the details of the
production process to determine if the pollutant was a raw material, by-
product, or a likely contaminant of any raw materials or solvents used in the
process. Finally, EPA contacted knowledgeable plant personnel to determine if
the pollutant was a known or likely contaminant, and to determine if the plant
5-36
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had also detected the pollutant during sampling; particularly if the pollutant
was detected during sampling conducted the same day EPA sampled and if the
sample was analyzed by the plant using the same or a similar analytical method
as EPA.
EPA sampling at the 20 facilities reported detection of 70
priority pollutants in pesticide manufacturing wastewaters. However, in many
cases, the priority pollutants were detected in only one sample at one sample
site, and the presence of the pollutants could not be confirmed after checking
all the sources described above. EPA's conclusion in these cases, where
detections could not be confirmed, is that the reported results are incorrect
and the pollutant is not in fact present. In addition, some of the pollutants
that were detected at the same sample point on multiple days were present in
only trace amounts and often very close to the analytical detection limit.
Table 5-8 presents priority pollutant characterization data for
raw process wastewaters based on EPA sampling at organic pesticide chemicals
(Subcategory A) manufacturing facilities. The table shows the minimum and
maximum concentrations detected for each priority pollutant that was confirmed
present during the sampling episodes. These data are aggregated to include
all sampling episodes, and, therefore, the minimum and maximum concentrations
may have been reported for wastewater samples collected at different
facilities. Table 5-8 also shows whether or not at least one of the
facilities where each priority pollutant was confirmed present either knew or
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Table 5-8
Priority Pollutant Data EPA Sampling
Organic Pesticide Chemicals Manufacturing
Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2 - Dichloroe thane
1,1, 1-Trichloroe thane
Hexachloroe thane
Chloroform
2 - Chlorophenol
1 , 2 - Dichlorobenzene
1 , 4-Dichlorobenzene
1 , 1-Dichloroethene
Trans- 1, 2-Dichloroethene
2 , 4-Dichlorophenol
Ethylbenzene
Methylene Chloride
Ch 1 o r ome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Nitrobenzene
Phenol
Tetrachloroethene
Toluene
Trichloroethene
Cyanide
Lead
Concentration
(/4J/L)
Minimum
16
892
38
1,007
30
34
12
40
70
84
133
16
11,890
71
14
55
93
22
21
27
32
25
51
27
19
50
930
Maximum
31,000
44,260
113
3,255,900
60
5,346
20,110
8,264
14,202
554
261
18
360,940
9,550
11,261,100
111
42,679
29,370
39,434
1,197
44
97,794
402,655
331,649
38
2,740,000
1,600
Known or Believed Present
Believed
Known
Known
Known
Believed
Believed
Known
Known
Known
Known
Known
Believed
Believed
Known
Known
5-38
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believed that the priority pollutant was present in their wastewaters. Of the
27 priority pollutants shown in the table, 15 (- 55%) were reported as either
known or believed present according to Facility Census responses from the
sampled facilities.
EPA also collected samples at three metallo-organic pesticide
manufacturing (Subcategory B) facilities. During two of the sampling
episodes, however, only one sample of raw process wastewater could be
collected at each facility. In all three episodes, the specific metal used in
the production of the metallo-organic pesticide (e.g., copper in organo-copper
pesticides) was detected in the raw wastewaters. The detected concentrations
were also much greater than the concentrations expected in wastewaters due to
equipment corrosion. Some organic priority pollutants were also reported, and
some of these were expected to be present due to solvent or raw material use
in the pesticide process. However, as mentioned earlier, in two sampling
episodes only one sample each was collected, and, therefore, there is some
doubt as to whether other priority pollutants that were reported are actually
present.
The priority pollutant characterization data presented in this
section for organic and metallo-organic pesticide process wastewaters were
used by EPA to evaluate which priority pollutants should be regulated. The
decision to regulate was not based solely on whether a priority pollutant was
verified present during sampling; EPA evaluated a number of other factors as
well, such as whether the pollutant was present in more than trace amounts.
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However, most of the priority pollutants shown in Table 5-8 are being
regulated as will be discussed in Section 6.
5.5.3 Pesticide Active Ingredient Pollutants
Raw wastewater data for PAIs are available from both industry
self-monitoring and EPA sampling. The industry self-monitoring data were not
quite as useful for quantifying PAI concentrations in raw wastewaters because
the sampling locations often represented commingled or partially treated
wastewaters. Unlike priority pollutants, PAIs detected in commingled
wastewaters could be attributed to the pesticide processes since other
industrial production at the facility would not generate wastewaters
containing PAIs. The facility self-monitoring data did confirm that when
wastewaters are generated during the production of a specific PAI, that PAI is
usually present in those wastewaters. Fifteen facilities submitted PAI data
for raw and partially treated wastewaters associated with 29 unique PAIs
manufactured in 1986. A total of 5,153 samples were analyzed by the 15
facilities, and PAIs were reported in concentrations above the detection
limits for 4,756 of these samples, or about 92% of the samples. In many
cases, the PAI was reported above the detection limit in every sample that was
analyzed.
EPA sampling also confirmed the presence of PAIs in raw process
wastewaters. As discussed earlier, EPA sampled at 20 pesticide manufacturing
facilities, and these sampling episodes were used to characterize pesticide
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wastewaters from 38 different PAI processes, as well as to evaluate analytical
methods for the PAIs. Detections were reported for 34 of the 38 PAIs in
samples of the raw process wastewaters; that is, about 90% of the PAI
processes sampled generated wastewaters containing the PAI at concentrations
above the analytical detection limit. Specific results obtained during EPA
sampling of raw process wastewaters are not presented in this document due to
confidentiality concerns in many cases, presenting results for specific PAIs
would identify where EPA conducted the sampling episodes.
5.5.4 Nonconventional Pollutants
Nonconventional pollutants include chemical oxygen demand (COD),
total organic carbon (TOG), as well as other organic pollutants not previously
mentioned. COD is a measure of organic material in a wastewater that can be
oxidized as determined by subjecting the waste to a powerful chemical
oxidizing agent (such as potassium dichromate) in an acidic medium.
Therefore, the COD test can show the presence of organic materials that are
not readily susceptible to attack by biological microorganisms. As a result
of this difference, COD values are almost invariably higher than BOD3 values
for the same sample. The COD test cannot be substituted directly for the BOD5
test because the COD/BOD3 ratio is a factor that is extremely variable and is
dependent on the specific chemical constituents in the wastewater. However, a
COD/BODj ratio for the wastewater from a single manufacturing facility with a
constant product mix or from a single manufacturing process may be
established. This ratio is applicable only to the wastewater from which it
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was derived and cannot be utilized to estimate the BOD3 of another facility's
wastewater. It is often established by facility personnel to monitor process
and treatment plant performance with a minimum of analytical delay. As
production rate and product mix changes, however, the COD/BOD5 ratio must be
reevaluated for the new conditions. Even if there are no changes in
production, the ratio should be reconfirmed periodically.
TOG measurement is another means of determining the pollution
potential of wastewater. This measurement shows the presence of organic
matter in wastewater and is especially applicable to small concentrations.
Certain organic compounds may be resistent to oxidation and the measured TOG
value will be less than the actual amount. The promulgated BPT limitations do
not include a limit for TOG. TOG is a parameter which is controlled under the
BOD5 and COD regulations. In addition, the most highly toxic TOG constituents
will be organic PAIs and priority pollutants, which will be individually
regulated.
EPA's sampling data collection efforts included analyses for non-
priority organic and metal pollutants. The metals found most frequently in
pesticide manufacturing plant wastewater include sodium, iron, barium,
calcium, manganese, potassium, iodine, and strontium. Other inorganic, non-
priority pollutants frequently detected include phosphorus, silicon, and
sulfur. Non-priority organic pollutants detected in more than 10 percent of
the samples collected include 2-propanone, 2-butanone, 1,4-dioxane, and
xylenes. However, many of the compounds discussed above were detected in
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commingled wastewaters and cannot be attributed to the PAI processes. Also,
in many cases, these compounds were detected in trace amounts or are currently
being controlled by treatment technologies in place at the facilities where
they were detected.
The only non-conventional pollutant currently regulated under BPT
(aside from the PAIs) is COD. Self-monitoring data submitted by pesticide
manufacturers included substantial amounts of COD analytical results. Similar
to the data submitted for the conventional pollutants, the industry data
indicate widely-scattered COD levels in in-plant process streams, but
consistently low COD levels in end-of-pipe discharge are summarized in Figure
5-5. The figure shows that the majority (>90%) of the COD results for end-of-
pipe discharge streams were below the industry average daily maximum BPT limit
of 1,025 mg/L (the calculation of industry average concentration-based BPT
limits is discussed in Section 5.5.1).
5.6 WASTEWATER POLLUTANT DISCHARGES
The concentration data discussed above were used by the Agency to
estimate pollutant loadings discharged by pesticide chemicals manufacturing
facilities. In estimating these wastewater pollutant discharges, EPA
accounted for in-plant and end-of-pipe treatment currently in-place at each
facility. The Agency's estimates for annual discharges of conventional
pollutants, priority pollutants, and nonconventional pollutants (including the
PAIs) are discussed below. The performance of the treatment technologis in-
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ui
I
1000
INDUSTRY SELF-MONITORING
figure 5-5
COD LEVELS IN FINAL EFFLUENT
DISCHARGE
Average BPT Limit
1025 mg/L
0-200
200-400 400-600 OO
COD Concentration (mg/L)
>1(X»
-------
place at pesticide manufacturing facilities are discussed later in Section 7.
The costs to upgrade current facility treatment systems to comply with the
proposed regulations are discussed in Section 8.
EPA estimates that approximately 2.7 million pounds per year of
the conventional pollutants BOD5 and TSS and 7.2 million pounds per year of
the nonconventional pollutant COD are discharged directly by organic pesticide
chemical manufacturing facilities. Because the BOD5 and TSS discharged by
this industry are compatible with POTWs, these parameters are not currently
monitored by any of the five indirect dischargers that manufacture metallo-
organic pesticides. Therefore, EPA cannot estimate the quantity of BOD5 or
TSS discharged to POTWs by these facilities; these facilities also do not
monitor for COD. There are no facilities that discharge process wastewater
resulting from the manufacture of organo-arsenic, organo-copper, or organo-
mercury PAIs directly to receiving streams.
The pesticide chemicals industry manufactures large volumes of
PAIs, and the use of contact process water, as well as the collection of
spills, leaks, and rainwater results in significant discharges of organic PAIs
and priority pollutants from this industry. EPA estimates that approximately
200,00 pounds of PAI's and 17,000 pounds of priority pollutants per year are
discharged directly to surface waters by Subcategory A plants after currently
available treatment. In addition, it is estimated that 5.8 million pounds per
year of volatile organic priority pollutants are present in PAI wastewaters
with considerable potential for volatilization to the atmosphere.
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Indirect dischargers in the pesticide manufacturing industry, like
the direct dischargers, use as raw materials, and produce as products or
byproducts many nonconventional pollutants (including PAIs) and priority
pollutants. As in the case of direct dischargers, they may be expected to
discharge many of these pollutants to POTWs at significant mass or
concentration levels, or both. EPA estimates that indirect dischargers of
organic pesticides annually discharge approximately 110,000 pounds of PAIs and
29,000 pounds of priority pollutants to POTWs.
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SECTION 6
POLLUTANT PARAMETERS SELECTED FOR REGULATION
6.0 INTRODUCTION
As discussed in Section 5, EPA evaluated all available wastewater
characterization data to determine the presence or absence of conventional,
non-conventional (including the PAIs), and priority pollutants in pesticide
process wastewaters. Using this information, EPA selected specific pollutants
to be proposed for regulation. This section presents the criteria used in the
selection process and identifies those pollutants to be regulated under BPT,
BAT, PSES, NSPS, and PSNS for the organic pesticides chemicals manufacturing
subcategory (Subcategory A). No new limitations and standards are being
proposed for the metallo-organic pesticide chemicals manufacturing subcategory
(Subcategory B), and, therefore, Subcategory B is not discussed in this
section. Section 14 presents the Agency's decision making for Subcategory B.
6.1 CONVENTIONAL POLLUTANT PARAMETERS
Conventional pollutants include BOD5, TSS, fecal coliform, pH, and
oil and grease. These pollutants are general indicators of water quality
rather than specific compounds. Current BPT for the organic pesticide
chemicals manufacturing subcategory regulates the pH and the quantity of BOD5
and TSS discharged in process wastewaters; except for the wastewater
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discharges from 25 specifically excluded organic PAIs and classes of PAIs.
These 25 specific PAIs and classes of PAIs were specifically excluded due to a
lack of treatment data available in 1978. Since then, the Agency has
collected data on 15 organic PAIs within the group of 25 PAIs and classes of
PAIs, and BPT will be amended to include these PAIs. These 15 PAIs are
presented below.
Ametryn Terbuthylazine
Prometon Glyphosate
Prometryn Phenylphenpl
Terbutryn Hexazinone
Cyanazine Sodium Phenlyphenate
Atrazine Biphenyl
Propazine Methoprene
Simazine
EPA has also developed analytical methods and collected effluent data to
support BPT coverage of organo-tin pesticides.
Although EPA is amending the applicability of BPT to cover
previously excluded PAIs and classes of PAIs, no additional conventional
pollutants are being selected for regulation. Limitations are not being
established for oil and grease and fecal coliform. Oil and grease
measurements in this industry are not related to petroleum oil. The
analytical method includes in the oil and grease measurement organic compounds
such as the priority pollutants and the PAIs, which are being regulated
separately under this proposed rulemaking. Also, fecal coliform is not
expected to be present at significant concentrations in pesticide process
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wastewaters. For these reasons, oil and grease and fecal coliform are not
being selected for regulation.
6.2 PRIORITY POLLUTANT
There are currently no regulations covering the discharge of
priority pollutants in wastewaters generated during organic pesticide
chemicals manufacturing, with the exception of those priority pollutants
regulated as PAIs under 40 CFR 455.20(b). Priority pollutants are indirectly
covered under 40 CFR 455.32 for the metallo-organic pesticides subcategory
since current BPT requires no discharge of process wastewater pollutants from
facilities in this subcategory.
As discussed in Section 5, EPA sampling verified the known or
believed presence of priority pollutants in many pesticide process
wastewaters, and also verified the presence of certain priority pollutants
that could be present due to the process chemistry. However, some priority
pollutants reported as known or believed present by facilities were not
confirmed during EPA sampling. In some cases, this was because EPA did not
sample at the facility reporting the priority pollutant, and in other cases,
the PAI process associated with the reported priority pollutant was not in
operation during EPA sampling at that facility.
Three priority pollutants which were not confirmed during EPA or
industry sampling, and therefore not shown on Table 5-10 or 5-11, are
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bromomethane, 1,2-dichloropropane, and 1,3-dichloropropene. However, the
Agency believes these priority pollutants are present in pesticide process
wastewaters. Bromomethane was reported as known to be present in wastewater
at two facilities due to use as a raw material in these PAI processes and
believed to be present at one other facility as a contaminant. One facility
reported that 1,2-dichloropropane was known present in wastewaters as a waste
product of the PAI process, and a separate facility believed this pollutant to
be present as a contaminant. The third priority pollutant, 1,3-
dichloropropene, is manufactured as a PAI and was also reported by one
facility as believed to be present as a contaminant. Because these three
priority pollutants are known or believed present in wastewaters at multiple
facilities, the Agency is selecting them for regulation. Limits have also
been developed for these pollutants under the OCPSF rulemaking, and, as will
be discussed in Section 7, limits are being transferred to cover these three
pollutants as well as the other priority pollutants discussed earlier in
Section 5.
Not all of the priority pollutants shown in Table 5-11 are being
selected for regulation by the Agency. Some of those priority pollutants were
detected in only trace amounts, will indirectly be controlled by the proposed
PAI limitations, or were detected in only one or a very small number of
wastewaters. After evaluating all of these factors, the Agency selected for
regulation 26 organic priority pollutants, lead, and total cyanide. The 28
priority pollutants selected for regulation are presented in Table 6-1. The
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Table 6-1
Priority Pollutants Selected for Regulation
Pollutant Number
004
006
007
010
Oil
023
024
025
027
029
030
031
032
033
034
038
044
045
046
047
048
051
055
065
085
Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1,2-Dichloroethane
1,1, 1-Trichloroethane
Chloroform
2-Chlorophenol
1 , 2-Dichlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethene
Trans- 1, 2-Dichloroethene
2 ,4-Dichlorophenol
1 , 2 - Dichloropropane
1 , 2-Dichloropropene
2 , 4-Dimethylphenol
E thy Ib enz ene
Methylene Chloride
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethene
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Table 6-1
(Continued)
Pollutant Number
086
121
122
Pollutant
Toluene
Cyanide
Lead
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development of limitations for these priority pollutants is discussed in
Section 7.
EPA is not selecting 95 priority pollutants for regulation, and
the reason for excluding or not regulating each of these pollutants is
discussed below.
• The pollutant has not been detected in the effluent with the
use of analytical methods promulgated pursuant to Section
304(h) of the Act or other state-of-the-art methods.
Acrylonitrile
1,1,2-Trichloroethane
2-Chloroethyl vinyl ether
3,3'-Dichlorobenzidine
2,6-Dinitrotoluene
4,6-Dinitro-o-cresol
Bis (2-Chloroisopropyl) ether
Bis (2-Chloroethoxy) methane
N-Nitrosodimethylaniine
N-Nitrosodiphenylamine
Pentachlorophenol
Butyl benzyl phthalate
Acenaphthalene
Benzo (A) pyrene
Benzo (GHI) perylene
Dimethyl phthalate
Dibenzo (A,H) anthracene
Ideno (1,2,3-CD) pyrene
Aldrin
Dieldrin
Chlordane
4, 4 '-DDT
4, 4 '-DDE
4,4'-DDD
ct-Endosulfan
/3-Endosulfan
Endosulfan sulfate
a-BHC
7-BHC
5-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
2,3,7, 8-Tetrachlorodibenzo-p-dioxin
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The pollutant is present only in trace amounts and is
neither causing nor likely to cause toxic effects. In
addition, the pollutant is present in amounts too small to
be effectively reduced by technologies known to the
Administrator.
2-Chloronaphthalene
1,3-Dichlorobenzene
2,4-Dinitrotoluene
1,2-Diphenylhydrazine
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
1,1-Dichloroethane
The pollutant is detectable in the effluent from only a
small number of sources and the pollutant is uniquely
related to only those sources.
Acenapthene
Acrolein
Benzidene
1,2,4-Trichlorobenzene
Hexachlo rob enz ene
1,1,2,2-Tetrachloroethane
Chloroethane
Bis (2-Chloroethyl) ether
Parachlorometacresol
Fluoranthene
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
Isophorone
Nitrobenzene
2-Nitrophenol
2,4-Dinitrophenol
Di-n-octyl Phthalate
Benzo (A) anthracene
Benzo fluoranthene
Benzo (B) fluoranthene
Chrysene
Anthracene
Fluorene
Phenanthrene
Pyrene
Vinyl chloride
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The pollutant will be effectively controlled by the
technologies which are the basis for controlling certain
pesticide active ingredients in the proposed effluent
limitations guidelines and standards.
Hexachloroethane
N-Nitrosodi-n-propylamine
Endrin aldehyde
Heptachlor epoxide
1,1,2-Trichloroethylene
2,4,6-Trichlorophenol
EPA is not regulating the following priority pollutants due
to lack of treatability data. These priority pollutants
were not detected during sampling but would be expected in
wastewaters from the manufacture of certain pesticides.
However, those pesticides were not in production when
sampling activities were scheduled by EPA.
Hexachlorobutadiene
Hexachlorocyclopentadiene
4-Nitrophenol
EPA is also not regulating Asbestos because there is no
promulgated Section 304(h) analytical method for that
pollutant in water.
6.3 NONCONVENTIONAL POLLUTANTS
Nonconventional pollutants selected for regulation by the Agency
include certain PAIs and one other non-conventional pollutant, COD. Current
BPT regulations limit the discharge of COD from both organic and metallo-
organic pesticide manufacturing subcategories. The BPT numerical limitations
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for COD discharged by the organic pesticides manufacturers are not being
amended although EPA is proposing to extend the applicability of BPT to cover
COD resulting from the manufacture of 15 previously excluded organic PAIs and
classes of PAIs and the organo-tin pesticides.
Under Subcategory A, 170 individual PAIs were manufactured in
1986; and 8 PAIs were manufactured from 1985-1989, but were not manufactured
in 1986. Therefore, a total of 178 individual PAIs are being considered for
potential regulation. Of these, 122 individual PAIs are being selected by the
Agency for regulation under either BAT, NSPS, PSES, or PSNS. EPA is not
proposing regulations for 56 individual PAIs. Of the 56 PAIs, all production
ceased for 12 PAIs before the Agency could gather data. Analytical methods
are unavailable for 14 other PAIs, so the Agency could not gather data. All
wastewaters for 14 other PAIs are currently disposed of in deep wells subject
to regulation under EPA's Underground Injection Control (UIC) program. EPA
decided to develop data and regulations for PAIs with actual discharges to
surface waters. For the remaining 16 PAIs, insufficient data exist on their
treatability. Either the plants do not monitor for the PAI or the available
data are inadequate to demonstrate that the technology in use is the best
available technology. In addition, the available bench scale treatability
data are inadequate and there are no structurally similar PAIs with data which
could be transferred. Available toxicity data indicates that these 16 PAIs
are less toxic than most of the 122 PAIs for which PAI effluent limitations
are proposed.
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SECTION 7
TECHNOLOGY SELECTION AND LIMITS DEVELOPMENT
7.0 INTRODUCTION
This section identifies and describes the wastewater control and
treatment technologies currently used or available for the reduction and
removal of conventional pollutants, PAIs, and priority pollutants discharged
in pesticide chemicals manufacturing process wastewater and presents a summary
of treatment performance achievable by technology based on industry
submissions and treatability tests on these control and treatment
technologies. This section also discusses the development of effluent
limitations guidelines and standards for PAIs and priority pollutants in
Subcategory A of the pesticide chemicals manufacturing industry.
Section 7.1 presents a summary of treatment performance databases
available to the Agency on wastewater control. The Agency has compiled three
databases; one from industry-submitted data, one from wastewater sampling
conducted by EPA, and a third from treatability studies conducted on
wastewaters or synthetic wastewaters containing PAIs.
Section 7.2 presents a description of in-plant versus end-of-pipe
treatment and an overview of the current and proposed treatment technologies
used in the pesticide chemicals manufacturing industry for treatment of
conventional pollutants, PAIs, and priority pollutants. This section also
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discusses the disposal of solid residues that are generated from wastewater
control and treatment technologies.
Section 7.3 presents treatment performance data for technologies
considered to be BAT and Section 7.4 presents the methodology used to develop
the limitations and standards for the pesticide chemicals manufacturing
industry. Section 7.4 also presents those cases where limitations requiring
no discharge of process wastewater pollutants have been proposed and discusses
options available for compliance with proposed zero discharge standards.
Effluent limitations guidelines and standards development for Subcategory B
PAIs are discussed in Section 14.
7.1 TREATMENT PERFORMANCE DATABASES
The sources of treatment performance data available for the
pesticide chemicals manufacturing industry include: analytical data on PAI
treatment submitted with the Pesticide Manufacturing Facility Census for 1986
or collected during EPA short-term sampling and treatability sampling efforts
between 1988 and 1991, EPA sponsored bench-scale treatability tests on
selected PAIs, and existing treatment performance databases. The treatment
performance database for conventional pollutant parameters and COD is from the
previous regulation of BPT under the pesticide chemicals manufacturing
subcategory. The treatment performance database for priority pollutants is
from the previous regulation of the OCPSF point source category. Sections
7.1.1 to 7.1.3 discuss these databases in more detail.
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7.1.1 Analytical Data Submitted with the Pesticide Manufacturing
Facility Census for 1986 and Associated Data
The U.S. EPA Engineering and Analysis Division (formerly the
Industrial Technology Division) of the Office of Water issued the Pesticide
Manufacturing Facility Census for 1986. As described in Section 3.1.3, this
questionnaire requested engineering and economic data regarding pesticide
manufacturing processes, wastewater generation, treatment, and handling
procedures from each plant that received the questionnaire. In addition, this
questionnaire requested submittal of all wastewater monitoring data collected
in 1986, in the form of individual data points. The intent of this request
was to obtain a full year of daily monitoring data from each respondent. The
questionnaire further requested that the data identify the sample points as
shown earlier in the questionnaire process and treatment diagrams,
specifically from wastewater streams leaving manufacturing processes and
entering and exiting treatment systems.
Additional data were obtained from some of the survey respondents
following the initial review of their 1986 data, and in many cases the
additional data included more recent information than 1986 monitoring data.
Data were also obtained from a previous (mid to late 1970's) EPA survey of
wastewater discharged by pesticide chemical manufacturers. This earlier
survey was similar to the 1986 survey because it was also conducted under the
authority of Section 308 of the Clean Water Act and requested the same type of
information.
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EPA sampled pesticide manufacturing process wastewater at various
locations throughout the wastewater generation, treatment, and discharge path
at 20 facilities to screen the wastewater for the presence of PAIs and
priority pollutants and to evaluate control technology performance. Included
for consideration with the data submitted with the EPA surveys were selected
data obtained from these EPA short-term sampling efforts conducted at
pesticide manufacturing facilities between 1988 and 1990.
Of the 90 pesticide manufacturing plants that responded to the
1986 survey, 51 plants submitted long-term wastewater monitoring data. When
the data submitted by a plant were found to be insufficient or to require
further explanation, a formal request for additional information was made to
the plant by EPA. In addition to the data submitted in response to the 1986
survey, the Agency reviewed and considered long-term data from six plants from
the earlier EPA survey (containing data from the mid- to late 1970s). The
data from this earlier survey do not differ significantly from the data of the
1986 survey in terms of format. Short-term sampling data collected during
site visits by EPA to pesticide manufacturing plants between 1988 and 1990
were also reviewed and considered by the Agency.
The industry-submitted long-term data, data from the earlier EPA
survey, and the short-term EPA sampling data were entered into an Agency
treatment performance database. The long-term data submitted by industry
contained mostly PAI data. The Agency evaluated these data extensively in the
course of developing limitations as discussed in Section 7.4.
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7.1.2 Treatability Test Data
In preparation of this proposed rulemaking effort for the
pesticide chemicals manufacturing industry, EPA undertook numerous bench-scale
treatability studies using both synthetic pesticide wastewaters, as well as,
where practical, actual process wastewaters. These treatability studies
investigated activated carbon adsorption, hydrolysis, membrane filtration, and
chemical oxidation (using alkaline chlorination and using ozonation enhanced
with ultraviolet (UV) light).
Activated Carbon Adsorption
Activated carbon adsorption isotherm tests were performed on 29
selected PAIs chosen from the list of 270 PAIs considered for regulation
grouped according to their production volume. The carbon isotherm studies
used PAIs selected from various structural groups to determine which groups
would be most adaptable to activated carbon technology. Some manufacturers of
some PAIs in a few of those groups were known to use activated carbon
technology to treat the wastewaters and treatability data from those
manufacturers were available; in this case, the purpose of the carbon isotherm
studies was to establish benchmarks for determining the potential efficacy of
activated carbon technology to other structural groups. Results were obtained
for all 29 PAIs. Twenty-five of the 29 PAIs tested exhibited some adsorption
capacity.
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Next, Accelerated Column Tests (ACTs) were conducted to generate
treatability data for the removal of atrazine, vapam, chlorothalonil, and
diazinon by the use of activated carbon. This technique was used to develop
effluent concentration breakthrough curves for atrazine, diazinon, and
chlorothalonil. For vapam, no calculations were made as the high feed
concentration resulted in immediate breakthrough. The atrazine and diazinon
wastewater were obtained from plants that operate full-scale carbon treatment
systems. The ACT data from both tests were comparable to the full-scale
system data with respect to carbon usage and carbon loading. Results of these
studies were used in estimating full-scale carbon systems designs and cost.
Hydrolysis
Hydrolysis was evaluated as a wastewater treatment technology
through a series of bench-scale tests to determine the hydrolysis rates of
selected PAIs in reagent grade water (i.e., not actual wastewater). General
factors in EPA's selection of specific PAIs for use in the synthetic
wastewaters were the availability of an analytical method for the specific PAI
and the ready availability of the PAI in a pure form from either government or
commercial sources.
The hydrolysis studies were conducted in some cases to confirm the
results of literature hydrolysis data for certain PAIs, and in other cases
were conducted because of the lack of any literature data to fill in those
gaps. All of the PAIs selected were expected to hydrolyze under some
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conditions. Thirty-nine PAIs from six structural groups were tested at three
different pHs (2, 7, and 12) and two different temperatures (20°C and 60°C).
The test results indicated that the hydrolysis rates of the PAIs varied from
almost immediate to virtually no reaction in the 24-hour test time for the
various PAIs and conditions tested. One phosphorodithioate PAI was tested in
a field study at pH 12 and 60°C. The half life ranged from 0.72 hours (at an
initial PAI concentration of 5 mg/1) to 1.94 hours (at an initial PAI
concentration of 57 mg/1).
Membrane Filtration
Membrane filtration was evaluated as a method of pesticide
removal. The membrane filtration studies used PAIs selected to span the
molecular weight range of the 270 PAIs and classes of PAIs under consideration
for regulation, because the effectiveness of membrane filtration tends to vary
with molecular weight. In the membrane filtration treatability studies, EPA
conducted a series of bench-scale tests to identify specific PAIs which could
be separated from water by various membrane materials. Synthetic test
solutions containing 19 PAIs were tested on 7 different types of membranes.
The membranes were manufactured from 3 types of materials (cellulose acetate,
thin-film composite, and Aramid) and were of various pore sizes, with nominal
molecular weight cut-offs ranging from 150 to 500. The test results indicated
that reverse osmosis was an effective method of pesticide removal. The best
results were obtained with the thin-film composite (TFC) membranes. Removals
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of 90% or greater were obtained throughout the test, with the majority of PAIs
being rejected at 99% or greater.
Alkaline Chlorination
Alkaline chlorination was evaluated as a method of PAI removal
using wastewater generated during the manufacture of 6 dithiocarbamate PAIs
(Metam, Namet, KN-Methyl, Nabonate, Dimet, and TCMTB). The treatability
studies using actual pesticide manufacturing process wastewater were conducted
to supplement full-scale treatment system performance data, to fill in gaps in
performance data where no treatability data were available for the PAI, and to
help assess performance of existing full-scale treatment systems where the
performance of those systems appeared to be inadequate compared to performance
of other facilities treating the same or similar PAIs. The PAIs selected for
study were the PAIs in production at the plants during the treatability study.
The bench-scale study was conducted at three chlorine dosages at three
different contact times. The test results indicate alkaline chlorination was
an effective treatment for all PAIs but TCMTB. The chlorine demand for TCMTB
was found to be greater than 100,000 mg/1 and therefore was not considered a
feasible treatment option.
Because alkaline chlorination of wastewater containing organic
matter may generate volatile organic toxic pollutants, which must subsequently
be controlled, EPA also conducted chemical oxidation treatability studies for
five of those same six PAIs using ozone rather than chlorine. The preliminary
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results of those studies indicate that ozone can achieve about the same degree
of PAI reduction as chlorine. Chemical oxidation with ozone is usually more
expensive than chemical oxidation with chlorine. However, ozone oxidation
does not produce volatile toxic pollutants. When the cost of controlling
those volatile toxic pollutants is added to the cost of alkaline chlorination,
the total cost for chlorination may exceed the cost of ozone oxidation.
7.1.3 Existing Treatment Performance Databases
The treatment performance databases used in the analysis of
treatment of conventional pollutants, COD, and priority pollutants include the
pesticide chemicals industry BPT database and the OCPSF database. These
databases are not repeated here but can be found in the following documents:
DevelopmentDocument for Final Effluent Limitations
Guidelines for the Pesticide Chemicals Manufacturing Point
Source Category. Found in the docket to this proposed
regulation and in the docket to the Tuesday, April 25, 1978
FRN which presents the final BPT regulations for the
pesticide chemical manufacturing point source category (also
available through the National Technical Information System
[NTIS]).
Development Document for Effluent Limitations Guidelines New
Source Performance Standards and Pretreatment Standards for
the Organic Chemicals and the Plastics and Synthetic Fibers
Point Source Category - Volume I and II. EPA 440/1-87/009.
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7.2 WASTEWATER TREATMENT IN THE PESTICIDE CHEMICALS MANUFACTURING
INDUSTRY
The major treatment technologies currently employed by plants in
the pesticide chemicals manufacturing industry to treat wastewaters on-site
are: biological treatment, activated carbon adsorption, on-site incineration,
chemical oxidation/chlorination/dechlorination, hydrolysis, steam stripping,
resin adsorption, hydroxide precipitation, and solvent extraction. The Agency
found that the pesticide chemicals manufacturing industry primarily selects
in-plant controls for the removal of highly concentrated pollutants from
process wastewaters. [These in-plant controls are then often followed by
biological treatment usually after these streams are combined with other
facility wastewater]. In addition, facilities performing recycle/reuse of
treated wastewaters do so in many cases following various in-plant treatment
units. End-of-pipe treatment systems employ physical, chemical, and
biological treatment and are designed to treat combined process and facility
wastewaters. The typical treatment sequence is physical-chemical treatment to
remove PAIs, followed by steam stripping to remove volatile priority
pollutants, followed by biological treatment to remove non-volatile priority
pollutants and other organic pollutants.
Table 7-1 summarizes the in-plant and end-of-pipe controls for the
removal of pollutants from pesticide industry process wastewaters. Table 7-1
also presents the number of plants that reported using each of the listed
technologies in the Facility Census for 1986. It should be noted that many
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plants use more than one type of treatment technology to effect significant
removals of pollutants.
At least some treatment is currently being provided to over 99% of
the wastewaters discharged directly and to about 92% of the wastewaters
discharged to POTWs. While many plants provide extensive treatment to remove
PAls, priority pollutants, and other pollutants, some plants provide no
treatment. The majority of plants have some treatment but that treatment
often needs to be upgraded to improve its effectiveness and to remove
additional pollutants. The following 14 technologies have been demonstrated
to provide treatment of PAIs and/or priority pollutants in the pesticide
chemicals manufacturing industry (these technologies are presented in no
particular order):
• Carbon Adsorption;
• Hydrolysis;
• Chemical Oxidation/Ultraviolet Decomposition;
• Resin Adsorption;
• Solvent Extraction;
• Distillation;
• Membrane Filtration;
• Biological Treatment;
• Evaporation;
• Chemical Precipitation/Filtration;
• Chemical Reduction;
• Coagulation/Flocculation;
• Incineration; and
• Steam Stripping.
A description of each of these technologies is presented below.
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Table 7-1
TREATMENT TECHNOLOGIES USED BY THE
PESTICIDE CHEMICALS MANUFACTURING INDUSTRY
AS REPORTED IN THE 1986 FACILITY CENSUS
Treatment Technology
Biological Treatment
Carbon Adsorption
Chemical Precipitation/Filtration
Chemical Oxidation
Coagulation/Flocculation
Distillation
Evaporation
Hydrolysis
Incineration
Resin Adsorption
Solvent Extraction
Steam Stripping
Ultraviolet Decomposition
Total Number
of Facilities
25
14
7
11
8
1
1
6
3
2
3
4
2
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7.2.1 Carbon Adsorption
Adsorption is the primary mechanism for removal of organic
pollutants from wastewater by activated carbon. Activated carbon has a very
large surface area per unit mass which is available for assimilation of
contaminants. The main driving forces for adsorption of a solute on the
adsorbent is attraction of the solute (or adsorbate) to the adsorbent and/or a
hydrophobic (water-disliking) characteristic of the adsorbate.
Biodegradation of contaminants from microbial growth on the carbon
can improve organics removal and reduce the carbon usage rate for certain
wastewaters, but adsorption is the primary mechanism for organics removal.
Some biologically degradable compounds are difficult to adsorb and prediction
of degradation rates is difficult, so biodegradation is not usually considered
in the design of activated carbon systems unless an extensive pilot-scale
study is conducted.
The carbon adsorption capacity (the mass of the contaminant
adsorbed per mass of carbon) for specific organic contaminants is related to
4
the characteristics of the compound, the carbon characteristics, the process
design, and the process conditions. In general, adsorption capacity is
inversely proportional to the adsorbate solubility. Within a homologous
series of organic compounds, adsorption increases with increasing molecular
weight since solubility decreases with increasing molecular weight (e.g.,
Parathion is more strongly adsorbed than EPTC). Thus nonpolar, high molecular
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weight organics with low solubility are adsorbed more readily than polar, low
molecular weight organics with high solubilities. Competitive adsorption of
other compounds has a major effect on adsorption (i.e., the carbon may begin
preferentially adsorbing one compound over another compound and may even begin
desorbing the other compound). Process conditions (such as pH and
temperature), process design factors (such as granular vs. powdered carbon,
contact time, and number of columns in series), and carbon characteristics
(such as particle size and pore volume) also effect adsorption capacity.
When the adsorptive capacity of the carbon is exhausted, the spent
carbon is either disposed of or regenerated, the choice generally to be
determined by economics. The carbon is regenerated by removing the adsorbed
organics from the carbon. Three methods for carbon regeneration are steam
regeneration, thermal regeneration, and physicochemical regeneration. Thermal
and steam regeneration volatilize the organics which are removed from the
carbon in the gas phase. Afterburners are required to ensure destruction of
the organic vapors and a scrubber may be necessary to remove particulates.
Physicochemical regeneration removes the organics by a solvent, which can be a
water solution. Thermal and steam regeneration are most commonly used for
carbon from wastewater treatment.
Activated carbon is commonly utilized in the form of granular-
carbon columns that operate in either an upflow or downflow mode. Powdered
carbon is used less frequently for wastewater treatment due to the difficulty
of regeneration and reactor system design considerations although it may be
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used in conjunction with biotreatment systems. Carbon adsorption is used as
both an in-plant and end-of-pipe treatment technology. In-plant carbon
adsorption protects treatment downstream from high concentrations of toxic
pollutants that could adversely affect system performance. For example,
carbon adsorption may remove pollutants which would be toxic to a downstream
biological treatment system. In-plant carbon adsorption treatment also
enables removal of pollutants from low volume waste streams before they are
commingled with other facility wastewaters. Commingling of untreated waste
streams contaminates much larger volumes of wastewater, which could then be
more difficult and costly to treat. On the other hand, activated carbon may
also be applied as end-of-pipe treatment when certain pollutants contained in
commingled wastewaters are not effectively removed by previous treatment
steps. For example, certain pollutants, although not toxic to a biological
treatment system, may not be effectively removed by the biological system and
an end-of-pipe activated carbon system may be necessary to treat the
pollutants effectively. The biological system may remove other organics
which, if not removed, could reduce total adsorptive capacity of the activated
carbon system.
In the pesticide manufacturing industry, activated carbon
adsorption is or has been used to treat PAIs in the following structural
groups: acetamides, aryl halides, benzonitriles, carbamates, phenols,
phosphorodithioates, pyridines, pyrethrines, s-triazines, tricyclic,
toluidines, and ureas. In addition, EPA and industry treatability studies
have demonstrated sufficient treatability of pesticides in the acetanilide,
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terephthalic acid, and uracil structural groups using carbon to establish this
treatment as a basis for control of specific PAIs in these groups. Carbon has
also been shown in treatability studies to be an effective polishing control
for thiocarbamate PAIs, although insufficient information is currently
available to determine the effluent quality achievable by full-scale treatment
systems for thiocarbamate PAIs.
In the case of many of the PAIs which are or have been treated
using carbon, expediency has appeared to drive treatment system selection
rather than optimal system design. For example, wastewaters from the
manufacture of carbamate and phosphorothioate PAIs which can be readily
hydrolyzed at alkaline conditions have instead been treated using activated
carbon. In those cases, carbon may have been chosen originally because of its
ability to remove other pollutants of concern from the wastewater, or because
of an incomplete assessment of treatment options. Due to the cost of carbon
regeneration or replacement, the use of activated carbon to treat high volume
streams is often a more expensive option than other physical-chemical
treatment methods; therefore an evaluation of other treatment technologies may
result in a system which provides equal performance at a lower cost.
7.2.2 Hydrolysis
Hydrolysis is a chemical reaction which occurs in water, alters
the target compound by reaction with water, and is not catalyzed by light or
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microorganisms. Usually the hydroxyl group (OH") is introduced into the
reactant, displacing another group:
0 0
II II
(RO)2-P-S-R + OH- ---> (R0)2 -P-OH + (SR)-
Carbamate hydrolysis occurs by the following reaction:
0
I
C
R,-N 0 Rj + H20 > RjOH + R,-NH + C02
I I
R, R,
The acid hydronium ion can also enter into hydrolysis reactions.
As the reactions above illustrate, hydrolysis is a destructive
technology in which the original molecule forms two or more new molecules. In
some cases, the reaction continues and other products are formed.
The primary design parameter considered for hydrolysis is the
half-life, which is the time required to react 50% of the original compound.
The half-life of a reaction is generally dependent on the reaction pH and
temperature and the reactant molecule. Hydrolysis reactions can be catalyzed
at low pH, high pH, or both, depending on the reactant. In general, an
increase in temperature will increase the hydrolysis rate. Improving the
conditions for the hydrolysis reaction results in a shorter half-life, and
therefore the size of the reaction vessel required is reduced.
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Hydrolysis is a treatment technology which should be strongly
considered for wastewaters which contain carbamate, phosphate,
phosphorothioate, phosphorodithioate, and phosphonothioate PAIs. For
virtually all PAIs in these structural groups for which treatability testing
was performed, a half-life less than 30 minutes was achieved at high
temperature (60°C) and high pH (pH 12). Literature data shows that many of
the PAIs in fact react even faster than EPA's study demonstrated. Study
conditions were such that the "zero" reaction time was in fact at least 15
minutes (i.e., 15 minutes had elapsed between the time the initial sample was
taken and analyzed). In some cases, the PAI had been completely destroyed
within that 15 minute period (i.e., the PAI was not detected in the sample).
In such cases, the half-life was estimated to be at less than 30 minutes, and
a 30-minute half-life was used in calculating reactor sizes and retention
times, hence cost, for treatment. Literature data, however, confirms that for
PAIs such as malathion the half-life is less than one minute.
For many compounds high pH and ambient temperature were enough to
result in a half-life less than an hour, especially for the carbamates. Acid
hydrolysis was only effective for a small number of compounds tested.
However, for organophosphorus and carbamate pesticide hydrolysis, alkaline
hydrolysis is usually faster than acid hydrolysis. The urea PAIs tested were
not hydrolyzed effectively, so long reaction times would be necessary to treat
most urea PAIs.
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Acid hydrolysis of dithiocarbamate PAIs can achieve short half-
lives; however, this reaction results in evolution of carbon disulfide gas;
therefore, hydrolysis is not considered to be feasible for dithiocarbamate
PAIs. Hydrolysis has also been used to treat triazine PAIs, but only at high
temperature with catalyst because this reaction proceeds very slowly in the
normal range of conditions used in wastewater treatment.
7.2.3 Chemical Oxidation/Ultraviolet Decomposition
Chemical oxidation is a reaction process in which one or more
electrons are transferred from the oxidizing chemical (electron donor) to the
targeted pollutants (electron acceptor) causing their destruction. Oxidants
typically used in industry include chlorine, hydrogen peroxide, ozone, and
potassium permanganate. Of these oxidants, chlorine is most commonly used
under alkaline conditions to destroy such compounds as cyanide (metal
finishing, inorganic chemicals, and pesticides industry) and pesticides.
Chemical oxidation has been demonstrated by the pesticide industry
to be effective at destroying alkyl halide, DDT-type, phenoxy,
phosphorothioate, and dithocarbamate PAIs in manufacturing wastewaters. In a
bench-scale alkaline chlorination treatability study by EPA, chlorine dosages
equivalent to 50, 100 and 125% of the chlorine demand for specific
dithiocarbamate pesticides wastewaters were evaluated. Treatment results
indicated alkaline chlorination could reduce the effluent PAI concentration
below the analytical detection limit; however, chlorine dosage requirements
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and reaction times varied for each pesticide evaluated. The major drawback to
alkaline chlorination of pesticide manufacturing wastewaters is the production
of chlorinated organic compounds which must subsequently be removed by an
additional treatment technology. Compounds not present in the raw wastewater
but detected in at least two of the test reactors included chloroform,
bromodichloromethane, dibromochloromethane, and acetone. Based on the past
performance of alkaline chlorination in the pesticide industry and on the
bench-scale treatment study, the effluent limitations for dithiocarbamates are
based on this technology but with the addition of a treatment technology
(steam stripping) to reduce chlorinated organics.
A recent oxidation technology to emerge for the oxidation of
dithiocarbamate PAIs is ozone in combination with ultraviolet light. This
technology, initially developed for the metal finishing industry to treat iron
complexed cyanide, has recently been suggested by EPA as an alternative to
chlorine oxidation for treatment of pesticide manufacturing wastewaters. The
ozone-UV light process focuses on the production of the highly oxidative
hydroxyl radicals from the absorption of UV light (254 run wavelength) by
ozone. These hydroxyl radicals completely oxidize the PAI (e.g., to carbon
dioxide, nitrate, sulfate and water) avoiding the formation of halogenated
organic compounds such as those produced during alkaline chlorination.
The oxidation of dithiocarbamate pesticides by ozone and UV light
has recently been demonstrated by EPA in a bench-scale treatability study.
The study, involving five different dithiocarmate PAIs spiked into deionized
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water, investigated various initial pHs and UV light intensities. Results
indicated the PAI concentration could be reduced to levels at or near the
analytical limit of detection within minutes at low UV light intensities and
at initial pHs between 7 and 9. Optimum treatment conditions have not yet
been determined.
The preliminary results of this study indicate that ozone can
achieve about the same degree of PAI reduction as chlorine. Chemical
oxidation with ozone is usually more expensive than chemical oxidation with
chlorine. However, ozone oxidation does not produce volatile toxic
pollutants. When the cost of controlling those volatile toxic pollutants is
added to the cost of alkaline chlorination, the total cost for chlorination
may exceed the cost of ozone oxidation.
7.2.4 Resin Adsorption
Resin adsorption is a separation technology that may be used to
extract and, in some cases, recover dissolved organic solutes from wastewater.
Resins are typically microporous styrene-divinylbenzenes, acrylic esters, or
phenol-formaldehydes. Each type may be produced in a range of densities, void
volumes, bulk densities, surface areas, and pore sizes. The formaldehyde
resins are granular, and the others are in the form of beads.
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Resin adsorption involves two basic steps:
The liquid waste stream is brought into contact with the
resin, allowing the resin to adsorb the solutes from the
solution; and
The resin is regenerated by removing the adsorbed chemicals,
often accomplished by simply washing with the proper
solvent.
Caustic, formaldehyde, or solvents such as methanol, isopropanol,
and acetone can accomplish regeneration of spent resin. Pesticide facilities
have used solvents such as methanol. Batch distillation of regenerant
solutions separate and return products to the process.
Resin adsorption is applicable for all members of the phenol
family as well as amines, caprolactam, benzene, chlorobenzen.es, and
chlorinated pesticides; however, the cost of this technology may be
prohibitive. The adsorption capacity of resins depends on the type and
concentration of specific organics in the wastewater as well as the pH,
temperature, viscosity, polarity, surface tension, and background
concentrations of other organics and salts. As with carbon adsorption, the
adsorptive capacity of resins increases as solubility decreases.
Resin adsorption is similar in nature to activated carbon with the
main difference being that resins are chemically regenerated while carbon is
usually thermally regenerated. A potential advantage of resins is that they
are more easily tailored for removal and recovery of specific pollutants.
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However, resins generally have a lower adsorptive capacity than carbon, and
are not likely to be competitive with carbon for the treatment of high volume
waste streams containing moderate or high concentrations of mixed wastes with
no recovery value. For this reason, resins have generally been restricted to
application where few other treatment options have proven useful.
7.2.5 Solvent Extraction
Solvent extraction, also referred to as liquid-liquid extraction,
involves the separation of the constituents of a liquid solution by contact
with another immiscible liquid for which the impurities have a high affinity.
The separation is based on physical differences that affect differential
solubility between solvents and may be enhanced by adding reagents to cause a
definite chemical reaction.
The end result of solvent extraction is to separate the original
solution into two streams--a treated stream and a recovered solute stream
(which may contain small amounts of water and solvent). Solvent extraction
may thus be considered a recovery process because the solute chemicals are
generally recovered for reuse of further treatment and disposal. The process
for extracting a solute from solution will typically include three basic
steps:
• Mixing of solvent with waste stream;
• Extraction and separation; and
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Recovery of solvent from the treated stream, either by
distillation or steam stripping.
Solvent extraction generates a treated wastewater residual, which is
discharged, and an extract, which in some cases may be recycled and reused.
The use of solvent extraction as a unit process operation is common in the
pesticide chemicals industry. Often, the process function and wastewater
treatment function of solvent extraction are integrated as water contaminants
are returned with the solvent to the process; in these cases, the facility
often does not consider the extraction to be a treatment process, although the
net result is to reduce total loading of pollutants discharged from the
process. Solvent extraction is most effectively applied to segregated process
streams where the potential for collecting specific residuals for reuse is
greatest.
7.2.6 Distillation
Distillation is the separation of the constituents in a wastewater
stream by partial vaporization of the mixture and separate recovery of vapor
and residue. The main use of distillation in pesticide manufacturing
operations is in the separation of alcohols used in the manufacture of esters
of phenoxy-based PAIs from wastewaters. The alcohols can then be reused in
future manufacturing, while the wastewater, once separated from alcohols and
solvents, can be reused in the manufacture of salts of phenoxy PAIs, or in
phenoxy product formulations. In this process, the phenoxy ester product is
heated, driving off the alcohol and water. The alcohol is then condensed.
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For non-phenoxy PAIs, distillation has been used to separate water
from pesticide process streams as a final purification stage. Although the
purity of the distillate will be a function of the volatility of the PAI, the
distilled wastewater will normally have no detectable concentration of the
PAI.
7.2.7 Membrane Filtration
Membrane filtration is a term applied to a group of processes that
can be used to separate suspended, colloidal, and dissolved solutes from a
process wastewater. Membrane filtration processes utilize a pressure driven,
semipermeable membrane to achieve selective separations. Much of the
selectivity is established by designations relative to pore size. The pore
size of the membrane will be relatively large if precipitates or suspended
materials are to be removed, or very small for the removal of inorganic salts
or organic molecules. During operation, the feed solution flows across the
surface of the membrane, clean water permeates the membrane, and the
contaminants and a portion of the feed remain. The clean or treated water is
referred to as the permeate or product water stream, while the stream
containing the contaminants is called the concentrate, brine, or reject.
In a typical industrial application, the product water steam will
either be discharged, or more likely, recycled back to the manufacturing
process. The reject stream is normally disposed, but in those situations
where the reject does not contain any specifically objectionable materials, it
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too can potentially be recycled back to the process. As an example, a reject
stream from a system treating a wastewater generated from many different
processes would likely have to be disposed. However, if the membrane system
were used on a process where the wastestream contained only a specific PAI,
the reject stream could possible be recycled back to the process. Depending
on the characteristics of the wastewater and the type of process used, 50-95%
of the feed stream will be recovered as product water.
Types of membrane filtration systems available include
microfiltration, ultrafiltration (UF), and reverse osmosis (RO). Microfilters
are generally capable of removing suspended and colloidal matter with
diameters greater than 0.1 micron (3.94 x 10~* inches). The systems can be
operated at feed pressures of less than 50 psig. The feed stream does not
require extensive pretreatment, and the membrane is relatively resistant to
fouling and can be easily cleaned. A microfiltration system would not be an
effective method of treatment unless the PAIs were insoluble or were attached
to other suspended material in the wastewater. Microfiltration has been used
in the pesticide industry in applications where an adsorbent material and/or
flocculent is added prior to the membrane system. The PAIs are adsorbed or
become attached to the floe which forms and is ultimately separated by the
microfilter. Microfilters are capable of recovering up to 95% of the feed
stream as product water.
Ultrafiltration is similar to microfiltration, with the difference
being that a UF membrane has smaller pores. The "tightest" UF membrane is
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typically capable of rejecting molecules having diameters greater than 0.001
micron (3.94 x 10"* inches) or nominal molecular weights greater than 2000.
The systems operate at feed pressures of 50-200 psig. Some pretreatment may
be necessary to prevent membrane fouling. UF systems would only be effective
in removing PAIs which are insoluble or attached to other suspended material
(most PAIs have molecular weights from 150 to 500 molecular weight units).
For most UF designs, the introduction of adsorbents or flocculants to the feed
stream is not recommended since they may plug the membrane module. UF systems
are also capable of recovery of up to 90-95% of the feed as product water.
Reverse osmosis systems have the ability to reject dissolved
organic and inorganic molecules. For organic (noncharged) molecules such as
PAIs, membrane rejection is a function of the membrane pore size. Typically,
membranes with a pore size of 0.0001 to 0.001 microns are used to remove PAIs.
RO membranes have been shown to be capable of removing the majority of PAIs
with molecular weights greater than 200. Unlike microfiltration and
ultrafiltration, RO membranes are capable of rejecting inorganic ions. The
mechanism for salt rejection is the electro-chemical interaction between the
membrane and the constituents in the wastewater. Based on the strength of
their ionic charge (valence), the ions are repelled from the charged surface
of the membrane and will not pass through the pores. Although RO membranes
may be rated based on molecular weight cutoff, they are normally rated on
their ability to reject sodium chloride. Typical sodium chloride rejection
for an industrial type membrane would be 90-95 percent.
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RO systems used in industrial applications are designed to operate
a feed pressures of 250-600 psig. RO membranes are very susceptible to
fouling and may require an extensive degree of pretreatment. Oxidants which
may attack the membrane, particulates, oil, grease, and other materials which
could cause a film or scale to form must be removed by pretreatment. The RO
product water stream will usually be of very high quality and suitable for
discharge, or more importantly, reuse in the manufacturing process. Standard
practice is to dispose of the reject stream. Dissolved solids present in the
feed stream will be concentrated in the reject and will limit the
opportunities for recycle. RO systems will be capable of recovering 50-90% of
the feed as product water. The recovery that can be obtained as well as the
required feed pressure to operate the system will be a function of the
dissolved solids concentration in the feed.
The membranes used in the filtration process are made from a
number of different materials. Microfiltration membranes are commonly made
from woven polyester or ceramic materials. UF and RO membranes are fabricated
from cellulose acetate, polysulfone, polyamide, or other polymeric materials.
The most common material is cellulose acetate. Although cellulose acetate
membranes are lower cost and not as susceptible to fouling, removal of some
low molecular weight PAIs such as carbaryl, fluometuron, chloropropham, and
atrazine have been shown to be only marginal. In addition, mass balances
conducted for short-term tests have shown a significant amount of the PAI
rejection may be due to adsorption to the membrane as opposed to rejection by
it.
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Bench- and pilot-scale studies have demonstrated excellent
rejection (>99%) of a wide range of PAIs using thin-film composite (TFC)
reverse osmosis membranes. TFC membranes usually consist of three distinct
layers, a polyester support layer, a porous interlayer (polysulfone), and a
proprietary ultrathin barrier coating (often polyamide). TFC membranes are
more expensive and in some cases, more susceptible to fouling than cellulose
acetate. For relatively clean wastestreams (no suspended solids or oil and
grease), TFC membranes appear to represent an effective method of removing the
target PAIs and producing a high quality product water stream. Bench- and/or
pilot-scale testing is, however, recommended for most potential applications
to ensure that the system will be properly designed to prevent or minimize
membrane fouling which will negatively impact the performance of the system.
7.2.8 Biological Treatment
Biological treatment is a destruction technology in which toxic
organic pollutants in wastewaters are degraded by microorganisms. These
microorganisms oxidize soluble organics and agglomerate colloidal and
particulate solids. This technology generates a waste biosludge.
Common forms of biological treatment include lagoons, activated
sludge, and trickling filter systems. In lagoon systems, wastewater is
biologically treated to reduce the degradable organics and also reduce
suspended solids by sedimentation. The biological process taking place in the
lagoon can either be aerobic or anaerobic, depending on the design of the
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lagoon. The activated sludge process is used primarily for the removal of
organic material from wastewater. It is characterized by a suspension of
aerobic and facultative microorganisms maintained in a relatively homogenous
state by mixing or by turbulence induced by aeration. These microorganisms
oxidize soluble organics and agglomerate colloidal and particulate solids in
the presence of dissolved molecular oxygen. The trickling filter system is an
attached-growth biological system based on trickling wastewater over the
surface of a biological growth on solid media (usually rock, wood, or
plastic). Trickling filters are effective for the removal of suspended or
colloidal materials, but less effective for the removal of soluble organics.
Biological treatment (including aerated lagoons, activated sludge,
and trickling filter systems) is most effective on those priority pollutants
which are effectively adsorbed onto the suspended solids in the system, where
biological activity occurs, and are readily biodegradable. The mechanism of
pollutant removal may be one or more of the following:
• Biological degradation of the pollutant;
• Adsorption of the pollutant onto sludge with is separately
disposed; or
• Volatilization of the pollutant into the air (in the case of
aerated systems).
In the last two cases, the pollutant is simply transferred from
one medium to another, rather than actually being "removed." Some pollutants
may require specially acclimated biomass and/or longer detention times to be
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effectively removed by biological treatment. In these cases, in-plant
biological treatment can be an effective and potentially less costly
alternative to carbon adsorption technology for control of these priority
pollutants and PAIs.
7.2.9 Evaporation
Evaporation occurs when a solvent, usually water, vaporizes from a
solution or slurry, and completion of the evaporation process results in
drying. This technology can be used to vaporize off water, thereby
concentrating the solute in the remaining solution, and is related to
distillation, sublimation, and stripping, because they are all processes based
on the common principles of vaporization.
In spray evaporation, or drying, a wet slurry is converted to a
vapor, which is released, and a dry, free flowing powder, which may be
recovered as product or disposed of as waste. A spray evaporation/drying
treatment system normally consists of a drying chamber. The waste slurry is
injected into the chamber through an atomizer which disperses the stream. A
cyclone is created by injecting a high flow warm air stream countercurrent to
the atomized slurry. In the spray drying chamber, the solids settle out of
the air while the moisture is evaporated.
The solids which settle out of the primary and secondary chambers
of the spray evaporation system may be either pesticide product ready for
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formulation and packaging, or a solid waste stream requiring disposal or
recycle. The water vapors are extracted from the primary chamber, filtered to
further remove particulate in the secondary chamber, and then exhausted to the
atmosphere, generating no wastewater. If the solvent is not water, it is
necessary to condense or scrub the vapors to prevent hazardous air emissions.
This technology is appropriate for separation of non-volatile and
insoluble PAIs from manufacturing wastewaters or from process solvents. It is
not appropriate for wastewater streams containing volatile organic priority
pollutants or cyanide, unless air pollution control devices are added to the
exhaust prior to venting to the atmosphere.
One pesticide manufacturer currently uses spray evaporation for
the control of effluents from two pesticide active ingredients. However,
sufficient data are not available to estimate the amount of PAI discharge
eliminated through the use of this technology.
7.2.10 Chemical Precipitation/Filtration
Chemical precipitation is a separation technology in which the
addition of chemicals during treatment results in the formation of insoluble
solid precipitates from the organic or inorganic compounds in the wastewater.
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Polishing filtration then separates the solids formed from the wastewater.
Chemical precipitation is generally carried out in four phases:
1. Addition of the chemical to the wastewater;
2. Rapid (flash) mixing to distribute the chemical
homogeneously into the wastewater;
3. Slow mixing to promote particle growth by various
flocculation mechanisms; and
4. Filtration to remove the flocculated solid particles.
Chemical precipitation is used frequently as a technology to remove metals
from industrial wastewaters. Chemical reagents are added to the wastewater
during treatment leading to the formation of insoluble solid precipitates from
the organic or inorganic compounds in the wastewater. The precipitated metals
may then be removed by physical means such as sedimentation, filtration, or
centrifugation.
Hydroxide precipitation is the conventional method of removing
metals from wastewater. Reagents such as slaked lime (CA(OH)2) or sodium
hydroxide are added to the wastewater to adjust the pH to the point where
metal hydroxides exhibit minimum solubilities and are precipitated. Sodium
hydroxide is more expensive than lime, but generates a smaller volume of
hydroxide sludge. Hydrogen sulfide, ferrous sulfide, or soluble sulfide
salts, such as sodium sulfide, are used to precipitate many heavy metal
sulfides. Because most metal sulfides are even less soluble than metal
hydroxides at alkaline pH levels, greater metal removal can often be
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accomplished through the use of sulfide rather than hydroxide as a chemical
precipitant. However, sulfide treatment may be more difficult to use due in
part to the possibility of evolution of highly toxic hydrogen sulfide gas.
Carbonate precipitation is another method of removing metals from wastewater
by adding carbonate reagents such as calcium carbonate to the wastewater to
precipitate metal carbonates.
Chemical precipitation is an effective technique for removing
metals from industrial wastewaters. This technology operates at ambient
conditions and is well suited to automatic control. Hydroxide precipitation
removes metal ions such as antimony, arsenic, trivalent chromium, copper,
lead, mercury, nickel, and zinc. Sulfide precipitation can be used to remove
mercury, lead, and silver while carbonate precipitation removes antimony and
lead from wastewater.
7.2.11 Chemical Reduction
Reduction is a chemical reaction in which electrons are
transferred to the chemical being reduced from the chemical initiating the
transfer (the reducing agent). Sulfur dioxide, sodium bisulfite, sodium
metabisulfite, and ferrous sulfate form strong reducing agents in aqueous
solution and are often used in industrial waste treatment facilities for the
reduction of hexavalent chromium to the trivalent form.
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In the pesticides industry, chemical reduction has been used to
treat wastewaters containing an alkyl halide PAI. The PAI is reduced with the
addition of sodium bisulfite and ultraviolet light (i.e., sunlight).
7.2.12 Coagulation/Flocculation
Coagulation and flocculation are commonly used in conjunction to
enhance settling of suspended particles ranging in size from those particles
large enough to settle readily to those small enough to remain suspended.
Coagulation is the chemical destabilization of the particles and flocculation
is the physical process that agglomerates particles (too small for
gravitational settling) so that they may be successfully removed in subsequent
settling processes such as sedimentation, clarification, or filtration.
Coagulation is the process of destabilizing colloidal particles so
that particle agglomeration can occur during flocculation. Chemical
coagulants are typically added to the wastewater in a rapid-mix tank to ensure
that they are dispersed in the wastewater stream as rapidly as possible.
Commonly used coagulants are those which are iron or aluminum-based (such as
alum), lime, and polymers. For a given wastewater, optimum coagulation
conditions depend on various factors including pH, temperature, chemical
composition of the wastewater, mixing conditions, and most importantly, the
coagulant used.
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Flocculation is a separation technique where the wastewater is
agitated in order to cause very small suspended particles to collide and
agglomerate into larger, heavier particles or floes and settle out. A common
type of flocculator used today is the paddle flocculator employed in a series
of flocculation chambers. The paddle gently agitates the water causing the
collision of the floe particles with one another, and the chambers lead to
laminar flow conditions to prevent floe destruction while providing sufficient
mixing to achieve floe formation.
Coagulation and flocculation are commonly used in the pesticide
manufacturing industry to remove metallo-organic PAIs and the metallic
byproducts of metallo-organic PAI manufacture from process wastewaters.
7.2.13 Incineration
Incineration is a destruction technology which involves heating
wastes to high temperatures in order to destabilize chemical bonds and destroy
toxic organic pollutants. Incineration is actually a combination of oxidation
and pyrolysis, both which involve chemical changes resulting from heat.
Oxidation involves reaction with oxygen, while pyrolysis refers to
rearrangement or breakdown of molecules at high temperatures in the absence of
oxygen. A controlled incineration process oxidizes solid, liquid, or gaseous
combustible wastes to carbon dioxide, water, and ash. Common types of
incinerators are rotary kiln, multiple hearth, liquid injection, fluidized
bed, and pyrolysis. This technology typically generates ash and scrubber
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water, although liquid injection incinerators typically generate only scrubber
water.
In the pesticide chemicals industry, incinerators destroy wastes
containing compounds such as: hydrocarbons, chlorinated hydrocarbons,
sulfonated solvents, and pesticides. Sulfur and nitrogen-containing compounds
will produce their corresponding oxides and should not be incinerated without
consideration of the effect on air quality. Halogenated hydrocarbons may not
only affect the air quality but may also corrode the incinerator surfaces.
7.2.14 Stripping
Steam stripping is a separation technology that removes relatively
volatile compounds from a wastewater by the passage of steam through the
wastewater. The stripped volatiles are usually processed further by recovery
or incineration. This technology generates air emissions from the stripping
treatment (which may be condensed to other liquid streams).
Steam stripping is essentially a fractional distillation of
volatile components from a wastewater stream. The volatile component may be a
gas or an organic compound that is soluble in the wastewater stream. This
treatment technology also removes water immiscible compounds such as
chlorinated hydrocarbons. Steam stripping employs super-heated steam to
remove volatile pollutants of varying solubility in wastewater. Specifically,
the technology involves passing super-heated steam through a preheated
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wastewater stream column packed with heat resistant packing material or metal
trays in counter-current fashion. Removal of the volatile compounds of the
wastewater.stream occurs because the organic volatiles tend to vaporize into
the steam until the compound's concentration in the vapor and liquid phases
(within the stripper) are in equilibrium.
The amount of volatiles that can be removed and the effluent
pollutant concentration levels that can be attained by a steam stripper are a
function of the height of the stripping column, the amount of packing material
and/or the number of metal trays in the column, and the steam pressure in the
column. After the volatile pollutant is extracted from the wastewater into
the superheated steam, the steam is condensed to form two layers of immiscible
liquids--the aqueous and volatile layers. The aqueous layer is recycled back
to the steam stripper influent feed stream because it may still contain low
levels of volatile compounds. The volatile layer is recycled to the process
or disposed of, depending on the specific plant's requirements.
Steam strippers are designed to remove individual volatile
pollutants based on a ratio of their aqueous solubility (tendency to stay in
solution) to vapor pressure (tendency to volatilize). This ratio is known as
the Henry's Law Constant. The column height and diameter, amount of packing
or number of trays, the operating steam pressure, and the temperature of the
heated wastewater feed of a steam stripper are varied according to the
strippability (using Henry's Law Constant) of the volatile pollutants to be
removed. Volatile compounds with lower Henry's Law Constants require greater
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column height, more trays or packing material, greater steam pressure and
temperature, more frequent cleaning, and generally more careful operation than
do volatiles with higher strippability. (See the final OCPSF rule, 52 FR
42540, for a further description of steam stripping technology).
7.2.15 Pre- or Post-Treatment
The pesticide chemicals manufacturing industry uses equalization,
neutralization, and/or filtration to pre- or post-treat process wastewaters.
Equalization
Equalization dampens flow and pollutant concentration variation of
wastewater prior to subsequent downstream treatment. By reducing the
variability of the raw waste loading, equalization can significantly improve
the performance of downstream treatment processes that are more efficient if
operated at or near uniform hydraulic, organic, and solids loading rates.
Increased treatment efficiency reduces effluent variability associated with
slug raw waste loadings. Equalization is accomplished in a holding tank or a
pond. The retention time of the tank or pond should be sufficiently long to
dilute the effects of any highly concentrated continuous flow or batch
discharges on treatment plant performance.
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Neutralization
Neutralization adjusts either an acidic or a basic waste stream to
a more neutral pH. Neutralization of acidic or basic waste streams is used in
the following situations:
• To enhance precipitation of dissolved heavy metals;
• To prevent metal corrosion and damage to other construction
materials;
• As a preliminary treatment allowing effective operation of
the biological treatment process;
• To provide neutral pH water for recycle uses; and,
• To reduce detrimental effects on a facility's receiving
water.
Neutralization may be accomplished in either a collection tank, rapid mix
tank, or equalization tank by commingling acidic and alkaline wastes, or by
the addition of chemicals. Alkaline wastewaters are typically neutralized by
adding sulfuric or hydrochloric acid, or compressed carbon dioxide. Acidic
wastewaters may be neutralized with limestone or lime slurries, soda ash, or
caustic soda. The selection of neutralizing agents depends upon cost,
availability, ease of use, reaction by-products, reaction rates, and
quantities of sludge formed. The most commonly used chemicals are lime (to
raise the pH) and sulfuric acid (to lower the pH).
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Filtration
Filtration is a separation technology designed to remove solids
from a wastewater stream by passage of most of the wastewater through a septum
or membrane that retains the solids on or within itself. Filters can be
classified by the following factors:
The driving force (i.e., the manner by which the filtrate is
induced to flow, either by gravity or pressure);
The function (i.e., whether the filtrate or the filtered
material is the product of greater value);
The operating cycle (i.e., whether the filter process occurs
continuously or batchwise);
The nature of the solids (i.e., the size of the particles
being filtered out); and
The filtration mechanism (i.e., whether the filtered solids
are stopped at the surface of the medium and pile up to form
a filter cake or are trapped within the pores or body of the
filter medium).
7.2.16 Disposal of Solid Residue from Treatment
Many of the wastewater treatment processes discussed in previous
parts of this section generate solid residues (i.e., sludges). Treatment
processes generating sludges include biological treatment, chemical
precipitation, and coagulation/flocculation treatment. Sludge is treated
prior to disposal to reduce its volume and to render it inoffensive (i.e.,
less odorous). Sludge treatment alternatives include thickening,
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stabilization, conditioning, and dewatering. Sludge disposal options include
combustion and disposal to land.
Sludge Treatment Alternatives
Sludge thickening is the first step in removing water from sludges
to reduce their volume. It is generally accomplished by physical means,
including gravity settling, flotation, and centrifugation. Stabilization
makes sludge less odorous and putrescible, and reduces the pathogenic organism
content. The technologies available for sludge stabilization include chlorine
oxidation, lime stabilization, heat treatment, anaerobic digestion, and
aerobic digestion. Conditioning involves the biological, chemical, or
physical treatment of a sludge to enhance subsequent dewatering techniques.
The most common methods used to condition sludge are thermal and chemical
conditioning. Dewatering is the removal of water from solids to achieve a
volume reduction greater than that achieved by thickening. This process is
desirable for preparing sludge for disposal and for reducing the sludge volume
and mass to achieve lower transportation and disposal costs. Some common
dewatering methods include filtration in a vacuum filter, filter press, or
belt filter, centrifugation, thermal drying in beds, and drying in lagoons.
Sludge Disposal Alternatives
Combustion serves as a means for the ultimate disposal of organic
constituents found in sludge. Some common equipment and methods used to
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incinerate sludge include fluidized bed reactors, multiple hearth furnaces,
atomized spray combustion, flash drying incineration, and wet air oxidation.
Environmental impacts of combustion technology that should be considered
include discharges to the atmosphere (particles and other toxic or noxious
emissions), to surface waters (scrubbing water), and to land (ash).
The disposal of sludge to land may include the application of the
sludge on land as a soil conditioner and as a source of fertilizer for plants.
This is typically used with sludges from biological treatment systems. In
addition, sludge can be stockpiled in landfills or permanent lagoons. In
selecting a land disposal site, consideration must be given to guard against
pollution of groundwater or surface water supplies.
7.3 TREATMENT PERFORMANCE DISCUSSION
EPA has collected and evaluated data available on potential BAT
treatment technologies for the pesticide chemicals manufacturing industry.
The following technologies are discussed in more detail, specifically in
reference to PAI treatment performance: carbon adsorption, hydrolysis,
chemical oxidation/ultraviolet decomposition, resin adsorption, solvent
extraction, distillation, biological treatment, oxidation/reduction and
physical separation, and incineration.
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7.3.1 Carbon Adsorption
In the pesticide manufacturing industry, activated carbon
adsorption is or has been used to treat PAIs in the following structural
groups: acetamides, benzonitriles, carbamates, phenols, phosphorodithioates,
pyridines, pyrethrins, s-triazines, tricyclic, toluidines, and ureas. In
addition, EPA and industry treatability studies have demonstrated sufficient
treatability of pesticides in the acetanilide, terephthalic acid, and uracil
structural groups using carbon to establish this treatment as a basis for
control of specific PAIs in these groups. Carbon has also been shown in
industry treatability studies to be an effective polishing control for
thiocarbamate PAIs, although insufficient information currently exists.
Based on long-term concentration data achieved using activated
carbon adsorption, the EPA is currently proposing limitations based on
activated carbon adsorption technology for individual PAIs in the following
structural groups: acetanilides, aryl halides, benzonitrils, bicyclics,
phenols, phosphorothioate compounds, pyrethrins, toluidines, and ureas.
Plants incorporating activated carbon adsorption into their PAI treatment
train currently achieve an average of 99.97% removal of the PAI loading from
their discharge. These systems currently account for the prevention of the
discharge of approximately 430,000 pounds of pesticide active ingredient per
year.
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One method of evaluating the performance of a treatment system in
removing pesticide active ingredients is to compare the long-term mean
effluent concentration of the PAI in the treated effluent with the detection
limit for the PAI in the sample matrix. For pesticide active ingredients
treated using activated carbon adsorption in treatment systems achieving BAT
performance levels, the long-term mean to detection limit (LTM/MDL) ratio
varies from 3.19 to 7.35 (i.e., for these compounds, the average concentration
following treatment ranged from 3.19 to 7.35 times the minimum detection limit
for the compound in the effluent). The use of this factor allows for the
comparison of different applications of activated carbon treatment. For
example, a dedicated activated carbon treatment unit prior to dilution at the
process area may achieve excellent percent removals but still have an effluent
concentration orders of magnitude higher than the concentration following
mixing and dilution with non-pesticide contaminated streams. However, the
minimum detection limit for the process discharge will reflect the ability to
treat and monitor treatment performance levels in the specific matrix, and
therefore indicates the bottom concentration limit at which efficient
treatment system operation can be maintained.
Data were collected from plant supplied long-term monitoring data,
when activated carbon influent and effluent data were both available, and from
EPA sampling data. Removal efficiency by group varies from 99.97% for aryl
halides, to 86.3% for pyrethrins.
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In addition to the PAI being treated, a number of factors can
effect the efficiency of the carbon systems. Both the efficiency and cost
effectiveness of activated carbon can be enhanced if the carbon treats
wastewater from a single process, and if PAI contaminated and non-PAI
contaminated process streams are further segregated. This is because of the
types of competitive effects which will occur between adsorption of various
compounds in complex wastewater matrices. In systems where a dedicated
activated carbon was the first stage used in removing the PAI from the
wastewater, an average of 99.2% removal was achieved across all PAIs.
When carbon was used as a polishing treatment following other PAI
removal treatment technologies, the average removal dropped to 84.5%, due to
the greatly reduced initial concentration of PAI. Also, besides the
competitive effects involved in treating complex matrices with activated
carbon, when the effluent concentration approaches the minimum detection
limit, the calculated removal efficiencies decrease due to the statistical
effects of analyses below the detection limit. However, while the calculated
efficiency of removing pesticides from less contaminated streams drops, for
those PAIs using carbon as a polishing step very low effluent concentrations
were achieved in the carbon effluent, with an average of 8.6 ppb PAI detected.
Therefore, the ratio of average concentration to minimum detection limit is
comparable to that of systems treating more concentrated process streams.
Using an activated carbon system dedicated to removal of a
specific PAI from the undiluted process discharge will also improve
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efficiency, as the pH and the rate of carbon bed changes can be optimized to
remove the targeted compound. For example, for all PAIs being treated in a
process-specific carbon system, average removals of 97.4% were achieved, with
a median of 99.1% removal. However, when PAI wastewaters were intermingled
prior to carbon adsorption, removal average efficiencies fell to 88.9%, with a
median of 90.0 percent.
In the case of many of the PAIs which are or have been treated
using carbon, expediency has appeared to drive treatment system selection
rather than optimal system design. For example, wastewaters from the
manufacture of phenoxy, carbamate, and phosphorothioate PAIs which can be
readily hydrolized at alkaline conditions have been treated using activated
carbon. Industry-wide, 89.15% removal of phosphorothioates is achieved using
activated carbon in BAT systems; however, for those phosphorothioates treated
in dedicated systems the removal efficiency through the use of activated
carbon improves to 99.07 percent. Operating activated carbon treatment
systems have achieved removal efficiencies of 99.87 99.99% for carbamate
PAIs and 99.95% for phenoxy PAIs. However, for both of these groups, BAT data
has been collected based on other, less expensive treatment technologies. In
those cases, carbon may have been chosen originally because of its ability to
remove other pollutants of concern from the wastewater, or because of an
incomplete assessment of treatment options. Due to the cost of carbon
regeneration or replacement the use of activated carbon to treat high volume
streams is often a more expensive option than other physical-chemical
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treatment methods. Therefore an evaluation of other treatment technologies
may result in a system which provides equal performance at a lower cost.
Through the use of activated carbon adsorption to comply with the
proposed BAT and PSES guidelines for organic pesticides chemicals
manufacturers, the EPA estimates that an additional 165,000 pounds of active
ingredient will be eliminated from plant discharges annually.
7.3.2 Hydrolysis
Hydrolysis has been identified as the most effective technology
for achieving high levels of destruction of pesticide active ingredients in
the carbamates and organophosphate structural groups. This technology has
been demonstrated at a number of manufacturing facilities, and in both EPA and
industry-supplied treatability studies.
Depending on the retention time, the temperature, and the pH, PAI
treatment systems based on hydrolysis can have excellent performance. For
facilities currently including hydrolysis as a stage in their wastewater
treatment system, an average of 99.55% removal of the PAI is achieved through
treatment. In reviewing current performances by industry in treating
pesticide wastewaters, the EPA has determined that PAI treatment systems
incorporating hydrolysis are responsible for removing approximately 93,700
pounds of pesticide from process discharges each year. These systems proved
capable of reducing the amount of PAI in wastewater to the extent that the
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average long-term mean effluent concentration for facilities using hydrolysis
as a PAI treatment technology was 2.69 times the minimum detection limit for
the individual PAI. At many of facilities, no PAI was detected at the
detection limit in more than half the sample results reported.
The EPA reviewed published sources for information on hydrolysis,
and documented the half-lives and effluent concentrations demonstrated at
different temperatures and pHs. In these studies, data with both experimental
conditions and half-lives reported were available for 96 of the PAIs covered
in this regulatory study. Within those, 51 PAIs had demonstrated half-lives
of less than 1 day, 33 had half-lives of less than 1 hour, and 14 had half-
lives of 10 minutes. The EPA sponsored treatability studies at more uniformly
controlled conditions on those PAIs which were manufactured in 1986 for which
hydrolysis appeared to be a potential BAT technology, and hydrolysis did prove
highly effective in destroying the targeted PAIs in aqueous solutions. For 30
of 36 PAIs tested in the phosphate, phosphorothioate, phosphonothioate, and
carbamate structural groups, a half-lives of less than 1/2 hour was achieved
by treating the PAI at temperatures of 60°C and a pH of 12. Confidential
industry data also supports the use of hydrolysis for the treatment of a
number of PAIs currently either discharged or deep-well injected untreated,
although this data has generally not contained sufficient detail for
determination of achievable concentration at full-scale systems.
The EPA is proposing hydrolysis as a technology basis for a number
of PAIs which are not currently treated using this technology, but for which
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treatability studies have demonstrated excellent destruction of the PAI. It
is estimated that the utilization of hydrolysis to treat these PAIs would
result in the removal of an additional 84,400 pounds of PAI from plant
discharges annually.
7.3.3 Chemical Oxidation/Ultraviolet Decomposition
Chemical oxidation has been demonstrated by industry to be
effective at destroying alkyl halide, DDT-type, phenoxy, phosphorothioate, and
dithiocarbamate PAIs in manufacturing wastewaters. For those facilities
currently incorporating chemical oxidation in their PAI treatment train, an
average of 99.42% destruction of PAI is achieved, preventing about 8,300
Ibs/year of PAI from being discharged.
While PAIs in a number of these groups may be treated using other
technologies, the use of chemical oxidation is an excellent candidate for the
treatment of dithiocarbamate PAIs. In treatability studies available,
dithiocarbamate PAIs do not appear to be uniformly treatable through the use
of activated carbon adsorption. Meanwhile, while these compounds are readily
hydrolyzable at acidic conditions, a byproduct of the acidic hydrolysis
reaction is carbon disulfide gas, which could result in dangerous conditions
due to the highly flammable nature of CS2 gas.
The EPA performed treatability studies on a number of actual
process wastewater samples containing dithiocarbamate PAIs using alkaline
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chlorination as a treatment technology. All dithiocarbamates tested proved
amenable to destruction through alkaline chlorination. However, during
sampling at a facility which utilized alkaline chlorination to treat
dithiocarbamate PAIs, the EPA did find that this treatment technology is
capable of generating chlorinated priority pollutants. Therefore, in
assessing the economic impacts of the use of alkaline chlorination to treat
dithiocarbamates, the EPA projected the use of steam stripping for the removal
of chlorinated organics. At the same time, EPA is conducting treatability
studies on technologies which are not currently used in the pesticide
manufacturing industry using ozonation and ultraviolet light (UV) catalyzed
ozonation to initiate oxidation of dithiocarbamates in water. The use of
ozonation would prevent the generation of halocarbons, and thus eliminate the
need for the use of additional priority pollution control technologies. The
ozone and UV catalyzed ozone treatability studies conducted so far, however
have not identified the best treatment conditions.
The EPA estimates that the use of alkaline chlorination to destroy
dithiocarbamate pesticide active ingredients not currently being treated will
result in the elimination of 5,700 pounds of PAI from plant discharges
annually.
7.3.4 Resin Adsorption
Resin adsorption is currently used to treat specific pesticide
active ingredients which have not proved amenable to other treatment
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technologies. The technology is similar to activated carbon, in that the
resin removes the pollutant from the wastewater stream, rather than destroying
it, and therefore will become saturated with the PAI over time. However,
regeneration of resin can be performed in place by washing the resin with a
solvent designed to dissolve and remove the PAI from the treatment unit. To
ensure adequate performance, it is critical that the resin be regenerated on a
sufficient frequency.
BAT treatment systems relying on resin adsorption achieve around
97% removal of the pesticide active ingredient from the water achieve very low
discharge concentrations ranging from 3 to 32 ppb PAI in the treated effluent.
BAT is being proposed based on resin adsorption for those PAIs for which
actual plant operating data on resin adsorption is available. Because this
technology is very specific to both the PAI and the wastewater matrix being
treated (high levels of other contaminants can quickly foul resins and degrade
performance), EPA did not select resin adsorption as a BAT technology for
those PAIs where no plant performance data currently exists.
7.3.5 Solvent Extraction
Solvent extraction is used by a number of facilities to remove
PAIs from high concentration process brines, either prior to additional
treatment or by itself. As the use of solvent extraction on wastewaters prior
to discharge from the manufacturing unit is often considered a process stage
rather than a treatment stage, long-term data does not exist on the treatment
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performance of these systems. During EPA sampling episodes, the influents and
effluents from many solvent extraction systems were sampled; an average PAI
removal of 86.1% was achieved.
There were wide differences in performance, as percent removals
ranged from 58% to 99.85%, while achievable concentrations ranged from less
than 9 ppb up to 50 ppm for individual units. This variation has to do with
the mechanism of solvent extraction, the solvents used and PAIs removed, as
well as the design factors (contacting method, decanting method, etc.) for
each unit. Solubility has the greatest impact on the system performance, as
the minimum achievable concentration of PAI in the wastewater is a function of
the solubility of the PAI in both the water and the solvent. If the solvent
extraction system has sufficient contact time between the solvent and the
wastewater, a very consistent effluent concentration will be achieved, as the
system will reach an equilibrium between the PAI concentration in the
wastewater and solvent phases. The EPA received data on one PAI which
demonstrated that solvent extraction alone, without other downstream treatment
technologies, could achieve BAT performance levels. Because sufficient
contact time must be maintained to ensure optimal system performance, the EPA
has projected costs for additional equalization capacity for those facilities
expected to comply with BAT/PSES guidelines through the use of existing
solvent extraction systems.
EPA estimates that through the use of equalization to enhance
existing solvent extraction systems, approximately 100 pounds of PAI discharge
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will be eliminated per year, and wide variations in effluent loadings would be
eliminated.
As the effective use of solvent extraction as a treatment stage is
highly dependent on the configuration of the process and the type of PAI, the
EPA is not proposing solvent extraction as a technology basis for any PAIs not
currently being treated through extraction. However, in a proper application
solvent extraction has the potential for reducing the loading to other
treatment systems, as well as to achieve economic benefits through the
recovery of product and raw materials.
7.3.6 Distillation
Distillation is the separation of the constituents in a wastewater
stream by partial vaporization of the mixture and separate recovery of vapor
and residue. The main use of distillation in pesticide manufacturing
operations is in the separation of alcohols used in the manufacture of esters
of phenoxy-based PAIs from wastewaters. The alcohols can then be reused in
future manufacturing, while the wastewater, once separated from alcohols and
solvents, can be reused in the manufacture of salts of phenoxy PAIs, or in
phenoxy product formulations. In this process, the phenoxy ester product is
heated, driving off the alcohol and water, and the alcohol is then condensed
separately from the water. Currently operational systems have demonstrated
the ability to generate a water stream containing the phenoxy product which is
almost completely free of alcohol, and can therefore either alone or through
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blending meet the water specifications necessary for use in product
formulations.
For non-phenoxy PAIs, distillation has been used to separate water
from pesticide process streams as a final purification stage. Although the
purity of the distillate will be a function of the volatility of the PAI, the
distilled wastewater will normally contain no detectable concentrations of the
PAI. The remaining solution can then be recycled into the process, or
disposed as a hazardous waste.
The EPA received no effluent monitoring data for use in evaluating
the performance of systems using distillation to eliminate the discharge of
pesticide wastewaters. In systems where distillation and complete recycle is
practiced, no wastewater is discharged from the process, and therefore no
monitoring is required. For those facilities relying on distillation to
separate PAI from the wastewater so that the water may be discharged,
monitoring pesticide concentrations in the wastewater is not currently
required.
7.3.7 Biological Treatment
In the case of one pesticide active ingredient, biological
treatment has been demonstrated to achieve PAI removal levels characteristic
of BAT performance. This facility currently achieves removals of greater than
98% PAI during biological oxidation, discharging less than 0.5 pounds of PAI
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in wastewater per million pounds of PAI manufactured. However, few PAIs
demonstrate this amount of biodegradability. This level of success using
biological treatment in treating pesticide wastewaters required the proper
acclimatization of the biomass to the PAI being controlled, as well as
significant attention to design and maintenance of proper hydraulic loading
rates to the biological treatment system.
7.3.8 Oxidation/Reduction and Physical Separation
For wastewaters contaminated with pesticides based on metal ions,
removal of the PAI can often be best achieved through the addition of
chemicals which enhance the ability of the PAI to be removed through physical
separation technologies such as settling or filtration. In the case of
wastewaters containing tri-organotin compounds, this can be achieved through
reacting the organotin complex with an oxidizing agent, thereby creating a tin
molecule which will settle out as a solid. In addition, the oxidizing agents
may react with other metals in the wastewater, thereby creating other
insoluble metal complexes which will scavenge unoxidized organotin compounds
during settling. Removal of organotins can also be enhanced through the use
of cationic polymers in combination with the oxidation step.
Industry treatability and operating data demonstrates that
oxidation/settling is an effective method for treating tri-organotin
compounds. Removal efficiencies of up to 99.5% have been achieved on a long-
term basis using this technology.
7-56
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7.3.9 Incineration
A number of pesticide manufacturing facilities currently utilize
on-site incineration as the primary method for disposing of all PAI
contaminated wastewaters. Properly operated incineration systems can be
capable of achieving virtually 100% destruction of the PAI in wastewater
streams. While the PAIs and other pollutants of concern are completely
destroyed, an effluent stream is generated from the scrubber on the
incinerator overheads. At some facilities, the incinerators do not achieve
100% efficiency, and trace amounts of PAI remain in the scrubber discharge.
EPA estimates that approximately 4,000 pounds of PAI are destroyed annually
through on-site incineration of PAI manufacturing wastewater.
7.4 EFFLUENT LIMITATIONS DEVELOPMENT FOR PAIs
This section discusses the development of effluent limitations
guidelines and standards for PAIs in Subcategory A of the pesticide chemicals
manufacturing industry. This section also presents those cases where
limitations requiring no discharge of process wastewater pollutants have been
proposed and discusses options available for compliance with proposed zero
discharge standards.
EPA identified two regulatory options for consideration to reduce
the discharge of PAIs by organic pesticide manufacturers. Option 1 would base
BAT, NSPS, PSES and PSNS limitations on the efficacy of hydrolysis, activated
7-57
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carbon, chemical oxidation, resin adsorption, biological treatment, solvent
extraction, and/or incineration to control the discharge of PAIs in
wastewater, as demonstrated by either industry monitoring data or by
treatability studies. Option 2 would require zero discharge of pesticide
manufacturing wastewater pollutants by PAI manufacturers, based on the use of
on-site or off-site incineration and/or recycle and reuse.
EPA is proposing BAT, NSPS, PSES, and PSNS limitations for
Subcategory A plants based upon Option 1. As discussed'elsewhere in this
section, the identified BAT control technologies achieve a high level of
pesticide pollutant removal while avoiding cross-media transfer of pollutants.
A zero discharge requirement is also proposed for certain PAIs under Option 1
where zero discharge has been demonstrated to be achievable through water
reuse or the lack of water use. The Agency proposes to reject the second
option, zero discharge of all pesticide manufacturing wastewater pollutants,
because of the cross-media implications of the transfer of pollutants as well
as the severe economic impacts that would result from implementing this
option.
Sections 7.4.1 through 7.4.6 provide a detailed discussion of the
steps followed in the determination of effluent limitations guidelines and
standards for PAIs. These steps include:
7.4.1 Statistical analysis of long-term self-monitoring
data;
7-58
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7.4.2 Calculation of effluent limitations guidelines under
BAT;
7.4.3 Calculation of effluent limitations guidelines under
NSPS;
7.4.4 Analysis of POTW pass-through for PAIs; and
7.4.5 Calculation of effluent limitations guidelines under
PSES and PSNS.
Where long-term self-monitoring data are available, the
calculation for the daily production-based limitation was performed by:
(1) fitting daily PAI concentration data to a modified delta-lognormal
distribution, the same statistical procedure that was used in the OCPSF
rulemaking, (2) estimating the 99th percentile of PAI concentration from the
fitted distribution of daily concentration measurements, (3) multiplying the
estimated 99th percentile of concentration by daily average flow, and
(4) dividing the result by daily average production to give the daily
production-based limitation. The 4-day average production-based limitation
was calculated similarly except that, by definition for 4-day average
limitations, the 95th percentile of the distribution of 4-day average values
was substituted for the 99th percentile of daily concentration measurements.
The 4-day average is equivalent to the monthly average because EPA is
proposing weekly (four times per month) monitoring to demonstrate compliance.
These procedures are discussed in the following section.
7-59
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7-4.1 Statistical Analysis of Long-Term Self-Monitoring Data
This subsection describes the statistical approach that was
applied to the industry-submitted long-term pesticides pollutant data to
estimate long-term averages and variability factors.
Many manufacturers who responded to the Facility Census submitted
data on concentrations of PAIs measured in process wastewater. To develop
concentration-based limitations and variability factors, EPA modeled the
concentration data for each plant-PAI combination using a modification of the
delta-lognormal distribution. This distribution was chosen because the data
for most PAI's consisted of a mixture of measured (i.e., detected) values and
nondetects. The modified delta-lognormal assumes that all nondetects occur at
the detection limit and that the measured concentrations follow a lognormal
distribution (i.e., the logarithms of the measured data are normally
distributed). The modified delta-lognormal1 distribution is identical to a
lognormal distribution if there are no nondetects in the data.
The mean, variance, 99th percentile, daily variability factor, and
the four-day variability factor were estimated by fitting the concentration
data to the modified delta-lognormal distribution. The estimated 99th
percentile of the distribution provides the concentration-based daily maximum
limitation for each plant-PAI combination. The daily variability factor is a
'This modification of the delta-lognormal distribution was used by EPA in
establishing limitations for the Organic Chemicals, Plastics, and Synthetic
Fibers point source category.
7-60
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statistical quantity that is defined as the ratio of the estimated 99th
percentile of a distribution divided by the expected value of the
distribution. Similarly, the four-day variability factor is defined as the
estimated 95th percentile of the distribution of four-day means divided by the
expected value of the four-day mean.
The modified delta-lognormal model is a mixture distribution in
which all the detected concentrations follow a standard lognormal distribution
(i.e., the logarithm of the concentration is normally distributed with mean n
and standard deviation a), and all the nondetects are assumed to have a
concentration value equal to the detection limit. The cumulative distribution
function, which gives the probability that an observed concentration (C) is
less than or equal to some specified level (c), can be expressed as a function
of the following quantities:
D = the detection limit,
5 = the probability of a nondetect,
I(c-D) = an indicator function which equals 1 for c>D and 0
otherwise,
H = the mean of the distribution of log transformed
concentrations,
a = the standard deviation of the distribution of log
transformed concentrations,
y = variable of integration.
7-61
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The equation of the cumulative distribution function is as follows
F(c) = P(csc) = 6l(c-D) + (i-d)
1— flexpf-
2^H y *A
2a2
The expected value E(C) of the concentration under this
distribution function is given by
= 6ZH(l-*)exp||i+-^|, (2)
and the variance V(C) is given by the following expression:
02 (3)
V(C) = (1-6) exp (2jn-a2) [exp (o2)-(l-5)] + 6 (1-6) D[£>-2exp (|i + i-)].
lO
The 99th percentile of the distribution can be expressed in terms of p, a, and
the inverse normal cumulative distribution function ($"') , as follows:
7-62
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Finally, the daily variability factor VF(1) is defined as the 99th percentile
divided by the mean:
VF(l) =
To estimate daily variability factors for each plant-PAI dataset,
the following calculations were performed. The estimate, /t, of the log mean
was calculated by taking the arithmetic average of the log transformed
detects. The estimate, a, of the log standard deviation was calculated by
taking the sum of the squared differences between the log concentrations and
/t, divided by the number of detects minus one. The estimated probability of a
nondetect, S, was calculated by dividing the number of nondetects by the
number of observations . These quantities were then substituted into equations
(2) and (4) to give estimates E(C) and C,, of the mean concentration and the
99th percentile, respectively. Finally, the resulting estimated mean and 99th
percentile were substituted into equation (5) to yield the daily variability
factor estimate,
The daily variability factor multiplied by the long-term mean
yields the value used by EPA as the daily maximum limitation. An analogous
measure of the maximum limitation for the average (or mean) of four daily
concentration measurements can also be defined and estimated from the data.
The definition of the four-day variability factor, VF(4) , is the 95th
7-63
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percentile of the distribution of four-day means, divided by the expected
value of four-day means.
The value of VF(4) can be estimated from the daily concentration
data by exploiting the statistical properties of the four-day mean, C4, and
approximating the distribution of C4 by the modified delta-lognormal model
(this approximation can be shown to be close to the actual distribution). To
develop the estimate of VF(4), first note that the logarithm of C4 is normally
distributed with unknown mean and standard deviation denoted by fj,4 and OA,
respectively. Also, E(C4) = E(C) because the expected value of a sum of
random variables divided by a constant is equal to the sum of their
expectations divided by that constant. And V(C4) = V(C)/4 because the
variance of a sum of independent random variables divided by a constant is
equal to the sum of their variances divided by the square of that constant.
Finally, the probability that C4 is a nondetect is 6", since the mean of four
independent concentrations is a nondetect only if all four are nondetects, and
the probability of this occurring is equal to the product of the component
probabilities, or 8* if the daily nondetect probability is S.
The following equations therefore hold:
= E(C) =
7-64
-------
i
V(C4) =-^(C)=(l-54)exp(2ji4+a42) (exp (042)
4t
and
C95(4) ^ma
2 - -
Equations (6) and (7) can be algebraically solved for cr4 in terms
of the mean and variance of the daily concentrations, the probability of a
nondetect, and the detection limit. This expression is as follows:
(9)
~42 42 -
To derive an estimate, a4, of the left-hand side of equation (9), each
quantity on the right-hand side was replaced by its estimate computed from the
daily concentration data; i.e., E(C) was replaced by E(C) , V(C) by 'fr(C) , and S
by 5. Next, the estimated cr4 together with S and E(C) were substituted into
(6), which was solved to yield an estimate jj,A of /*4. Finally, /j,4 and <74 in (8)
were replaced by their estimates to yield an estimated value of the 95th
percentile of the distribution of the four- day mean, and this estimate was
divided by E(C) to give the estimated variability factor
Most plants provided a single detection limit for each PAI .
However, seven plant-PAI combinations reported multiple detection limits.
Because the modified delta- lognormal distribution is based on a single
7-65
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detection Limit, EPA had to select the detection limit to be used for the
statistical analyses in these cases.
When multiple detection limits were reported for a plant-PAI
dataset, the detection limit associated with the greatest number of nondetects
was used to estimate limitations. Daily limitations would not have changed
significantly if alternative detection limits had been selected. This can be
seen by examining equation (4), which shows that the daily limitation equals
the maximum of two terms: detection limit D, and a second term independent of
D. When this equation was evaluated, the second term exceeded D for all
alternative detection limits, showing that the daily limitation was
independent of the detection limit.
The estimated four-day limitation value is affected, but only
minimally, by the choice of detection limit, as seen by equation (8), which
shows that the limitation is the maximum of two terms: the detection limit D,
and a second term that is itself a function of D. To determine how the four-
day limitation values vary with changes in D, they were calculated for each
reported alternative detection limit. The results showed that the four-day
limitation is highly insensitive to changes in the assumed detection limit.
A change in detection limit affects the values of both the daily
and four-day variability factors, which are defined as the ratios of the
respective limitations to the mean concentration. The numerator of the ratio
for the daily variability factor does not depend on D, but the denominator
7-66
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(see equation (2)) is an increasing function of D. This means that selection
of a higher detection limit would have resulted in a lower estimated daily
variability factor.
Changes in detection limit have a lesser effect on estimated four-
day variability factors than on daily variability factors, because both the
numerator and denominator of the four-day variability factor ratio increase
when D increases.
7.4.2 Calculation of Effluent Limitations Guidelines Under BAT
The Agency based BAT limitations for organic PAIs on the
performance of hydrolysis, activated carbon, chemical oxidation, biological
treatment, solvent extraction, resin adsorption, and/or incineration treatment
systems. Limitations development was based on:
Long-term data obtained on PAIs with BAT performance data;
and
The transfer of statistical data in combination with the
results of treatability studies for PAIs for which there are
no BAT performance data.
Where long-term data were available, production-based mass limitations were
calculated using daily average production (in pounds per day) and mass
discharge. For the PAIs without BAT treatment performance data, BAT treatment
performance for PAIs having similar chemical structures were established and
7-67
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then compared for applicability. Effluent limitations were generated for the
PAIs for which there were no performance data by:
Setting achievable concentrations for each structural group
and technology performance based on treatability study
results;
Applying variability factors for each structural group and
for each technology; and
Determining mass discharge allowances based on long-term
average flow and annual production levels.
EPA identified 69 PAI structural groups. These groups and the
PAIs in them are listed in Table 7-2. The Agency is proposing numerical and
zero discharge limits for 93 PAIs and salts and esters of PAIs in 33 of these
groups. These PAIs and groups are listed in Table 7-3. Fifteen of these PAIs
and salts and esters are receiving zero discharge limitations because there
are plants manufacturing these pesticides who are currently achieving zero
discharge. The zero discharge technologies in-place at the BAT facilities for
these PAIs include dry manufacturing processes, manufacturing processes which
do not discharge wastewater, recovery and reuse of wastewater, on-site
incineration of wastewater, and distillation of wastewater for reuse.
Numerical limitations are being proposed for the remaining 78 PAIs and salts
and esters. Of these 78 PAI groups, 62 are associated with plants that have
full-scale treatment systems in place.
The Agency based BAT limitations for these 62 PAIs on actual data
of PAI concentrations in wastewaters treated by the full-scale BAT treatment
7-68
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Table 7-2
PAI STRUCTURAL GROUPS
Structural Group
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
Acetamide
Acetamide
Acetamide
Acetanilide
Acetanilide
Acetanilide
Acetanilide
Alcohol
Alkyl Acid
Alkyl Halide
Alkyl Halide
Alkyl Halide
Aryl
PAI #
14
15
15
16
16
17
27
30
31
34
46
47
238
115
136
242
26
54
70
165
36
227
81
92
160
67
PAI Name
2,3,6-T, S&E
2,4,5-T
2,4,5-T, S&E
2,4-D, S&E
2,4-D
2,4-DB, S&E
MCPA, S&E
Dichlorprop, S&E
MCPP, S&E
Chlorprop , S&E
CPA, S&E
MCPB, S&E
Silvex
Diphenamide
Fluor oacetamide
Sodium fluoroacetate
Propachlor
Alachlor
Butachlor
Metolachlor
HAE
Propionic acid
Chloropicrin
Dalapon
Methyl bromide
Biphenyl
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
No Discharge
Numerical
No Discharge
No Discharge
No Discharge
No Discharge
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved (PP Reg)
No Discharge
7-69
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Table 7-2
(Continued)
Structural Group
Aryl Amine
Aryl Halide
Aryl Halide
Aryl Halide
Aryl Halide
Aryl Halide
Aryl Halide
Benzeneamine
Benzoic Acid
Benzoic Acid
Benzonitrile
Benzonitrile
Bicyclic
Bicyclic
Bicyclic
Bicyclic
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
PAI #
116
20
80
98
110
129
205
204
53
78
69
69
123
123
177
262
13
38
40
42
48
55
61
62
75
76
PAI Name
Diphenylamine
Dichloran
Chloroneb
Dicamba
DCPA
Chlorobenzilate
PCNB
Pendimethalin
Acifluorfen
Chloramben
Bromoxynil
Bromoxynil octanoate
Endothall
Endothall, S&E
MGK 264
Toxaphene
Landrin 2
Landr in 1
Methiocarb
Polyphase
Aminocarb
Aldicarb
Bendiocarb
Benomyl
Carbaryl
Carbofuran
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved
Numerical
Reserved
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved
No Discharge
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
7-70
-------
Table 7-2
(Continued)
Structural Group
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate/Urea
Chlorobenz amide
Chlorophene
Chlorophene
Chlorophene
Chloropropionanilide
Chloropropionanilide
Coumarin
Coumarin
Cyclic Ketone
DDT
DDT
DDT
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
PAI #
77
95
100
145
156
166
170
195
260
272
146
39
9
10
11
41
82
43
265
91
1
101
158
23
87
102
PAI Name
Carbosulfan
Desmedipham
Thiophanate ethyl
Propham
Me thorny 1
Mexacarbate
Napropamide
Oxamyl
Thiophanate methyl
Chloropropham
Karbutilate
Pronamide
Hexachlorophene
Tetrachlorophene
Dichlorophene
Propanil
Chlorothalonil
Coumafuryl
Warfarin
Cycloheximide
Dicofol
Perthane
Methoxychlor
Sulfallate
Mancozeb
EXD
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
7-71
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Table 7-2
(Continued)
Structural Group
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
EDB
EDB
EDB
Ester
Ester
Ester
Ester
HCp
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
PAI #
134
151
152
167
172
218
219
220
241
243
261
267
268
3
5
97
64
117
157
216
93
28
32
35
49
175
FAI Name
Ferbam
Maneb
Manam
Metiram
Nab am
Bus an 85
Bus an 40
KN Methyl
Carbarn- S
Vapam (Metham Sodium)
Thiram
Zineb
Ziram
EDB
Dichloropropene
DBCP
Benzyl benzoate
MGK 326
Methoprene
Piperonyl butoxide
Dienochlor
Octhilinone
Thiabendazole
TCMTB
Etridiazole
Norflurazon
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Numerical
Reserved
No Discharge
7-72
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Table 7-2
(Continued)
Structural Group
Heterocyclic
Heterocyclic
Heterocyclic
Hydrazide
Iminamide
Indandione
Isocyanate
Lindane
Lindane
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
PAI #
210
240
259
2
59
114
118
63
147
21
29
37
71
90
96
153
164
196
201
209
214
221
225
228
235
244
PAI Name
Nemazine
Sodium bentazon
Dazomet
Maleic Hydrazide
Amitraz
Diphacinone
Nabonate
BHC
Lindane
Bus an 90
Pindone
Chlorophacinone
Giv-gard
Fenvalerate
Amobam
Mefluidide
Quinomethionate
Oxyfluorfen
Propoxur
Phenmedipham
Phosphamidon
Metasol J26
Propargite
Previcur N
Rotenone (Mexide)
Sulfoxide
Limit Type
Reserved
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
7-73
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Table 7-2
(Continued)
Structural Group
Miscellaneous
Miscellaneous
NR4
NR4
NR4
NR4
NR4
NR4
NR4
NR4
! NR4
Nitrobenzoate
Organoantimony
Organoarsenic
Organoarsenic
Organoarsenic
Organoarsenic
Organocadmium
Organocopper
Organocopper
Organocopper
Organomercury
Organotin
Organozinc
Phenol
PAI #
269
270
7
56
105
120
121
149
159
162
217
66
273
6
72
161
188
189
88
89
190
191
192
266
44
PAI Name
Triallate
Phenothrin
Dowicil 75
Hyamine 3500
Benzethonium chloride
Metasol DGH
Dodine
Malachite Green
Methyl benzethonium
chloride
Hyamine 2389
PBED (Bus an 77)
Bifenox
Or gano -Antimony
Thenarsazine Oxide
Cacodylic acid
Monosodium methyl
arsenate
Organo- Arsenic
Organo - Cadmium
Bioquin (Copper)
Copper EDTA
Organo -Copper
Organo -Mercury
Or gano -Tin
Zinc MBT
DNOC
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
7-74
-------
Table 7-2
(Continued)
Structural Group
Phenol
Phenol
Phenol
Phenol
Phenol
Phenylcrotonate
Phophorothioate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphonate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
PAI #
112
206
206
211
258
19
94
12
22
24
84
108
109
173
111
128
138
138
139
52
143
154
106
113
126
127
PAI Name
Dinoseb
PCP; sodium salt
PCP
Phenylphenol
Tetrachlorophenol
Dinocap
Demeton
Dichlorvos
Mevinphos
Chlorfenvinfos
Stirofos
Dicrotophos
Crotoxyphos
Naled
Trichlorofon
Fenamiphos
Glyphosate, S&E
Glyphosate
Glyphosine
Acephate
Isofenphos
Methamidophos
Dimethoate
Dioxathion
Ethion
Ethoprop
Limit Type
Numerical
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
No Discharge
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
No Discharge
Reserved
Reserved
No Discharge
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved
7-75
-------
Table 7-2
(Continued)
Structural Group
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
PAI #
150
155
183
185
185
185
186
197
199
200
212
213
251
255
85
86
103
107
131
133
179
180
181
182
FAI Name
Malathion
Methidathion
Disulfoton
Pho sine t , s ingl e
crystallized
Phosmet, double
crystallized
Phosmet
Azinphos Methyl
(Guthion)
Bolstar
Santox (EPN)
Fonofos
Phorate
Phosalone
Bensulide
Terbufos
Chlorpyrifos methyl
Chlorpyrifos
Diazinon
Parathion methyl
Famphur
Fenthion
Sulfotepp
Aspon
Coumaphos
Fensulfothion
Limit Type
Numerical
Reserved Not Mfg in 1986
Numerical
No Discharge
No Discharge
Reserved
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
7-76
-------
Table 7-2
(Continued)
Structural Group
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorotrithioate
Phosphorotrithioate
Phthalamide
Phthalimide
Phthalimide
Phthalimide
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyridine
Pyridine
Pyrimidine
Quinolin
PAI #
184
187
198
203
222
234
253
236
263
176
73
74
137
57
208
229
230
231
232
233
271
275
215
215
132
50
PAI Name
Fenitrothion
Oxydemeton methyl
Suprofos oxon
Parathion ethyl
Profenofos
Fenchlorphos (Ronnel)
Temephos
DBF
Merphos
Naptalam
Captafol
Cap tan
Folpet
Allethrin
Permethrin
Pyrethrin coils
Pyre thrum I
Pyre thrum II
Pyrethrins
Resmethrin
Tetramethrin
Pyrethrin I & II
Picloram
Picloram
Fenarimol
Ethoxyquin
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Numerical
Numerical
Reserved
No Discharge
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
No Discharge
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Numerical
Reserved Not Mfg in 1986
7-77
-------
Table 7-2
(Continued)
Structural Group
Quinolin
Quinone
Sulf anil amide
Sulfonamide
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocyanate
Thiocyanate
Thiosulphonate
Toluamide
Toluidine
Toluidine
Toluidine
Toluidine
Triazathione
Tricyclic
Tricyclic
Tricyclic
Tricyclic
Uracil
Uracil
PAI #
51
99
194
207
130
141
245
246
247
248
249
65
163
250
171
125
144
178
264
45
79
122
124
140
68
68
PAI Name
Quinolinol sulfate
Dichlone
Oryzalin
Perfluidone
Butylate
Cycloprate
Cycloate
EPTC
Molinate
Pebulate
Vernolate
Le thane 60
Nalco D-2303
HPTMS
Deet
Ethalfluralin
Isopropalin
Benfluralin
Trifluralin
Metribuzin
Chlordane
Endosulfan
Endrin
Heptachlor
Bromacil; lithium salt
Bromacil
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Numerical
Numerical
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Numerical
No Discharge
Numerical
7-78
-------
Table 7-2
(Continued)
Structural Group
Uracil
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
PAI #
254
83
104
119
135
148
168
169
174
237
252
4
8
18
25
33
58
60
142
223
224
226
239
256
257
PAI Name
Terbacil
Chloroxuron
Diflubenzuron
Diuron
Fluometuron
Linuron
Monuron TCA
Monuron
Norea
Siduron
Tebuthiuron
Vancide TH
Triadimefon
Anilazine
Cyanazine
Belclene 310
Ametryn
Atrazine
Hexazinone
Prometon
Prometryn
Propazine
Simazine
Terbuthylaz ine
Terbutryn
Limit Type
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved
Numerical
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
7-79
-------
Table 7-3
PAIs AND PAI STRUCTURAL GROUPS WITH PAI LIMIT DEVELOPMENT METHODOLOGIES
Structural Group
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
Acetanilide
Acetanilide
Acetanilide
Aryl
Aryl Halide
Aryl Halide
Aryl Halide
Benzeneamine
Benzoic Acid
Benzonitrile
Benzonitrile
BIcyclic
Bicyclic
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Chlorobenz amide
Chloropropionanilide
PAI #
16
16
17
27
30
31
26
54
70
67
80
110
205
204
53
69
69
123
262
55
62
75
76
156
39
41
PAI Name
2,4-D
2,4-D, S&E
2,4-DB, S&E
MCPA, S&E
Dichlorprop, S&E
MCPP, S&E
Propachlor
Alachlor
Butachlor
Biphenyl
Chloroneb
DCPA
PCNB
Pendime thai in
Acifluorfen
Bromoxynil
Bromoxynil octanoate
Endothall, S&E
Toxapbene
Aldicarb
Benomyl
Carbaryl
Carbofuran
Me thomyl
Pronamide
Propanil
Limit Type
Numerical
No Discharge
No Discharge
No Discharge
No Discharge
No Discharge
Numerical
Numerical
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
CO
DIS/REC/ND
DIS/REC/ND
DIS/REC/ND
ND
DIS/REC/ND
AC
AC
AC
ND
CO
AC, BO
AC
IN
HD
AC
AC
ND
AC
HD
HD
HD
HD
HD
AC
BO
7-80
-------
Table 7-3
(Continued)
Structural Group
Chloropropionanilide
DDT
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Heterocyclic
Heterocyclic
Heterocyclic
Isocyanate
Miscellaneous
Organotin
Phenol
Phosphate
Phosphate
Phosphate
Phosphate
Phosphor oamidate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphorodithioate
Phosphor odithioate
Phosphorodithioate
Phosphorodithioate
PAI #
82
158
172
218
219
220
241
243
35
175
259
118
90
192
112
12
22
84
173
138
52
154
113
126
150
183
PAI Name
Chlorothalonil
Methoxychlor
Nab am
Bus an 85
Bus an 40
KN Methyl
Garb am -S
Vapam (Metham Sodium)
TCMTB
Norflurazon
Dazomet
Nabonate
Fenvalerate
Organo-Tin
Dinoseb
Dichlorvos
Mevinphos
Stirofos
Naled
Glyphosate, S&E
Acephate
Methamidophos
Dioxathion
Ethion
Malathion
Disulfoton
Limit Type
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
No Discharge
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
BO
CO
CO
CO
CO
CO
CO
CO
HD
DIS/REC
CO
CO
HD, BO, SE
CO, CL
AC
HD
HD
HD
ND
ND
IN
HD, AC
HD, AC
AC
HD
HD, BO, AC
7-81
-------
Table 7-3
(Continued)
Structural Group
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphor otrithioate
Phosphorotrithioate
Phthalimide
Pyrethrin
Pyrethrin
Pyrimidine
Toluidine
Toluidine
Toluidine
Toluidine
Triazathione
Tricyclic
Tricyclic
Uracil
PAI #
185
185
186
197
212
255
86
103
107
133
182
203
236
263
73
208
230
132
125
144
178
264
45
124
140
68
PAI Name
Phosmet, double crystallized
Phosmet, single crystallized
Azinphos Methyl (Guthion)
Bolstar
Phorate
Terbufos
Chlorpyrifos
Diazinon
Parathion methyl
Fenthion
Fensulfothion
Parathion ethyl
DEF
Merphos
Captafol
Permethrin
Pyre thrum I
Fenarimol
Ethalfluralin
Isopropalin
Benfluralin
Trifluralin
Metribuzin
Endrin
Heptachlor
Bromacil
Limit Type
No Discharge
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
ND
ND
HD, BO, AC
HD, BO, AC
IN
IN
CO
AC
HD, BO
HD, AC
HD, BO, AC
HD, BO
HD, BO, AC
HD, BO, AC
IN
AC, RA
IN
IN
AC
IN
AC
AC
HD, AC
RA
RA
AC
7-82
-------
Table 7-3
(Continued)
Structural Group
Uracil
Uracil
Urea
Urea
Urea
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
PAI #
68
254
119
148
252
8
25
58
60
223
224
226
239
256
257
PAI Name
Bromacil; lithium salt
Terbacil
Diuron
Linuron
Tebuthiuron
Triadimefon
Cyanazine
Ametryn
Atrazine
Prometon
Prometryn
Propazine
Simazine
Terbuthylazine
Terbutryn
Limit Type
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
ND
AC
AC, BO
AC, BO
IN
HD, AC
HD, BO
AC
HD, BO
AC
AC
AC
AC
AC
AC
AC = Activated Carbon
BO = Biological Oxidation
CL = Clarification
CO = Chemical Oxidation
DIS = Distillation
HD = Hydrolysis
IN = Incineration
ND = No Discharge
RA = Resin Adsorption
REC = Recycle
SE = Solvent Extraction
7-83
-------
systems operated at BAT levels at these plants, when such full-scale data were
available. In some cases, pilot-scale data for BAT treatment systems were
used when data from the full-scale systems were not available. In other
cases, data were available for PAIs manufactured by plants that had full-scale
treatment systems in-place, but the treatment systems were not achieving BAT
treatment levels in final effluent. At some plants this was due to design
factors such as equalization capacity, or due to operational factors such as
reagent addition or carbon bed regeneration rate, which resulted in less than
optimum treatment system performance. In these cases, E-PA based BAT limits on
treatability study data demonstrating the achievable optimum performance. At
other plants, the BAT treatment was not applied to all the process wastewater
streams generated during the manufacture of a particular PAI. In these cases,
EPA based BAT limits on the full-scale treatment data extrapolated to cover
all process wastewater streams.
BAT treatment system data were not available for 16 of the 78
PAIs. For 15 of these PAIs, short-term treatability study data were used in
combination with variability factors transferred from plants operating full
scale systems with the same BAT treatment technologies. For the remaining PAI
group (pyrethrins), the Agency is proposing zero discharge limitations based
on off-site incineration. Given the high toxicity of pyrethrins and the
relatively low wastewater flow rates generated during pyrethrin manufacture,
off-site incineration is the most economical treatment option.
7-84
-------
More specifically, for each of the 62 PAI groups mentioned above,
control technologies (including process controls and wastewater treatment
systems) are already in place in at least one plant which manufactures the
PAI. For 47 of these PAIs, sufficient full-scale data are available,
including mass discharge rates and production rates, to develop BAT mass-based
limitations. Daily maximum and four-day maximum average discharge limitations
were based on achievable effluent concentrations demonstrated by in-place and
currently-operating BAT treatment, i.e., the results of plant self-monitoring.
The achievable daily maximum and four-day maximum average concentrations were
then multiplied by average long-term flow rates to determine the long-term
mass discharge of PAI, and then divided by long-term production rates to
generate discharge limitations based on the production of the specific PAI.
Flow and production data were obtained, in order of preference, from available
data either supplied with the self-monitoring data set, from 1986 or 1977
Section 308 census data submissions, or from EPA sampling data or site visit
reports.
For six of the PAIs manufactured at plants with BAT-type
technology in-place, BAT limitations are based on structurally similar (and
analytically indistinguishable) PAIs manufactured at the plants. For example,
one facility manufactures two similar phosphorotrithioates, and has monitoring
data indicating effective treatment, through hydrolysis, of one of these PAIs.
The second phosphorotrithioate cannot be analytically distinguished from the
first because it rapidly oxidizes to it. The second PAI would either react
via hydrolysis at the same rate as the first or would oxidize to the first and
7-85
-------
then hydrolyze. The second PAI can achieve the same BAT limit as the first
PAI. In the same way, two toluidine PAIs cannot be analyzed separately and
apart from a third toluidine PAI; therefore, the BAT limitations for these two
PAIs have been set equal to the BAT limitations for the third toluidine PAI.
The same methodology was used to develop BAT limitations for a benzonitrilile
PAI, a dithiocarbamate PAI, and a phosphorothioate PAI. These PAIs are not
analytically discernable from structurally similar PAIs, and therefore have
been regulated based upon the BAT limitations for their matching PAIs.
For nine of the PAIs manufactured at plants with BAT-type
technology in-place, the technology is either being used to control only a
portion of the process wastewater or is not operating at BAT performance
levels. In these cases, BAT limitations were based on the effluent quality
which could be achieved through extending and optimizing BAT technology to
control all process wastewaters. For those PAIs manufactured at plants
employing BAT technology on only a portion of the process wastewater, the
achievable daily maximum and four-day maximum average concentrations were
multiplied by average long-term flow rates for the entire process wastewater
discharge, treated and untreated wastewater, to determine the long-term PAI
mass discharge. For those PAIs manufactured at plants employing BAT
technology but not operating at BAT performance levels, BAT limitations were
based on discharge concentrations demonstrated to be achievable either by
plant data or by treatability studies, and on variability factors derived from
actual system performance. Daily maximum and four-day maximum average
7-86
-------
discharge limitations were then calculated by multiplying by the average long-
term flow rates and then dividing by the long-term production rates.
Numerical BAT limitations are being proposed for 15 PAIs, in 8
structural groups, based on treatability study data combined with data
transfer of actual system performance data. As discussed earlier in this
section, treatability studies were conducted to characterize the efficacy with
which activated carbon, hydrolysis, and chemical oxidation could treat certain
PAIs. When PAI concentration data were not available for wastewater streams
treated by full-scale BAT treatment systems, the Agency based BAT on the
transfer of limitations and estimated performance data for structurally
similar PAIs. Variability factors for the treatment of these PAIs were based
on the performance of BAT treatment systems utilizing the same technology, and
when sufficient data were available, on PAIs with similar structures.
EPA is proposing BAT limitations for two uracil PAIs, one
chlorobenzamide PAI, one phosphorodithioate PAI, and four s-triazine PAIs
based on short-term activated carbon adsorption treatability study data,
because there are no available full-scale operating data. A treatability
study provided isotherm and continuous column data for the treatment of these
PAIs in activated carbon adsorption systems. The treatability study data were
used to demonstrate that the PAIs are treatable to achievable BAT
concentrations; however, it was necessary to relate this information to actual
operating systems to generate achievable daily maximum and four-day average
maximum BAT concentrations, as well as the mass-based effluent limitations.
7-87
-------
In order to do this, EPA transferred arithmetic factors (as described below)
and variability factors from other activated carbon adsorption systems
operating at low PAI effluent concentrations.
The arithmetic factor deals with the practicality of analyzing for
the PAI at concentrations very close to the detection limit. For all PAIs
treated using activated carbon adsorption, an arithmetic factor was developed
to reflect the amount that the mean effluent concentration was above the
detection limit used to analyze that matrix. It was assumed that each
facility utilizes as low a detection limit as is practical to achieve
consistent long-term analyses for each PAI in each plant's wastewater matrix.
This factor is a ratio of the long-term mean effluent concentration (LTM) to
minimum detection limit (MDL), and ranged from 1.03 to 7.35 for the systems
considered, with an average ratio of 4.31. This ratio was used in conjunction
with the minimum detection limit used by one of the PAI manufacturing plants
in their analysis of the PAI in treated wastewater samples to calculate an
achievable long-term mean concentration. In no cases did this calculation
procedure generate concentrations lower than those achieved in treatability
testing.
The statistical variability factors applied to limitations
development were those calculated for average BAT activated carbon systems.
BAT operating data for 6 full-scale activated carbon systems and one small
scale activated carbon system which rely on activated carbon to control
pesticides were used to develop daily maximum and four-day maximum average
7-88
-------
variability factors. The data sets used to develop these factors were not
necessarily generated from systems incorporating the two optimal design
parameters recommended above and, therefore, effluent concentrations were
higher than would be expected with these optimizations. The average
variability factors calculated were 7.15 (daily) and 2.41 (four-day).
Achievable daily maximum and four-day average BAT effluent concentrations were
then calculated using the arithmetic and variability factors and the
treatability study concentrations. These concentrations were converted to
mass normalized limitations using the long-term average process discharge flow
for each specific PAI, and the average production for each specific PAI
manufacturing process which discharges water.
In the case of the four s-triazine PAIs, industry did provide EPA
with long-term monitoring data characterizing treated effluent (though not
from activated carbon) from the manufacture of two other s-triazine PAIs. EPA
therefore used the average long-term monitoring data results as a target for
the performance levels achievable for s-triazines manufactured by other
facilities. EPA treatability studies on plant wastewater demonstrated that
even greater s-triazine removal rates could be achieved through the use of
granular activated carbon (GAG) adsorption. Additional treatability study
information supporting this conclusion was available from the s-triazine
manufacturers themselves. The BAT limitations were therefore based on the
removal rates achievable through the use of granular activated carbon.
Variability, factors were transferred and mass-based BAT limitations were
calculated based on the methodology discussed above.
7-89
-------
EPA is proposing BAT limitations for a phosphorodithioate PAI
based on short-term hydrolysis treatability study data, because there are no
available full-scale operating data. This treatability study was conducted on
a "synthetic" wastewater stream; that is, deionized water spiked with the PAI.
Hydrolysis is used to treat a variety of other phosphorodithioate PAIs, with
treatment efficacy quantified through long-term self-monitoring data on these
PAIs. Literature data demonstrates that hydrolysis for this PAI takes place
faster than hydrolysis of other phosphorodithioates; therefore, EPA concluded
that wastewater from the manufacture of this PAI can be -treated to equal
effluent concentrations.
Similar to the methodology used to evaluate carbon adsorption as
BAT technology, daily and four-day variability factors (4.88 and 1.92,
respectively) and the LTM/MDL factor (3.40) were transferred from hydrolysis
effluent data for other phosphorodithioate PAIs to describe BAT hydrolysis
system performance in treating this PAI. These factors were used in
conjunction with the minimum detection limit reported by one of the
manufacturing plants for their PAI analysis to calculate BAT concentrations
for this PAI. These concentrations were then converted to mass normalized
limitations using the long-term average process discharge flow and average
production for this PAI at this plant,
EPA is proposing BAT limitations for a carbamate PAI based on
short-term hydrolysis treatability study data, because there are no available
full-scale operating data. As with the phosphorodithioate PAI discussed
7-90
-------
above, this treatability study was conducted on a "synthetic" wastewater
stream; that is, deionized water spiked with the PAI. Hydrolysis is used to
treat a variety of other carbamate PAIs, with treatment efficacy quantified
through additional EPA treatability studies on these PAIs. In particular, one
plant that manufactures this PAI also manufactures two other carbamate PAIs,
and treats the process wastewater with hydrolysis. It was observed that
hydrolysis of this carbamate PAI takes place faster than hydrolysis of other
carbamates; therefore, EPA concluded that wastewater generated during the
manufacture of this PAI can be treated to equal effluent concentrations.
The daily and four-day variability factors (3.57 and 1.59,
respectively) and the average LTM/MDL ratio (1.19) were developed based on the
treatment data for the hydrolysis of the two carbamate PAIs manufactured with
this PAI. These factors were used in conjunction with the minimum detection
limit reported by a carbamate manufacturing plant for their PAI analysis to
calculate BAT concentrations. These concentrations were then converted to
mass normalized limitations using the long-term average process discharge flow
and average production for the PAI at this plant.
EPA is proposing BAT limitations for three dithiocarbamates PAIs
and one isocyanate PAI based on short-term chemical oxidation treatability
study data, because there are no available full-scale operating data. The
dithiocarbamates were treated as one group because the analytical method for
dithiocarbamates does not distinguish among individual PAIs. The isocyanate
PAI is included with the dithiocarbamates because it is manufactured and
7-91
-------
treated using technologies common to dithiocarbamate PAIs; in addition, the
analytical method cannot distinguish between the isocyanate PAI and the
dithiocarbamate PAIs.
Self-monitoring and chemical oxidation treatability study data
were available at one plant utilizing chemical oxidation to treat
dithiocarbamate PAIs. The plant self-monitoring data was not directly used to
set BAT limitations because this plant was treating to meet specific
limitations, rather than treating to achieve maximum PAI removal. The
facility did report occasional non-detects, and achieved non-detects during
EPA sampling. EPA checked these results by conducting a chemical oxidation
treatability study on actual plant wastewater samples containing
dithiocarbamate PAIs. Results of the treatability study demonstrated that
effluent concentrations at or below the method detection limit were achievable
for each of these PAIs through chemical oxidation. Variability factors were
developed based on the performance of the operating chemical oxidation system
at this plant, and these factors were applied to the proposed achievable
concentration and used with flow and production data from the same facility to
develop mass based limitations.
EPA is proposing BAT limitations for a heterocyclic PAI based on
short-term hydrolysis treatability study data, because there are no available
full-scale operating data. The treatability study data indicates that
hydrolysis of this PAI occurs very rapidly. While there are no data on the
hydrolysis of any PAIs with a similar heterocyclic structure to this PAI,
7-92
-------
treatability data are available for a number of PAIs with hydrolysis systems
performing at BAT levels that have half-lives approximately equal to this PAI.
Therefore, variability factors and LTM/MDL ratios were averaged from the list
of all hydrolysis-treated PAIs. The average LTM/MDL was 2.44, and the average
variability factors were 4.18 (daily maximum) and 1.74 (four-day maximum
average). Using this method, achievable daily maximum and four-day maximum
average BAT effluent concentrations were calculated. These concentrations
were then converted to mass normalized limitations using the long-term average
process discharge flow and average production for the heterocyclic PAI at this
plant.
A synthetic pyrethrin manufacturing facility currently discharges
a low volume of highly concentrated pyrethrin process wastewater to a POTW
without treatment. Due to the high concentration of pyrethrin in the plant's
discharge water, and the relatively high toxicity of this PAI, treatment prior
to disposal is required. Because the flow rate of the waste stream is low,
off-site incineration, rather than implementation of on-site treatment, has
been determined to be the treatment option with the least cost.
7.4.3 Calculation of Effluent Limitations Guidelines Under NSPS
NSPS represents the most stringent numerical values attainable
through the application of the best available demonstrated treatment
technologies. The reasonableness of costs to implement the best treatment
technologies for new plants is considered when setting NSPS limitations. EPA
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is proposing NSPS limitations for all the PAIs for which BAT limitations are
being proposed. The pesticide chemicals industry is unique, however, in that
expansion or changes in the industry are not likely to occur through the
manufacture of currently-produced PAIs at new facilities. Instead, it is more
likely that only new PAIs would be manufactured at new facilities. Since the
nature of the treatability of new PAIs cannot be readily predicted, the Agency
does not believe it is possible to develop NSPS guidelines for treatment of
new PAIs.
The Agency considered four options for NSPS limitations. Two
options are the same as the two BAT options discussed previously: basing
limitations on the demonstrated efficacy of BAT control technologies and
requiring zero discharge. The other two options include basing limitations on
the treatment performance data available for BAT technologies modified to
reflect the capability for wastewater flow reduction at new facilities, and
basing limitations on BAT treatment, flow reduction, and application of
membrane filtration technology for further pollutant reduction.
As part of EPA's evaluation of options for NSPS/PSNS PAI
guidelines, the Agency investigated trends in reduction of contaminated
wastewater discharges by newer manufacturing facilities. To derive the
average flow reduction achieved, the Agency compared the 1977 Census industry
responses with the 1986 Census responses to determine which PAI processes in
operation in 1986 were not in operation during or before 1977. For
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Subcategory A, EPA identified 36 processes at 29 plants which appear to have
started-up since 1977.
EPA determined the total process wastewater flow to treatment for
each product, and then calculated the average flow to treatment per pound of
product for both older (pre-1977) and newer (post-1977) plants. EPA did not
include flows identified as storm water because the amount of stormwater is
not related to production process or production rate. (There will be higher
storm water flows in rainy areas of the country than in arid areas.)
"Older" (pre-1977) processes manufactured 737 million pounds of
PAIs per year, and generated 1,141 million gallons of total process
wastewater, of which 801 million gallons were contact wastewater. This
results in production normalized wastewater discharges of 1.55 gallons per
pound of PAI for total process wastewater. The corresponding "newer" (post-
1977) processes manufacture 94 million pounds of PAIs per year, and generate
104 million gallons of total process wastewater. This results in production
normalized wastewater discharges of 1.11 gallons per pound of PAI for total
process wastewater.
Between the "Older" and "Newer" plants, there is a difference of
0.44 (1.55-1.11) gallons per pound in total wastewater discharged,
representing a 28% reduction in flow.
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This reduction reflects both the higher degree of source
segregation practiced in newer processes, as well as a trend toward processes
generating only scrubber or stripper overheads through the use of closed loop,
solvent recovery systems. Newer facilities also incorporate a greater degree
of segregation between contact streams resulting from pre-PAI formation steps
and post-PAI formation steps in the processes. It is clear that selective
treatment using PAI destruction/removal technologies of only contaminated
wastewater streams can also reduce the flow to and therefore the cost of PAI
treatment processes. Source segregation reduces the amount of PAI-
contaminated wastewater requiring treatment by a PAI destruction/removal
technology. As a result, the size and throughput as well as the corresponding
cost of the PAI treatment step are reduced in newer facilities.
There are two factors which affect the projected flow reductions
achievable. First, the pesticides produced at the post-1977 plants typically
are new PAIs instead of new production of PAIs already being manufactured. As
a result, it is generally not possible to directly compare wastewater flow
rates from "Old" and "New" plants manufacturing the same PAI. "New" plants,
however, would have the capability to better segregate wastewater streams and
therefore minimize the flow rate of PAI-contaminated wastewater to PAI
treatment. Therefore, EPA believes that flow reduction equal to or greater
than 28% is achievable (except as described below for two PAIs), since
industry has already demonstrated this reduction in the newer plants. Second,
despite dividing the industry into pre- and post-1977 processes, some of the
flows documented as pre-1977 values may in fact already reflect some flow
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reduction due to process modifications which have reduced or further
segregated flow. Because information concerning modifications is not readily
available, these changes are not included in this analysis, but it is possible
that additional data would document a higher overall flow reduction than 28%
from the pre-1977 plants.
The Agency is proposing NSPS effluent limitations for
Subcategory A PAIs to be the BAT limitations modified by 28% flow reduction
(except as described below). In other words, NSPS for each PAI with a
numerical BAT effluent limitation is equal to the BAT limit multiplied by
0.72. The Agency decided not to equate the NSPS limitations with the BAT
limitations, because EPA believes that flow reduction has been demonstrated
and is achievable. In addition, because flow reduction may decrease the BAT
treatment costs, new plants will likely include flow reduction as an integral
part of the plant design. The Agency decided not to require zero discharge of
process wastewater pollutants as the NSPS limitations because the costs and
associated economic impacts of this option are considered to be essentially
the same as those for BAT Option 2, since the costs of on-site or off-site
incineration (and associated transportation costs) and recycle/reuse would be
the same at new and existing plants. The NSPS zero discharge option, like BAT
Option 2, therefore would be extremely expensive. The Agency proposes to
reject this option because the economic impact of this option would be too
severe. The Agency decided not to base NSPS on the addition of membrane
filtration technology to BAT treatment plus flow reduction because the removal
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levels that this technology can achieve have not been demonstrated at any
pesticide chemicals manufacturing plant.
There are two PAIs (carbofuran and DEF) being proposed for
regulation (with non-zero limitations) that are being produced at plants or
process lines constructed after 1977. Data from these newer plants/processes
show that they have achieved flow reductions of at least 28% compared to
similar production processes employed at older plants. Therefore, because
there is no information demonstrating that further flow" reductions are
possible, EPA is setting the proposed NSPS limitations for these two PAIs
equal to the proposed BAT limitations. In addition, equivalent NSPS
limitations are being set for merphos and DEF, because they are analytically
indistinguishable PAIs.
The Agency has determined that limitations that are more stringent
then BAT limitations required for existing plants can be achieved both
technically and economically. These limitations provide for reduction of
pollutants discharged into the environment beyond that which is achieved by
BAT. In addition, enhanced cross-media pollution control would be realized,
due to the reduction in wastewater flow prior to treatment.
7.4.4 Analysis of POTW Pass-Through for PAIs
Indirect dischargers in the pesticide manufacturing industry, like
the direct dischargers, use as raw materials and produce as products or
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byproducts, many nonconventional pollutants (including PAIs) and priority
pollutants. As in the case of direct dischargers, they may be expected to
discharge many of these pollutants to POTWs at significant mass or
concentration levels, or both. EPA estimates that indirect dischargers of
organic pesticides annually discharge approximately 110,000 pounds of PAIs and
29,000 pounds of priority pollutants to POTWs.
EPA determines which pollutants to regulate in PSES on the basis
of whether or not they pass through, interfere with, or are incompatible with
the operation of POTWs (including interference with sludge practices) The
Agency evaluates pollutant pass through by comparing the pollutant percentage
removed by POTWs with the percentage removed by BAT technology applied by
direct dischargers. A pollutant is deemed to pass through POTWs when the
average percentage removed nationwide by well-operated POTWs (those meeting
secondary treatment requirements) is less than the percentage removed by
directly discharging pesticides manufacturing facilities applying BAT for that
pollutant.
There is very little empirical data on the PAI removals actually
achieved by POTWs. Therefore, the Agency is relying on lab data to estimate
the PAI removal performance that would be achieved by biotreatment at well-
operated POTWs applying secondary treatment. The results of this laboratory
study are reported in the Domestic Sewage Study (DSS) (Report to Congress on
the Discharge of Hazardous Waste to Publicly Owned Treatment Works, February
1986, EPA/530-SW-86-004). The DSS provides laboratory data under ideal
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conditions to estimate biotreatment removal efficiencies at POTWs for
different organic PAI structural groups.
For each of these PAI structural groups, the DSS shows that BAT
removal efficiencies are considerably greater than the PAI removals achieved
by biotreatment under laboratory conditions (99% removal by BAT versus an
optimistic estimate of 50% or less removal by the POTW as reported in the
DSS). Results of this analysis indicate that organic PAIs that could be
efficiently removed by pretreatment technologies would pass through the
treatment systems at POTWs.
In addition to pass-through, many of the pollutants in pesticide
manufacturing wastewaters are present at concentrations which may inhibit
biodegradation in POTW operations. In some cases, discharges into POTWs have
caused severe upsets at POTWs resulting in documented pass-through of PAIs and
operational problems at the POTWs (a more detailed analysis is presented in
the public record DCN 4002).
7.4.5 Calculation of Effluent Limitations Guidelines Under PSES and PSNS
Based on the results of the pass-through analysis, EPA is
proposing PSES limitations for the same PAIs that are receiving BAT
limitations. Since indirect discharging organic pesticide manufacturing
facilities generate wastewaters with similar pollutant characteristics as
direct discharging facilities, the same treatment technologies discussed
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previously for BAT are considered applicable for PSES. The Agency considered
the same two limitation development options as for BAT: basing limitations on
the demonstrated efficacy of BAT control technologies and requiring zero
discharge. EPA is proposing PSES limitations based on the first option;
setting PSES equal to BAT. Under this option, PSES for organic PAIs would be
set equal to BAT guidelines based on the use of hydrolysis, activated carbon,
chemical oxidation, resin adsorption, solvent extraction, and/or incineration.
This option is economically achievable and greatly reduces pollutants
discharged into the environment, as pollutants not recycled or reused are
destroyed by treatment. Option 2 is proposed to be rejected because of the
cross-media implications of the transfer of pollutants as well as the severe
economic impacts that would result from implementing this option.
Pretreatment standards for new sources were based on the pass-
through analysis utilized in the development of the PSES limitations and on
the flow reduction methodology utilized in the development of NSPS
limitations. The pass-through analysis demonstrated the need for pretreatment
standards equivalent to the standards set for direct discharging pesticide
manufacturing facilities. The flow reduction methodology demonstrated the 28%
reduction in wastewater flow generated by "new" (post-1977) pesticide
manufacturing facilities/processes. Since new indirect discharging
facilities, like new direct discharging facilities, have the opportunity to
incorporate the best available demonstrated technologies, including process
changes, in-plant controls, and end-of-pipe treatment technologies, the PSNS
limitations should be equivalent with NSPS limitations. The same technologies
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discussed previously for BAT, NSPS, and PSES are available as the basis for
PSNS. Proposed PSNS for Subcategory A are based on the proposed PSES
technologies, modified to reflect the flow reduction capable at certain new
facilities. EPA also considered the zero discharge option, but it was
rejected due to the resulting severe economic impact.
7.5 EFFLUENT LIMITATIONS DEVELOPMENT FOR PRIORITY POLLUTANTS
This section discusses the development of effluent limitations
guidelines and standards for priority pollutants in Subcategory A of the
pesticide chemicals manufacturing industry. As discussed in Section 13, EPA
is proposing to reserve further regulations for Subcategory B priority
pollutants.
EPA is proposing effluent limitations and pretreatment standards
for 28 priority pollutants. For 23 of these 28 priority pollutants, EPA is
relying on the OCPSF database to set limits that are identical to the limits
set for these pollutants in the OCPSF guidelines. For four other priority
pollutants which were not regulated under OCPSF and for which there are no
treatment performance data, EPA is using limitations set in the OCPSF
guidelines for other priority pollutants that are deemed to have similar
"strippabilities". This is the same procedure used in the OCPSF rulemaking
for developing limitations when performance data was lacking for certain
priority pollutants. Limitations for one priority pollutant, cyanide, are
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proposed based on actual long-term full-scale data from the pesticide
industry.
For 23 priority pollutants, the Agency proposes to transfer BAT
limitations form the OCPSF category. As discussed earlier in Section 3, 55 of
the 90 pesticide chemicals manufacturing facilities also manufacture compounds
regulated under the OCPSF category. Typically, wastewaters from pesticide
manufacture are ultimately commingled with OCPSF wastewaters generated at the
site and treated in the same end-of-pipe (EOP) wastewater treatment systems.
Even though pesticide wastewaters may be pre-treated to remove PAIs, their
priority pollutants are removed in the same EOP treatment system that removes
priority pollutants from OCPSF wastewaters.
7.5.1 Calculation of Effluent Limitations Guidelines Under BAT
In the OCPSF rulemaking, EPA identified treatment technologies
that have been shown to be effective and the best available for removing
priority pollutants from commingled OCPSF and pesticide manufacturing
wastewater streams. EPA has determined that 23 priority pollutants (22
volatile and semi-volatile organic priority pollutants and lead) regulated in
the OCPSF guidelines also may be found in wastewater streams from pesticides
manufacturing. EPA therefore is proposing that the BAT limitations for these
23 pollutants be directly transferred to the pesticide chemicals manufacturing
category as BAT effluent limitations guidelines. Four priority pollutants
(bromomethane, tribromomethane, bromodichlormethane, and
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dibromochloromethane), detected at significant concentrations in pesticide
manufacturing wastewaters, were not regulated for BAT under the OCPSF
category. EPA is proposing to set BAT effluent limitations for those four
pollutants by transferring OCPSF limitations for compounds that have similar
strippabilities. BAT limitations for cyanide are being proposed based on
treatment data from pesticide manufacturing facilities.
7.5.1.1 Volatile and Semi-Volatile Organic Pollutants
In the OCPSF rulemaking, EPA based its BAT limitations and costs
for volatile organic priority pollutants on in-plant steam stripping alone for
plants without end-of-pipe biological treatment. For the volatiles limited on
the end-of-pipe biological treatment subcategory, the combination of steam
stripping and end-of-pipe biological treatment were used for limitations and
costing. The data used to derive these limits for the end-of-pipe biological
treatment subcategory were taken from plants which exhibited good volatile
pollutant reduction across the entire wastewater treatment system. To
establish limits for the non-end-of-pipe biological treatment subcategory, EPA
used steam stripping data for volatile organic pollutants collected from
plants that either did not have end-of-pipe biological treatment or provided
data on the separate performance of the in-plant steam stripping treatment
technology.
Steam stripping employs super-heated steam to remove volatile
pollutants of varying solubility in wastewater. Specifically, the technology
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involves passing super-heated steam through a preheated wastewater stream
column packed with heat resistant packing materials or metal trays in counter-
current fashion. Stripping of the organic volatiles constituents of the
wastewater stream occurs because the organic volatiles tend to vaporize into
the steam until their concentrations in the vapor and liquid phases (within
the stripper) are in equilibrium.
Steam strippers are designed to remove individual volatile
pollutants based on a ratio (Henry's Law Constant) of their aqueous solubility
(tendency to stay in solution) to vapor pressure (tendency to volatilize).
The column height, amount of packing or number of trays, the operating steam
pressure and temperature of the heated feed (wastewater) are varied according
to the strippability (using Henry's Law Constant) of the volatile pollutants
to be stripped. Volatiles with lower Henry's Law Constants require greater
column height, more trays or packing material, greater steam pressure and
temperature, more frequent cleaning and generally more careful operation than
do volatiles with higher strippability. (See the final OCPSF rule, 52 FR
42540, for a further description of steam stripping technology).
The final OCPSF data consisted of performance results from 7 steam
strippers at 5 plants for 15 volatile organic pollutants. The data were
edited to ensure only data representing BAT level design and operation were
used to develop limitations.
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The Agency also identified two other treatment technologies as the
technology basis for the removal of certain semi-volatile organic pollutants
under the OCPSF regulations. These two technologies are activated carbon
adsorption and in-plant biological treatment. EPA also relied on the ability
of end-of-pipe biological treatment to achieve some additional pollutant
removal beyond carbon adsorption and in-plant biological treatment. See 52 FR
42543-44 for a discussion of these technologies and a description of the data
that EPA relied on for setting the OCPSF limitations on these semi-volatile
organic pollutants. Two of the pollutants (phenol and 2,4-dimethylphenol) are
among the 22 OCPSF organic priority pollutants that also occur in pesticides
manufacturers wastewaters and for which EPA is proposing today to set
limitations that are transferred from the OCPSF rule.
For some of the OCPSF volatile and semi-volatile pollutants
(including some of the ones for which limitations are also being proposed in
today's notice for pesticides manufacturers), the available effluent data
consisted of measurements so low that very few exceeded the analytical
threshold level (10 ppb, the minimum level for most pollutants see
Section X, Comment 7 of the OCPSF final rule, 52 FR 42562, November 5, 1987).
Since variability factors could not be calculated directly for these
pollutants, in the OCPSF rule, EPA transferred variability factors from
related pollutants (see 52 FR 42541). EPA determined that the data from these
plants provided an adequate basis to set limitations for the OCPSF industry.
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EPA finds that it is appropriate to transfer the limitations for
volatile and semi-volatile organic pollutants in the OCPSF industry to this
rulemaking to set limitations on the same pollutants in the wastestreams of
pesticides manufacturers. The technologies identified (steam stripping
technology, in-plant biological treatment, and activated carbon adsorption,
combined in some cases with end-of-pipe biological treatment) are available at
pesticides manufacturing plants (these technologies are all already in use at
certain pesticides manufacturing plants or combined OCPSF/pesticides
manufacturing plants). In addition, these technologies will be capable of
removing from pesticides manufacturers' wastewaters the amounts of volatile
and semi-volatile pollutants necessary to meet the transferred limitations.
Specifically, EPA finds that applying these technologies to pesticides
manufacturers wastewaters will result in treatability levels for volatile and
semi-volatile organic pollutants that are similar to the treatability levels
of these same pollutants in OCPSF wastewaters. EPA stated in the OCPSF rule
that although the degree to which a compound is stripped can depend to some
extent upon the wastewater matrix, the basis for the design and operation of
steam strippers is such that matrix differences were taken into account for
the compounds the Agency evaluated. A sort of the strippability data
confirmed that process wastewater matrices in the OCPSF industry generally do
not preclude compliance with the concentration levels established in the OCPSF
rulemaking (52 FR 42540-41). The wastewater matrices in the pesticides
manufacturers industry are generally similar to those in the OCPSF industry,
and so they generally would not preclude compliance with the concentration
levels being proposed for volatile pollutants.
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As explained above, the proposed rule does not derive limits
independently for 23 priority pollutants but expressly relies on the OCPSF
rulemaking and accompanying record for setting these limits. In the
litigation over the OCPSF rule, an issue arose over EPA's methodology for
setting these priority pollutant limits. Specifically, the issue concerned
EPA's decision to establish one set of priority pollutant limits for direct
discharger plants that do not use end-of-pipe biological treatment and a
different set of limits for those direct dischargers that do.
Some, but not all, OCPSF plants use end-of-pipe biological
treatment to meet their limitations on conventional pollutants. These plants
rely on other technologies to reduce their priority (toxic) pollutants;
however, the biological treatment has the incidental effect of removing some
further amount of the priority pollutants. The OCPSF rule, therefore,
accounts for this further removal of toxics by the end-of-pipe biotreatment
systems by establishing one set of priority pollutant limitations for those
facilities that do not use end-of-pipe biotreatment (the OCPSF "Subcategory J"
limitations) and a different, generally more stringent set of limitations for
those plants that do (the OCPSF "Subcategory I" limitations).
In the OCPSF litigation, NRDC claimed that EPA had not
sufficiently aired this methodology for comment. Also, on the merits, NRDC
claimed that EPA's approach is improper because it allows facilities to meet
fewer and less stringent limits on the priority pollutants by choosing not to
use end-of-pipe biological treatment to treat their conventionals. The court
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remanded this issue to EPA for further notice-and-comment proceedings, and the
Agency is in the midst of a new rulemaking to resolve this issue for the OCPSF
rule.
On remand, EPA reconsidered this methodology and issued a
re-proposal in December, 1991 that adopts the same approach that was
originally promulgated (56 FR 63897). The re-proposal discusses NRDC's claims
and explains in detail why EPA still believes the original approach is
appropriate. To summarize that discussion, the Agency recognized that certain
OCPSF facilities, such as chlorosolvent plants, have BOD3 levels that are too
low to allow for effective biological wastewater treatment and do not require
end-of-pipe biological treatment to meet their BPT limitations. A biological
system cannot operate effectively without a sufficient mass of organic
biodegradable material to sustain the microorganisms that consume the
biodegradable waste. EPA concluded that these plants should not have their
BAT effluent limitations based on the performance of in-plant controls and
end-of-pipe biological treatment. Therefore, the OCPSF Subpart J effluent
limitations were based solely on the performance of in-plant controls such as
steam stripping.
NRDC urged the EPA to establish a raw waste "floor" level below
which biological end-of-pipe treatment is not appropriate or to limit the
applicability of Subpart J to those categories of OCPSF production that tend
to have low raw waste levels. This suggestion appeared logical in theory but
EPA concluded that it was not feasible in practice. The Agency explained
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that, due to the wide variety and complexity of raw materials and processes
used and of products manufactured in the OCPSF industry, it would be nearly
impossible to analyze each plant's wastestream to determine a technically
defensible BOD5 floor, or series of floors for different plants with different
operating and wastewater characteristics, especially when the literature does
not provide a theoretical basis for a BOD5 cutoff.
EPA also determined that the BOD5 floor suggested by NRDC was not
necessary. Common sense and economic considerations dictate that OCPSF plants
will not opt to forego end-of-pipe biological treatment in order to qualify
for the Subpart J BAT limitations. Moreover, the Agency found that Subpart J
will not result in significantly greater environmental loadings than
Subpart I.
In addition, EPA found that NRDC's suggestions could result in
undesirable treatment decisions. The Agency's OCPSF regulatory scheme gives
the regulated community some degree of management discretion in selecting
appropriate combinations of source controls or pollution prevention techniques
as well as appropriate in-plant or end-of-pipe wastewater management and
treatment techniques. The Agency is concerned that the attempt to establish a
BOD5 floor would result in plants making undesirable treatment decisions that
the Agency did not intend; for example, a plant that has already installed or
is considering installing in-plant product and by-product recovery may feel
compelled to reduce the effectiveness of in-plant control to ensure that
sufficient organic matter is available to be able to operate an end-of-pipe
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biological treatment system, or to operate such a system in a cost-effective
fashion.
The proposed rule for the pesticides chemicals manufacturers, by
using limitations for priority pollutants that are directly transferred from
the OCPSF rulemaking, follows the OCPSF approach of setting two sets of
limits, one for plants that use end-of-pipe biological treatment and one for
plants that do not. As with the OCPSF industry, some pesticides manufacturers
fall into each category. EPA is proposing this approach in order to be
consistent with what was promulgated (and now re-proposed) for OCPSF.
Moreover, consistency with the OCPSF regulations is necessary in some cases to
avoid having two different sets of limits applicable to the same pollutant
being discharged by a single combined OCPSF/pesticides plant. EPA expects
that any change it may adopt in this approach when the December, 1991 OCPSF
re-proposal is made final will also be reflected in the final pesticides
manufacturing rule.
EPA notes that there are two priority pollutants (2-chlorophenol
and 2,4-dichlorophenol) for which limitations are proposed for plants that use
end-of-pipe biological treatment but for which limitations are not proposed
for plants that do not use end-of-pipe biological treatment. This reflects
the approach used in the OCPSF rulemaking. In the OCPSF rule, limitations for
these two priority pollutants were not proposed for plants without end-of-pipe
biological treatment.because of a lack of treatability data and because a
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transfer of limitations was not possible (see the OCPSF Development Document,
Section 7).
In this proposal for pesticides chemicals manufacturers, even for
those plants that use end-of-pipe biological treatment, the costs of that
treatment were not counted as part of the costs of meeting BAT. This is
because end-of-pipe biological treatment is already being applied by these
plants to meet their existing BPT limits.
In considering NRDC's suggestions, EPA concluded in the December,
1991 OCPSF re-proposal that the OCPSF point source category was too complex
for the Agency to approach perfect plant-specific knowledge of the industry.
The Agency noted, however, that in a smaller, less complex industry it might
be possible to assess more completely the intricacies of each plant's or each
plant category's treatment system. The pesticides manufacturing industry does
contain a fewer number of plants than the OCPSF industry, but the types of
products and processes are nevertheless varied and complex. EPA therefore
finds that, as with the OCPSF rulemaking, plant-specific knowledge of
pesticides manufacturing plants is similarly infeasible and it is thus
appropriate to follow the OCPSF rulemaking approach in this proposed rule.
7.5.1.2 Brominated Organic Pollutants
Four priority pollutants (bromomethane, tribromomethane,
bromodichlormethane, and dibromochloromethane), detected at significant
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concentrations in pesticide manufacturing wastewaters, were not regulated for
BAT under the OCPSF category. EPA is proposing to set BAT effluent
limitations for those four pollutants by transferring OCPSF limitations for
compounds that have similar strippabilities.
Of the four brominated organic compounds found in pesticide
manufacturing process wastewater, one, bromomethane, was excluded from
consideration under OCPSF guidelines because it was determined to be uniquely
related to specific sources. The other three, tribromomethane,
bromodichloromethane, and dibromochlormethane, were excluded because they were
only detected in trace amounts and therefore not expected to result in toxic
effects. However, all 4 of these priority pollutants may be expected in the
discharge from processes which manufacture brominated PAIs such as bromacil
and bromoxynil, and 1 or more were detected in 7 of 20 EPA sampling episodes
between 1988 and 1990.
Based on comparisons of Henry's Law coefficients for these
compounds with other priority pollutants which were regulated under OCPSF, it
appears that all may be removed by steam stripping. Two, bromomethane and
bromodichloromethane, would be identified as "highly strippable" under the
criteria utilized during OCPSF compliance costing, while the others,
dichlorobromomethane and tribromomethane, would be identified as "medium
strippable."
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BAT guidelines are being proposed based on a comparison with
compounds having Henry's Law coefficients above and below the brominated
compound. These compounds, with their Henry's Law coefficients (as listed in
the OCPSF development document, in mg/1 in air/mg/1 in water), are as follows:
Brominated Compound
Bromomethane
Tribromomethane
Bromodichloromethane
Dibromochloromethane
8.21
0.023
0.10
0.041
Regulated Compound (high)
none
Naphthalene
Chloroform
1 , 2-Dichloroethane
0.019
0.14
0.046
Regulated Compound (low)
1 , 1-Dichloroethene
Hexachlorobenzene
Methylene Chloride
1,1, 2-Tetr achloroethane
7.92
0.028
0.096
0.032
EPA decided to base BAT concentration guidelines on the compounds closest to
the Henry's Law coefficients of the brominated compound which have the highest
limitations under OCPSF. These concentrations are as follows:
Brominated Compound
Bromomethane
Tribromomethane
Bromodichloromethane
Dibromochloromethane
Regulated Compound
1, 1-Dichloroethene
Naphthalene
Methylene Chloride
1, 2-Dichloroethane
Dally Max
25 ppb
59 ppb
89 ppb
211 ppb
Four -day Max
16 ppb
22 ppb
40 ppb
68 ppb
7.5.1.3
Lead
The OCPSF rule set a concentration-based limitation on lead, to be
applied only to the flows discharged from metals-bearing process wastewaters
(see 52 FR 42542). Compliance could be monitored in-plant or, after
accounting for dilution by nonmetal-bearing process wastewater and non-process
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wastewaters, at the outfall. The OCPSF rule stated that the permit writer
may, on a case-by-case basis, provide additional discharge allowances for
metals in non-OCPSF process or other wastewaters where they are present at
significant levels. When BAT limits have not been established, these
allowances must be based upon the permit writer's best professional judgment
of BAT.
The OCPSF concentration limits for lead were based on the use of
hydroxide precipitation technology, which is the standard metals technology
that forms the basis for virtually all of EPA's BAT metals limitations for
metal-bearing wastewaters. Because very little OCPSF data on the
effectiveness of hydroxide precipitation technology were available, EPA
decided to transfer data for this technology from the Metal Finishing
Industry.
EPA finds that it is appropriate to transfer the limitations for
lead in the OCPSF industry to this rulemaking to set limitations on lead in
the wastestreams of pesticides manufacturers. The technology identified,
hydroxide precipitation, is available at pesticides manufacturing plants. In
addition, this technology will be capable of removing from pesticides
manufacturers wastewaters the amounts of lead necessary to meet the
transferred limitations.
Specifically, EPA finds that applying this technology to
pesticides manufacturers wastewaters will result in a treatability level for
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lead that is similar to the treatability level of lead in OCPSF wastewaters.
The concentrations of lead in pesticides manufacturers wastewaters are
generally in the range found at OCPSF plants. As discussed in the OCPSF rule,
this transfer of technology and limitations from the Metal Finishing Industry
Category to the OCPSF rule, and now to the pesticides manufacturers rule, is
further supported by the principle of precipitation. Given sufficient
retention time and the proper pH (which is achieved by the addition of
hydroxide, frequently in the form of lime), and barring the binding up of
metals in strong organic complexes (which are not present in pesticides
manufacturers wastewaters), a metal exceeding its solubility level in water
can be removed to a particular level that is, the effluent can be treated to
a level approaching its solubility level for each constituent metal. This is
a physical/chemical phenomenon that is relatively independent of the type of
wastewater (barring the presence of strong complexing agents) (see discussion
at 52 FR 42543).
7.5.1.4 Cyanide
The proposed limitations for total cyanide are not transferred
from OCPSF but instead are based on the median values of the effluent data
from treatment systems incorporating chemical oxidation and biological
treatment at two pesticide manufacturing facilities and five organic chemicals
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manufacturing facilities, along with effluent data from one pesticides
manufacturing facility with biological treatment only. The effluent data are:
Plant Type
A
A
A
B
B
B
B
B
Treatment
BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
# Analyses (# > DL)
703 (703)
2 (1)
3 (1)
6 (6)
1 (0)
4 (4)
1 (0)
25 (23)
Median = 0.0854 mg/L
Daily VF = 7.4
Four-Day VF - 2 . 6
Effluent Long -Term
Average (mg/L)
0.7398
0.0750
0.0147
0.2960
0.0100
0.4576
0.0100
0.0959
Daily Limit =0.64 mg/L
Monthly Limit =0.22 mg/L
Footnotes:
A Pesticide Manufacturing Plant BO Biological Oxidation
B Organic Chemical Manufacturing Plant CO Chemical Oxidation
7.5.2
Calculation of Effluent Limitations Guidelines Under NSPS
The Agency is proposing to set NSPS limitations equal to BAT for
priority pollutants discharged by Subcategory A pesticide manufacturing plants
because the limitations are concentration-based. The capability of reduced
wastewater flow at new plants would be taken into account by the permit writer
to arrive at mass-based permit limits.
7.5.3
Calculation of Effluent Limitations Guidelines Under PSES
To evaluate the need for PSES for the priority pollutants, EPA
relied on an analysis originally done to support the OCPSF regulations. (See
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Section 6 of the OCPSF Technical Development Document.) Prior to promulgation
of the OCPSF effluent guidelines, EPA conducted a study of well-operated POTWs
that use biological treatment (the "50-Plant Study"). The 50-Plant study
determined the extent to which priority pollutants are removed by POTWs. The
principal means by which the Agency evaluated pollutant pass-through was to
compare the pollutant percentage removed by POTWs with the percentage removed
to comply with BAT limitations.
Because some of the data collected for evaluating POTW removals
included influent levels of priority pollutants that were close to the
detection limit, the POTW data were edited to eliminate influent levels less
than 100 ppb and the corresponding effluent values, except in cases where none
of the influent concentrations exceeded 100 ppb. In the latter case, where
there were no influent data exceeding 100 ppb, the data were edited to
eliminate influent values less than 20 ppb and the corresponding effluent
values. These editing rules were used to allow for the possibility that low
POTW removals simply reflected the low influent levels.
EPA then averaged the remaining influent data and also averaged
the remaining effluent data for the POTWs. The percent removal achieved for
each priority pollutant was determined from these averaged influent and
effluent levels. This percent removal was then compared to the percent
removal achieved by BAT treatment technology. Based on this analysis, EPA
determined that 47 priority pollutants of the 63 priority pollutants regulated
under OCPSF passed-through POTWs. Not all of these priority pollutants are
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present in pesticides manufacturers wastewaters. As noted, 23 of the priority
pollutants present in OCPSF wastewaters are also present in pesticides
manufacturers wastewaters. The OCPSF pass-through analysis shows that 21 of
these 23 priority pollutants pass through; the only priority pollutants of
those 23 for which pass-through is not demonstrated are 2-chlorophenol and
2,4-dichlorophenol.
Consistent with the OCPSF rulemaking, EPA is setting the
pretreatment standards for existing sources for the priority pollutants equal
to the set of BAT limitations that applies to plants that do not have end-of-
pipe biological treatment. In the OCPSF pass-through analysis for setting
pretreatment standards, POTW removals were compared to BAT-level removal at
plants that did not have end-of-pipe biological treatment.
There are very little data to determine POTW removals for the four
brominated priority pollutants: bromomethane, bromoform (tribromomethane),
dicromochloromethane, and bromodichloromethane. However, these pollutants are
structurally very similar to chloromethane and chloroform (trichloromethane),
which were shown to pass through by the OCPSF analysis. In addition, EPA
sampling at pesticide plants where the brominated priority pollutants are
found shows that extensive volatilization occurs in sewers rather than removal
via treatment, and the Agency would expect similar volatilization to occur
when the pollutants are discharged to a POTW. This volatilization would not
occur with BAT treatment, which removes (and destroys or recycles) the
pollutants from the wastewater before volatilization can occur. Therefore,
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the Agency proposes to determine that pass-through does occur for these four
brominated priority pollutants.
Based on the 50-plant study, the average percent removal of
cyanide by well-generated POTWs achieving secondary treatment is about 54%
whereas, based on full-scale data, the BAT technology removes more than 99
percent. Therefore, pass through does occur for cyanide.
Based upon the above considerations, EPA has concluded that PSES
regulations are warranted for all of the pollutants regulated under BAT for
direct dischargers, except 2-chlorophenol and 2,4-dichlorophenol.
7.5.4 Calculation of Effluent Limitations Guidelines Under PSNS
The Agency is proposing PSNS limitations for 26 of the 28 priority
pollutants addressed under NSPS. As discussed under PSES, two priority
pollutants, 2-chlorophenol and 2,4-dichlorophenol, have not been shown to pass
through a POTW and therefore are not being proposed for regulation under PSNS.
EPA is proposing concentration-based PSNS limitations equal to the PSES
limitations.
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7.6 EFFLUENT LIMITATIONS DEVELOPMENT FOR CONVENTIONAL POLLUTANTS AND
COD
BPT limitations set in 1978 for Subcategory A PAIs control the
discharge of COD, BOD5, TSS, and pH when their presence in wastewaters results
from the manufacture of any PAIs, except for 25 PAIs specifically exempted.
As discussed in Section 9, EPA is today proposing to amend the BPT
applicability provision for Subcategory A PAIs to include 15 of these 25
previously excluded PAIs, as well as the organotin pesticides. As discussed
in Section 13, no BCT treatment technologies were identified that passed the
BCT cost test. As a result, the Agency is proposing to set the BCT
limitations for Subcategory A PAIs equal to the BPT limitations.
NSPS effluent limitations and standards would also be set equal to
BPT limitations but would reflect a reduction in wastewater flow of 28% in the
manner described above for PAIs.
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SECTION 8
ENGINEERING COSTS
8.0 INTRODUCTION
This section discusses the costs for treatment technologies for
the pesticide chemicals manufacturing industry for compliance with the BAT,
NSPS, and PSES/PSNS effluent limitations guidelines. This section also
describes the engineering costing methodology for specific treatment
technologies.
8.1 ENGINEERING COSTING
This section describes the costing methodologies used to develop
treatment costs for the treatment technology options upon which the effluent
limitations guidelines are based.
8.1.1 Cost Methodologies
First, the processes of each plant were evaluated to determine raw
pollutant discharges. Next, the pollutant discharge levels were compared with
the proposed effluent concentration levels for each of two options: the
achievable concentration levels in effluent from the treatment technology
identified as the best demonstrated and available for Option 1, and no
discharge of process wastewater pollutants for Option 2. Finally, the
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specific treatment technology or treatment technology sequence upon which the
proposed effluent concentration levels are based was selected and sized for
each individual process. The cost, both purchase price (capital cost) and
annual operation and maintenance cost (annual O&M cost), was then calculated
for the additional treatment.
8.1.2 Cost Procedures
Figures 8-1 and 8-2 diagram the procedures, followed in designing
additional treatment systems for individual pesticide manufacturing facilities
and calculating the costs for each system. Figure 8-1 presents the flowchart
used to determine treatment costs for PAIs, and Figure 8-2 presents the
flowchart used to determine treatment costs for priority pollutants.
Pesticide Active Ingredients
As presented in Figure 8-1, a treatment system has been designed
for each plant handling a PAI that requires additional treatment. For plants
that have multiple PAIs requiring additional treatment, a treatment train (or
trains) is designed such that PAIs requiring the same type of treatment (such
as activated carbon) are commingled and fed to the same system. This train is
then optimized, based on the wastewater flow rate through the system and
required PAI removal efficiencies, and costs are calculated for the resulting
8-2
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Figure 8-1
FLOWCHART USED TO DETERMINE TREATMENT COSTS FOR PAIS
UstofPAIs
Manufactured
a! Plant
Is PAI
to be regulated
under
BAT?
• plant
currently meeting
BAT performance in
PAI treatment?
Do any
other PAte made
at plant require same
BAT tech?
Can
astawater* from
different PAto be treated
same system
No PAI BAT Costs,
Proceed to
Priority PoHutam
Analyse*
Determine flow and
concentration of
PAI oomam mated
wntewater
Project Combined
Treatment System.
Determine flow and
concentration
Run Cost
Model
for PAi
Treatment
Technology
No
Have
all PAto made
at Plant been analyzed
compliance
I Yea
Proceed to
Priority Pollutant
Analyse*
8-3
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Figure 8-2
FLOWCHART USED TO DETERMINE TREATMENT COSTS FOR PRIORITY POLLUTANTS
Wanflfy Prtorty
Pollutants Produced
by PAI rrrig Procaaa,
or during PAI BAT
traatmant.
Projact Concentration
of Priority Pollutant in
Procaaa Wastewatar
and Plant DJaehanja
Priority PolL
below OCPSF trigger
for Procaaa
Priority Poll
in compteno* tf
Dlacnarget
No BAT cost
for Analynd
Priority Pollutant
Prtorty PolluUnt
require* costing tar
BATtrMBTiwrt
List atf PPoh mad*
in procMS which raquln
sain* tiMtmwit _
No
No BAT oast
for group of
priority potutants
Wai
Ttraatm
for PPoHi)
during OCPSF
Did
OCPSF
coating induda
capacity (or paat
Uit Priority Pollutants tor
All PM Manufacturing
Procauas - «v«Juata
oombinad traatmant
Can
PPolsfrom
iffarantPAIsbatr
in combinad
systam
Dotarmm* fbw and
Priority Pollutant concentrations
for combinad BAT
traatmant sy»tam
Datarmina flow and
Priority Pollutant concantrxtion
for procaaa spwatic BAT
traatmant ayatam
8-4
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design. This design and cost process is repeated for any other PAIs that
require treatment at the facility. The total treatment costs are then summed
for the facility, and individual PAI treatment costs are allocated by dividing
the applicable set of treatment costs by the PAI wastewater contribution,
which is based on daily average wastewater flow rates and annual production
days. Finally, BAT/PSES compliance monitoring costs are calculated for each
pesticide manufacturing facility. These monitoring costs will be incurred
regardless of whether a plant will require additional treatment. To be
conservative, EPA estimated monitoring costs for all plants regardless of
whether a plant already conducts monitoring of PAI concentrations.
Priority Pollutants
Additional treatment system design specifications and costs for
the removal of priority pollutants for individual pesticide manufacturing
facilities are calculated using the same procedure as the one used to
calculate treatment system design specification and costs for the removal of
PAIs. The only difference is that organic chemicals, plastics, and synthetic
fibers (OCPSF) limits and treatment technologies, such as steam stripping and
distillation, are applied to the priority pollutants (with the exception of
cyanide, which has a BAT/PSES limit specific to this rule). In some cases,
the current priority pollutant loadings for an individual facility might not
exceed OCPSF limits; however, the treatment technology installed to bring the
PAI levels within BAT/PSES compliance may actually increase one or more of
the priority pollutant loadings to levels exceeding OCPSF limits. One example
8-5
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of this is the application of alkaline chlorination (chemical oxidation to
remove dithiocarbamate PAIs; this treatment may result in elevated levels of
chlorinated hydrocarbon priority pollutants). In these instances, additional
treatment was designed and costed to bring these priority pollutant levels
into compliance with OCPSF limits. In the example above, plants costed for
alkaline chlorination were also costed for steam stripping, which was designed
to remove the resulting chlorinated hydrocarbons.
8.2 COST MODELING
This section provides a discussion of the cost model concept used
to calculate the compliance costs of the various treatment technologies. This
section also discusses the evaluation criteria and the cost models evaluated
by the Agency, and presents an in-depth explanation of the selected cost
model.
8.2.1 Model Evaluation
Cost Model Concept
Cost estimates of wastewater treatment systems are required to
determine the economic impact of the regulations. One method of estimating
costs would be to design the anticipated treatment system for each plant and
estimate the costs based on actual vendor quotes for that design. Multiple
designs and vendor price quotes would be gathered to estimate the costs for
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each treatment technology represented within the industry. This procedure,
however, is labor intensive for more than a few plants. A more practical (yet
still accurate) method to estimate costs is to develop a mathematical cost
model. In a cost model, design and vendor information is combined to develop
equations which describe costs as a function of system parameters. This
method permits iterative cost estimates to be calculated without requiring
detailed design and quote information for each iteration.
EPA developed a computer-based cost model to estimate the cost for
pesticide manufacturers to comply with the wastewater effluent guidelines.
EPA designed the model to be:
Capable of calculating the compliance costs for the
guidelines;
Computer-based and capable of multiple iterations to cost
various treatment options needed to evaluate and support
the regulation;
Detailed enough to calculate compliance costs for all the
plants and active ingredients impacted by BAT and PSES
guidelines;
Capable of estimating compliance costs for all the proposed
BAT treatment technologies over a range of characteristic
flow rates; and,
Capable of representing various treatment processes
individually or in combination. The model contains
independent modules to represent individual wastewater
treatment processes. The model is able to link the modules
together to represent an entire wastewater treatment
system.
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EPA supplemented this cost model with Lotus 1-2-3 spreadsheets set
up to calculate treatment costs for individual plants requiring activated
carbon, hydrolysis, and chemical oxidation treatment units. Lotus
spreadsheets were also used to calculate compliance monitoring costs.
Evaluation Criteria
A computer-based cost model incorporates design and cost equations
which represent the desired treatment processes. Several models currently
exist which estimate compliance costs for wastewater treatment facilities.
EPA investigated the applicability of these models to the pesticide
manufacturing industry. These models were chosen because either they are
available in the public domain and are used for costing wastewater treatment
facilities, or they have been used by EPA to estimate compliance costs for
other wastewater effluent guidelines.
EPA used the following criteria to evaluate seven existing cost
models for their potential use as the pesticide industry cost model:
(1) Does the model contain modules to represent wastewater
treatment technologies in use or planned for use in the
pesticide industry, and are the modules representative of
the flow rates for that industry?
(2) Can the model be adapted to represent the wastewater
treatment processes in use or planned for use in the
pesticide industry?
(3) Can the model change the base year for costs calculated in
the model?
8-8
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(4) Has the model been successfully used to estimate costs for
actual wastewater treatment facilities?
(5) Is sufficient documentation available, regarding the
assumptions and sources of data, such that the model is
credible and defensible?
(6) Is the model structured in a manner that is usable for the
pesticide industry, or are only the basic design and cost
equations usable?
Each model evaluated is discussed below.
Models Evaluated
1. CAPDET
The Computer Assisted Procedure for the Design and Evaluation of
Wastewater Treatment Systems (CAPDET) was developed by the U.S. Army Corps of
Engineers. The model is intended to provide planning level cost estimates to
analyze alternate design technologies for wastewater treatment plants. The
model includes modules which represent physical, chemical, and biological unit
treatment processes. Equations in the modules are based on rigorous engineer-
ing principles historically used for wastewater treatment system design. The
user may link the modules into trains which represent entire treatment
processes. The model then designs and costs various treatment trains and
ranks them with respect to present worth, capital, operating, or energy cost.
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Several of the modules within CAPDET (carbon adsorption, biologi-
cal treatment, clarification) represent treatment processes in use in the
pesticide industry. Although originally designed to cost municipal wastewater
treatment facilities, these modules are adaptable for the pesticide
manufacturing industry by entering design parameter values that are
representative of actual data from industry.
The cost basis for CAPDET relies on an input block of data
labelled unit costs. These data include construction cost indices (Marshall
and Swift, Engineering News Record) and unit costs for typical construction
and operating items (concrete, piping, operator labor, basic chemical feed-
stocks) which can be entered for any desired time frame. The program uses
these data to calculate the costs for the various modules. The cost output
can therefore be referenced to any year for which the data can be obtained.
EPA encourages the use of CAPDET in facilities planning and
provides for the acceptance of CAPDET generated cost estimates for POTWs.
Significant documentation (1,600 page design manual, 300 page users manual)
supports the CAPDET methodology. Design equations for each module are clearly
stated with references and examples provided. For these reasons, EPA selected
CAPDET as the primary model to estimate compliance costs for the pesticide
chemicals manufacturing industry. The individual modules were modified to
account for wastewater flows encountered at pesticide facilities.
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2. OCPSF
The model developed by EPA to support the Organic Chemicals and
Plastics and Synthetic Fibers (OCPSF) industry effluent guidelines consists of
three Lotus 1-2-3 spreadsheets, one each for the BPT/BAT/PSES treatment
technologies. Each spreadsheet contains cost equations for the treatment
processes which represent these technologies.
The cost equations were developed in the following manner. For
each treatment process, EPA selected a design module from a previously
available cost model. For example, CAPDET was used for carbon adsorption and
biological treatment, while a Water General Corporation cost estimation method
was used for steam stripping. EPA then collected and averaged data (pollutant
type and loading, design constants and physical parameters) from the OCPSF
industry to use as input values for the significant design parameters involved
in the selected modules. Using industry-specific data as input, EPA ran the
chosen module for typical wastewater flow rates and generated cost curves as a
function of flow. Cost equations were then derived from these curves. EPA
compared the estimated costs calculated from these equations to actual
industry costs and modified the cost equations as necessary to match the
actual data. The base year for the cost data was 1982. EPA then used these
modified equations in the spreadsheets.
Although the equations in the OCPSF model represent treatment
processes found in the pesticide industry, the equations were not used
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directly in the pesticide cost model because they were derived using OCPSF
data and 1982 costs.
3. Wastewater Treatment System Design and Cost Model
The Wastewater Treatment System Design and Cost Model was
developed by the EPA/EAD Metals Industry Branch. The model was used to
determine the cost of compliance for effluent guidelines for point source
categories for the following industries: aluminum forming, copper forming,
coil coating, non-ferrous metal forming, non-ferrous metal manufacturing
(phases I and II) and battery manufacturing.
One module (carbon adsorption) directly represents a treatment
process commonly used in the pesticide industry; the other modules represent
treatment processes which deal primarily with the precipitation and separation
of metals from aqueous streams. The direct application of these other modules
is therefore generally limited to metallo-organic pesticides. The cost data
were obtained from vendors using 1982 as a base year, and no method of
changing this base is provided.
Both this model and CAPDET represent actual wastewater treatment
systems by a combination of modules and they generate design and cost informa-
tion using this building block approach. Although EPA followed this approach
for the pesticide industry cost model, EPA did not use the individual cost
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modules included in this model because they were developed primarily for the
Metals Industry.
4. CORA
The Cost of Remedial Action Model (CORA), created by the EPA
Office of Emergency and Remedial Response, provides order of magnitude cost
estimates for remedial actions at Superfund sites. The model consists of two
parts: an expert system and a cost calculation program. The expert system
helps users select technologies for sites where physical data are not
available and where a specific remedial plan has not been established. The
costing program calculates capital, first-year operation, and site preparation
costs for various containment, removal, treatment, and disposal technologies
(modules) included in the model library.
Because CORA was developed as a model for Superfund remedial
actions, many of the individual modules are not applicable to the pesticide
industry. Moreover, the modules which represent treatment technologies that
are potentially applicable to the pesticide manufacturing industry, such as
carbon adsorption, biological treatment, and off-site landfill, are not
designed to handle flow rates and wastewater characteristics typical in the
pesticide manufacturing industry. For these reasons, EPA did not use this
model to estimate compliance costs for the pesticide manufacturing industry.
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5. ESE Cost Estimation Method
Previous work in developing effluent guidelines for the pesticide
industry included cost of compliance estimates. The estimates consisted of a
set of sizing and cost equations for each of the treatment processes used in
the pesticide industry.
However, no direct sources of data were provided for the sizing
and cost equations, nor was a method provided to vary the equations for a
different time period. For these reasons, EPA did not use these cost of
compliance estimates to develop the pesticide industry model.
6. RCRA Risk-Cost Model
The RCRA Risk-Cost Model was developed by EPA. The model is
designed to facilitate the development of regulations governing hazardous
waste treatment, storage, and disposal facilities. The model consists of a
database which can be viewed as a three-dimensional matrix. Each cell within
the matrix contains information related to a combination of wastes, an
environment, and a management practice (not facility).
Although the technologies for the model include carbon adsorption
and biological treatment, the equations for design and costing are too general
to be of specific use for the pesticide industry. Therefore, EPA did not use
this model to develop the pesticide industry cost model.
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7. ASPEN
The Advanced System for Process Engineering (ASPEN) was developed
at the Massachusetts Institute of Technology. The model is a computer aided
design package for chemical plants that performs engineering calculations to
either design a system or evaluate an existing one. Because the model is
primarily intended as a process simulation tool, it requires too much detailed
site-specific information for its design calculations to be useful in develop-
ing the overall cost estimates which will be required from the pesticide cost
model. In addition, steam stripping is the only applicable unit process for
the pesticide industry. For these reasons, EPA did not use ASPEN in the
development of the new pesticide cost model.
8.2.2 CAPDET
Based on the evaluation of existing models, CAPDET was judged to
be the most suitable for use in the development of a cost model for the
pesticide industry. EPA supplemented the CAPDET modules with Lotus 1-2-3
spreadsheets set up to calculate treatment costs for plants requiring
activated carbon, hydrolysis, and chemical oxidation treatment units. CAPDET
does not contain modules for hydrolysis nor chemical oxidation, and the Lotus
spreadsheet developed to estimate costs associated with activated carbon
systems is better suited to the pesticide industry than the CAPDET module.
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General Structure
The general structure of CAPDET includes independent programs
called modules which design and estimate the cost for various individual
wastewater treatment technologies. The model can combine these individual
modules to represent an entire treatment system and can estimate the costs for
that system. The model can also design several different systems and can rank
these systems with respect to construction, capital, annual operating, or
energy costs. The model includes input data files for influent and effluent
stream characteristics, cost data, and process specifications for individual
treatment technologies to further define the physical system which is to be
modelled. This general structure meets the requirements for the pesticide
industry cost model.
Design Methodology
Each module within CAPDET represents a specific wastewater
treatment technology. For each technology, the representative module is based
on specific equipment that accomplishes the desired treatment. Each module
includes a set of process design equations which mathematically represents the
physical and chemical processes which occur in the technology. The module
then calculates the number and size of the specific equipment, structural,
building, and piping items necessary to perform the physical and chemical
processes. These equations are based on general engineering principles
related to the individual treatment technology.
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For example, a. typical carbon adsorption system includes two steel
towers, filled with granular activated carbon, arranged in series flow. These
towers and associated feed, backwash, and carbon handling equipment comprise
the physical system required to perform carbon adsorption treatment of
wastewater. The CAPDET module for carbon adsorption therefore includes this
equipment. Based on the input data for a given system and the design
equations, the module determines the number of parallel pairs of adsorbers
required and sizes the individual towers. The module also designs the feed,
backwash, and carbon handling equipment. After the equipment is designed, the
module generates a cost estimate. (This methodology was followed in the Lotus
spreadsheets used to calculate activated carbon treatment costs for some of
the PAIs.)
Cost Methodology
The CAPDET model estimates the costs of purchasing, constructing,
operating, and maintaining wastewater treatment systems. To determine these
costs, CAPDET uses a combination of parametric and unit cost estimating
techniques. Parametric cost estimation calculates costs based on the price of
similar equipment at other locations, using equations in which the costs of
different sizes of equipment are calculated as a function of the wastewater
flow rate. Unit cost estimation calculates costs for individual elements by
multiplying the unit price for the element by the quantity of that element
used in the specific treatment technology, and then totalling the costs for
all of the various elements. For example, if CAPDET determines that multiple
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hydrolysis vessels are required at a plant, the model will estimate the cost
of one vessel based on the plant flow rate and multiply that cost by the
number of vessels required.
In CAPDET, the costs of constructing a wastewater treatment
facility are divided into three categories: unit process construction costs,
other direct construction costs, and indirect project costs. Unit process
construction costs account for the purchase and construction of all the
equipment and associated structures and buildings for a treatment technology
within battery limits. The battery limits are assumed to be the physical
dimensions of the treatment technology plus 5 feet. For example, the battery
limits for the activated carbon module include the carbon adsorption towers
and the feed, backwash and carbon handling systems. The unit process
construction costs for activated carbon therefore include the purchase and
construction of these items. Other direct construction costs are site-
specific items used to connect treatment technologies together to form a total
facility. Unit process construction costs and other direct construction costs
account for total construction costs. Indirect project costs are non-
construction costs including planning, design, administrative and legal
services, and other contingency factors. Indirect project costs are
calculated as a percentage of total construction costs.
To estimate unit process construction costs, CAPDET uses the
results of the process design calculations discussed in the design methodology
section. For each module, these calculations identify the following major
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items: (1) concrete and structures, (2) installed equipment, (3) buildings
and housings, and (4) piping and insulation. These items comprise
approximately 75% of the unit process construction costs, therefore, each of
these items is estimated separately. Electrical, control systems, and other
facilities costs are calculated as a factor of the major costs.
Concrete and structural items include reinforced concrete,
earthwork removal, and structural steel. CAPDET estimates these items by
multiplying the quantities required by the appropriate unit costs. Equipment
items include the purchase and installation of individual pieces of equipment,
along with the minor electrical work, minor piping, foundations, and painting
required for a complete installation. CAPDET uses parametric cost equations
to estimate the cost of equipment items. Buildings are based on the area
required for the given equipment. The area required multiplied by the unit
costs then provides the building cost estimate. Piping items include the
purchase and installation of piping, valves, fittings, and insulation. CAPDET
estimates these costs by multiplying the quantities required by the unit
costs.
CAPDET also calculates the operation and maintenance costs for a
facility after construction. The following items for each treatment
technology are considered: (1) labor requirements, (2) electrical energy for
operation, (3) materials, (4) chemicals and other supplies, and (5) the
replacement schedule. For each item in each technology, an equation relates
the amount of the item required to the flow rate used for the technology.
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CAPDET then multiplies the unit costs for the items by the calculated quantity
of the items to estimate operating and maintenance costs for a treatment
technology. For example, if CAPDET determines that 500 man-hours are required
annually to operate an activated carbon system at a specific flow rate, an
estimated hourly salary will be multiplied by 500 to account for annual labor
costs.
CAPDET accounts for cost changes over time using two methods.
First, if the actual costs for a specific item at a specific time are known,
the user may enter these costs in the model. These costs will then be used in
the cost estimating equations. Second, for unit costs that are not entered by
the user, the model multiplies the default value of the unit cost by a ratio
of a construction index. This ratio uses the values of the index for a
desired year and the default year. By multiplying the unit cost by this
ratio, CAPDET adjusts the default information to the base year desired by the
user. The following is a list of sources of where current, or relevant, year
data may be obtained:
(1) Dodge Guide for Estimating Public Works Construction Costs;
(2) Means Building Construction Cost Data;
(3) "Chemical Engineering," a bi-weekly magazine;
(4) "Journal Water Pollution Control Federation;" and
(5) "Engineering News Record."
8-20
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Input/Output
Various types of input data are required for the model to design
and estimate costs for wastewater treatment systems. To operate the model, a
user enters information into eight different input sections, which are:
(1) Facility selection: CAPDET design and cost modules are
separated by flow rate: large facilities that generate wastewater at flow
rates greater than 0.5 million gallons per day (MGD), and small facilities
that generate wastewater at flow rates below 0.5 MGD. The two flow ranges
include some but not all of the same modules. The user must select the
applicable facility size.
(2) Unit process specification: The CAPDET model contains
design and costing modules for 69 treatment technologies for large facilities
and 27 treatment technologies for small facilities (Tables 8-1 and 8-2) (The
pesticide cost model only uses a subset of these treatment technologies.) The
model labels these technologies "unit processes." In this section of input
data, the user may enter specific values for the design parameters in the
design equations for each of the individual modules. Because each module has
its own set of design equations, each module also has its own list of
parameters. If design parameter values are not entered by the user, default
data are provided by the module.
8-21
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Table 8-1
CAPDET LARGE FACILITY UNIT PROCESSES
1. Flotation thickening
2. Secondary clarification (activated sludge)
3. Aerated lagoon
4. Aerobic digestion
5. Anaerobic digestion
6 . Anion exchange
7 . Attached growth denitrification
8. Belt filter for sludge dewatering
9. Carbon adsorption
10. Cation exchange
11. Centrifugation
12. Chlorination
13. Secondary clarification (user-specified)
14. Coagulation
15. Comminution
16. Complete mix activated sludge
17. Contact stabilization activated sludge
18. User-specified costs for unit processes
19. Counter current ammonia stripping
20. Cross current ammonia stripping
21. Denitrification (suspended growth)
22. Secondary clarification (suspended growth denitrification)
23. Drying beds
24. User-specified liquid process
25. Equalization
26. Extended aeration activated sludge
8-22
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Table 8-1 (Continued)
CAPDET LARGE FACILITY UNIT PROCESSES
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
Filtration
First stage recarbonation (lime treatment)
Flocculation
Flotation
Filter press
Fluidized bed incineration
Gravity thickening
Grit removal
Sludge hauling and land
filling
High rate activated sludge
Primary clarification (two-step lime clarification)
Lagoons (stabilization ponds)
Microscreening
Multiple hearth incineration
Secondary clarification
Neutralization
Nitrification (suspended
(suspended growth nitrification)
growth)
Nitrification (rotating biological contactor)
Nitrification (trickling
Secondary clarification
filter)
(oxidation ditch)
Overland flow land treatment
Oxidation ditch
Plug flow activated sludge
Postaeration
Primary clarification
Secondary clarification
(pure oxygen)
8-23
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Table 8-1 (Continued)
CAPDET LARGE FACILITY UNIT PROCESSES
53. Intermediate pumping
54. Pure oxygen activated sludge
55. Rapid infiltration land treatment
56. Raw sewage pumping
57. Rotating biological contactor
58. Recarbonation
59. Secondary clarification (RBC)
60. Screening
61. Second stage recarbonation (lime treatment)
62. Slow infiltration land treatment
63. Sludge drying lagoons
64. Step aeration activated sludge
65. Secondary clarification (trickling filters)
66. Trickling filtration
67. User-specified sludge process
68. Vacuum filtration
69. Wet oxidation
8-24
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Table 8-2
CAPDET SMALL FACILITY UNIT PROCESSES
1. Activated sludge
2. Aerated lagoon
3. Bar screens
4. Chlorination
5. Coagulation
6. User-specified costs for unit processes
7. Drying beds
8. User-specified liquid process
9. Equalization
10. Filtration
11. Flotation
12. Intermittent sand filtration
13. Lagoons
14. Secondary clarification (oxidation ditch)
15. Overland flow land treatment
16. Oxidation ditch
17. Postaeration
18. Primary clarification
19. Intermediate pumping
20. Rapid infiltration land treatment
21. Raw sewage pumping
22. Secondary clarification (trickling filter)
23. Septic tanks and tile fields
24. Slow infiltration land treatment
25. Sludge drying lagoons
26. Trickling filtration
27. User-specified sludge process
8-25
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(3) Title card: The user may select a title for individual computer
runs and enter this title in this section of input data. The output data
sheets will then be identified by this title.
(4) Scheme descriptions: In this data section, the user may combine
several unit processes which, when taken together, simulate an entire
wastewater treatment system. The model will design and cost this combination
of unit processes as one scheme. If desired, a user may enter a total of four
different schemes for design and costing at one time.
(5) Waste influent characteristics: The CAPDET model manipulates and
tracks 20 characteristics of the wastewater as the treatment system is
designed (Table 8-3). The user may enter specific values for these
characteristics in the influent stream, or the model will enter default data
based on municipal wastes. The user must enter a value for the influent flow
rate, as no default value for this characteristic is provided.
(6) Desired effluent characteristics: The same 21 characteristics
that are discussed above may also be used to specify the effluent. The user
may specify values for these characteristics in the effluent if desired,
otherwise the values for them will be determined during the design of the
system. No default data are provided by the model for effluent stream
characteristics.
8-26
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Table 8-3
WASTE INFLUENT CHARACTERISTICS
Characteristics
Minimum Flow
Average Flow
Final/Initial
Maximum Flow
Temperature Summer/Winter
Suspended Solids
Volatile Solids
Settleable Solids
BODS
SBOD (Soluble)
COD
SCOD (Soluble)
pH
Cations
Anions
P04 (as P)
TKN (as N)
NH3 (as N)
N02 (as N)
N03 (as N)
Oil and Grease
Units
MGD
MGD
MGD
DEC C
MG/L
% of Suspended
ML/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
Default Values1
23/10
200
60
15
250
75
500
400
7.6
160
160
18
45
25
0
0
80
'Default values are from original CAPDET model, based on municipal waste.
Default values were used if the default values accurately represented the
actual wastewater characteristics. Where the actual wastewater
characteristics were significantly different, the actual characteristics were
used instead of the default values.
8-27
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(7) Unit cost data: The user may enter values for a total of 38
different cost indices, construction unit costs, operating unit costs, and
indirect cost category parameters (Table 8-4). Default values are provided
for each of these parameters, with the values being valid for 1989 in the
current version of the CAPDET program. The base year for the cost estimates
for the regulation is 1986; EPA therefore entered 1986 data for these unit
costs.
(8) Program control: The last section of input data provides the user
with a choice of determining the types of output that the model will generate
for a particular run (Table 8-5). The user may select various control
statements that will then provide the desired output data. Material balance
information, design information for the individual unit processes, and
summaries of cost information can all be generated by the model.
After the user enters the above data, the model executes the
design and cost estimating programs and generates the requested output.
8.2.3 Pesticide Industry Cost Model
After EPA evaluated the CAPDET model and determined that it could
serve as a suitable basis for the pesticide industry cost model, the Agency
adapted CAPDET to estimate costs for the installation of treatment
technologies in the pesticide manufacturing industry. EPA developed and added
8-28
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Table 8-4
UNIT COST DATA
Unit Cost
1.
2.
3.
4.
5.
6.
7-
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
Building Cost
Excavation
Wall Concrete
Slab Concrete
Marshall & Swift Index
Crane Rental
EPA Construction Cost Index
Canopy Roof
Labor Rate
Operator Class II Labor Rate
Electricity
Lime
ENR Cost Index
Handrail
Pipe Cost Index
Pipe Installation Labor Rate
8" Cast Iron Pipe
8" Cast Iron Pipe Bend
8" Cast Iron Pipe Tee
8" Cast Iron Plug Valve
Small City EPA Index
Land Cost
Miscellaneous Nonconstruction Cost
Administrative/Legal Cost
201 Planning Cost
1986 Value
$51.39/sf
4.19/cy
477.37/cy
105.04/cy
797.6
112.09/hr
403.0
8.61/sf
19.52/hr
16.32/hr
0 . 049/kWh
0.03/lb
4,290.51
40.94/lf
373.4
22.16/hr
36.00/lf
131.09 ea
156.09 ea
1,104.63 ea
228.7
*
5.00%
2.00%
3.50%
8-29
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Table 8-4 (Continued)
UNIT COST DATA
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
Inspection Cost
Contingency Cost
Profit and Overhead Cost
Technical Cost
Aluminum
Iron
Polymer
Blowers, rotary positive displacement
Blowers, multistage centrifugal
Blowers, single stage centrifugal
Replacement life for blowers (33)
Replacement life for blowers (34)
Replacement life for blowers (35)
2.00%
8.00%
22.00%
2.00%
**
**
**
**
**
**
**
**
**
*Land costs are calculated using a separate Lotus spreadsheet.
**These items are included in CAPDET, but are not required for pesticide
waste-water treatment modules.
8-30
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Table 8-5
PROGRAM CONTROL/OUTPUT SELECTION
Statement
Analyze
List Total
Present Worth
Construction
Project
Energy
Operation and Maintenance
Output Quantities
Summary
GO
Output
Prints unit process design data as program
is executed.
1. Prints schematic of trains.
2. Prints total costs of trains.
Prints unit process design data and
expected effluent data for different
trains, ranked by present worth cost.
Prints unit process design data and
expected effluent data for different
trains, ranked by total construction costs.
Prints unit process design data and
expected effluent data for different
trains, ranked by total project costs.
Prints unit process design data and
expected effluent data for different
trains, ranked by total energy costs.
Prints unit process design data and
expected effluent data for different
trains, ranked by operation and maintenance
costs .
Prints calculated quantities used to
estimate costs for each unit process.
Suppresses printing of design data, prints
only influent and effluent data and the
cost summary of each train.
No output is generated; however, this card
initiates the execution of the program and
it must be included as program control
input .
8-31
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modules for treatment technologies that were not part of the original CAPDET
model but were applicable treatment technologies for wastewater treatment in
the pesticide manufacturing industry. EPA also created three Lotus 1-2-3
spreadsheets for use in calculating treatment technology costs for activated
carbon, chemical oxidation, and hydrolysis systems. EPA also created a Lotus
spreadsheet for use in calculating compliance monitoring costs.
EPA obtained the necessary input data, design parameters, and unit
costs from industry sources, engineering references, and the public domain and
entered them into the model to generate the cost estimates for the pesticide
industry.
The following sections describe the design and cost methodologies
for the treatment technologies used in the pesticide manufacturing industry.
8.3 TREATMENT TECHNOLOGIES
Section 7A identified and described the wastewater control and
treatment technologies used or available for use to reduce or remove PAIs and
priority pollutants from wastewater discharged by pesticide chemical
manufacturers. This section describes how the cost model represents each of
these treatment technologies. Specific assumptions regarding equipment used,
flow ranges, input and design parameters, design and cost calculations, and
8-32
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disposal cost estimates for each technology are included for the following
technologies:
Activated carbon;
Biological treatment;
Chemical oxidation;
Contract hauling and incineration;
Distillation;
Equalization;
Filtration;
Hydrolysis;
Hydroxide precipitation;
Resin adsorption; and
Steam stripping.
This section also discusses how EPA estimated monitoring costs for compliance.
Individual plant treatment costs, for pesticide manufacturing
plants that will require additional treatment to meet the BAT/PSES limits
specified in Option 1, are listed on Table 8-6. The table lists the treatment
costs estimated for each plant, broken down by capital, operating and
maintenance, land, and residual waste disposal costs.
8-33
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Table 8-6
PESTICIDES OPTION 1 TOTAL COSTS BY PLANT
Plant ID
0028
0046
0180
0288
0402
0448
0563
0705
1063
1189
1287
1562
1606
1624
1820
1848
1900
2008
2080
2160
2302
2446
2507
Total Capital
Cost($)
2,613,673
0
0
0
468,626
0
0
0
450,379
3,761,850
0
0
0
0
0
1,628,512
0
0
0
218,295
40,697
0
2,546,993
Total O&M
Cost ($/yr)
1,932,135
40,730
31,785
13,680
57,470
83,690
47,200
4,760
35,193
2,105,966
1,920
55,550
1,180
6,540
23,920
1,662,363
34,860
15,540
25,880
79,825
248,904
35,580
1,162,428
Total Land
Cost ($/yr)
8,250
0
0
0
17,176
0
0
0
7,695
1,469
0
0
0
0
0
6,480
0
0
0
2,000
1,280
0
17,853
Residual
Waste
Disposal
Cost ($/yr)
303,602
0
0
0
134,534
0
0
0
26,000
102,200
0
0
0
0
0
107,959
0
0
0
0
0
0
633,374
8-34
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Table 8-6 (Continued)
PESTICIDES OPTION 1 TOTAL COSTS BY PLANT
Plant ID
2543
2561
2605
2767
2847
2865
3043
3061
3141
3169
3187
3203
3285
3329
3560
3668
3828
3864
3908
3944
3962
4024
4060
Total Capital
Cost($)
1,026,950
23,402
0
0
0
0
0
713,335
254,190
597,495
0
19,583
0
0
0
0
0
446,229
0
0
1,464,209
0
596,408
Total O&M
Cost ($/yr)
1,176,142
10,189
5,280
21,160
22,660
6,160
42,380
222,625
207,090
89,462
4,620
46,847
11,520
6,840
26,660
21,580
7,440
48,415
1,180
33,080
248,361
2,860
69,344
Total Land
Cost ($/yr)
5,400
0
0
0
0
0
0
5,970
2,600
5,970
0
17,660
0
0
0
0
0
6,480
0
0
9,740
0
3,588
Residual
Waste
Disposal
Cost ($/yr)
107,062
0
0
0
0
0
0
228,360
0
20,426
0
994
0
0
0
0
0
77,132
0
0
104,448
0
1,398
8-35
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Table 8-6 (Continued)
PESTICIDES OPTION 1 TOTAL COSTS BY PLANT
Plant ID
4168
4220
4248
4284
4462
4505
4863
4881
4989
5005
5247
5283
5461
5504
5522
Total Capital
Cost($)
0
925,987
0
663,692
2,488,845
119,012
0
555,136
175,015
45,734
2,346,222
0
0
0
0
Total O&M
Cost ($/yr)
8,500
300,262
12,098
154,689
3,207,192
18,043
1,180
404,795
62,351
82,413
367,481
48,880
27,340
10,620
31,605
Total Land
Cost ($/yr)
0
4,050
800
5,188
15,367
12,787
0
2,403
2,403
3,856
1,492
0
0
0
0
Residual
Waste
Disposal
Cost ($/yr)
0
6,169
0
120,888
8,410
7,000
0
0
0
75,189
0
0
0
0
0
8-36
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8.3.1 Activated Carbon
Activated carbon adsorption is a physical separation process in
which highly porous carbon particles remove a variety of substances from
water. Activated carbon can be used both as an in-plant process for the
recovery of organics from individual waste streams and as an end-of-pipe
treatment for the removal of dilute concentrations of organics from
wastewaters prior to discharge or recycle. Activated carbon can be used to
remove both PAIs and priority pollutants.
PhyslealEquipment
The activated carbon module in the pesticide industry cost model
is based on vendor information for packaged activated carbon adsorption units.
The module includes a packaged unit which consists of three skid-mounted
adsorption towers and the necessary pumps and piping for filling, feeding,
backwashing, and emptying the towers. In addition to the packaged equipment,
the module includes a feed tank for wastewater influent and a separate tank
for treated water to be stored for backwashing requirements.
Input and Design Parameters
EPA used the CAPDET activated carbon module to calculate costs for
activated carbon treatment systems designed to remove priority pollutants, and
the Lotus spreadsheet module to calculate costs for activated carbon treatment
8-37
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systems designed to remove PAIs. The CAPDET activated carbon module uses
influent flow rate and influent and effluent Chemical Oxygen Demand (COD)
concentrations as input for the cost estimation methodology. The Lotus
spreadsheet module uses influent flow rates and PAI concentrations (labelled
"COD" in the module) from the Facility Census submittals or from EPA sampling
data as input for the cost estimation methodology. Effluent COD
concentrations were set at the detection limit for the specific PAI in the
treated matrix. The adsorber capacity and the empty bed residence time were
used as design parameters. Values for empty bed residence time (EBRT) and
adsorption capacities were obtained from treatability studies, on waters
containing the specific PAI to be removed.
The modules determine the size of the activated carbon system as a
function of flow rate, influent and effluent concentrations, and empty bed
residence time. Adsorber capacity is used to determine the exhaustion rate of
the carbon given the flow rate and concentration difference. After the system
is sized, the modules then estimate the cost of the system, including
auxiliaries.
Cost Calculations
The modules calculate the capital and O&M costs of the activated
carbon system components as a function of the size of the system. Parametric
equations relate tower cost, pump costs, etc. to the system flow rate. The
results of the design calculations provide the sizes of the packaged unit and
8-38
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auxiliary equipment. Vendor supplied information was used to generate
equations that set costs as a function of size for these pieces of equipment.
With the sizes of the equipment determined from the design calculations, the
individual equipment costs were then calculated. The modules then summed the
individual costs and multiplied the total by a contingency factor to account
for miscellaneous other costs. These overall totals were the capital and
operation costs for the activated carbon system.
In these analyses, the activated carbon system capital costs
include influent surge tank and pumps; package granular activated carbon
system; backwash system and pumps, and enclosure for system. The O&M costs
account for operation and maintenance labor, energy requirements, materials
and supplies, and replacement carbon. The costs for each of these elements of
the O&M cost were developed from the vendor data associated with specific
activated carbon pre-packaged units. The activated carbon O&M costs include
operation and maintenance labor; maintenance materials; electricity or other
energy requirements; and replacement activated carbon (including regeneration
or disposal). Operation and maintenance costs were calculated on a PAI basis
and summed for total O&M cost.
8.3.2 Biological Treatment
Biological treatment is used in industrial wastewater treatment to
remove organic chemicals from wastewater streams through the use of biological
media. The biological treatment process used to develop compliance costs for
8-39
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the pesticide industry cost model is an extended aeration activated sludge
system.
Physical Equipment
The CAPDET module for extended aeration activated sludge was used
to calculate the compliance costs for the installation and operation and
maintenance of biological treatment processes for the pesticide chemical
manufacturers. In the extended aeration activated sludge module, the CAPDET
model assumes that a package unit can be provided to accomplish the entire
treatment process. The unit includes the necessary components, such as the
aeration tank, settling tank, sludge recycle equipment, and aeration piping to
perform the treatment. Foundations are not included in the package unit;
however, the module calculates these costs independently and adds them to the
cost for the package unit. The extended aeration activated sludge process is
better suited for facilities with small flow rates as it is easier to operate
than other modifications of the activated sludge process and does not require
as highly skilled operators.
Input and Design Parameters
For the extended aeration activated sludge module, the input
values are influent stream characteristics, including; flow rate, Biological
Oxygen Demand (BOD), Chemical Oxygen Demand (COD), suspended solids, volatile
suspended solids, non-biodegradable fraction of volatile suspended solids, pH,
8-40
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acidity, nitrogen, phosphorous, oil and grease, toxic or special
characteristics, heavy metals, and temperature. Design parameters include
hydraulic and solid detention times, a metabolism constant, a synthesis
factor, the endogenous respiration factor, and a temperature correction
coefficient. Values for the flow rate were obtained from census data from the
specific plant sites. Influent BOD concentrations were obtained from the
census data or from data generated during sampling activities at the
facilities. Values for the remaining input data and design parameters were
taken from average values developed for the same cost module for the OCPSF
industry. Since no better data are available for the pesticide industry, the
Agency is using the average values from the OCPSF industry data for these
design parameters. The design parameters for the biological treatment module
are presented in Table 8-7.
Design Calculations
The CAPDET module for extended aeration activated sludge
determines the size of the packaged system as a function of the input data and
design parameters. The volume of the aeration tank is calculated from the
detention time and flow rate. Solids generation, sludge recycle requirements,
and effluent conditions are calculated as functions of the design parameters
and the calculated aeration tank volume. After these variables have been
calculated, the module uses them to estimate the costs of a package biological
treatment unit.
8-41
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Table 8-7
DESIGN PARAMETERS FOR THE BIOLOGICAL TREATMENT
COST MODULE
Design Parameter
Units
Default Values
Reaction rate constant
Fraction BOD synthesized
Fraction BOD oxidized
Air requirement
Endogenous respiration rate
(sludge basis)
Endogenous respiration rate
(oxygen basis)
Nonbiodegradable fraction of
volatile suspended solids in
influent
Degradable fraction of the mixed
liquor volatile suspended solids
Oxygen transfer ratio
Oxygen saturation ratio
Horsepower
Food/microorganism ratio
Standard transfer efficiency
L/mg/hr
scfm/1,000 gal
L/day
L/day
hp/1,000 gal
Ib BOD/lb MLVSS
Ib 02/hp hr
0.00135
0.73
0.52
20
0.057
0.15
0.5
0.53
0.9
0.9
0.5
6
8-42
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Cost Calculations
For the packaged extended aeration system, the costs are
determined parametrically, based on vendor information for standard sized
packaged units.
The total capital costs include the packaged unit and the
necessary foundations. The operation and maintenance costs include:
• Operation and Maintenance Labor;
• Materials;
• Energy;
• Sludge Disposal O&M costs; and
• Sludge Disposal.
The capital costs for the extended aeration system are expressed as a function
of flow rate and tank volume and the operation and maintenance costs are
expressed as a function of flow rate. The costs for the foundations are
determined from the size of the foundation (calculated in the design
calculations section) and the unit cost of concrete. Other miscellaneous
costs are assumed to be a factor of the calculated costs. Land costs are the
product of the regional unit price per acre cost and the amount of land
required.
8-43
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Sludge Disposal from Biological Treatment
The use of biological treatment as a wastewater treatment
technology results in the generation of wasted biological treatment sludge
from the clarification step. Dewatering equipment costs were calculated for
plants with a flowrate greater than 50,000 gpd. In the cost estimation module
for the pesticide industry, packaged rotary drum vacuum filters are used as
the mechanical dewatering equipment for sludges generated by the packaged
extended aeration system. EPA determined that it is not cost efficient for
plants with a wastewater flow rate less than 50,000 gpd to install dewatering
equipment and, therefore, costs were estimated for these facilities to
transport sludge without dewatering. Off-site incineration is the sludge
disposal method since the volumes of sludge generated are below the volumes
needed to justify the capital investment of an on-site incinerator.
The cost for sludge disposal for plants with a flowrate greater
than 50,000 gpd includes the capital cost for the mechanical dewatering
equipment, the O&M costs for the mechanical dewatering equipment, and the
disposal costs at an off-site incinerator. The packaged rotary drum vacuum
filters are skid-mounted units that include filter, vacuum pump, filtrate
pump, pre-coat mix tank with agitator, and dust collection for the pre-coat
(pre-coat material is usually diatomaceous earth). The packaged unit does not
include equipment for storage or slurry of feed sludge. Base prices for the
packaged dewatering units were obtained from vendors and are a function of the
sludge generation rate from the extended aeration system.
8-44
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Operation and maintenance costs include labor and supervision,
energy, chemical conditioning, maintenance and miscellaneous overhead for
operating the filter on a continuous basis. Disposal of the sludge after
mechanical dewatering will require shipment to an off-site incinerator. For
the pesticide industry biological treatment cost module, the sludges are
considered hazardous. The disposal costs include transportation costs and the
disposal fee.
8.3.3 Chemical Oxidation
For the pesticide manufacturing industry, a packaged chemical
oxidation-alkaline chlorination system is used. The model specifies chlorine
as the oxidizing agent because chlorine is frequently used and sufficient data
is available to calculate cost estimates. Costs were developed for this
module based on a vendor quote from an application developed for the organic
chemicals, plastics, and synthetic fiber industry. Parametric equations were
developed based on capital and O&M costs calculated at different flows for
flow rates above 5,000 gpd. Capital costs for plants with wastewater flow
rates below 5,000 gpd were assumed to be the same as those for the 5,000 gpd
system. However, O&M costs were adjusted based on the actual flow rate.
The physical equipment included in this application are a
chlorinator, bulk storage tank, chemical feed pump, caustic feed module, and
electric control panel. Design parameters for this module include influent
flow rate, reactor retention time, and chemical feed system size.
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Capital costs include the purchase and installation costs of the
alkaline chlorination system and auxiliary equipment. The base purchase costs
are multiplied by factors to adjust for indirect costs and cost indices to
bring the costs to 1986 basis. O&M costs for continuously operating systems
include operating labor, maintenance, power, miscellaneous, and chemical
costs. O&M costs for batch systems are the same as continuous systems, except
that they are multiplied by a ratio of the actual flow rate to the minimum
flow rate for continuous operation, 5,000 gpd.
8.3.4 Off-Site Incineration
The off-site incineration module consists of cost estimate
calculations for storage on-site, transportation to an incineration facility,
and incinerator/disposal costs.
Assumptions for the off-site incineration disposal module include
the following:
All wastes are treated as hazardous liquids and are disposed
of by incineration;
5,000 gallon tank trucks are used for hauling wastewater to
a disposal site, and only one tank truck will visit a site
at a time;
Wastes are stored on-site no longer than 45 days in a 10,000
gallon storage tank; and,
The pumping station is only operated while loading the tank
truck.
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Capital equipment costs and operational and maintenance costs are
determined parametrically through the use of cost curves. Transportation and
disposal costs are determined by multiplying the calculated quantities of
wastewaters by appropriate transportation and disposal fees.
Physical Equipment
Equipment for storing the waste on-site includes a 10,000 gallon
vertical atmospheric tank (tank containing liquid with an approximate vapor
pressure of 15 psia). The tank is made of carbon steel with a flat top and
bottom. A package high service pumping station is used to transfer liquids
from the storage tank to the hauling vehicle. A 70 gpm pump is used because
it can empty a 10,000 gallon tank in approximately two hours. Equipment used
in the operation and maintenance of the tank and the transportation and
disposal of the waste are factored into those specific costs.
Storage time is determined by dividing tank size (5,000 gallons)
by the flow rate in gallons per day. If storage time is less than 45 days per
year (flows greater than 111 gal/day), costs are calculated based on a 5,000
gallon tank truck hauling waste away once every interval of the storage time.
If storage time is greater than 45 days (flows less than 111 gal/day), then
costs are calculated based on the wastes being stored in 55 gallon drums and
the drums being hauled away once every interval of storage time with a maximum
storage time of 90 days.
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The RCRA limit for storing hazardous wastes is 90 days. The
division between whether a facility will use drum storage or tank storage is
whether there is enough wastewater to fill up one tank truck within 45 days.
If a facility can fill a tank truck within 45 days, then the pesticide
manufacturing facility would have a 10,000 gallon tank and a pumping system,
and the waste would be hauled in tanker trucks. If not, the facility would
store the waste in 55 gallon drums. A truck would stop by when there were
enough drums to fill a truck, at least once every 90 days.
Input Data/Design Parameters
The only input for this module is waste water flow in million
gallons per day (MGD). Design parameters include size of equipment, time of
operation, distance travelled, and unit prices. Equipment size parameters
include the size of the storage tank and tank truck, the capacity of the
pumping station, and drum capacity per truck load. Operation time parameters
include the number of production days for the plant, the time to connect and
disconnect the pump and tank truck, and the time to inspect the equipment.
Travel distance parameters are the unloaded distance from the disposal site to
the pesticide manufacturing facility and the loaded distance from the facility
to the disposal site. The module uses the default value of 500 miles for
travel distance. Cost parameters include the drum purchase price, bulk and
drum disposal fees, demurrage fee, tank truck costs and sample analysis fees.
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Design Calculations
The storage time was determined by dividing the capacity of the
truck by the wastewater flow rate of the facility. With a 5,000 gallon tank
truck, a facility would need a flow of at least 111 gallons per day to require
a 10,000 gallon tank. If a facility can use drum storage, the storage time
was determined by dividing drum capacity by the wastewater flow rate. The
maximum allowable storage time was 90 days.
Cost Calculations
Compliance costs are made up of capital and annual costs. Capital
costs include the purchase of equipment. Annual costs include operation and
maintenance of equipment, and transportation and disposal of the waste.
No capital costs were calculated for facilities storing their
waste in 55 gallon drums. Capital costs for plants storing their wastes in
10,000 gallon tanks include in the purchase of the tanks and pumping systems.
Costs for this equipment are determined parametrically by cost curves
dependent on capacity, tank capacity, and pumping capacity.
Annual costs for plants storing their waste in 55 gallon drums
includes drum replacement, drum inspection, drum transportation, drum
disposal, labor, and disposal by incineration. Annual costs for plants
storing their waste in 10,000 gallon tanks includes operation and maintenance
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of tanks, pumping station, and trucks; labor; transportation of waste; and
disposal by incineration.
Costs for the operation and maintenance of equipment are
determined parametrically by cost equations dependent on the capacity of the
equipment. These costs account for inspection, operation, energy usage,
upkeep, and repair of the equipment.
Transportation costs include the loading and distance costs
multiplied by the frequency of trips. Loading costs are equal to the time it
takes to load the truck multiplied by a demurrage fee. Distance costs include
both the unloaded travel to the pesticide manufacturing plant and the loaded
return to the disposal facility.
Disposal costs are the costs to sample and incinerate the waste
multiplied by the frequency of trips. Disposal and sampling fees are
dependent on the quantities and type of waste disposal.
8.3.5 Distillation
A small distillation system, designed to handle solvent recovery,
can be used in the separation of water and alcohol to facilitate the reuse of
esterification reaction water. Distilling reaction wastewater by controlling
the temperatures used during evaporation of solvent and water from the
reaction mixture yields water suitable for use in salt formations. Plants can
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reduce or even eliminate their discharge of pesticide active ingredients and
alcohol contaminated wastewater by reusing the esterification wastewater.
The contaminant mixture is first pumped into the distillation
chamber. The unit then burns thermal oil to heat the mixture and vaporize the
solvent. During heating, a pure solvent vapor, consisting of the alcohol used
in manufacturing the specific phenoxy ester, enters the water cooled condenser
and is liquefied. The purified alcohol is then piped to storage drums while
the water remains in the distillation chamber and is automatically discharged
and available for reuse. Reuse of the esterification reaction waste water is
dependent upon the separation of the alcohol from the water.
It has been demonstrated at several pesticide manufacturing plants
that distillation of esterification reaction water to recover alcohols for
recycle in the esterification process and reuse of the water recovered from
the distillation is technically feasible.
Distillation capital costs included purchase and installation of
equipment. Installation includes electrical hookups for control panel In
nonhazardous area, transportation, assembly, and initial labor to install the
equipment. Operation and maintenance costs include energy, electricity for
power supply, thermal oil for heating, labor, and supplies. Land costs are
negligible.
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8.3.6 Equalization
Flow equalization design calculations consisted of determining the
required additional capacity, sizing the feed tank, and calculating capital,
O&M, and land costs.
The required equalization capacity was determined by multiplying
the maximum daily feed rate by the required storage time. The required number
of feed tanks was determined by dividing required storage time by the largest
feed tank size available.
The capital cost includes purchase and installation of the feed
tanks and is calculated by multiplying the number of feed tanks by the net
cost of each tank. Additional operation and maintenance costs due to the feed
tanks was assumed negligible in comparison with overall plant operations and
maintenance cost. Land cost was calculated by multiplying the unit land cost
for the respective state by the required area.
8.3.7 Filtration
Filtration is the removal of suspended solids through a porous
medium. For the pesticide manufacturing industry, two types of filters were
costed for wastewater treatment: multimedia filtration, and filter presses.
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Physical Equipment
In general, the equipment required for a filtration system
includes the filter frame (usually concrete or steel) and the filtration media
(usually sand). In addition, the filter press requires a plate shifter, the
press itself, a conveyor system, and a roof to prevent rain from contacting
the squeezed cake.
Input and Design Parameters
The input parameter for the multimedia filter cost estimates from
CAPDET was the wastewater flow rate. Default values were used for other
design parameters, such as hydraulic loading rate, sand size and shape, bed
size, and filter media characteristics. Design parameters for the filter
press were specified in a treatability study for the plant.
Design and Cost Calculations
Design calculations for the filters were based on the filter
requirements; effluent characteristics; quantities of supplies, materials, and
equipment; energy and other operation and maintenance requirements. Capital
costs for the multimedia filter were based on purchase and installation costs
for the filter and auxiliary equipment. Capital costs for the filter press
were based on vendor quotes. O&M costs for the multimedia filter and the
filter press were based on purchasing filter supplies and material and running
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the equipment. Additional land costs were assumed negligible in comparison to
existing wastewater treatment systems at the plant.
8.3.8 Hydrolysis
Treatment of pesticide active ingredients by hydrolysis is common
in the pesticide industry. This wastewater treatment technology uses hydroxyl
ions to catalyze hydrolysis of the PAIs in the wastewater. The Facility
Census shows that hydrolysis treatment may be conducted either continuously or
on a batch basis.
A typical hydrolysis system consists of a hydrolysis vessel, a
storage and delivery system for caustic, heat exchange equipment, and
associated pumps and piping. The wastewater is heated to 60°C (140°F) either
prior to treatment or during treatment to increase the rate of reaction.
Sodium hydroxide is added to the wastewater to increase the pH to
approximately 12. Many plants use higher temperatures and higher pH to
further increase the rate of hydrolysis. After the desired retention time in
the hydrolysis vessel at basic pH and high temperature, the treated wastewater
is then pumped out of the hydrolysis vessel and discharged for further
treatment or disposal.
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Physical Equipment
The Agency was unable to identify an existing cost model that
provided adequate design and cost information for hydrolysis treatment. A
costing module was therefore developed using existing operating hydrolysis
units for reference. The design is based on treatment of wastewater at
elevated temperatures and at a basic pH. The successful reduction of PAI
concentrations from actual influent to desired effluent requires the
wastewater to be maintained at the temperature and pH conditions for a
sufficient period of time. This residence time is determined by the kinetics
of the hydrolysis chemical reaction and the influent and effluent
concentrations. A more detailed discussion of hydrolysis is presented in
Section 7.0.
Inputand Design Parameters
The hydrolysis module requires wastewater flow rates for design
and costing. Design parameters such as rate constants for the hydrolysis
reactions for individual active ingredients, batch cycle time, influent
concentrations, desired effluent concentrations, and the mode of operation
(continuous or batch) are also required. Other parameters such as caustic and
steam addition rates (to bring the wastewater to a pH of 12 and a temperature
of 60°C) are fixed in the module.
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Design Calculations
The hydrolysis cost module calculates the vessel volume as a
function of the wastewater flow rate and the necessary residence time. The
length of the residence time is a function of influent concentrations,
pollutant half-lifes, rate constants, and the desired effluent concentrations.
The module calculates the necessary residence time to achieve the very low
effluent levels, and accordingly determines the size and number of hydrolysis
vessels based on the batch flow rate and batch cycle time of wastewater.
Other equipment in the system are sized as a function of the wastewater flow
rate.
Cost Calculations
After the individual equipment items are designed, the hydrolysis
module calculates the costs for each item. For each item, parametric cost
equations were either obtained from existing literature sources or developed
from vendor data. These parametric equations calculate the capital cost of
the equipment as a function of the size of the equipment. The costs for each
item were then added together and multiplied by a factor to include other
miscellaneous capital costs not specifically calculated. The resulting total
represents the capital cost of a hydrolysis system. The hydrolysis capital
costs include sodium hydroxide storage and delivery systems; heat exchanger;
hydrolysis vessel(s); pumps (including feed and transfer pumps); and other
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miscellaneous items including structural steel, concrete, piping, electrical
supply, etc.
Operating and maintenance costs were calculated by first
determining the quantity of utilities, manpower, materials, and supplies
required for the operation of the design hydrolysis system. The quantities
were then multiplied by their respective unit costs and summed to generate a
total O&M cost. The O&M costs include operation and maintenance labor;
maintenance materials; steam; energy; and supplies/chemicals.
8.3.9 Hydroxide Precipitation
Precipitation using lime (or NaOH) is used for removal of metals
from solution. Metal ions in solution react with the hydroxyl ions as the pH
is raised to form insoluble metal hydroxides. Polymer is added to aid the
flocculation of the precipitate.
Three operating modes of the hydroxide precipitation process are
accommodated by the computer model: continuous, batch, and low-flow batch.
Selection of the appropriate treatment mode is based on the magnitude of the
influent flow rate. Because of the low flow rates at PAI plants requiring
this technology, compliance costs for this treatment technology were estimated
using only the low-flow batch regime. In low-flow batch chemical
precipitation, sufficient retention time is allowed for solids settling to
occur in the reaction vessel. Therefore, the treated effluent stream is the
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clarified overflow from the reaction vessel. Another stream requiring
disposal is the underflow (settled solids), which are dewatered and
subsequently disposed as a hazardous waste.
Equations for this module were based on the chemical precipitation
module used in developing compliance costs for the metals and machinery branch
effluent guidelines. Inputs into the module include the wastewater flow rate
and the number of wastewater productions days. Design parameters include the
residence time and the design safety factor. Computations made include the
volume and rate of lime addition, size of physical equipment, and sludge
disposal costs.
Capital costs are the purchase and installation costs of the
fiberglass batch tank, agitators, and pumps multiplied by factors for
engineering/administration/legal and contingencies/contractor costs.
Operation and maintenance costs are the cost of the lime, the labor, and
maintenance on the physical equipment, and insurance costs. Land costs were
assumed to be negligible because of the low wastewater flows and size of
equipment. Sludge production was a. factor of the volume of lime added to the
process multiplied by a unit disposal cost.
8.3.10 Resin Adsorption
Compliance costs were estimated for resin adsorption at a specific
plant to increase the frequency of regeneration of the resin column.
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Regeneration of the resin bed is done through washing the bed with methanol.
Additional resin bed regeneration can be completed with existing equipment.
Therefore, no additional capital or land costs will be incurred as a result of
increasing the frequency of regeneration. Additional methanol and methanol
disposal will be required to increase the frequency of regeneration. For this
reason, additional operation and maintenance costs will be incurred. Purchase
price of the methanol was calculated by determining the amount of additional
methanol needed and multiplying by a unit cost for methanol. Additional
disposal cost was calculated by multiplying the quantity of additional
methanol needed by a unit disposal cost. Additional purchase and disposal
costs were summed to yield the additional O&M cost.
8.3.11 Steam Stripping
Steam stripping is used in industrial chemical production for
recovery and/or recycle and in industrial waste treatment to remove volatile
organic chemicals from wastewater streams by discharging steam into a tray or
packed distillation column. For the pesticide manufacturing industry, steam
stripping is used to remove volatile priority pollutants from pesticide
wastewater.
Physical Equipment
EPA used the Water General Corporation model (Process Design
Manual for the Stripping of Organics, EPA-600/2-84-139) for the design of the
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steam stripping systems for the pesticide industry. EPA previously used this
model to design steam stripping systems for the development of effluent
guidelines for the Organic Chemicals and Plastics and Synthetic Fibers (OCPSF)
industry. This model defines the steam stripping process as a steam stripping
column (tray or packed), the associated heat transfer equipment (reboiler,
condenser, and feed heat exchanger), and fluid transfer equipment (pumps).
Although packed towers are less expensive than sieve tray columns, sieve tray
columns operate more efficiently, can operate for a wider range of liquid flow
rates, and are more easily cleaned. For these reasons, costs were estimated
for steam stripping systems with sieve tray columns. Feed tanks for the
equalization of wastewater influent are also included for this model. To
satisfy practical design constraints, a minimum column diameter of 1 foot and
a minimum column height of 10 feet was established.
The minimum column size of 1 foot in diameter and 10 feet in
height corresponds to a daily flow rate of approximately 35,000 gallons of
wastewater influent per day. For plants with flow rates below 35,000 gallons
per day, the module calculated capital costs for the minimum sized system,
35,000 gallons and decreased the operation costs by a ratio of the actual flow
to the minimum flow.
Input and Design Parameters
Twenty-two input variables are used in the Water General
Corporation steam stripping model, including physical properties such as
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specific heat, activity coefficients, densities and viscosities; operating
characteristics such as feed flow rate, steam flow rate, and temperature; and
mechanical characteristics such as column tray type. The feed flow rate and
influent and effluent concentrations affect the size of the steam stripping
system; these variables were therefore used as input parameters for the plants
costed.
An important characteristic that determines the effectiveness of
steam stripping and the design of the column is the relative volatility or
vapor pressure of the organic(s) that is being stripped form the wastewater.
About one third of the 126 priority pollutant chemicals have vapor pressures
high enough to be effectively stripped from aqueous waste streams. For
aqueous mixtures, this vapor-liquid equilibrium can be expressed by Henry's
Law Constant. The Water General design uses a stripping factor (S) to
determine the tower specifications; this factor is related to the Henry's Law
Constant of the pollutant to be stripped, as shown below.
S = KV Where K «= Henry's Law Constant (atm) _ Henry's Law Constant
Tower Operating Pressure (atm) 1.0 atm
V = Vapor Rate (Ib/hr)
L = Liquid Rate (Ib/hr)
Tower Operating Pressure = 1.0 atm
Given the direct relationship between tower dimensions and
pollutant Henry's Law Constant, and the relationship between tower dimensions
and costs, EPA decided to divide the priority pollutants into two groups (high
strippability and medium strippability) by their Henry's Law Constant values
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for the purposes of costing (see Table 8-8), A representative pollutant from
each group was used in the cost study; benzene represents the high Henry's Law
Constant pollutants, and hexachlorobenzene represents the medium Henry's Law
Constant pollutants.
The design parameters for the steam stripping cost module and the
parameter values for the representative high and medium Henry's Law Constant
pollutants are presented in Table 8-9. The Agency used these values for the
design parameters for the steam stripping module.
Design Calculations
The Water General steam stripping module methodology designs the
stripping column and auxiliary equipment by determining a material and energy
balance for the system, the number of equilibrium stages required for the
separation, the stage efficiency, and the pressure drop across the column.
The method follows standard distillation column design practice and provides
the results of a column diameter and height that will accomplish the
separation and achieve the required effluent quality.
Cost Calculations
EPA obtained size and cost information for actual steam stripping
units within the OCPSF industry. To provide a basis for the development of
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Table 8-8
PRIORITY POLLUTANTS DIVIDED INTO GROUPS ACCORDING TO
HENRY'S LAW CONSTANT VALUES
High
3 x 102 to 10-1
Benzene
Carbon Tetrachloride
Chlorobenzene
1,1, 1-Trichloroethane
Chloroethane
1 , 1 - Dichloroe thane
Chloroform
Chlorome thane
Toluene
Vinyl Chloride
1 , 1-Dichloroethene
1 , 2-Trans-dichloroethene
Trichloroethene
Tetrachloroethene
Hexachloro -1,3 -butadiene
Hexachlorocyclopentadiene
Bromome thane
Dichlorobromome thane
1 , 3 -Dichlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene
Medium
10-2 to 10-3
Acenaphthene
Acrylonitrile
1 , 2-Dichloroethane
Hexachloroe thane
1, 1,2-Trichloroethane
1, 1,2,2-Tetrachloroethane
Methylene Chloride
1 , 2 -Dichloropropane
1 , 3-Dichloropropene
1,1, 1-Tribromoethane
Bis(2-Chloroisopropyl) Ether
4-Chlorophenyl Phenyl Ether
4-Bromophenyl Phenyl Ether
1 , 2 -Dichlorobenzene
1 , 2 , 4-Trichlorobenzene
Hexachlorobenzene
4-Nitrophenol
4, 6-Dinitro-o-cresol
Acenaphthylene
Anthracene
Benzo (k) f luoranthene
Fluorene
Naphthalene
Phenanthrene
Dimethyl Nitrosamine
Diphenyl Nitrosamine
Henry s Law constant units are mg/mymg/nv}.
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Table 8-9
STEAM STRIPPING DESIGN PARAMETERS FOR HENRY'S LAW CONSTANT PARAMETERS
Design Parameter
Representative Pollutant
CP = Specific heat of reflux
DIFL = Liquid-phase diffusivity
DIFV = Gas -phase diffusivity of pollutant into
water vapor
FC = Final concentration of organic
G = Steam rate into tower
GAMD = Activity coefficient of pollutant in
aqueous phase
GAMS •= Activity coefficient of pollutant in
aqueous phase
1C = Initial concentration of organic
K — Vapor- liquid equilibrium constant
L — Liquid feed into tower
LPRIM = Latent heat of steam
MU = Gas -phase viscosity
PSI = Fractional entrainment mass fraction
Units
cal/g-°K
ft2/hr
ftVhr
mg/1
MGD
unitless
unitless
mg/1
atm/atm
MGD
cal/g
Ib/ft-hr
mole/mole
Medium Strippabillty
Hexachlorobenzene
1.0
9.918 x 10-5
0.311
Option I - 1.0
Option II = 0.01
0.10 x L
1.0
3.775 x 106
390
37.3
0.01-1.00
542.0
294.3 x lO'3
0.008
High Strippability
Benzene
1.0
1.623 x 10*
0.501
Option I - 1.0
Option II - 0.01
0.10 x L
1.0
660
390
253.3
0.01-1.00
542.0
294.3 x lO'3
0.008
CD
-------
Table 8-9
(Continued)
; Design Parameter
Representative Pollutant
PR «= Operating pressure of column
REFLUX - Reflux ratio
RHOG - Vapor density
RHOL - Liquid density
SAFE - Safety factor for Vm
SIGL - Liquid surface tension
TB - Boiling point of aqueous reflux
TR - Reflux temperature
XPRF = Tray construction indicator
Units
atm
unitless
ib.yft*
ib.yfe
unitless
dyne/cm
°C
°C
unitless
Medium Strlppabllity
Hexachlorobenzene
1.0
0.0
0.037
60
0.75
58.9
100
9
Perforated
High Strippabillty
Benzene
1.0
0.0
0.037
60
0.75
58.9
100
9
Perforated
CO
-------
steam stripping costs, data were extracted from the OCPSF Supplemental 308
Questionnaires submitted by those facilities utilizing steam strippers on
their waste streams. The capital and O&M costs taken from the Questionnaires
were scaled up using the appropriate economic indices. Where installation
costs were not provided, they were assumed to be 50% of the capital costs.
EPA analyzed these data to determine the relationship between the
capital and O&M costs and significant steam stripper design parameters. The
analysis shows that capital costs are best related to the diameter (D) and
height (H) of the distillation column, while O&M costs are best related to the
diameter of the distillation column and wastewater flow (F).
The costs calculated by these equations are then converted to the
1986 year basis by multiplying them by the ratio of cost indices for 1982 and
1986.
In these analyses, the steam stripper capital costs include
purchase and installation for a feed tank (with approximately a 24-hour
detention time); a feed heat exchanger; a reboiler; a distillation column
(tray type); a condenser; and pumps.
The steam stripper operation and maintenance costs include
operation and maintenance labor; maintenance materials; steam energy;
electricity; and steam stripper overhead disposal costs.
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For plants with flow rates below 35,000 gallons per day, the O&M
costs were multiplied by the ratio of the actual flow to 35,000 gal/day. This
reduction in O&M cost reflect the operation of the minimum sized column (1
foot in diameter, 10 feet in height) on a batch basis. EPA assumed that
plants with small wastewater streams requiring steam stripping would install
the minimum sized system and operate it batchwise as the wastewater
accumulated.
Steam Stripping Overhead Disposal Cost Estimates
The use of steam stripping as a wastewater treatment technology
results in the generation of an organic stream from the column overhead. This
organic waste stream must be disposed of, and this disposal represents
additional costs for the operation of the steam stripper. Based on steam
stripper manufacturers' information, this overhead waste stream flow is
estimated to be 1% of the total waste stream flow. For the pesticide
industry, disposal of the organic stream from steam stripping is based on off-
site incineration, as the size of the stripping units does not require an on-
site incinerator. Estimates of the cost incurred for the disposal of steam
stripper overhead were developed based on vendor quotations.
For plants utilizing steam stripping at higher flow rates
(>50,000 gpd), costs for disposing the steam stripper overhead were very high.
While disposal costs increase directly with increasing flow, capital costs of
steam strippers increase at a much slower rate with increasing flows. EPA
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determined that it is therefore cost efficient to install a second-stage steam
stripper to treat the overhead from the primary steam stripper. Although
capital costs essentially doubled, disposal costs decreased by a factor of
100. The net result of the second steam stripper represented a substantial
savings.
8.3.12 Monitoring for Compliance
To ensure compliance with the regulations, plants will sample and
test their wastewater treatment for regulated PAIs and priority pollutants.
Testing methods have been developed and promulgated for all PAIs and priority
pollutants proposed for regulation. The monitoring costs incurred by
facilities depend on the method employed to analyze their effluent wastewaters
and the number of times monitoring occurs annually. To estimate monitoring
costs, EPA assumed that the proposed analytical methods will be used for each
regulated PAI. Costs for analytical methods proposed for individual PAIs do
not vary significantly; thus, in cases which the proposal allows several
analytical methods to be used, EPA estimated monitoring costs assuming one
method would be used. For the priority pollutants, EPA assumed that Methods
624 and 625 will be used to analyze volatile and semivolatile pollutants
respectively, and Method 200.7 is assumed to be used for all metals except
cyanide for which Method 335 is to be used. EPA assumed that the permitting
authority would require monitoring of regulated PAIs and limited priority
pollutants at least once per week of production. EPA also, assumed that plants
would be required to monitor all priority pollutants at least once per day of
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production. Next, the cost of each method of analysis was determined in 1986
dollars by using cost indices to factor current costs back to 1986. The
annual cost for each facility was determined by multiplying the cost of each
method by the frequency of each method used at that facility. Then the costs
for each method of analysis were summed. To be conservative, EPA estimated
monitoring costs for all plants regardless of whether a plant already
conducted monitoring of PAIs or priority pollutants.
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SECTION 9
BEST PRACTICABLE CONTROL TECHNOLOGY (BPT)
9.0 INTRODUCTION
The Agency promulgated effluent limitations based on the best
practicable control technology (BPT) currently available for the Pesticide
Chemicals Point Source Category on April 25, 1978 (43 FR 17776) and
September 29, 1978 (43 FR 44846). BPT effluent limitations guidelines
promulgated in 1978 for Subcategory A are presented in Table 9-1, and these
guidelines excluded from coverage discharges resulting from the manufacture of
25 PAIs and classes of PAIs. These PAIs, presented in Table 9-2, were
excluded from coverage due to a lack of treatment data available in 1978.
Since then, the Agency has collected effluent data on 15 organic PAIs within
the group of 25 PAIs and classes of PAIs. The Agency is proposing to amend
the applicability of BPT to include these 15 organic PAIs and organo-tin PAIs.
9.1 BPT APPLICABILITY
Effluent data were originally collected by the manufacturing
facilities themselves in order to monitor their discharges. The organic PAIs
for which EPA has collected these data are ametryn, prometon, prometryn,
terbutryn, cyanazine, atrazine, propazine, simazine, terbuthylazine,
glyphosate, phenylphenol, hexazinone, sodium phenlyphenate, biphenyl, and
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Table 9-1
EXISTING BPT EFFLUENT LIMITATIONS FOR THE
PESTICIDE CHEMICALS POINT SOURCE CATEGORY (40 CFR PART 455)
ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY:
Effluent
Characteristic
COD
BOD5
TSS
Total Pesticides
pH
Maximum for
any 1 day**
13.000
7.400
6.100
0.010
*
Average of daily values for 30
consecutive days shall not exceed **
9.0000
1.6000
1.8000
0.0018
*
*Within the range 6.0 to 9.0.
**Metric units: Kilogram/1,000 kg of PAI produced; English units: Pound/1,000
Ib of PAI produced; established on the basis of pesticide production.
METALLO-ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY:
There shall be no discharge of process wastewater pollutants to
navigable waters.
PESTICIDE CHEMICALS FORMULATING AND PACKAGING SUBCATEGORY:
There shall be no discharge of process wastewater pollutants to
navigable waters.
9-2
-------
Table 9-2
ORGANIC PESTICIDE CHEMICALS EXCLUDED
FROM THE 1978 BPT SUBCATEGORY A GUIDELINES
PAI Code
057
064
067
037
043
114
123
102
138
157
211
216
225
164
233
235
244
211.05
265
PAI
Allethrin
Benzyl Benzoate
Biphenyl
Bisethylxanthogen1
Chlorophacinone
Coumafuryl
Dimethyl Phthalate1
Diphacinone
Endothall Acid
EXD (Herbisan)
Gibberellic Acid1
Glyphosate
Methoprene
Naphthalene Acetic Acid1
Phenylphenol
Piperonyl Butoxide
Propargite
1, 8-Naphthalic Anhydride1
Quinomethionate
Resmethrin
Rotenone
Sulfoxide
Sodium Phenylphenate
Triazines2
Warfarin
1 Not included in the list of 270 PAIs considered for this regulation.
2 Includes 14 specific triazine PAIs.
9-3
-------
methoprene. EPA has also developed analytical methods and data for organo-tin
pesticides, which were not covered in the BPT guidelines.
EPA believes that the 15 organic PAIs listed above and the organo-
tin pesticides should be covered by BPT because the NPDES permits for these
facilities were based on BPT, and the data and engineering judgement indicate
the facilities are capable of achieving the limitations.
EPA is therefore proposing to amend the BPT applicability
provision for Subcategory A to include the 15 previously excluded PAIs listed
in Section 9.0 and the organo-tin pesticides. Table 9-3 presents these 15
PAIs and the organo-tin PAIs.
EPA is not proposing to make the BPT total pesticide limitations
guideline for the organic pesticide chemicals manufacturing subcategory (which
applies to the combined discharge of 49 specified PAIs) applicable to these
PAIs, because new BAT limitations are being proposed today that will apply to
each of them individually.
The effect of this proposed amendment is to set the BPT
limitations at the performance level achievable by these facilities under
their NPDES permits and to establish a baseline on which to evaluate
incremental costs of candidate BCT technologies. Because the facilities are
in compliance with NPDES permits that are already based on these BPT
9-4
-------
Table 9-3
PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT
PAI Code
025
058
060
067
138
142
157
192
211
211.05
223
224
226
239
256
257
PAI
Cyanazine
Ametryn
Atrazine
Biphenyl
Glyphosate
Hexazinone
Methoprene
Organo-tin Pesticides
Pheny Ipheno 1
Sodium Phenylphenate
Prometon
Prometryn
Propazine
Simazine
Terbuthy laz ine
Terbutryn
9-5
-------
limitations, EPA projects that there will be no costs incurred by any of
thesefacilities in connection with today's proposed rule. Plants
manufacturing three of the PAIs proposed to be included in BPT are currently
meeting BPT limitations through no discharge of process wastewater: one
plant's process is dry and the two other plant's processes do not discharge
any wastewater generated to waters of the United States.
9-6
-------
SECTION 10
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)
10.0 INTRODUCTION
The factors considered in establishing the best available
technology economically achievable (BAT) level of control include: the age of
process equipment and facilities, the processes employed, process changes, the
engineering aspects of applying various types of control techniques, the costs
of applying the control technology, non-water quality environmental impacts
such as energy requirements, air pollution and solid waste generation, and
such other factors as the Administrator deems appropriate (Section
304(b)(2)(B) of the Act). In general, the BAT technology level represents the
best existing economically achievable performance among plants with shared
characteristics. Where existing wastewater treatment performance is uniformly
inadequate, BAT technology may be transferred from a different subcategory or
industrial category. BAT may also include process changes or internal plant
controls which are not common industry practice.
This section summarizes the proposed BAT guidelines. Specific
discussions regarding their development are included in Section 6 (Pollutant
Selection), Section 7 (Technology Selection and Limits Development), and
Section 8 (Cost and Effluent Reduction Benefits).
10-1
-------
10-1 SUMMARY OF BAT EFFLUENT LIMITATIONS GUIDELINES
The Agency considered 126 priority pollutants and 144 PAIs and
classes of PAIs (178 individual PAIs) for regulation under the BAT effluent
limitations guidelines for the organic pesticide chemicals manufacturing
subcategory. A complete discussion of pollutant selection for BAT are
discussed in Sections 6.2 and 6.3. EPA is proposing to establish limitations
for 28 priority pollutants and 91 PAIs and classes of PAIs (a total of 122
individual PAIs).
The Agency considered two regulatory options in developing BAT
effluent limitations: (1) limitations based on the use of hydrolysis,
activated carbon, chemical oxidation, resin adsorption, and/or incineration;
and (2) no discharge of process wastewater pollutants. The BAT limits
established must be economically achievable. In making this determination,
the Agency takes into consideration factors such as plant closures, product
line closures, and total cost effectiveness (dollar per pound-equivalent
removal). Although costs are considered in this manner, the primary
determinant of BAT is the effluent reduction capability of the control
technology. A complete discussion of the two options considered for BAT are
discussed in Sections 7.4.2 and 7.5.2, along with the option selected for
regulation.
As described in Section 8, the Agency estimated the engineering
cost of compliance with the proposed BAT effluent limitations guidelines
10-2
-------
options and the associated pollutant reduction benefits. For Option 1, which
the Agency is proposing to adopt, EPA estimates that the proposed BAT
regulation will result in the incremental removal (beyond that achieved by
BPT) of 160,000 pounds per year (Ibs./yr.) of PAIs and 14,000 Ibs./yr. of
priority pollutants. EPA estimates that costs for compliance with the
proposed Option 1 BAT are capital costs of $14.5 million and annualized costs
of $14.8 million (in 1986 dollars). (See "Economic Impact Analysis of
Effluent Limitations and Standards of the Pesticide Manufacturers").
10.2 IMPLEMENTATION OF THE BAT EFFLUENT LIMITATIONS GUIDELINES
10.2.1 National Pollutant Discharge Elimination System (NPDES) Permit
Limitations
The proposed BAT effluent limitations guidelines for organic PAIs
are mass-based limitations. No discharge of process wastewater pollutants
means, as a practical matter, that the regulated pollutant is not detectable
at the final outfall from a facility (i.e., at end-of-pipe). However, because
some facilities provide employee showers and laundry facilities, which are not
covered by this proposed rule, the permit writer or POTW may need to require
in plant monitoring of PAI process wastewaters prior to commingling with these
other streams to effectively determine compliance. In the case where a
facility may manufacture a parent acid with a numerical limit, such as 2,4-D,
r.nd a salt or ester of that PAI, with a limitation of no discharge, compliance
might be determined by a total plant limit based solely on the 2,4-D acid
10-3
-------
limit (since the method for 2,4-D does not differentiate between 2,4-D and its
salts and esters).
PAIs that have numerical limits may be monitored for compliance
either in plant or at end-of-pipe (EOF). If treatment to destroy the PAI is
so efficient at the plant that the PAI would be reduced to about the detection
limit, then dilution with other plant wastewater after this point would render
compliance monitoring meaningless. Therefore, in these cases, monitoring for
compliance should be done at the exit of the in-plant treatment system prior
to dilution. Otherwise, compliance at EOP is calculated as the mass
limitation multiplied by the facility's daily production while in operation,
to determine the acceptable daily mass discharge.
The proposed BAT effluent limitations guidelines for priority
pollutants are concentration-based limits and the permit writer must use a
reasonable estimate of pesticide plant process wastewater flow for each PAI
and the concentration limitations to develop mass limitations. In most cases,
plants that manufacture more than one regulated PAI do not manufacture them
simultaneously. The permit writer should ascertain what production has been
demonstrated to occur simultaneously and sum those flows. The limit can then
be calculated by multiplying the concentration-based limitation by flow and
the appropriate conversion factors to obtain the acceptable daily mass
discharge.
10-4
-------
For facilities that also generate process wastewater from OCPSF
operations (more than half of the pesticide plants), 23 of the regulated
priority pollutants are the same. For those priority pollutants that are
different, the discharger should provide additional priority pollutant
characterization data to show which wastestreams (pesticides or OCPSF) are
dilution water.
These BAT limitations, once promulgated, will be included in the
National Pollutant Discharge Elimination System (NPDES) permit issued to
direct discharges [see 40 CFR §122.44(a)]. The final NPDES permit limitations
will include mass effluent limitations for pesticide chemicals manufacturing,
as well as non-pesticide chemicals manufacturing and nonprocess wastewater
discharges.
10.2.2 NPDES Monitoring Requirements
The NPDES regulations provide guidelines setting forth minimum
monitoring and reporting requirements for NPDES dischargers. Section 122.48
requires that each permit specify requirements regarding monitoring type,
intervals, and frequency sufficient to yield data that are representative of
the monitored activity. Sections 122.41, 122.44, and 122.48 contain numerous
other requirements concerning monitoring and reporting. Therefore, this
proposed rule does not establish monitoring requirements. As stated in
Section 8, EPA assumed a monitoring frequency of once per week for all limited
10-5
-------
PAI pollutants and once per month for all limited priority pollutants in
estimating monitoring costs.
10.3 BAT EFFLUENT LIMITATIONS GUIDELINES
The proposed BAT effluent limitations for organic PAIs and classes
of PAIs and priority pollutants under the organic pesticide chemicals
manufacturing subcategory (Subcategory A) are listed in Tables 10-1, 10-2, and
10-3.
10-6
-------
Table 10-1
BAT EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDE ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient (PAI)
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acif luorfen
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 403 [Potassium N-
hydroxymethyl -N-
methyldithiocarbamate ]
Busan 853 [Potassium
dimethyldithiocarbamate ]
BAT effluent, limitations
Daily Maximum Shall Not Exceed Lb./ 1,000 Ib. PAI
production
1.19 x 10-4
Honthly
Average Shall
not Exceed
lb./l,000 Ub.
FAX production
3.40 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.32 x 10-2
8.82 x 10"
7.23 x 10-4
2.10 x 10-3
2.56 x 10-3
2.74 x lO'2
3.22 x W-4
1.91 x 10-'
8.79 x 10-3
2.68 x 10"
3.12 x 10"
9.14 x 10"
1.02 x 10-3
1.41 x lO'2
1.09 x 10"
5.14 x 10-2
No discharge of process wastewater pollutants
1.69 x 10-2
8.72 x 10-3
No discharge of process wastewater pollutants
1.24 x 10-1
3.95 x 10-3
3.95 x 10-3
5.74 x ID'3
5.74 x 10-3
4.18 x 10-2
1.27 x 10-3
1.27 x 10-3
1.87 x 10-3
1.87 x 10-3
10-7
-------
Table 10-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Butachlor
Captafol
Carbarn S3 [Sodium
dimethyldithiocarbamate ]
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cy anaz ine
Dazomet3
DCPA
DEF
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
BAT effluent limitations
Daily Maximum Shall Hot Exceed Lb./ 1,000 It. PAI
production
3.53 x 1C'3
Monthly
Average Shall
not Exceed
Ib. /I, 000 Ib.
PAI production
1.09 x 10-3
No discharge of process wastewater pollutants
5.74 x lO'3
1.60 x ID'3
1.18 x 10"
8.16 x 10-2
1.51 x 10'3
3.27 x 10"
1.63 x lO"3
5.74 x lO'3
7.79 x 10-2
1.15 x lO'2
2.82 x lO'3
1.87 x 10-3
7.30 x 10"
2.80 x ID'5
3.31 x 10-2
4.57 x 10"
9.96 x ID'5
8.11 x 10"
1.87 x lO'3
2.64 x 10-2
5.58 x lO'3
1.12 x lO'3
No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x 10-2
7.33 x ID'3
3.15 x lO'2
2.95 x lO'5
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x 10-2
No discharge of process wastewater pollutants
2.20 x lO'2
5.10 x 10-3
10-8
-------
Table 10-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Ethalfluralin1-2
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Me thoxy ch lor
Metribuzin
Mevinphos
Nab am3
Nabonate3
BAT effluent limitations
Daily Maximum Shall Hot Exceed lb./ 1,000 Ib. FAI
production
3.22 x 10*
7.37 x 10-4
1.02 x 10-'
1.48 x 10-2
1.83 x lO'2
5.40 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 Ub.
FAI production
1.09 x 10"
2.99 x 10*
3.61 x lO'2
7.64 x lO'3
9.45 x 10-3
2.08 x 10-3
No discharge of process wastewater pollutants
8.80 x 10-3
7.06 x ID'3
5.74 x 10-3
2.69 x 10-3
2.35 x 10*
2.90 x 10-3
2.49 x lO'3
1.87 x 10-3
1.94 x 10-3
9.55 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.46 x ID'2
3.82 x 10-3
3.23 x ID'3
1.36 x lO'2
1.44 x 10*
5.74 x lO'3
5.74 x 10-3
5.58 x lO'3
7.53 x 10-3
1.76 x 10-3
1.31 x lO'3
7.04 x 10-3
5.10 x 10-5
1.87 x 10-3
1.87 x 10-3
10-9
-------
Table 10-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Naled
Norf lurazon
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendime thai in
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
BAT effluent limitations
Daily Maximum Shall Hot Exceed lb./ 1,000 li>. PAI
production
Monthly
Average Shall
not Exceed
lb./l,000 lb.
PAI production
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.72 x 10-2
7.72 x IQ-4 •
1 .72 x 10-4
5.75 x 10-4
3.21 x lO'3
2.32 x 10-4
2.51 x 10"4
7.42 x ID'3
3.43 x 10^
3.43 x 10-1
1.90 x lO"4
1.06 x 10-3
6.06 x 10-5
7.53 x 10-4
No discharge of process wastewater pollutants
2.10 x 10-3
2.10 x 10-3
2.00 x W*
5.34 x 10-3
1.06 x 10-3
2.10 x 10-3
9.14 x 10-4
9.14 x 10-4
6.90 x 10-5
1.66 x 10-3
4.84 x 10^
9.14 x lO-4
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.10 x 10-3
4.10 x lO'3
2.88 x lO"4
9.78 x ID'2
1.51 x 10-'
9.14 x W-4
1.35 x 10'3
8.96 x 10-5
3.40 x 1C'2
5.12 x lO'2
10-10
-------
Table 10-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Terbufos
Terbuthylaz ine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [Sodium
methyldithiocarbamate ]
Ziram3 [Zinc
dimethyldithiocarbamate ]
BAT effluent limitations
Daily Maximum Shall Rot Exceed Ib./ 1,000 U>. PAI
production
4.09 x 10^
2.10 x 10-3
2.10 x 10-3
1.02 x 10-2
6.52 x 10-2
3.22 x 10^
5.74 x lO'3
5.74 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 li.
PAI production
1.06 x 10"
9.14 x 10-4
9.14 x 10-4
3.71 x 10-3
3.41 x 10-2
1.09 x 10"
1.87 x 10-3
1.87 x 10°
'Monitor and comply after in-plant treatment before mixing with other
wastewaters.
2Monitor and report as total toluidine PAIs, as Trifluralin.
3 Monitor and report as total dithiocarbamates, as Ziram.
4 Monitor and report as total tin.
5 Applies to purification by recrystalization portion of the process.
10-11
-------
Table 10-2
BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR DIRECT DISCHARGE
POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 ,2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
2-Chlorophenol
1 , 2 -Diehlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
2 , 4-Dichlorophenol
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 , 4 - D ime thy Ipheno 1
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT effluent limitations1
Hair! «mim for
Any One Day
Gtg/U
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
25
59
89
211
59
26
Ma-^mnn. £Or Monthly
Average
(MS/I)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
16
22
40
68
22
15
10-12
-------
Table 10-2
(Continued)
Priority Pollutant
Tetrachloroethylene
Total Cyanide
Total Lead2
BAT effluent limitations1
Maximum for
Any One Day
<«5/L)
56
640
690
Maiinnsn for Monthly
Average
(W5/IO
22
220
320
'All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
10-13
-------
Table 10-3
BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR DIRECT DISCHARGE
POINT SOURCES THAT DO NOT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroe thane
Trichlorome thane
1 , 2 -Dichlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Ch 1 o r ome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
BAT effluent limitations1
Ma-ri imim for
Any One Day
C/ig/L)
134
380
380
574 -
59
46
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Ma-r-imum for Monthly
Average
(06/L)
57
142
142
180
22
21
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
10-14
-------
Table 10-3
(Continued)
Priority Pollutant
Total Cyanide
Total Lead2
BAT effluent limitations1
Maximum for
Any One Day
(«5/U
640
690
Maximum for Monthly
Average
(MJ/U
220
320
'All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
10-15
-------
SECTION 11
NEW SOURCE PERFORMANCE STANDARDS (NSPS)
11.0 INTRODUCTION
New source performance standards (NSPS) under Section 306 of the
Clean Water Act represent the most stringent numerical values attainable
through the application of the best available demonstrated control technology
for all pollutants (conventional, nonconventional, and priority pollutants).
This section summarizes the proposed NSPS guidelines. The
specific discussions regarding their development are included in Section 6
(Pollutant Selection), Section 7 (Technology Selection and Limit Development),
and Section 8 (Cost and Effluent Reduction Benefits).
11.1 SUMMARY OF NSPS EFFLUENT LIMITATIONS GUIDELINES
The Agency based NSPS for conventional pollutants and COD on the
promulgated BPT limitations and for organic PAIs and priority pollutants on
the performance of BAT technologies. The Agency determined that limitations
that are more stringent than BAT limitations proposed for existing plants can
be achieved and are justified in some cases; in the remaining cases, NSPS is
proposed to be set equal to BAT. BAT limits were modified to reflect the
capability for wastewater flow reduction at new facilities. The Agency is
11-1
-------
proposing to transfer the organic pesticide chemicals manufacturing
subcategory NSPS for 23 priority pollutants from the OCPSF point source
category and is developing NSPS for four brominated priority pollutants and
total cyanide.
The Agency considered four technology options in developing NSPS:
basing NSPS on the BAT limits with no additional flow reduction, transference
of BAT limits for organic PAIs after incorporation of a 28% flow reduction,
flow reduction plus membrane filtration, and no discharge of process
wastewater pollutants. In the assessment of these NSPS options, the Agency
considered the reasonableness of costs to implement these treatment
technologies. A complete discussion of the four options considered for NSPS
are discussed in Sections 7.4.4 and 7.5.4, along with the option selected for
regulation.
11.2 IMPLEMENTATION OF THE NSPS EFFLUENT LIMITATIONS GUIDELINES
11.2.1 National Pollutant Discharge Elimination System (NPDES) Permit
Limitations
The proposed NSPS for conventional pollutant parameters, COD, and
organic PAIs are mass-based limitations and the proposed NSPS for priority
pollutants are concentration-based limits. Limitations should be developed
using guidance given for the implementation of BAT effluent limitations
guidelines (see Section 10.2.1).
11-2
-------
These NSPS, once promulgated, will be included in the National
Pollutant Discharge Elimination System (NPDES) permit issued to direct
dischargers [see 40 CFR §122.44(a)]. The final NPDES permit limitations will
include mass effluent limitations for pesticide chemicals manufacturing, as
well as non-pesticide chemicals manufacturing and nonprocess wastewater
discharges.
11.2.2 Monitoring Requirements
The NPDES regulations provide guidelines setting forth minimum
monitoring and reporting requirements for NPDES dischargers. Section 122.48
requires that each permit specify requirements regarding monitoring type,
intervals, and frequency sufficient to yield data that are representative of
the monitored activity. Sections 122.41, 122.44, and 122.48 contain numerous
other requirements concerning monitoring and reporting. Therefore, the
proposed rule does not establish monitoring requirements. As stated in
Section 8, EPA assumed a monitoring frequency of once per week for all limited
PAI pollutants and once per month for all limited priority pollutants in
estimating monitoring costs.
11.3 NEW SOURCE PERFORMANCE STANDARDS (NSPS)
The proposed NSPS for conventional pollutants, organic PAIs and
classes of PAIs, and priority pollutants under the organic pesticide chemicals
11-3
-------
manufacturing subcategory (Subcategory A) are listed in Tables 11-1, 11-2, 11
3, and 11-4.
11-4
-------
Table 11-1
NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD
Effluent
Characteristic
COD
BOD5
TSS
pH
Maximum for Any
1 Day
9.36
5.33
4.39
*
Average of Daily Values
Consecutive Days Shall Not
for 30
Exceed**
6.48
1.15
1.30
*
'These standards incorporate a 28 percent flow reduction achievable by new
sources.
*Within the range 6.0 to 9.0.
**Metric units: Kilogram/1,000 kg of PAI produced; English units:
Pound/1,000 Ib of PAI produced; established on the basis of pesticide
production.
11-5
-------
Table 11-2
PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Ac if luorfen1
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 403
Busan 853
Butachlor
New Source Performance Standards (NSPS)
Daily Maximum Shall Hot Exceed Uo./l.OOO
IB. PAI production
8.51 x ID'5
Monthly Average
Shall Hot Exceed
lb./l,000 It. PAI
production
2.42 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.67 x 10-2
6.35 x 10"
5.21 x 10-*
1.52 x 10-3
1.84 x ID'3
1.97 x 10-2
2.32 x 10"
1.37 x 10-'
6.33 x lO'3
1.93 x 10"
2.25 x 10"
6.59 x 10"
7.33 x 10"
1.02 x 10-2
7.82 x 10-5
3.70 x 10-2
No discharge of process wastewater pollutants
1.21 x 10-2
6.28 x 10-3
No discharge of process wastewater pollutants
8.90 x ID'2
2.84 x 10-3
2.84 x ID'3
4.13 x 10-3
4.13 x 10-3
2.54 x 10-3
3.00 x 10-2
9.11 x 10"
9.11 x 10"
1.35 x 10-3
1.35 x 10-3
7.90 x 10"
11-6
-------
Table 11-2
(Continued)
Organic Pesticide Active
Ingredient
Captafol
Carbarn S3
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cyanazine
Dazomet
DCPA
DEF [S,S,S-Tributyl
phosphorotri thioate ]
Diazinon1
Dichlorprop , salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
New Source Performance Standards (NSPS)
Daily Maximum Shall Hot Exceed It. /I, 000
11. PAI production
Monthly Average
Shall Hot Exceed
It. /I, ODD It. PAI
production
No discharge of process wastewater pollutants
4.10 x lO'3
1.18 x 10-3
1.18 x 10"
5.87 x 10-2
1.08 x 10-3
2.35 x 10"
1.18 x 10-3
4.10 x ID'3
5.60 x 10-2
1.15 x 10-2
2.04 x 10-3
1.37 x 10-3
5.24 x 10"
2.80 x 10-5
2.38 x 10-2
3.29 x 10"
7.19 x 10-5
5.84 x W-4
1.37 x 10-3
1.90 x 10-2
5.58 x 10-3
8.13 x 10"
No discharge of process wastewater pollutants
6.91 x 10-5
3.41
2.44 x 10-2
5.27 x 10-3
2.27 x 10-2
2.11 x 10-5
1.03
9.31 x 10-3
2.73 x 10-3
1.01 x 10-2
No discharge of process wastewater pollutants
1.57 x 10-2
2.32 x 10"
3.69 x 10-3
7.82 x 10-5
11-7
-------
Table 11-2
(Continued)
Organic Pesticide Active
Ingredient
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Methoxychlor
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norflurazon
New Source Performance Standards (NSPS)
Daily Maximum Shall Hot Exceed lb./ 1,000
Lb. PAI production
5.31 x 10-»
7.33 x 10-2
1.06 x 10-2
1.31 x lO'2
3.90 x 10-3
Monthly Average
Shall Not Exceed
It. 11, 000 lb. PAI
production
2.15 x 10"4
2.62 x lO'2
5.50 x 10-3
6.80 x 10-3
1.50 x 10-3
No discharge of process wastewater pollutants
6.31 x ID'3
5.07 x 10-3
4.13 x 10-3
1.94 x 10-3
1.69 x 10-4
2.06 x 10-3
1.82 x 10-3
1.35 x 10-3
1.40 x 10-3
6.88 x 10-»
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x lO'2
1.05 x ID'2
2.76 x 10-3
2.32 x 10-3
9.79 x lO'3
1.03 x 10-4
4.10 x 10-3
4.13 x 10-3
5.58 x 10-3
5.42 x 10-3
1.27 x lO'3
9.45 x 10"4
5.06 x 10-3
3.65 x lO'5
1.37 x 10-3
1.35 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
11-8
-------
Table 11-2
(Continued)
Organic Pesticide Active
Ingredient
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Pentachlorophenol, salts
and esters
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
New Source Performance Standards (NSPS)
Daily Maximum Shall Not Exceed li./ 1,000
Il>. PAI production
1.25 x ID'2
5.55 x 10"
5.55 x 10"
4.16 x 10"
2.31 x 10-3
Monthly Average
Shall Hot Exceed
Ib./l.OOO li. PAI
production
5.35 x 10-3
2.47 x 10"
2.47 x 10"
1.38 x 10"
7.64 x 10"
No discharge of process wastewater pollutants
1.68 x 10"
1.81 x 10"
4.38 x lO'5
5.42 x ID'5
No discharge of process wastewater pollutants
1.52 x 10-3
1.52 x 10-3
1.44 x 10"
3.85 x ID'3
7.64 x 10"
1.52 x 10-3
6.59 x 10"
6.59 x 10"
4.97 x ID'5
1.19 x 10-3
3.49 x 10"
6.59 x 10"
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.52 x 10-3
2.95 x 10-3
2.07 x 10"
7.05 x lO-2
1.09 x 10-'
2.95 x 10"
6.59 x 10"
9.72 x 10"
6.45 x lO'5
2.45 x 10-2
3.68 x 10-2
7.59 x 10-5
11-9
-------
Table 11-2
(Continued)
Organic Pesticide Active
Ingredient
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin'-2
Vapam3 [ Sodium
methyldithiocarbamate]
Ziram3 [Zinc
dimethyldi thiocarbamate ]
New Source Performance Standards (NSPS)
Dally Maximum Shall Not Exceed 11, / 1,000
Ib. PAX production
1.52 x 10-3
1.52 x 10-3
7.34 x 10-3
4.70 x 10-2
2.32 x 10"
4.13 x ID'3
4.13 x 10-3
Monthly Average
Shall Hot Exceed
lb./l,000 Ib. PAI
production
6.59 x 10-4
6.59 x 10"
2.67 x 1C'3
2.46 x ID'2
7.82 x 10-5
1.35 x 10-3
1.35 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
wastewaters.
2Monitor and report as total toluidine PAIs, as Trifluralin.
3Monitor and report as total dithiocarbamates, as Ziram.
4Monitor and report as total tin.
5Applies to purification by recrystallization portion of the process.
11-10
-------
Table 11-3
NSPS FOR PRIORITY POLLUTANTS FOR PLANTS WITH END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
2-Chlorophenol
1,2- Dichlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
2 ,4-Dichlorophenol
1, 2-DIchloropropane
1, 3-Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
BAT/NSPS effluent limitations1
Maximum for
Any One Day
<«5/L)
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
25
59
89
211
59
Ma-riimim for Monthly
Average
C/ig/L)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
16
22
40
68
22
11-11
-------
Table 11 3
(Continued)
Priority Pollutant
Phenol
Tetrachloroethylene
Total Cyanide
Total Lead2
BAT/NSPS effluent limitations1
Maximum for
Any One Day
(W5/IO
26
56
640
690
Maximum for Monthly
Average
(W5/D
15
22
220
320
1 All units are micrograms per liter.
2 Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
11-12
-------
Table 11-4
NSPS FOR PRIORITY POLLUTANTS FOR PLANTS THAT DO NOT HAVE
END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Carbon Tetrachloride
Chlorobenzene
1 , 2 - Dichloroe thane
1,1, 1-Trichloroe thane
Chloroform
1, 2-Dichlorobenzene
1 ,4-Dichlorobenzene
1 , 1-Dichloroethylene
1 ,2-trans-Dichloroethylene
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Methylene Chloride
Methyl Chloride
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT effluent limitations'
Ma-yiimii^ for
Any One Day
Otg/L)
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
60
47
170
574
47
47
Ma-j-itmim for Monthly
Average
<«; A.)
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
22
19
36
180
19
19
11-13
-------
Table 11-4
(Continued)
Priority Pollutant
Tetrachloroethylene
Toluene
Total Cyanide
Total Lead2
BAT effluent limitations1
Maximum for
Any One Day
(W5/IO
164
74
640
690
Maximum for Monthly
Average
Cpg/I.)
52
28
220
320
'All units are micrograms per liter.
2 Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
11-14
-------
SECTION 12
PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES) AND
PRETREATMENT STANDARDS FOR NEW SOURCES (PSNS)
12.0 INTRODUCTION
Section 307(b) of the Clean Water Act (CWA) calls for EPA to
promulgate pretreatment standards for existing sources (PSES). PSES are
designed to prevent the discharge of pollutants that pass through, interfere
with, or are otherwise incompatible with the operation of publicly owned
treatment works (POTWs). The legislative history of the Clean Water Act of
1977 indicates that pretreatment standards are to be technology-based, and
analogous to the best available technology economically achievable for direct
dischargers.
Section 307(c) of the CWA calls for EPA to promulgate pretreatment
standards for new sources (PSNS) at the same time that it promulgates new
source performance standards (NSPS). New indirect discharging facilities,
like new direct discharging facilities, have the opportunity to incorporate
the best available demonstrated technologies, including process changes, in-
plant controls, and end-of-pipe treatment technologies, and to use plant site
selection to ensure adequate treatment system installation.
12-1
-------
General pretreatment regulations applicable to all existing and
new source indirect dischargers appear at 40 CFR Part 403. These regulations
describe the Agency's overall policy for establishing and enforcing
pretreatment standards for new and existing users of a POTW, and delineate the
responsibilities and deadlines applicable to each party in this effort. In
addition, 40 CFR Part 403, Section 403.5(b), outlines prohibited discharges
that apply to all users of a POTW.
Indirect dischargers in the pesticide manufacturing industry, like
the direct dischargers, use as raw materials, and produce as products or
byproducts many nonconventional pollutants (including PAIs) and priority
pollutants. As in the case of direct dischargers, they may be expected to
discharge many of these pollutants to POTWs at significant levels. EPA
estimates that indirect dischargers of organic pesticides annually discharge
110,000 pounds of PAIs and 29,000 pounds of priority pollutants to POTWs,
This section summarizes the proposed PSES and PSNS guidelines.
Specific discussions regarding their development are included in Section 6
(Pollutant Selection), Section 7 (Technology Selection and Limits
Development), and Section 8 (Cost and Effluent Reduction Benefits).
12-2
-------
12.1 SUMMARY OF PSES AND PSNS
The Agency considered pollutants to regulate in PSES and PSNS on
the basis of whether or not they pass through, cause an upset, or otherwise
interfere with the operation of a POTW. EPA is proposing to develop PSES and
PSNS for 26 of the 28 priority pollutants and for the same 91 PAIs and classes
of PAIs proposed under BAT and NSPS. Two priority pollutants, 2-chlorophenol
and 2,4-dichlorophenol, do not pass through or interfere with POTW operation,
so PSES and PSNS are not being set for these two pollutants.
The Agency considered the same technologies discussed for BAT and
NSPS since indirect dischargers are expected to generate wastewaters with the
same pollutant characteristics. However, end-of-pipe biological treatment
would not be required for priority pollutants, since the primary function of
biological treatment is to reduce BOD loadings, whether at the plant or at a
POTW. A complete discussion of the options considered for PSES and PSNS are
included in Sections 7.4.6 and 7.5.6, along with the options selected for
regulation.
EPA estimates that the proposed PSES regulation will result in the
incremental removal of 105,000 pounds per year of pesticide active
ingredients, and 29,000 pounds per year of priority pollutants. EPA estimates
that cost for compliance with the proposed PSES are capital costs of $9.1
million and annualized costs of just over $6.4 million (1986 dollars). (See
12-3
-------
"Economic Impact Analysis of Effluent Limitations and Standards of the
Pesticide Manufacturers".)
12.2 PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)
The proposed pretreatment standards for existing and new sources
(PSES/PSNS) for organic PAIs and classes of PAIs and priority pollutants under
the organic pesticide chemicals manufacturing subcategory (Subcategory A) are
listed in Tables 12-1, 12-2, 12-3, and 12-4.
12-4
-------
Table 12-1
PSES FOR ORGANIC PESTICIDE ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient (PAI)
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 403 [Potassium N-
hydroxymethyl-N-
methyldithiocarbamate]
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed lb./l,000 ti>. PAI
production
1.19 x 10^
Monthly
Average Shall
not Exceed
U>./1,000 Ib.
FAI production
3.40 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.32 x 10-2
8.82 x 10-4
7.23 x 10-4
2.10 x 10-3
2.56 x 10-3
2.74 x ID'2
3.22 x 10^
1.91 x 10-'
8.79 x 10-3
2.68 x 10-*
3.12 x W-4
9.14 x 10-*
1.02 x 10-3
1.41 x 10-2
1.09 x 10-4
5.14 x 10-2
No discharge of process wastewater pollutants
1.69 x 10-2
8.72 x 10-3
No discharge of process wastewater pollutants
1.24 x 10-1
3.95 x 10-3
3.95 x 10-3
5.74 x ID'3
4.18 x 10-2
1.27 x 10-3
1.27 x lO'3
1.87 x 10-3
12-5
-------
Table 12-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Busan 853 [Potassium
dimethyldithiocarbamate ]
Butachlor
Captafol
Carbarn S3 [Sodium
dimethyldithiocarbamate ]
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cy anaz ine
Dazomet3
DCPA
DEF
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed U»./ 1,000 li. PAI
production
5.74 x 10-3
3.53 x 10-3 -
Monthly
Average Shall
not Exceed
It. /1, 000 Ib.
PAI production
1.87 x 10-3
1.09 x 10-3
No discharge of process wastewater pollutants
5.74 x 10-3
1.60 x lO'3
1.18 x 10-4
8.16 x 10-2
1.51 x 10-3
3.27 x 10-4
1.63 x 10-3
5.74 x 10-3
7.79 x 10-2
1.15 x 10-2
2.82 x 10-3
1.87 x 10-3
7.30 x 10-*
2.80 x 1C'5
3.31 x 10-2
4.57 x 10-1
9.96 x 10-5
8.11 x 10-4
1.87 x 10-3
2.64 x 10-2
5.58 x 10-3
1.12 x ID'3
No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x lO'2
7.33 x 10-3
3.15 x 10-2
2.95 x 10-5
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x 10-2
12-6
-------
Table 12-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
Ethion
Fenarimol
Fens ul f o th i on
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Methoxychlor
Metribuzin
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed lb./l,OOD li>. PAI
production
Monthly
Average Shall
not Exceed
IB. /1, 000 Ib.
PAI production
No discharge of process wastewater pollutants
2.20 x lO'2
3.22 x 10^
7.37 x 10-4
1.02 x 10-'
1.48 x 10-2
1.83 x 10-2
5.40 x 10-3
5.10 x lO'3
1.09 x 10-1
2.99 x W^
3.61 x 10-2
7.64 x 10-3
9.45 x lO'3
2.08 x 10-3
No discharge of process wastewater pollutants
8.80 x lO'3
7.06 x lO'3
5.74 x 10-3
2.69 x lO'3
2.35 x 10-4
2.90 x 10-3
2.49 x 10-3
1.87 x lO'3
1.94 x lO'3
9.55 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.46 x 10-2
3.82 x 10-3
3.23 x 10-3
1.36 x 10-2
5.58 x 10-3
7.53 x 10-3
1.76 x lO'3
1.31 x 10-3
7.04 x 10-3
12-7
-------
Table 12-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Mevinphos
Nab am3
Nabonate3
Naled
Norflurazon
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
Pretreatment Standards for Existing Sources
(PSES)
Daily Haxlimm Shall Hot Exceed Ib./l.OOO lb. PAI
production
1.44 x 10*
5.74 x 10-3
5.74 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 It.
PAI production
5.10 x 10-5
1.87 x lO'3
1.87 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.72 x 10-2
7.72 x 10"
7.72 x 10*
5.75 x 10*
3.21 x lO'3
2.32 x 10"
2.51 x 10"
7.42 x 10-3
3.43 x 10"
3.43 x 10"
1.90 x 10"
1.06 x ID'3
6.06 x 1C'5
7.53 x 10"
No discharge of process wastewater pollutants
2.10 x 10-3
2.10 x lO'3
2.00 x 10"
5.34 x lO'3
1.06 x 10-3
2.10 x 10-3
9.14 x 10"
9.14 x 10"
6.90 x lO'5
1.66 x 10-3
4.84 x 10"
9.14 x 10"
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.10 x lO'3
9.14 x 10"
12-8
-------
Table 12-1
(Continued)
Organic Pesticide Active
Ingredient (PAI)
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [Sodium
methyldithiocarbamate ]
Ziram3 [Zinc
dimethyldithiocarbamate ]
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed Ib./l.OOO JJb. PAI
production
4.10 x lO'3
2.88 x 10"
9.78 x 1C'2
1.51 x ID'1
4.09 x 10^
2.10 x 10-3
2.10 x 1C'3
1.02 x 10-2
6.52 x 10-2
3.22 x 10-4
5.74 x 10-3
5.74 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 It.
PAI production
1.35 x lO'3
8.96 x 10-5
3.40 x 10-2
5.12 x 10-2
1.06 x 10"
9.14 x W^
9.14 x 10"4
3.71 x 10-3
3.41 x 10--
1.09 x W-4
1.87 x ID'3
1.87 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
wastewaters.
2Monitor and report as total toluidine PAIs, as Trifluralin.
3Monitor and report as total dithiocarbamates, as Ziram.
4Monitor and report as total tin.
5Applies to purification by recrystalization portion of the process.
12-9
-------
Table 12-2
PSES FOR PRIORITY POLLUTANTS
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2 -Dichloroethane
1,1, 1-Trichloroe thane
Trichlorome thane
1 , 2-Dichlorobenzene
1 ,4-Dichlorobenzene
1 , 1-Dichloroethylene
1 , 2-Trans-Dichloroethylene
1, 2-Dichloropropane
1 , 3-Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chi o r ome thane
Bromome thane
Tr ib r omome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
Pretreatment Standards
for Existing (PSES)1
Ma-rimimi £Or Any One Day
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Maximum for Monthly
Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
12-10
-------
Table 12-2
(Continued)
Priority Pollutant
Total Cyanide
Total Lead2
Pretreatment Standards
for Existing (PSES)1
Maximum for Any One Day
640
690
Maximum for Monthly
Average
220
320
'All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead and zinc from complexed metal-bearing process wastewater
are not subject to these limitations.
12-11
-------
Table 12-3
PSNS FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen1
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1'2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 403
Busan 853
Butachlor
Captafol
Carbarn S3
Pre treatment Standards for New Sources (PSNS)
Daily Maximum Shall Hot Exceed Ub./l,000
Lb, PA1 production
8.54 x lO'5
Monthly Average
Shall Mot Exceed
It, /I. 000 Ib. FAX
production
2.45 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.67 x 10-2
6.35 x 10"
5.21 x 10-4
1.51 x 10-3
1.85 x 10-3
1.97 x 10-2
2.32 x 10"
1.37 x 10-'
0
1.22 x 10-2
6.33 x 1C'3
1.93 x 10"
2.25 x 10"
6.58 x 10"
7.32 x 10"
1.02 x lO'2
7.82 x lO'5
3.70 x 10-2
0
6.27 x 10-3
No discharge of process wastewater pollutants
8.89 x 10-2
2.84 x 10-3
2.84 x 10-3
4.14 x 10-3
4.14 x 10-3
2.54 x 10-3
3.01 x 10-2
9.14 x 10"
9.11 x 10"
1.35 x 10-3
1.35 x 10-3
7.87 x 10"
No discharge of process wastewater pollutants
4.14 x 10-3
1.35 x 10-3
12-12
-------
Table 12-3
(Continued)
Organic Pesticide Active
Ingredient
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cyanazine
Dazomet
DCPA
DEF [S,S,S-Tributyl
phosphorotrithioate ]
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
Ethion
Fenarimol
Fensulfothion
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Not Exceed Ub./l,000
Lb. PAX production
1.07 x 10-3
1.18 x 10^
5.87 x 10-2
1.09 x 10-3
2.35 x W-4
1.18 x 10-3
4.14 x lO-3
5.61 x 10-2
1.15 x 10-2
2.05 x 10-3
Monthly Average
Shall Not Exceed
li./l,000 li. PAI
production
4.76 x 10-4
2.80 x 10-5
2.39 x 10-2
3.29 x 10^
7.17 x 10-5
5.84 x 10"4
1.35 x lO'3
1.90 x lO'2
5.58 x 10-3
8.13 x 10-4
No discharge of process wastewater pollutants
6.88 x 10-5
3.41
1.51 x 10-'
5.28 x 10-3
2.27 x 10-2
2.13 x 10-5
1.03
5.76 x 10-2
2.72 x lO'3
1.01 x 10-2
No discharge of process wastewater pollutants
1.77 x lO'2
2.32 x 10-*
5.31 x 10-4
7.31 x 10-2
1.06 x 10-2
5.25 x 10-3
7.85 x lO'5
2.15 x 10-*
2.60 x 10-2
5.50 x 10-3
12-13
-------
Table 12-3
(Continued)
Organic Pesticide Active
Ingredient
Fenthion
Fenvalerate
Glyphosate , salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Me thami dopho s
Methomyl1
Methoxychlor
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norf lurazon
Organotins4
Parathion Ethyl
Farathion Methyl
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Kot Exceed Ub./l,000
li. PAI production
1.32 x 10-2
3.91 x 10-3
Monthly Average
Shall Not Exceed
li./l,000 IJb. PAI
production
6.79 x 10-3
1.50 x 10-3
No discharge of process wastewater pollutants
5.42 x 10-3
5.07 x 10-3
4.14 x 10-3
1.94 x 10-3
1.69 x 10"4
1.73 x lO'3
1.82 x lO'3
1.35 x lO'3
1.40 x 10-3
6.88 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.05 x 10-2
2.75 x 10-3
2.34 x 10-3
9.80 x 10-3
1.03 x 10-*
4.14 x 10-3
4.14 x 10-3
5.58 x 10-3
5.42 x ID'3
1.27 x lO'3
9.25 x 10-*
5.06 x 10-3
3.69 x 10-5
1.35 x lO'3
1.35 x lO'3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.25 x 10-2
5.56 x W*
5.56 x 10-*
5.36 x ID'3
2.45 x W*
2.45 x 10-4
12-14
-------
Table 12-3
(Continued)
Organic Pesticide Active
Ingredient
PCNB
Pendimethalin
Pentachlorophenol, salts
and esters
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
S imaz ine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthy laz ine
Terbutryn
Toxaphene
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Not Exceed li./ 1,000
li. PAI production
4.16 x 10-1
8.81 x 1C'3
Monthly Average
Shall Hot Exceed
Ub./l.OOO It. PAI
production
1.38 x 10^
2.79 x 10-3
No discharge of process wastewater pollutants
1.68 x 10-4
1.81 x W-*
4.39 x lO'5
5.43 x 10-3
No discharge of process wastewater pollutants
1.51 x 10-3
1.51 x 10-3
1.28 x 10-1
3.84 x 10-3
7.63 x 10-4
1.51 x 1C'3
6.58 x 10-*
6.58 x 10"1
4.34 x lO'5
1.19 x 10°
3.48 x 10-4
6.58 x 10^
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.51 x lO'3
2.95 x 10-3
2.07 x 10-4
7.04 x 10-2
1.09 x 10-'
2.95 x 10-*
1.51 x 10-3
1.51 x 10-3
7.35 x 10-3
6.58 x 10^
9.72 x 10-*
6.45 x 10-5
2.45 x 10-2
3.69 x 10-2
7.62 x 10-5
6.58 x 10^
6.58 x 10-4
2.67 x 1C'3
12-15
-------
Table 12-3
(Continued)
Organic Pesticide Active
Ingredient
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Hot Exceed li>./1,000
Lb. FAX production
Monthly Average
Shall Hot Exceed
tb./l.bOO li. PAI
production
Triadimefon
Trifluralin1'2
Vapam3 [Sodium
methyldithiocarbamate]
Ziram3 [Zinc
dimethyldithiocarbamate]
4.69 x 10-2
2.32 x 10*
3.86 x 10-3
4.14 x 10-3
2.46 x 10-2
7.82 x 10-5
1.39 x 10-3
1.35 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
wastewaters.
2Monitor and report as total toluidine PAIs, as Trifluralin.
3Monitor and report as total dithiocarbamates, as Ziram.
"Monitor and report as total tin.
5Applies to purification by recrystallization portion of the process.
12-16
-------
Table 12-4
PSNS EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-Trans-Dichloroethylene
1, 2-Dichloropropane
1 , 3-Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tr ib romome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
Pretreatment Standards
for New Sources (PSNS)1
MaTriimim for Any One Day
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Maximum for Monthly
Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
12-17
-------
Table 12-4
(Continued)
Priority Pollutant
Total Cyanide
Total Lead2
Pretreatment Standards
for New Sources (PSNS)1
Mailman for toy One Day
640
690
Maximum for Monthly
Average
220
320
'All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead and zinc from complexed metal-bearing process wastewater
are not subject to these limitations.
12-18
-------
SECTION 13
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY (BCT)
13.0 INTRODUCTION
The 1977 Amendments to the Clean Water Act added Section
301(b)(2)(E), establishing "best conventional pollutant control technology"
(BCT) for the discharge of conventional pollutants from existing industrial
point sources. Section 304(a)(4) designated the following as conventional
pollutants: BOD5, TSS, fecal coliform, pH, and any additional pollutants
defined by the Administrator as conventional. On July 30, 1979 (44 FR 44501),
the Administrator designated oil and grease as a conventional pollutant.
The BCT effluent limitations guidelines are not additional
guidelines, but instead, replace guidelines based on the application of the
"best available technology economically achievable" (BAT) for the control of
conventional pollutants. BAT effluent limitations guidelines remain in effect
for nonconventional and toxic pollutants. Effluent limitations based on BCT
may not be less stringent than the limitations based on "best practicable
control technology currently available" (BPT). Thus, BPT limitations are a
"floor" below which BCT limitations cannot be established.
In addition to other factors specified in Section 304(b)(4)(B),
the CWA requires that the BCT effluent limitations guidelines be assessed in
light of a two-part "cost-reasonableness" test [see American Paper Institute
13-1
-------
EPA. 660 F 2d 954 (4th Cir. 1981)]. The first test compares the cost for
private industry to reduce its discharge of conventional pollutants with the
cost to publicly owned treatment works (POTWs) for similar levels of reduction
in their discharge of these pollutants. The second test examines the cost-
effectiveness of additional industrial treatment beyond BPT. EPA must find
that the limitations are "reasonable" under both tests before establishing
them as BCT. If the BCT technology fails the first test, there is no need to
conduct the second test, because the technology must pass both tests. EPA
promulgated a methodology for establishing BCT effluent "limitations guidelines
on July 9, 1986 (51 FR 24974).
13.1 JULY 9, 1986 BCT METHODOLOGY
The BCT methodology promulgated in 1986 addressed the costs that
the EPA must consider when deciding whether to establish BCT effluent
limitations guidelines. EPA evaluates BCT candidate technologies (those that
are technologically feasible) by applying a two-part cost test including: (1)
the POTW test; and (2) the industry cost effectiveness test.
To "pass" the POTW test, EPA must determine that the cost per
pound of conventional pollutant removed by industrial dischargers in upgrading
from BPT to a BCT candidate technology is less than the cost per pound of
conventional pollutant removed in upgrading POTWs from secondary treatment to
advanced secondary treatment. The upgrade cost to industry must be less than
the POTW benchmark of $0.25 per pound in 1976 dollars for industries whose
13-2
-------
cost per pound is based on long-term performance data (Tier I POTW benchmark),
or less than $0.14 per pound for industries whose cost per pound is not based
on long-term performance data (Tier II POTW benchmark).
If a candidate technology passes the POTW cost test, the industry
cost-effectiveness test is then applied. For each industry subcategory, EPA
computes a ratio of two incremental costs. The first is the cost per pound of
conventional pollutants removed by the BCT candidate technology relative to
BPT; the second is the cost per pound of conventional pollutants removed by
BPT relative to no treatment (i.e., the second cost compares raw wasteload to
pollutant load after application of BPT). The ratio of the first cost divided
by the second is a measure of the candidate technology's cost-effectiveness.
The ratio is compared to an industry cost benchmark, which is based on POTW
cost and pollutant removal data. The benchmark, like the measure for a
candidate technology, is a ratio of two incremental costs: the cost per pound
to upgrade a POTW from secondary treatment to advanced secondary treatment
divided by the cost per pound to initially achieve secondary treatment from
raw wasteload. If the industry ratio is lower than the benchmark, the
candidate technology passes the industry cost-effectiveness test. The Tier I
benchmark for industries whose ratio is based on long-term performance data is
1.29. The Tier II benchmark for industries whose ratio is not based on long-
term performance data is 0.68.
In calculating this ratio, EPA considers any BCT cost per pound
less than $0.01 to be the equivalent of zero costs. There may be cases where
13-3
-------
the numerator for the industry cost ratio and therefore the entire ratio is
taken to be zero. EPA believes any zero cost per pound for a candidate BCT
technology meets Congressional intent concerning the concept of reasonableness
for purpose of the second test.
If a candidate technology fails the POTW test or passes the POTW
test and fails the industry cost-effectiveness test, then that technology is
not used as the basis of BCT.
13.2 BCT TECHNOLOGY OPTIONS
The primary technology option the Agency identified to attain
further TSS and BOD reduction for the organic pesticide chemicals subcategory
was the addition of multi-media filtration to existing BPT systems.
The Agency also considered the options of carbon adsorption,
membrane filtration, incineration, evaporation, additional biological
oxidation (above the level required to meet BPT). and clarification through
the use of settling ponds.
Both carbon adsorption and membrane filtration require filtration
of wastewater prior to treatment; therefore, the cost of filtration plus
carbon adsorption or membrane filtration would be more than the cost of
filtration alone. In addition, while these two technologies can be effective
in removing specific compounds from wastewater, they may not be particularly
13-4
-------
effective in removing those materials exerting biochemical oxygen demand.
Incineration and evaporation were projected to have much higher costs than
multi-media filtration due to the need to purchase fuel. Therefore, due to
their costs, the Agency excluded both incineration and evaporation from
further consideration. Biological oxidation and clarification were used as
the basis for BPT, and there are no data to demonstrate that higher effluent
quality could be achieved for PAI manufacturing wastewaters by increasing
biological residence time, increasing mixed liquor suspended solids, or
through the addition of settling ponds, and so these options were rejected.
Finally, the Agency studied the use of polymers and coagulants to enhance
clarification. While some facilities use these chemical agents on specific
pesticide-containing wastewaters to enhance treatment system performance,
there was no data available to demonstrate additional removal of the
conventional pollutants. Therefore, this option was rejected for lack of
data. Therefore, only multi-media filtration was considered further as a BCT
technology upgrade for the organic pesticide subcategory.
EPA is reserving BCT for Subcategory B because BPT limitations
already require zero discharge of process wastewater pollutants. This is the
most stringent limitation possible; there is no need for BCT regulations
reflecting more stringent control techniques.
13-5
-------
13.3 BCT COST TEST ANALYSIS
The Agency evaluated multi-media filtration technology to
determine whether it passed the POTW test (and if necessary the industry cost
effectiveness test).
13.3.1 The POTW Cost Test
To determine the cost per pound of conventional pollutants removed
for a technology upgrade from BPT to BCT for the organic pesticide chemicals
subcategory, the Agency calculated:
The increase in the total annual cost for the BPT to BCT
technology upgrade. Total annual costs include capital
costs, interest, and operation and maintenance costs.
Capital costs are amortized over 30 years at a 10 percent
interest rate. The cost estimates were indexed to 1976
dollars for a consistent comparison to the POTW benchmark.
(51 FR 24982)
The increase in the removal of conventional pollutants for
the BPT to BCT technology upgrade. The increase in removal
is expressed as the yearly increase in the total pounds of
BODj and TSS removed, due to the upgrade. Conventionals
considered in the total include BOD5 and TSS.
The increase in the total annual cost was then divided by the increase in
conventionals removed and this result ($/lb) was compared to the Tier I ($0.25
per pound) POTW benchmark.
13-6
-------
13.3.2 Application to the Organic Pesticide Chemicals Manufacturing
Subcategory
The Agency used the CAPDET cost model for costing the multi-media
filtration technology upgrade considered for BCT. Input parameters to the
filtration module include:
• Flow;
• Influent BOD and TSS concentrations; and
• Effluent BOD and TSS concentrations.
The module runs in two modes; high flow (flow greater than 0.5 million gallons
per day (MGD)) and low flow (flow less than 0.5 MGD). The unit cost of
treatment would be lower at the high flow plant due to economics of scale.
Pesticide facilities with information on PAI wastewater flows and
PAI production rates were split into either the high flow or low flow
categories. A median flow and yearly PAI production rate were then determined
for each flow category. Only one facility fell into the high flow category;
the remaining facilities fell into the low flow category.
Long-term BPT data for BOD and TSS were used to determine the
influent BOD and TSS concentrations to the multi-media filter. Since these
BOD and TSS data are mass based (i.e. 1.12 Ib. BOD/1000 Ibs. of production and
1.31 Ib. TSS/1000 Ibs. of production), the high flow and low flow production
13-7
-------
values and flows were used with the mass-based long-term data to determine BOD
and TSS influent concentrations.
To determine the effluent BOD and TSS concentrations for the
CAPDET module, BOD and TSS removal efficiencies through a multi-media filter
were estimated from available sampling data on a filtration unit (Pesticide
Sampling Episode 1332). These removal data represent a settling pond followed
by a sand filter system. It was assumed, for the purpose of this analysis,
that all of the BOD and TSS removal that occurred was due to the sand filter;
this assumption provides the sand filter with the best chance of passing the
cost test (since during the sampling episode, some removal probably occurred
due to the settling pond). This assumption will overestimate the removal
efficiency of the sand filter and will also yield a cost effectiveness for the
filter that is as low as possible since the cost of the sand filter alone must
be less than the cost of a sand filter plus a settling pond. The BOD and TSS
removals from the combined sand filter/settling pond system during sampling
were 48 percent BOD removal and 53 percent TSS removal.
Using the flows and the influent and effluent BOD and TSS
concentrations discussed above in the CAPDET module, annualized costs (in 1976
dollars) for the technology upgrade from BPT to BCT were calculated. The
yearly pounds of conventional pollutants removed by the technology upgrade
from BPT to BCT was then determined for both the high and low flow categories.
The conventionals considered in this calculation were BOD and TSS.
13-8
-------
Finally, a. removal cost ($/lbs. of conventional pollutants
removed) was determined by dividing the incremental annual cost by the BOD and
TSS removal for each flow category. Since long-term data were available for
Subcategory A, the removal costs for each flow scenario were compared to the
Tier I POTW test value of $0.25/lb. of conventional pollutants removed. The
results of the POTW cost test, including the annual costs ($/yr), BOD and TSS
removals (Ib/yr), and removal costs ($/lb), are presented in Table 13-1.
13.4 CONCLUSIONS
As seen in Table 13-1, the proposed BCT technology, multi-media
filtration, fails the POTW cost test. Therefore, multi-media filtration is
not a technology basis for BCT in the organic pesticide chemicals
manufacturing subcategory and the Agency is proposing to set BCT equal to BPT
for this subcategory.
EPA is reserving BCT for the metallo-organic pesticide chemicals
manufacturing subcategory.
13-9
-------
Table 13-1
POTW COST TEST RESULTS FOR THE
ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY
Facility
Type
High Flow
Low Flow
($/yr)
Annual Cost
1976 $
87,622
45,116
(Ib/yr)
BOD & TSS
Removal
200,800
23,061
($/lb)
Removal
Cost
0.44
1.96
POTW
Test
Pass/Fail*
Fail
Fail
*The removal costs ($/lb.) were compared against $0.25/lb. of conventional
pollutant removed. This POTW removal cost represents the Tier I value which
is used when long-term data are available for an industry.
13-10
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SECTION 14
METALLO-ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY
The Agency is proposing to reserve BCT, BAT, NSPS, PSES , and PSNS for
the metallo-organic pesticide chemicals manufacturing subcategory. In 1986,
there were only eight facilities producing pesticides in this subcategory, and
no facility was manufacturing organo-cadmium pesticides. Current BPT requires
no discharge of process wastewater pollutants from facilities producing metallo-
organic pesticides containing arsenic, copper, cadmium, or mercury. Therefore,
BCT, BAT and NSPS regulations for Subcategory B are unnecessary.
Metallo-organic pesticide processes generate much smaller volumes of
wastewater than organic pesticide processes. As discussed in Section 5,
Subcategory B processes generated only about 3 million gallons of wastewater in
1986 compared to about 1.5 billion gallons from Subcategory A processes. Only
about 600,000 gallons of this Subcategory B wastewater were discharged to POTWs.
In addition, the Agency estimates that current discharges of metallo-organic PAIs
and priority pollutants in Subcategory B wastewaters total only 60 pounds per
year. (Since there are no analytical methods for the specific metallo-organic
PAIs, these compounds are monitored by measuring the amount of total arsenic,
copper, or mercury present in the wastewater.)
The Agency considered proposing PSES requiring no discharge of
process wastewater pollutants, but determined that the only way the facilities
could achieve this standard is by off-site disposal. Off-site disposal was
14-1
-------
determined not to be economically achievable because two of the five indirect
discharging facilities in this subcategory are projected to close if forced to
meet that standard. Other options, such as imposing treated discharge
requirements, were considered unnecessary since the existing indirect dischargers
are already subject to locally imposed pretreatment limits which EPA believes
provide adequate protection for the POTW and the environment. Imposing
additional controls based on the BAT technologies would result in the additional
removal of only three of the 60 pounds of priority pollutants currently being
discharged annually by these five facilities. In light of the relatively small
amount of pollutants being discharged, EPA proposes not to establish regulations
for existing indirect dischargers in this subcategory.
Concerning PSNS, the Agency believes it is unlikely that there will
be any new manufacturers of metallo-organic pesticides currently being
manufactured. New manufacturing plants, to the extent there are any, would very
likely produce only new pesticides not registered in 1986. EPA believes that no
new producers of metallo-organic pesticides are likely since there have been no
new plants and no new me tallo-organic PAIs produced in this subcategory for more
than 20 years.
14-2
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SECTION 15
NON-WATER QUALITY ENVIRONMENTAL IMPACTS
15.0 INTRODUCTION
The elimination or reduction of one form of pollution may create
or aggravate other environmental problems. Therefore, Sections 304(b) and 306
of the Clean Water Act call for EPA to consider the non-water quality
environmental impacts of certain regulations. Pursuant to these provisions,
EPA has considered the effect of the BAT regulations on air pollution, solid
waste generation, and energy consumption.
The non-water quality environmental impacts associated with this
regulation are described in subsections 15.1 to 15.3.
15.1 AIR POLLUTION
Pesticide facilities generate wastewaters that contain significant
concentrations of organic compounds, some of which are also on the list of
Hazardous Air Pollutants (HAP) in Title 3 of the Clean Air Questionnaire
(CAAA) of 1990. These wastewaters typically pass through a series of
collection and treatment units that are open to the atmosphere and allow
wastewaters containing organic compounds to contact ambient air. Atmospheric
exposure of these organic-containing wastewaters may result in significant
15-1
-------
volatilization of both volatile organic compounds (VOC), which contribute to
the formation of ambient ozone, and HAP from the wastewater.
VOC and HAP are emitted from wastewater beginning at the point
where the wastewater first contacts ambient air. Thus, VOC and HAP from
wastewater may be of concern immediately as the wastewater is discharged from
the process unit. Emissions occur from wastewater collection units such as
process drains, manholes, trenches, sumps, junction boxes, and from wastewater
treatment units such as screens, settling basins, equalization basins,
biological aeration basins, air or stream strippers lacking air emission
control devices, and any other units where the wastewater is in contact with
the air.
The proposed regulations are based on the use of steam stripping
rather than air stripping as an in-plant technique for controlling volatile
organic compounds. Also, steam strippers are proposed in conjunction with
chemical oxidations systems as a combined BAT-level technology to prevent air
emissions of chlorinated priority pollutants from the chemical oxidation
effluent.
No negative air pollution impacts are expected due to the proposed
regulations. Instead, the implementation of steam stripping as an in-plant
control technique should decrease air emissions of volatile wastewater
pollutants. Based on raw wastewater loading estimates, air emissions of
volatile priority pollutants would decrease by about 6 million pounds per year
15-2
-------
due to steam stripping when used as an in-plant control technology. Also,
steam strippers are proposed in conjunction with chemical oxidation systems to
ensure no air emissions of chlorinated priority pollutants from the chemical
oxidation effluent. The proposed regulation, however, does not require steam
stripping or any specific technology, but only establishes the amount of
pollutant that can be discharged to navigable waters.
The Agency in the OCPSF rule concluded that the issue of volatile air
emissions is best addressed under laws that specifically direct EPA to control
air emissions. (EPA notes, however, that all of the pesticides manufacturing
plants that currently use stripping are using steam strippers and not air
strippers.) There are, in fact, activities underway under the Clean Air Act
to address emissions of VOCs from industrial wastewater. Specifically, the
Agency plans to issue a Control Techniques Guideline (CTG) for Industrial
Wastewater (IWW) under Section 110 of the CAA (Title 1 of the 1990 CAAA). The
Pesticide Chemicals Industry is one of several industries that would be
covered by the IWW CTG. The IW¥ CTG will provide guidance to the States in
recommending reasonably available control technology (RACT) for VOC emissions
from industrial wastewater at facilities located in areas failing to attain
the National Ambient Air Quality Standards for ozone. The Agency also plans
to issue a National Emission Standard for Hazardous Air Pollutants (NESHAP)
under Section 112 of the CAA to address air emissions of the HAP listed in
Title 3 of the 1990 CAAA. This NESHAP will define maximum achievable control
technology (MACT). MACT standards are technology-based standards. The 1990
CAAA set maximum control requirements on which MACT can be based for new and
15-3
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existing sources. RACT for the CTG and MACT for the NESHAP will be based on
the same control strategy. That control strategy is:
1. Identify wastewater streams requiring control;
2. Control the conveyance of the wastewater to the treatment unit
(hardpipe, control vents and openings);
3. Treat the wastewater to remove or destroy the organic compound
(e.g. steam stripping);
4. Control air emissions from the treatment unit; and
5. Control residuals removed during treatment.
In view of the upcoming air emission guidelines and standards, the
Agency encourages facilities to consider integrated multi-media approaches
when designing methods of complying with the upcoming pesticide effluent
guidelines. Combining compliance with the effluent guidelines and upcoming
CAA regulations will be more economical than individual compliance with each
rule.
No significant increase in air emissions are expected due to
implementation of biological treatment as a BAT since volatile pollutants, if
present in significant quantities, would be removed prior to biotreatment by
in-plant steam stripping. There is also no significant impact in air
emissions expected due to incineration because of the small volume of
wastewater (less than 50,000 gallons per year) estimated to be disposed of in
this manner.
15-4
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15.2 SOLID WASTE
Solid waste would be generated due to the following technologies,
if implemented to meet proposed regulations: steam stripping, hydroxide
precipitation, and biotreatment. The solid wastes generated due to the
implementation of the technologies discussed above were costed for disposal by
off-site incineration. These costs were included in the economic evaluation
of the proposed technologies.
The overhead stream from steam stripping is assumed to represent
an organic waste and was costed for disposal. In some cases, due to the large
volume of the overhead stream, the Agency costed two steam strippers in
series, with the second steam stripper treating the overheads stream from the
first stripper. In these cases, the only organic waste that would need
disposal is the overheads from the second steam stripper. EPA estimates that
about 12 million pounds per year of organic waste would be generated due to
steam stripping. While EPA believes that much of this may be amenable to
recovery and reuse, EPA was unable to quantify the amount that could be
recovered and therefore assumed that all would be incinerated. To provide
perspective on the potential incremental increase in solid waste generation
due to the proposed rule, EPA reviewed national capacity for organic waste
disposal. The national incinerator capacity, including kilns and boilers, is
estimated by EPA to be greater than 3 billion pounds per year.
15-5
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Hydroxide precipitation technology utilizes calcium hydroxide or a
similar chemical reagent to treat metal-containing wastewaters. The
precipitated solids represent a solid waste. It is estimated that 31 thousand
pounds per year of precipitated solids would be generated due to the
implementation of hydroxide precipitation at one facility. For comparison,
EPA estimates from the Toxic Release Inventory (TRI) database that 445 million
pounds of toxic chemicals were disposed in landfills in 1989.
Biotreatment is the proposed technology for controlling PAI
wastewater discharges at two facilities. Biosludge is continuously generated
during biotreatment, and part of the sludge must be discharged from the
treatment system to ensure proper operation. It is estimated that 48,000
pounds per year of biosludge will be generated due to the proposed
regulations. For comparison, EPA estimates that 15,000 POTWs generate almost
8 million tons of sludge annually, while compliance with OCPSF BAT effluent
guidelines is projected to increase solid waste generation by over 22,000 tons
annually.
15.3 ENERGY REQUIREMENTS
Energy requirements will increase minimally due to pumping needs
associated with the proposed technologies. However, the main energy
requirement in this regulation is due to steam use by the proposed steam
strippers. Steam provides the heat energy necessary to separate volatile
pollutants from wastewater streams treated by this technology. It is
15-6
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estimated that about 800 million pounds per year of steam would be required by
steam strippers; this amounts to an estimated use of 187,000 barrels per year
of fuel oil; the United Stated currently consumes about 19 million barrels per
day.
15-7
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SECTION 16
ANALYTICAL METHODS
16.0 REGULATORY BACKGROUND AND REQUIREMENTS
16.1 CLEAN WATER ACT (CWA)
Under the Clean Water Act, EPA promulgates guidelines establishing
test procedures for the analysis of pollutants (see 304(h), 33 U.S.C. Section
1314(h)). The Administrator has made these procedures applicable to
monitoring and reporting of National Pollutant Discharge Elimination System
(NPDES) permits and to implementation of pretreatment standards.
Under the Clean Water Act, the Agency regulates three broad
categories of pollutants: conventional pollutants, toxic pollutants, and non-
conventional pollutants.
The pollutants designated as conventional pollutants under Section
304(a)(4) of the CWA are: (1) Biological Oxygen Demand (BOD), (2) Total
Suspended Solids (TSS), (3) Fecal Coliforms, (4) pH, and (5) Oil and Grease.
The list of these pollutants has been promulgated at 40 CFR Part 401.16.
The pollutants designated as toxic pollutants under Section
307(a)(l) of the CWA are the list of 65 compounds and classes of compounds
16-1
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promulgated at 40 CFR 401.15, and expanded to the list of 126 "Priority
Pollutants" presented at 40 CFR Part 423, Appendix A.
The pollutants designated as non-conventional pollutants under the
CWA are those pollutants not -identified as either conventional pollutants or
toxic pollutants.
Pesticides industry wastewaters contain conventional pollutants
and many of the toxic pollutants, and most active ingredients are non-
conventional pollutants.
Analytical methods for conventional pollutants, toxic pollutants,
and some non-conventional pollutants have been promulgated under Section
304(h) of the CWA at 40 CFR Part 136. In addition to the methods developed by
EPA and promulgated at 40 CFR Part 136, certain methods developed by other
Agencies and by associations such as the American Public Health Association
which publishes "Standard Methods for the Examination of Water and Wastewater"
have been incorporated by reference into 40 CFR Part 136.
Many of the currently approved promulgated methods for PAIs do not
include the most recent advances in technology, particularly the clean-up
procedures necessary to eliminate interferences and improve reliability, nor
do they account for the latest and most sensitive detection devices, which
permit accurate detection of PAI pollutants at very low concentrations. This
latest technology is used by many companies to monitor wastewaters, and was
16-2
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used by EPA in its sampling of pesticide manufacturing industry wastewaters.
All of the PAI pollutant data EPA is relying on for the proposed effluent
limitations used analytical methods employing the latest in analytical
technology. EPA is proposing that compliance monitoring of effluent from the
manufacture of the 122 PAIs proposed for regulation must employ methods listed
in Table 16-1, and will not be permitted to use the methods promulgated at
40 CFR Part 136 (except where the Part 136 method is identical to the proposed
method in Part 455).
16.1.1 Safe Drinking Water Act (SDWA)
The SDWA authorizes the Agency to set primary drinking water
regulations for public water suppliers. Public water suppliers are required
to perform routine monitoring to demonstrate compliance with these
regulations. To support this monitoring, EPA has provided a set of test
procedures for measurement of pollutants in drinking water. These procedures
have been promulgated at 40 CFR Part 136.
Publications containing methods for the determination of many
pesticide active ingredients are EPA/600/4-88/039 "Methods for Determination
of Organic Compounds in Drinking Water" (December 1988), and EPA/600/4-90/020
"Methods for Determination of Organic Compounds in Drinking Water
Supplement I" (July 1990). EPA is proposing to allow use of these drinking
water methods in monitoring pesticide active ingredients in pesticide industry
wastewaters.
16-3
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Table 16-1
TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS
EPA
Survey
Code
8
12
16
17
22
25
26
27
30
31
35
39
41
45
52
53
54
Pesticide Name
Triadimefon
Dichlorvos
2,4-D; 2,4-D Salts and
Esters [2,4-
Dichlorophenoxyacetic acid]
2,4-DB; 2,4-DB Salts and
Esters [2,4-
Dichlorophenoxybutyric acid]
Mevinphos
Cyanazine
Propachlor
MCPA; MCPA Salts and Esters
[2-Methyl-4-
chlorophenoxyacetic acid]
Dichlorprop; Dichlorprop
Salts and Esters [2- (2, 4-
Dichlorophenoxy) propionic
acid]
MCPP; MCPP Salts and Esters
[2-(2-Methyl-4-
chlorophenoxy) propionic
acid]
TCMTB [2-
(Thiocyanomethylthio)
benzothiazole ]
Pronamide
Propanil
Metribuzin
Acephate
Acifluorfen
Alachlor
CAS Number
43121-43-3
00062-73-7
00094-75-7
00094-82-6
07786-34-7
21725-46-2
01918-16-7
00094-74-6
00120-36-5
00093-65-2
21564-17-0
23950-58-5
00709-98-8
21087-64-9
30560-19-1
50594-66-6
15972-60-8
EPA Analytical
Method Number (s)
507/633/525.1
1657/507/622/525.1
1658/515.1/615
1658/515.1/615
1657/507/622/525.1
629
508/608.1/525.1
1658/615
1658/515.1/615
1618/615
637
525.1
632.1
507/633/525.1/1656
1656
515.1/1656
505/507/645/525 . 1/1656
16-4
-------
Table 16-1
(Continued)
EPA
Survey
Code
55
58
60
62
67
68
69
69
70
73
75
76
80
82
84
86
90
103
107
110
112
113
118
119
Pesticide Name
Aldicarb
Ametryn
Atrazine
Benomyl
Biphenyl
Bromacil; Bromacil Salts and
Esters
Bromoxynil
Bromoxynil octanoate
Butachlor
Captafol
Carbaryl [Sevin]
Garb o fur an
Chloroneb
Chlorothalonil
Stirofos
Chlorpyrifos
Fenvalerate
Diazinon
Parathion methyl
DCPA [Dimethyl 2,3,5,6-
tetrachloroterephthalate ]
Dinoseb
Dioxathion
Nabonate [Disodium
cyanodithioimidocarbonate ]
Diuron
CAS Number
00116-06-3
00834-12-8
01912-24-9
17804-35-2
00092-52-4
00314-40-9
01689-84-5
01689-99-2
23184-66-9
02425-06-1
00063-25-2
01563-66-2
02675-77-6
01897-45-6
00961-11-5
02921-88-2
51630-58-1
00333-41-5
00298-00-0
01861-32-1
00088-85-7
00078-34-2
00138-93-2
00330-54-1
EPA Analytical
Method Number (s)
531.1
507/619/525.1
505/507/619/525.1/1656
631
1625/642
507/633/525.1/1656
1661/1625
1656
507/645/525.1/1656
1618
531.1/632
531.1/632
508/608.1/525.1
508/608.2/525.1/1656
1657/507/622/525.1
1657/508/622
1660
1657/507/614/622/525.1
1657/614/622
508/608.2/525.1/1656
1658/515.1/615
614.1
630.1
632
16-5
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Table 16-1
(Continued)
EPA
Survey
Code
123
124
125
126
127
132
133
138
140
144
148
150
154
156
158
172
173
175
178
182
183
185
186
192
Pesticide Name
Endothall
Endrin
Ethalfluralin
Ethion
Ethoprop
Fenarimol
Fenthion
Glyphosate [N-
(Phosphonomethyl) glycine]
Heptachlor
Isopropalin
Linuron
Malathion
Me thami dopho s
Me thorny 1
Methoxychlor
Nab am
Naled
Norflurazon
Benfluralin
Fensulfothion
Disulfoton
Phosmet
Azinphos Methyl
Organo-tin pesticides
CAS Number
00145-73-3
00072-20-8
55283-68-6
00563-12-2
13194-48-4
60168-88-9
00055-38-9
01071-83-6
00076-44-8
33820-53-0
00330-55-2
00121-75-5
10265-92-6
16752-77-5
00072-43-5
00142-59-6
00300-76-5
27314-13-2
01861-40-1
00115-90-2
00298-04-4
00732-11-6
00086-50-0
12379-54-3
EPA Analytical
Method Number (s)
548
1656/505/508/608/617/5
25.1
627*/1656*
1657/614/614.1
1657/507/622
507/633.1/525.1/1656
1657/622
547/140A
1656/505/508/608
/617/525.1
627/1656
632
1657/614
1657
531.1/632
1656/505/508/608.2
/617/525.1
630/630.1
1657/622
507/645/525.1/1656
627*/1656*
1657/622
1657/507/614/622/525 . 1
1657/622.1
1657/614/622
200. 7/200. 9/IND-01
16-6
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Table 16-1
(Continued)
EPA
Survey
Code
197
203
204
205
206
208
212
218
219
220
223
22"4
226
230
232
236
239
241
243
252
254
Pesticide Name
Bolster
Parathion
Pendimethalin
Pentachloronitrobenzene
Pentachlorophenol
Permethrin
Phorate
Busan 85 [Potassium
dimethyldithioearbamate ]
Busan 40 [Potassium N-
hydr oxyme thy 1 - N -
methyldithiocarbamate ]
KN Methyl [Potassium N-
methyldithiocarbamate ]
Prometon
Prometryn
Propazine
Pyrethrin I
Pyrethrin II
DEF [S,S,S-Tributyl
phosphorotrithioate ]
Simazine
Carbarn- S [Sodium
dimethyldithiocarbanate ]
Vapam [Sodium
methyldithiocarbamate ]
Tebuthiuron
Terbacil
GAS Number
35400-43-2
00056-38-2
40487-42-1
00082-68-8
00087-86-5
52645-53-1
00298-02-2
00128-03-0
51026-28-9
00137-41-7
01610-18-0
07287-19-6
00139-40-2
00121-21-1
00121-29-9
00078-48-8
00122-34-9
00128-04-1
00137-42-8
34014-18-1
05902-51-2
EPA Analytical
Method Number (s)
622
1657/614
1656
1656/608.1/617
625/1625
608.2/508/525.1/1656
/1660
1657/622
630/630.1
630/630.1
630/630.1
507/619/525.1
507/619/525.1
507/619/525.1
508/1660
508/1660
1657/1618
505/507/619/525.1
630/630.1
630/630.1
507/525.1
507/633/525.1
16-7
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Table 16-1
(Continued)
EPA
Survey
Code
255
256
257
259
262
263
264
268
Pesticide Name
Terbufos
Terbuthy laz ine
Terbutryn
Dazomet
Toxaphene
Merphos [Tributyl
phosphorotrithioate ]
Trifluralin
Ziram [Zinc
dimethyldithiocarbamate ]
CAS Number
13071-79-9
05915-41-3
00886-50-0
00533-74-4
08001-35-2
00150-50-5
01582-09-8
00137-30-4
EPA Analytical
Method Number (s)
1657/507/614.1/525.1
619
507/619/525.1
131/630/630.1/1659
1656/505/508/608/617
1657/1618/525.1
1656/508/617/627/525 . 1
630/630.1
Monitor and report as total Trifluralin.
16-8
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16.2 PROPOSED METHODS
16.2.1 Methods for PAI Pollutants
EPA has not previously promulgated methods for most of the PAI
pollutants in the proposed rule. In 1985, as part of the promulgation of
effluent limitations guidelines and standards for the Pesticide Industry, FPA
promulgated methods for 61 PAIs (50 FR 40672, October 4, 1985). These methods
were contained in a methods compendium titled "Methods for Nonconventional
Pesticides Chemicals Analysis Municipal and Industrial Wastewater," EPA
440/1-83/079-C. This document is presently out of print and unavailable
except in photocopy form. The methods were also published in their entirety
in the October 4, 1985, Federal Register. The promulgated methods were
withdrawn as a part of the withdrawal of the 1985 proposed rule to allow for
further testing and possible revision.
Since 1986, EPA has conducted additional methods development for
PAI pollutants to incorporate the most recent advances in technology,
particularly the clean-up procedures necessary to eliminate interferences and
improve reliability, and to account for the latest and most sensitive
detection devices, which permit accurate detection of PAI pollutants at very
low concentrations. In addition, EPA requested and received new analytical
methods from pesticide manufacturing facilities which monitor their
wastewater. EPA is proposing that all of these methods be available for
compliance monitoring of effluent from the manufacture of the 122 PAIs
16-9
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proposed for regulation; for many PAIs, more than one analytical method is
being proposed. The availability of more than one method for a specific PAI
allows flexibility to the analyst to select the analytical method that
provides the most accurate results; proposal of alternative methods also
allows commenters to provide comparative data which may lead to further
improvements in methods or to rejection of some of the proposed methods where
data demonstrates that the proposed method is inadequate.
The proposed analytical methods will be used by pesticide
manufacturers, by regulatory agencies including POTWs, by commercial testing
laboratories, and by others, to determine compliance with the proposed
effluent limitations guidelines and standards. There is at least one method
for each PAI, at least two methods for most PAIs, and three methods for many
PAIs. EPA's intent in proposing multiple methods is to permit as much
flexibility as possible while controlling the quality of the methods approved.
In addition to flexibility in method selection, a certain amount of
flexibility within each method is permitted. This flexibility was detailed in
the preamble to 40 CFR Part 136 wastewater methods [49 FR 43234, October 26,
1984] and allows modification of the method to overcome interference problems.
These alternate procedures and techniques may be employed provided that the
quality control (QC) criteria within the method are all met.
16-10
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16.2.2 Methods for Metals
EPA's Environmental Monitoring Systems Laboratory in Cincinnati,
Ohio (EMSL-Ci) has recently developed a set of methods titled "Methods for the
Determination of Metals in Environmental Samples" (EPA 600/4-91/010). This
methods set includes techniques such as inductively coupled plasma/atomic
emission spectrometry (Method 200.7) and stabilized temperature graphite
furnace atomic absorption spectrometry (Method 200.9) to measure metals at low
levels. EPA proposes to permit the use of Methods 200.7, 200.9, and industry
method IND-01 for the measurement of organo-tin compounds in pesticides
industry wastewaters.
16.2.3 Development of Methods
Since the previous methods set was published, the trend of
pesticides and herbicides produced and applied in the U.S. has continued from
chlorinated compounds to phosphorus-containing compounds and other molecules
found to be less persistent in the environment. This change has necessitated
the development of analytical methods to measure these compounds in wastewater
discharges and in other environmental samples. EPA has therefore developed
additional methods as a part of its data gathering efforts for the1 proposed
rule.
Where possible, EPA avoids development of a new method by testing
existing methods to determine if an active ingredient can be measured by these
16-11
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existing methods. If these tests are successful, EPA revises the method to
incorporate the new analyte. In addition, EPA has attempted to consolidate
multiple methods for the same analyte by selecting a given method or writing a
revised or new method and including as many analytes as possible in this
method. For example, EPA has used wide-bore, fused silica capillary columns
in recently developed gas chromatography (GC) methods for pesticide active
ingredients to increase resolving power so that more analytes can be measured
simultaneously and so that these analytes can be measured at lower levels.
Drinking water methods 507^ 508, 515.1, and wastewater methods 1656, 1657, and
1658 represent GC methods that encompass a large number of analytes.
On the other hand, it is frequently not possible to include an
analyte or group of analytes in an existing method because the nature of the
molecule(s) does not lend itself to the techniques in the method. In these
instances, an entirely separate method must be developed. In the methods
proposed for the rule, Method 1659 for Dazomet, Method 1660 for the Pyrethrins
and Pyrethroids, and Method 1661 for Bromoxynil represent examples of methods
that were developed. The method for Dazomet employs a base hydrolysis to
convert Dazomet to methyl isothiocyanate (MITC) and gas chromatography with a
fused silica capillary column and nitrogen/phosphorous detector for selective
detection of MITC. The method for the Pyrethrins and Pyrethroids employs
acetonitrile extraction of a salt-saturated wastewater sample and high-
performance liquid chromatography (HPLC) for selective detection of these
analytes. The method for Bromoxynil employs direct aqueous injection HPLC.
16-12
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16-2.4 Procedures for Development and Modification of Methods
In many instances, EPA has combined method development with data
gathering to support the effluent limitations and guidelines in the proposed
rule. In this process, commercial analytical laboratories compete to apply an
existing method, modify an existing method, or develop a new method under
"Special Analytical Services" contracts. EPA then works closely with the
laboratory selected to assure that all quality assurance program requirements
will be met. The laboratory outlines the exact tests to be undertaken to
modify the method (if required) or to develop a new procedure. EPA approves
the approach before samples are collected.
Samples are collected at the facility that manufactures the given
active ingredient or group of pesticides. Frequently, multiple pesticides
requiring different procedures are required. In this instance, more than one
laboratory may be involved in the determination of multiple pesticides.
Samples collected are of in-process wastewater, untreated effluent, treated
effluent, and other streams. The samples are preserved and shipped to the
laboratory.
After receipt at the laboratory, analysts attempt to measure the
active ingredient in each waste stream type using the method specified by EPA
or with the modification approved by EPA. If the attempt is successful,
routine analysis of the samples beings; if unsuccessful, EPA works closely
with its scientific consultants and the laboratory to try other approaches.
16-13
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Frequently, the industry is consulted as to how to solve an analytical problem
because industry scientists are often most familiar with the measurement of a
given active ingredient in their particular wastewater. When an approach is
successful, the laboratory documents the approach and performs an initial
precision and recovery study to demonstrate the accuracy and reproducability
of the method. The requirement for an initial precision and recovery study
forms one of the cornerstones of the wastewater methods, and is described in
detail in the preamble to the proposal and promulgation of these methods
(e.g., 49 FR 43234).
After completing the initial precision and recovery study, the
laboratory begins analysis of wastewater samples using the procedure specified
by EPA or with the modification as approved by EPA. In addition to analyzing
the samples directly, a sample of each wastewater type is spiked (fortified)
with the active ingredient of interest. This spiked samples is then analyzed
to determine the recovery of the analyte from the actual sample, and assures
that the active ingredient can be measured accurately in each type of
wastewater sample.
After all samples are analyzed, the laboratory prepares a report
containing a "Narrative" of exactly what modifications were required in order
to apply a method or modification to a given sample. The report also contains
result summaries, run chronologies (showing that analyses were performed in
the correct order on a calibrated instrument), and includes raw data so that
16-14
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EPA can reconstruct the results as a part of the audit process. The report is
then submitted to EPA by the laboratory.
EPA has its audit team review the report and obtained from the
laboratory any missing or incomplete results. EPA also audits the data
submitted for adherence to method specifications and consistency with data
collected from other laboratories. Deficiencies are corrected by the
laboratory and the data are included in the package for guideline development.
16.2.5 Method Writing and Modification
After data are collected and reviewed by EPA, methods are written
or modified to include the active ingredient. For example, the active
ingredient Methamidophos is highly soluble in water but not soluble in organic
solvents. The procedure suggested by industry for extraction of Methamidophos
used a combination of saturating the water with salt and a powerful solvent
combination for the extraction. The laboratory applied this technique and
found that Methamidophos could be recovered at 95 percent. Further, the
laboratory found that pre-extraction of the sample with an organic solvent
could be used to remove nearly all potential interferents from the sample, so
that the aggressive extraction would result in only Methamidophos and similar
highly water-soluble molecules in the final extract. EPA then modified Method
1657 to incorporate the pre-extraction and aggressive extraction procedure for
highly water-soluble analytes.
16-15
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16.3 INVESTIGATION OF OTHER ANALYTICAL TECHNIQUES
In addition to methods developed for the proposed rule, EPA is
investigating other methods and other analytical techniques to aid in the
determination of non-conventional pesticides and other analytes of concern.
EPA is interested in simplifying methods where possible and in reducing the
potential pollution threat caused by the volumes of solvents used in some
methods. An example of a simplification technique is the use of an
immunoassay specific to a given analyte (such as a pesticide) or analyte group
(such as the phenoxyacid herbicides) to allow EPA to screen rapidly for these
analytes in discharges and in other environmental samples. EPA is also
investigating the use of "solid phase extraction" (liquid-solid extraction) as
a means of reducing the amount of solvent used in conventional extraction
procedures. Solid phase extraction (SPE) has been successfully applied to
drinking water matrices, but initial tests with wastewaters containing high
dissolved solids yielded low recoveries of the analytes of concern. More
recent materials have yielded recoveries more consistent with conventional
extraction techniques. EPA will continue to investigate these and other
analytical techniques with the objective of producing lower cost, more rapid,
and potentially less environmentally damaging analytical methods.
16-16
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SECTION 17
GLOSSARY
Act The Clean Water Act
Agency U.S. Environmental Protection Agency.
BAT - The best available technology economically achievable, applicable to
effluent limitations to be achieved by July 1, 1984, for industrial discharges
to surface waters, as defined by sec. 304(b)(2)(B) of the Act.
BCT The best conventional pollutant control technology, applicable to
discharges of conventional pollutants from existing industrial points sources,
as defined by sec. 304(b)(4) of the Act.
BMP Best management practices, as defined by sec. 304(e) of the Act.
BPT The best practicable control technology currently available, applicable
to effluent limitations to be achieved by July 1, 1977, for industrial
discharges to surface waters, as defined by sec. 304(b)(l) of the Act.
Clean Water Act The Federal Water Pollution Control Act Amendments of 1972
(33 U.S.C. 1251 et seq.), as amended by the Clean Water Act of 1977 (Pub. L.
95-217), and the Water Quality Act of 1987 (Pub.L. 100-4).
Conventional Pollutants Constituents of wastewater as determined by sec.
304(a)(4) of the Act, including, but not limited to, pollutants classified as
biochemical oxygen demand, suspended solids, oil and grease, fecal coliform,
and pH.
Direct Discharger An industrial discharger that introduces wastewater to a
receiving body of water with or without treatment by the discharger.
Effluent Limitation A maximum amount, per unit of time, production or other
unit, of each specific constituent of the effluent that is subject to
limitation from an existing point source. Allowed pollutant discharge may be
expressed as a mass loading in pound per 1,000 pound PAI produced or as a
concentration in milligrams per liter.
End-of-Pipe Treatment (EOP) Refers to those processes that treat a plant
waste stream for pollutant removal prior to discharge. EOP technologies
covered are classified as primary (physical separation processes), secondary
(biological processes), and tertiary (treatment following secondary)
processes. Different combinations of these treatment technologies may be used
depending on the nature of the pollutants to be removed and the degree of
removal required.
17-1
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Indirect Discharger - An industrial discharger that introduces wastewater into
a publicly-owned treatment works.
In-Plant Control or Treatment Technologies Controls or measures applied
within the manufacturing process to reduce or eliminate pollutant and
hydraulic loadings of raw wastewater. Typical in-plant control measures
include process modification, instrumentation, recovery of raw materials,
solvents, products or by-products, and water recycle.
Nonconventional Pollutants Parameters selected for use in developing
effluent limitation guidelines and new source performance standards which have
not been previously designated as either conventional pollutants or priority
pollutants.
Non-Water Environmental Quality Impact Deleterious aspects of control and
treatment technologies applicable to point source category wastes, including,
but not limited to air pollution, noise, radiation, sludge and solid waste
generation, and energy used.
NPDES National Pollutant Discharge Elimination System, a Federal program
requiring industry and municipalities to obtain permits to discharge
pollutants to the nation's waters, under sec. 402 of the Act.
NSPS New source performance standards, applicable to industrial facilities
whose construction is begun after the publication of the proposed regulations,
as defined by sec. 306 of the Act.
QCPSF Organic chemicals, plastics, and synthetic fibers manufacturing point
source category.
Point Source Category A collection of industrial sources with similar
function or product, established by sec. 306(b)(l)(A) of the Federal Water
Pollution Control Act, as amended for the purpose of establishing Federal
standards for the disposal of wastewater.
POTW Publicly-owned treatment works. Facilities that collect, treat, or
otherwise dispose of wastewaters, owned and operated by a village, town,
county, authority or other public agency.
Pretreatment Standard Industrial wastewater effluent quality required for
discharge to a publicly-owned treatment works.
Priority Pollutants The toxic pollutants listed in 40 CFR Part 423, Appendix
A.
PSES Pretreatment Standards for existing sources of indirect discharges,
under sec. 307(b) of the Act.
PSNS Pretreatment standards for new sources of indirect discharges under
sec. 307(b) and (c) of the Act.
17-2
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SIC Standard Industrial Classification, a numerical categorization scheme
used by the U.S. Department of Commerce to denote segments of industry.
Technical Development Document Development Document for Proposed Effluent
Limitations Guidelines and Standards for the Pesticides Chemicals
Manufacturing Point Source Category.
17-3
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SECTION 18
REFERENCES
1- Aly, 0. M., and M. A. El-Dib, "Studies on the Persistence of Some
Carbamate Insecticides in the Aquatic Environment - I Hydrolysis
of Sevin, Baygon, Pyrolan, and Dimethilan in Waters", Water
Research. 5(12):1191-1205, 1971.
2. American Paper Institute v. EPA. 660 F. 2d 954 (4th Cir. 1980).
3. BASF Wyandotte Corp. v. Costle. 614 F. 2d 21 (1st Cir. 1980).
4. BASF Wvandotte Corp. v. Costle. 596 F. 2d 637 (1st Cir. 1979),
cert, denied.
5. Biello, L. J., et al., "Final Report of Laboratory Study of
Pesticides Wastewater Treatability", Environmental Science and
Health. B12(2):129-146, 1977.
6. Brown, N. P. H., and B. T. Graysen, "Base-Catalyzed Hydrolysis of
(E) and (Z) Mevinphos", Pesticide Science. 14(6):547-549,
1983.
7. Budavari, Susan, editor, The Merck Index: An Encyclopedia of
Chemicals. Drugs and Biologicals - Eleventh Addition. Merck & Co,
Rahway, NJ, 1989.
8. The Bureau of National Affairs, Pesticides: State and Federal
Regulation. Bureau of National Affairs, Rockville, MD, 1987.
9. Callahan, M. A., et al., Water-Related Environmental Fate of 129
Priority Pollutants. Volume I: Introduction and Technical
Background. Metals and Inorganics. Pesticides and PCBs. EPA-44/4-
79-029a, United States Environmental Protection Agency, Washington
DC, 1979.
10. Chau, Alfred S. Y., and B. K. Afghan, Analysis of Pesticides in
Water. Volumes I. II. and III. CRC Press, Boca Raton, FL, 1982.
11. Chemical Specialities Manufacturers Association, et. al., v. EPA.
(86-8024).
12. Cowart, R. P., F. L. Bonner, and E. A. Epps, Jr., "Rate of
Hydrolysis of Seven Organophosphate Pesticides", Bulletin of
Environmental Contamination and Toxicology. 6(3):231-234, 1971.
18-1
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REFEREENCES
(Continued)
13- Crittenden, J. C., J. K. Berrigan, and D. W. Hand, "Design of
Rapid Small-Scale Adsorption Tests for a Constant Diffusivity",
Journal WPCF. Volume 58, Number 4, April 1986.
14- Dennis, W. H., Jr., Methods of Chemical Degradation of Pesticides
and Herbicides - A Review. USAMEERU No. 73-04, United States Army
Medical Envionmental Engineering Research Unit, Edgewood Arsenal,
Maryland, 1972.
15. Dobbs, Richard A., and Jesse M. Cohen, "Carbon Adsorption
Isotherms for Toxic Organics", EPA Report Number EPA-60/8-80-023.
April 1980.
16. "Domestic Sewage Study", DSS - Report to Congress on the Discharge
of Hazardous Waste to Publicly Owned Treatment Works. EPA/530-SW-
86-004, February 1986.
17. Drevenkar, V., et al., "The Fate of Pesticides in Aquatic
Environment II - Hydrolysis of Dichlorvos in a Model System and in
River Water" (translation of "Archivza Higijenu Rada"),
Toksikolgigu 27(4) 297-305, 1976.
18. El-Dib, M. A., and 0. A. Aly, "Persistance of Some Phenylamide
Pesticides in the Aquatic Environment I Hydrolysis", Water
Research. 10(12):1047-1050, 1976.
19. Eli Lilly v. Costle. 444 U.S. 1096, 1980.
20. "EPA Method 632", Federal Register. Volume 50, No. 193, October 4,
1985.
21. Eto, M., Organophosphorus Pesticides: Organic and Biological
Chemistry. CRC Press, Cleveland, OH, 1974.
22. Faust, S. D., and H. M. Gomaa, "Chemical Hydrolysis of Some
Organic Phosphorus and Carbamate Pesticides in Aquatic
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23. Fest, C., and K. J. Schmidt, The Chemistry of Organophosphorus
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24. Freed, V. H., C. T. Chiou, D. W. Schmedding, "Degradation of
Selected Organophosphate Pesticides in Water and Soil", Journal of
Agricultural Food Chemicals. 27(4):706-708, 1979.
18-2
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REFEREENCES
(Continued)
25. Gardner, David A., and Gregory L. Huibregtse, Radian Corporation,
and Thomas J. Holdsworth, Glenn M. Shaul, Kenneth M. Dostal, Water
and Hazardous Wastes Treatment Research Division, Risk Reduction
Engineering Laboratory, Accelerated Column Testing of Pesticide
ManufacturinE Wastewaters. EPA Contract No. 68-03-3371, December
1990.
26. Gardner, D. A., Radian Corporation, and G. M. Shaul and K. A.
Dostal, Water and Hazardous Wastes Treatment Research Division,
Risk Reduction Engineering Laboratory, Activated Carbon Isotherms
for Pesticides. EPA Contract No. 68-03-3371, September 1989.
27. Gomaa, H. M., I. H. Suffet, and S. D. Faust, "Kinetics of
Hydrolysis of Diazinon and Diozoxan", Residual Review. 29:171 190,
1969.
28. Hand, D. W., J. C. Crittenden, and W. E. Thacker, "Simplified
Models for Design of Fixed-Bed Adsorption Systems", Journal of the
American Society of Civil Engineers, Environmental Engineering
Division. 110(2):440-456, April 1985.
29. Hineline, D. W., J. C. Crittenden, and D. W. Hand, "Use of Rapid
Small-Scale Column Tests to Predict Full-Scale Adsorption Capacity
and Performance", Proceedings of the AWWA Annual Meeting. Kansas
City, MO, June 1987.
30. Hinton, J. F., Hydrolytic and Photochemical Degradation of
Organophosphorus Pesticides. Publication No. 63, University of
Arkansas, Fayetteville, AK, 1978.
31. Houghton, Mary J., The Clean Waters Act Amendments of 1987, The
Bureau of National Affairs, Washington DC, 1987.
32. Kuhr, R. J., and H. W. Dorough, Carbamate Insecticides:
Chemistry. Biochemistry and Toxicology. CRC Press, Cleveland, OH,
1976.
33. Lande, S. S., Identification and Description of Chemical
Deactivation/Detoxification Methods for the Safe Disposal of
Selected Pesticides SW-165C, United States Environmental
Protection Agency, Washington DC, 1978.
18-3
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REFEREENCES
(Continued)
3^- Lemley, A. T., et al., "Investigation of Degradation Rates of
Carbamate Pesticides Exploring a New Detoxification Method", ASC
Symposium Series. 259 (Treatment and Disposal of Pesticide
Wastes): 245-259, 1984.
35. Macalady, D. L., and N. L. Wolfe, "New Perspectives on the
Hydrolytic Degradation of the Organophosphorothioate Insecticide
Chlorpyrifos", Journal of Agricultural Food Chemicals. 31(6):1139-
1147, 1983.
36. Mahoney, William D., Means Site Work Cost Data 1989. R. S. Means
Company, Inc., Kingston, MA, 1988.
37. Marehenko, P. V., A. V. Grechki and E. V. Kravets, "Application of
the Hydrolysis of Organophosphorus Pesticides in the Purification
of Effluents", Soviet Journal of Water Chemistry and Technology.
3(5):62-65, 1981.
38. Marco, Gino J., Robert M. Hollingsworth, and Jack R. Plummer,
editors, Regulation of Agrochemicals: A Driving Force in Their
Evolution. American Chemical Society, Washington DC, 1991.
39. Melnikov, N. N., "Decomposition of Organophosphorus Pesticides",
(translation of "Khimiya v Seskom Khosyaistve"), Pesticides and
the Environment. 12(3):49-57, 1975.
40. "Methods for Chemical Analysis for Water and Wastes", EPA-600/4-
79/020, EMSL, 1983.
41. NRDC. et. al.. v. Reillv. Civ. No. 89-2980.
42. Pereira, Percival E., Dodge Construction Cost Information System
1986. McGraw-Hill Information Systems, Princeton, NJ, 1985.
43. Perry, Robert H., and Don Green, Perry's Chemical Engineer's
Handbook, McGraw-Hill Book Company, New York, 1984.
44. Radian Corporation, Alkaline Chlorination and Alkaline Hydrolysis
Treatability Study of Pesticide Manufacturing Wastewaters. EPA
Contract No. 68-C8-0008, July 1991.
45. Radian Corporation, Draft Pesticide Manufacturers Database Report,
EPA Contract No. 68-C8-0008, March 1990.
18-4
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REFEREENCES
(Continued)
46. Radian Corporation, Hydrolysis Treatability Study Final Report.
EPA Contract No. 68-C8-0008, July 1991.
47. Radian Corporation, Membrane Filtration Treatability Study Final
Report. EPA Contract No. 68-C8-0008, April 1990.
48. Sieber, J. N., M. P. Catahan, and C. R. Barril, "Loss of
Carbofuran from Rice Paddy Water: Chemical and Physical Factors",
Journal of Environmental Science and Health. B13(2):131 148, 1978.
49. Sine, Charlotte, editorial director, Farm Chemicals Handbook '90.
Meister Publishing Company, Willoughby, OH, 1990.
50. Sittig, Marshall, editor, Pesticide Manufacturing and Toxic
Materials Control Encyclopedia. Noyes Data Corporation, Park
Ridge, NJ, 1980.
51. Sontheimer, H., J. C. Crittenden, and R. S. Summers, Activated
Carbon for Water Treatment. 2nd Edition, DVGW Forschurgsstelle,
Karlsruhu, West Germany, Distributed by AWWA Research Foundation,
Denver, CO, 1988.
52. Speth, T. F., and R. S. Miltner, "Adsorption Capacity of GAG for
Synthetic Organics", AWWA Research Foundation. 82(2):72-75,
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53. "Standard Methods for the Examination of Water and Wastewater",
15th Edition, American Public Health Association, Washington DC,
1981.
54. Summers, R. S., and J. C. Crittenden, The Use of Mini-Columns for
the Prediction of Full-Scale GAG Behavior Design and Use of
Granular Activated Carbon: Practical Aspects, AWWA Research
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55. Tchobanoglous, George, and Edward D. Schoeder, Water Quality.
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56. United States Congress, The Clean Water Act of 1972 and 1977.
Public Law 95-217.
57. United States Congress, The Clean Water Act as Amended by the
Water Quality Act of 1987. Public Law 1004.
18-5
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REFEREENCES
(Continued)
58. United States Congress, The Pollution Prevention Act of 1990.
Public Law 101-508.
59. United States Environmental Protection Agency, Development
Document for Effluent Limitations Guidelines and Standards for the
Organic Chemicals. Plastics, and Synthetic Fibers - Point Source
Category. Volumes I and II. United States Environmental Protection
Agency 440/1-87/009, Washington DC, 1987.
60. United States Environmental Protection Agency, Development
Document for Effluent Limitations Guidelines and Standards for the
Pesticide (Final) Point Source Category. United States
Environmental Protection Agency, Washington DC 1985.
61. United States Environmental Protection Agency, Effluent Guidelines
Division, EPA Method 630. Washington DC, January 1983.
62. United States Environmental Protection Agency, EPA Method 637.
Effluent Guidelines Division, Washington DC, October 1985.
63. United States Environmental Protection Agency, Effluent Guidelines
Division, EPA Method 1613A. Washington DC, March 1989.
64. United States Environmental Protection Agency, Office of Water
Regulations and Standards, EPA Method 1916. Sample Control Center,
Alexandria, VA.
65. United States Environmental Protection Agency, Effluent Guidelines
Division, EPA Method 1624/1625. Washington DC, July 1988.
66. United States Environmental Protection Agency, Office of Drinking
Water Health Advisories, Drinking Water Health Advisory:
Pesticides. Lewis Publishers, Chelsea, MI, 1989.
67. United States Environmental Protection Agency, "Best Conventional
Polluntant Control Technology; Effluent Limitations Guidelines
Final Rule", 40 CFR Parts 405, 406, 407, 408, 409, 411, 412, 418,
422, 424, 426, and 432, Federal Register. FRL 2941-9, Volume 51,
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68. United States Environmental Protection Agency, "Effluent
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29. 1990.
18-6
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REFEREENCES
(Continued)
69. United States Environmental Protection Agency, "General
Pretreatment Regulations for Existing and New Sources Final
Rule" 40 CFR Part 403, Federal Register. OW-FRL 3006-4, Volume 52,
No. 9, January 14, 1987.
70. United States Environmental Protection Agency. FIFRA and TSCA
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71. United States Environmental Protection Agency, "Guidelines
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the Clean Water Act; Final Rule and Interim Final Rule and
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72. United States Environmental Protection Agency, "Notice of Plan to
Review and Promulgate Effluent Guideline Regulations", Federal
Register. FRL 3626-3, Volume 55, No. 1, January 2, 1990.
73. United States Environmental Protection Agency, "Organic Chemicals,
Plastics, and Synthetic Fibers Category Effluent Limitations
Guidelines, Pretreatment Standards, and New Source Performance
Standards Proposed Regulation", 40 CFR Parts 414 and 416,
Federal Register. Volume 48, No. 55, March 21, 1983.
74. United States Environmental Protection Agency, "Organic Chemicals,
Plastics, and Synthetic Fibers Category Effluent Limitations
Guidelines, Pretreatment Standards; and Standards of Performance
for New Sources - Notice of Availability and Request for
Comments", 40 CFR Parts 414 and 416, Federal Register, OW-FRL-
2863-6, Volume 50, No. 187, July 17, 1985.
75. United States Environmental Protection Agency, "Organic Chemicals,
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Guidelines, Pretreatment Standards, and New Source Performance
Standards - Extension of Comment Period, Correction Notice, and
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76. United States Environmental Protection Agency, "Organic Chemicals,
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1987.
18-7
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REFEREENCES
(Continued)
77. United States Environmental Protection Agency, "Organic Chemicals,
Plastics, and Synthetic Fibers Category Effluent Limitations
Guidelines, Pretreatment Standards, and New Source Performance
Standards Final Rule Technical Amendments and Revocation of
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Volume 54, No. 124, June 29, 1989.
78. United States Environmental Protection Agency, "Organic Chemicals,
Plastics, and Synthetic Fibers Category Effluent Limitations
Guidelines, Pretreatment Standards, and New Source Performance
Standards Final Rule", 40 CFR Part 414, Federal Register. FRL
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79. United States Environmental Protection Agency, "Organic Chemicals,
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80. United States Environmental Protection Agency, "Pesticide
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81. United States Environmental Protection Agency, "Pesticide
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82. United States Environmental Protection Agency, "Pesticide
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18-8
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REFEREENCES
(Continued)
84. United States Environmental Protection Agency, "Pesticide
Chemicals Manufacturing Point Source Category Part 455, Subchapter
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85. United States Environmental Protection Agency, "Pesticide
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86. United States Environmental Protection Agency, Pesticide Fact
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87. United States Environmental Protection Agency, Pesticide
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88. United States Environmental Protection Agency, Process Design
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89. United States Environmental Protection Agency, Proposed Effluent
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90. United States Environmental Protection Agency, ToxicRelease
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91. Viesman, Warren, Jr., and Mark J. Hammer, Water Supply and
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92. Weber, W. J., Jr., Physicochemical Processes., John Wiley and
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93. Weigman, Diana L., editor, Pesticides inthe Next Decade: The
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