United States
 Environmental Protection
 Agency
Office of Water
Mail Code 4303
EPA-821-R-93-016
September 1993
 Development Document For
Effluent limitations  Guidelines,
Pretreatment Standards, And
New Source  Performance
Standards For The

Pesticide Chemicals Manufacturing
Point Source Category

(Final)

-------

-------
              DEVELOPMENT DOCUMENT

                      FOR

        EFFLUENT LIMITATIONS GUIDELINES,

          PRETREATMENT STANDARDS, AND

        NEW SOURCE PERFORMANCE STANDARDS

                    FOR THE

   PESTICIDE CHEMICALS MANUFACTURING CATEGORY
                 Carol Browner
                 Administrator
               Martha G. Prothro
Acting 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
                 September  1993
       Engineering and Analysis Division
       Office  of  Science  and  Technology
     U.S.  Environmental Protection Agency
            Washington, D.C.  20460

-------

-------
                              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  	  1-3
       1.1.3      Pollution Prevention Act	1-4
       1.1.4      Prior Regulation and Litigation for the Pesticide
                  Chemicals Category  	  1-4

1.2    SCOPE OF TODAY'S RULE	1-8

SECTION 2 - SUMMARY

2.0    OVERVIEW OF THE INDUSTRY   	2-1

2.1    SUMMARY OF THE FINAL REGULATIONS   	2-2
       2.1.1      Applicability of the Final Regulations	2-2
       2.1.2      BPT	2-2
       2.1.3      BCT	2-4
       2.1.4      BAT	2-4
       2.1.5      NSPS	2-6
       2.1.6      PSES	2-22
       2.1.7      PSNS	2-22

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 Consideration	3-2
       3.1.3      The "Pesticide Manufacturing Facility Census of
                  1986"	3-3
       3.1.4      Industry Self-Monitoring Data	3-21
       3.1.5      EPA's 1988-1991 Sampling of Selected Pesticide
                  Manufacturers 	 3-22
       3.1.6      EPA Bench-Scale Treatability Studies  	 3-24
       3.1.7      Data Submitted After Proposal	 3-26
       3.1.8      Data Transferred from the OCPSF Rulemaking	3-27

3.2    OVERVIEW OF THE INDUSTRY   	3-28
       3.2.1      Geographical Location of Manufacturing Facilities .  .  . 3-28
       3.2.2      SIC Code Distribution	3-31
       3.2.3      Age of Facilities	3-31
       3.2.4      Market Types	3-31
       3.2.5      Type of Facilities	3-31

-------
                         TABLE OF  CONTENTS  (Continued)
3.3     PESTICIDE PRODUCTION   	 3-34
        3.3.1      Types of Pesticides	3-34
        3.3.2      1986 Pesticide Active Ingredient Production 	 3-35
        3.3.3      Distribution of PAI Production by Facility    	3-43
        3.3.4      Distribution of PAI Production During the Year  .... 3-43

3.4     PESTICIDE MANUFACTURING  PROCESSES  .  .  	 3-43
        3.4.1      Batch vs. Continuous Processes  	 3-46
        3.4.2      General Process Reactions 	 3-47
        3.4.3      Intermediate/By-product Manufacture 	 3-55

3.5     CHANGES  IN THE  INDUSTRY	3-58

SECTION 4 - INDUSTRY SUBCATEGORIZATION

4.0     INTRODUCTION    	4-1

4.1     BACKGROUND   	4-1
        4.1.1      November 1, 1976, Interim Final BPT Guidelines  ....  4-2
        •4.1.2      April 25, 1978, Promulgated BPT Guidelines  	  4-2
        4.1.3      November 30, 1982, Proposed BAT, BCT,  NSPS, PSES,
                  PSNS Guidelines	4-3
        4.1.4      June 13, 1984, Notice of Availability (NOA)	4-3
        4.1.5      October 4,  1985, Promulgated BAT,  NSPS,  PSES,  and
                  PSNS Guidelines	4-4

4.2     CURRENT  SUBCATEGORIZATION  BASIS  	  4-4
        4.2.1      Product Type and Raw Materials	4-4
        4.2.2      Manufacturing Process and Process Changes 	  4-5
        4.2.3      Nature of Waste Generated 	  4-5
        4.2.4      Dominant Product	4-5
        4.2.5      Plant Size	4-5
        4.2.6      Plant Age	4-6
        4.2.7      Plant Location	4-6
        4.2.8      Non-Water Quality Characteristics 	  4-6
        4.2.9      Treatment Costs and Energy Requirements 	  4-7

4.3     FINAL  SUBCATEGORIES  	  4-7
        4.3.1      Organic Pesticide Chemicals Manufacturing 	  4-7
        4.3.2      Metallo-Organic Pesticide Chemicals Manufacturing ...  4-8
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	5-3


                                      ii

-------
                         TABLE OF CONTENTS (Continued)


                                                                          Page

        5.1.2      Other Pesticide Wastewater Sources  	  5-5
        5.1.3      Other Facility Wastewater Co-Treated with
                  Pesticide Wastewater  	  5-7

5.2     WASTEWATER VOLUME BY DISCHARGE MODE	5-9
        5.2.1      Definitions	5-9
        5.2.2      Discharge Status of Pesticide Manufacturing Facilities  5-11
        5.2.3      Flow Rates by Discharge Status	5-11

5.3     RAW WASTEWATER DATA COLLECTION   	5-14
        5.3.1      Industry-Supplied Self-Monitoring Data	5-14
        5.3.2      EPA Pesticide Manufacturers Sampling Program  	 5-15

5.4     WASTEWATER CHARACTERIZATION	5-16
        5.4.1      Conventional Pollutants  	 5-16
        5.4.2      Priority Pollutants	5-22
        5.4.3      Pesticide Active Ingredients  	 5-27
        5.4.4      Non-conventional Pollutants (other than Pesticide Active
                  Ingredients)  	 5-28

5.5     WASTEWATER POLLUTANT DISCHARGES  	 5-29

SECTION 6 -  POLLUTANT PARAMETERS SELECTED FOR REGULATION

6.0     INTRODUCTION   	6-1

6.1     CONVENTIONAL POLLUTANT PARAMETERS   	  6-1

6.2     PRIORITY POLLUTANTS	6-2

6.3     NONCONVENTIONAL POLLUTANTS   	  6-8

SECTION 7 -  TECHNOLOGY SELECTION AND LIMITS DEVELOPMENT

7.0     INTRODUCTION   	7-1

7.1     POLLUTION  PREVENTION AND RECYCLING PRACTICES   	  7-1
        7.1.1      Overview of Pollution Prevention and Recycling
                  Practices	7-3
        7.1.2      Recirculation and Recycle Practices for Non-
                  Wat er/Wastewater Streams	7-4
        7.1.3      Recirculation and Recycle Practices for
                  Water/Wastewater Streams  	 7-12
        7.1.4      Incorporation of Pollution Prevention and
                  Recycling Practices Into the Final Rule	7-14
        7.1.5      Process Complexity in the Pesticide Chemicals
                  Manufacturing Industry   	 7-30
                                      iii

-------
                         TABLE  OF  CONTENTS  (Continued)
7.2    TREATMENT  PERFORMANCE DATABASES	7-32
       7.2.1      Analytical Data Submitted with the Pesticide
                  Manufacturing Facility Census for 1986  	 7-32
       7.2.2      Sampling and Analytical Programs	7-33
       7.2.3      Treatability Test Data	7-33
       7.2.4      Data Submitted After Proposal 	 7-35
       7.2.5      Existing Treatment Performance Databases  	 7-36

7.3    WASTEWATER TREATMENT IN THE PESTICIDE CHEMICALS MANUFACTURING
       INDUSTRY   	7-36
       7.3.1      Carbon Adsorption 	 7-39
       7.3.2      Hydrolysis	7-40
       7.3.3      Chemical Oxidation/Ultraviolet Decomposition  	 7-42
       7.3.4      Resin Adsorption  	 7-43
       7.3.5      Solvent Extraction	7-44
       7.3.6      Distillation	7-44
       7.3.7      Membrane Filtration	7-45
       7.3.8      Biological Treatment  	 7-47
       7.3.9      Evaporation	7-48
       7.3.10     Chemical Precipitation/Filtration 	 7-48
       7.3.11     Chemical Reduction  	 7-49
       7.3.12     Coagulation/Flocculation  	 7-49
       7.3.13     Incineration  	 7-50
       7.3.14     Stripping 	 7-51
       7.3.15     Pre- or Post-Treatment	7-51
       7.3.16     Disposal of Solid Residue from Treatment  	 7-53

7.4    TREATMENT  PERFORMANCE DISCUSSION   	7-54
       7.4.1      Carbon Adsorption 	 7-54
       7.4.2      Hydrolysis	7-56
       7.4.3      Chemical Oxidation/Ultraviolet Decomposition  	 7-56
       7.4.4      Resin Adsorption	7-57
       7.4.5      Solvent Extraction	7-57
       7.4.6      Distillation	7-58
       7.4.7      Biological Treatment  	 7-59
       7.4.8      Oxidation/Reduction and Physical Separation	7-59
       7.4.9      Incineration	7-59

7.5    EFFLUENT LIMITATIONS DEVELOPMENT FOR PAIs	7-60
       7.5.1      Statistical Analysis of Long-Term Self-Monitoring
                  Data	  . 7-61
       7.5.2      Calculation of Effluent Limitations Under
                  BAT	7-65
       7.5.3      Calculation of Effluent Limitations
                  Guidelines Under NSPS	7-88
       7.5.4      Analysis of POTW Pass-Through for PAIs	7-92
       7.5.5      Calculation of Effluent Limitations Guidelines
                  Under PSES and PSNS	7-94


                                      iv

-------
                        TABLE OF CONTENTS  (Continued)
7.6    EFFLUENT LIMITATIONS DEVELOPMENT FOR PRIORITY POLLUTANTS   ....  7-94
       7.6.1      Calculation of Effluent Limitations Guidelines
                  Under BAT	7-95
       7.6.2      Calculation of Effluent Limitations Guidelines
                  Under NSPS	7-103
       7.6.3      Calculation of Effluent Limitations Guidelines
                  Under PSES	7-103
       7.6,4      Calculation of Effluent Limitations Guidelines
                  Under PSNS	7-106

7.7    EFFLUENT LIMITATIONS DEVELOPMENT FOR CONVENTIONAL POLLUTANTS
       AND COD	7-107

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	8-1

8.2    COST MODELING	8-5
       8.2.1      Model Evaluation	8-5
       8.2.2      CAPDET	8-9
       8.2.3      Pesticide Industry Cost Model	8-21

8.3    TREATMENT TECHNOLOGIES         	  8-21
       8.3.1      Activated Carbon	8-23
       8.3.2      Biological Treatment  	  8-27
       8.3.3      Chemical Oxidation	  8-30
       8.3.4      Off-Site Incineration 	  8-31
       8.3.5      Distillation	8-33
       8.3.6      Equalization	8-34
       8.3.7      Filtration  .	8-34
       8.3.8      Hydrolysis	8-35
       8.3.9      Hydroxide Precipitation 	  8-37
       8.3.10     Resin Adsorption	8-37
       8.3.11     Steam Stripping	8-38
       8.3.12     Monitoring for Compliance 	  8-44


SECTION 9 - BEST PRACTICABLE CONTROL TECHNOLOGY (BPT)

9.0    INTRODUCTION   	9-1

9.1    BPT APPLICABILITY	9-1
       9.1.1      Revisions to BPT	9-1
       9.1.2      Applicability of Final  BPT  Limitations	9-5

-------
                         TABLE  OF  CONTENTS  (Continued)


                                                                          Page

SECTION 10 - BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)

10.0    INTRODUCTION   	10-1

10.1    SUMMARY  OF BAT EFFLUENT LIMITATIONS GUIDELINES   	10-1

10.2    IMPLEMENTATION OF THE BAT  EFFLUENT LIMITATIONS GUIDELINES  .... 10-2
        10.2.1     National Pollutant Discharge Elimination System
                  (NPDES) Permit Limitations  	 10-2
        10.2^2     NPDES Monitoring Requirements 	 10-3

10.3    BAT EFFLUENT LIMITATIONS GUIDELINES  	 10-3
        10.3.1     Revisions to BAT Limitations	10-3

SECTION 11 - NEW SOURCE PERFORMANCE STANDARDS (NSPS)

11.0    INTRODUCTION   	11-1

11.1    SUMMARY  OF NSPS  EFFLUENT LIMITATIONS GUIDELINES	11-1
        11.1.1     Revisions to New Source Performance Standards 	 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 	 11-2

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    	12-1
        12.1.1     Revisions to PSES and PSNS	 12-2

12.2    PRETREATMENT STANDARDS  FOR EXISTING AND NEW  SOURCES  (PSES/PSNS)  . 12-2

12.3    COMPLIANCE DATE	12-2

SECTION 13 -  BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY (BCT)

13.0    INTRODUCTION   	13-1

13.1    JULY  9,  1986 BCT METHODOLOGY   	13-1

13.2    BCT TECHNOLOGY OPTIONS   	13-2
                                      vi

-------
                         TABLE OF CONTENTS  (Continued)
                                                                          Page
13.3    BCT  COST TEST  ANALYSIS         	13-3
        13.3.1     The POTW Cost Test	13-3
        13.3.2     Application to the Organic Pesticide Chemicals
                  Manufacturing Subcategory 	 13-4

13.4    CONCLUSIONS	13-5

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	15-3

15.3        ENERGY REQUIREMENTS	15-4

SECTION 16 - ANALYTICAL METHODS

16.0    REGULATORY BACKGROUND AND REQUIREMENTS   	16-1

16.1    CLEAN WATER ACT  (CWA)	16-1
        16.1.1     Safe Drinking Water Act (SDWA)  	16-2

16.2    PROMULGATED METHODS    	16-2
        16.2.1     Methods for PAI Pollutants	16-2
        16.2.2     Methods for Metals  	   16-12
        16.2.3     Development of Methods	16-12
        16.2.4     Procedures for Development and
                  Modification of Methods	16-13
        16.2.5     Method Writing and Modification	16-14

16.3    INVESTIGATION  OF OTHER ANALYTICAL TECHNIQUES   	16-15

SECTION 17 - GLOSSARY

SECTION 18 - REFERENCES
                                     vii

-------
                                LIST OF TABLES


                                                                          Page

2-1    PAIs ADDED TO BPT	2-3

2-2    BCT EFFLUENT LIMITATIONS FOR THE ORGANIC PESTICIDE CHEMICALS
       MANUFACTURING SUBCATEGORY  	  2-5

2-3    ORGANIC PESTICIDE ACTIVE INGREDIENT EFFLUENT LIMITATIONS BEST
       AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT) AND
       PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES)   	  2-7

2-4    BAT EFFLUENT LIMITATIONS AND NSPS FOR  PRIORITY POLLUTANTS FOR
       DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL
       TREATMENT    	2-12

2-5    BAT EFFLUENT LIMITATIONS AND NSPS FOR  PRIORITY POLLUTANTS FOR
       DIRECT DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE
       BIOLOGICAL TREATMENT   	 2-14

2-6    NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD     . 2-16

2-7    NSPS AND PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES
       ACTIVE INGREDIENTS (PAIs)  	 2-17

2-8    EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS PRETREATMENT
       STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)   	 2-23

3-1    LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIs)	3-5

3-2    TREATMENT UNIT OPERATIONS SAMPLED	3-23

3-3    COMPARISON OF THE GEOGRAPHIC DISTRIBUTION OF THE OCPSF vs.
       PESTICIDE INDUSTRY BY REGION   	 3-30

3-4    DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES BY DECADE OF
       OPERATION	3-33

3-5    PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS REPORTED TO
       BE MANUFACTURED IN 1986	3-36

3-6    NUMBER OF PESTICIDE ACTIVE INGREDIENTS PRODUCED BY NUMBER OF
       MANUFACTURING FACILITIES   	 3-44

3-7    NUMBER OF MANUFACTURING FACILITIES BY  NUMBER OF PESTICIDE
       ACTIVE INGREDIENTS PRODUCED  	 3-44

3-8    DISTRIBUTION OF FACILITIES BY QUANTITY OF PAI PRODUCTION   .  .  .   .3-45

5-1    PESTICIDE ACTIVE INGREDIENT PROCESS WASTEWATERS GENERATED IN
       1986 BY EFFLUENT TYPE  .	5-6

                                     viii

-------
                          LIST OF TABLES  (Continued)
                                                                          Page

5-2     WASTEWATER GENERATED IN 1986 FROM OTHER PESTICIDES  WASTEWATER
        SOURCES	 .  5-8

5-3     OTHER FACILITY WASTEWATER GENERATED IN 1986  FROM SOURCES  OTHER
        THAN  PESTICIDE PRODUCTION AND CO-TREATED WITH PESTICIDE
        WASTEWATER  	5-10

5-4     TOTAL PROCESS  WASTEWATER FLOW IN 1986  BY TYPE OF DISCHARGE    .  . . 5-12

5-5     PESTICIDE  PROCESS WASTEWATER FLOW IN 1986  FOR THE ORGANIC
        PESTICIDE  SUBCATEGORY (SUBCATEGORY A)  AND  THE METALLO-ORGANIC
        PESTICIDE  SUBCATEGORY (SUBCATEGORY B)   	 5-13

5-6     PRIORITY POLLUTANT  DATA-FACILITY SELF  MONITORING   	 5-23

5-7     PRIORITY POLLUTANT  DATA-EPA SAMPLING ORGANIC PESTICIDE
        CHEMICALS  MANUFACTURING  	 5-25

5-8     PRIORITY POLLUTANT  DATA - EPA SAMPLING ORGANIC PESTICIDE
        CHEMICALS  MANUFACTURING  	 5-24

6-1     PRIORITY POLLUTANTS SELECTED FOR REGULATION	6-4

7-1     TYPES OF NON-WATER  STREAMS THAT  ARE RECIRCULATED AND RECYCLED   .  7-6

7-2     PAIs  WHOSE MANUFACTURE CURRENTLY INCLUDES  RECIRCULATION OR
        RECYCLE  OF NON-WATER STREAMS  	  7-7

7-3     PLANTS THAT MANUFACTURE PAIs WHOSE PROCESS INCLUDES
        RECIRCULATION  AND RECYCLE OF NON-WATER STREAMS   	7-10

7-4     TYPES OF WATER/WASTEWATER THAT ARE RECIRCULATED AND RECYCLED    . . 7-13

7-5     PAIs  WHOSE MANUFACTURE INCLUDES  WATER  OR WASTEWATER
        RECIRCULATION  AND RECYCLE	7-15

7-6     PLANTS THAT MANUFACTURE PAIs WHOSE PROCESS INCLUDES
        RECIRCULATION  AND/OR RECYCLE OF  WATER/WASTEWATER   	7-17

7-7     BAT PAIs (GROUP A)	7-19

7-8     REGULATED  PAIs   	7-25

7-9     TREATMENT  TECHNOLOGIES USED BY FACILITIES  IN THE PESTICIDE
        CHEMICALS  MANUFACTURING INDUSTRY   	  7-38

7-10    PAI STRUCTURAL GROUPS	7-67
                                      ix

-------
                          LIST OF TABLES (Continued)
                                                                          Page
7-11    PAIs  AND PAI  STRUCTURAL GROUPS WITH  PA1 LIMIT  DEVELOPMENT
        METHODOLOGIES 	 7-76

8-1     CAPDET LARGE  FACILITY UNIT  PROCESSES  	 8-14

8-2     CAPDET SMALL  FACILITY UNIT  PROCESSES  	8-17

8-3     WASTE INFLUENT CHARACTERISTICS   	 8-18

8-4     UNIT  COST DATA   	8-19

8-5     PROGRAM CONTROL/OUTPUT  SELECTION   	 8-22

8-6     PESTICIDES OPTION  1  - TOTAL COSTS BY PLANT   	 8-24

8-7     DESIGN PARAMETERS  FOR THE BIOLOGICAL TREATMENT COST MODULE   .  .  . 8-29

8-8     PRIORITY POLLUTANTS  DIVIDED INTO GROUPS ACCORDING TO HENRY'S
        LAW CONSTANT  VALUES	8-40

8-9     STEAM STRIPPING  DESIGN  PARAMETERS FOR HENRY'S  LAW CONSTANT
        PARAMETERS   	8-41

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     ADDITIONAL PAIs  INCLUDED IN FINAL RULE UNDER BPT   	9-6

10-1    ORGANIC PESTICIDE  ACTIVE INGREDIENT  EFFLUENT LIMITATIONS  BEST
        AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)   	 10-7

10-2    BAT EFFLUENT  LIMITATIONS FOR PRIORITY POLLUTANTS FOR DIRECT
        DISCHARGE POINT  SOURCES THAT USE END-OF-PIPE BIOLOGICAL
        TREATMENT	10-12

10-3    BAT EFFLUENT  LIMITATIONS 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   .  . 11-4

11-2    NSPS  EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES ACTIVE
        INGREDIENTS (PAIs)   	11-5

-------
                          LIST OF TABLES (Continued)
                                                                          Page

11-3   NSPS FOR PRIORITY POLLUTANTS FOR PLANTS WITH  END-OF-PIPE
       BIOLOGICAL TREATMENT   	  11-10

11-4   NSPS FOR PRIORITY POLLUTANTS FOR PLANTS THAT  DO NOT  HAVE
       END-OF-PIPE BIOLOGICAL TREATMENT   	  11-12

12-1   ORGANIC PESTICIDE ACTIVE INGREDIENT  EFFLUENT  LIMITATIONS
       PRETREATMENT STANDARDS FOR EXISTING  SOURCES (PSES)   	 12-3

12-2   PSES AND PSNS FOR PRIORITY POLLUTANTS	12-8

12-3   PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES ACTIVE
       INGREDIENTS (PAIs)   	 12-9

13-1   POTW COST TEST RESULTS FOR THE ORGANIC PESTICIDE CHEMICALS
       MANUFACTURING SUBCATEGORY  	 13-6

16-1   TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS	16-3
                                      xi

-------
                               LIST OF FIGURES


                                                                          Page

3-1    FLOW CHART FOR DETERMINING INCLUSION OF PAI  IN  PESTICIDE
       MANUFACTURING FACILITY CENSUS FOR 1986   	3-4

3-2    DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES BY EPA
       REGION   	3-29

3-3    1986 PESTICIDE MARKET COMPOSITION	3-32

3-4    REACTION MECHANISMS FOR s-TRIAZINES AND ATRAZINE AND AMETRYN   .   . 3-48

3-5    REACTION MECHANISMS FOR CARBOFURAN AND NABAM   	3-50

3-6    REACTION MECHANISMS FOR PROPANIL AND ALACHLOR	3-52

3-7    REACTION MECHANISMS FOR ISOPROPALIN	3-53

3-8    REACTION MECHANISMS FOR 2,4-D	3-54

3-9    REACTION MECHANISMS FOR PARATHION AND PHORATE	3-56

3-10   REACTION MECHANISM FOR GLYPHOSATE	3-57

5-1    EXAMPLE OF PESTICIDE ACTIVE INGREDIENT MANUFACTURING PROCESS   .   .  5-2

5-2    INDUSTRY SELF-MONITORING BOD LEVELS IN FINAL EFFLUENT DISCHARGE   . 5-19

5-3    INDUSTRY SELF-MONITORING TSS LEVELS IN FINAL DISCHARGE   	5-20

5-4    INDUSTRY SELF-MONITORING pH LEVELS IN FINAL  DISCHARGE	5-21

5-5    INDUSTRY SELF-MONITORING COD LEVELS IN FINAL DISCHARGE   	5-30

8-1    FLOWCHART USED TO DETERMINE TREATMENT COSTS  FOR PAIs   	8-2

8-2    FLOWCHART USED TO DETERMINE TREATMENT COSTS  FOR PRIORITY
       POLLUTANTS   	8-3
                                     XI1

-------
                                   SECTION 1

                                 INTRODUCTION

1.0         LEGAL AUTHORITY

            This regulation is being promulgated 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.

            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
category.  The Act establishes BAT as the principal national means of
controlling the direct discharge of priority pollutants and nonconventional
                                      1-1

-------
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 30i(b)(2)(E) to che 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 (BOD5) ,
total suspended solids (TSS), fecal colifona, 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).

            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.  \American 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
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
                                      1-2

-------
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.
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 304(m) 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.  Shortly before the end of July 1993, EPA asked the Court for a limited
extension of this deadline.
                                     1-3

-------
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 to
be the national policy of the United States.  The Act declares that pollution
should be prevented or reduced at the source whenever feasible; pollution that
cannot be prevented should be recycled or reused in an environmentally safe
manner whenever feasible; pollution that cannot be recycled should be treated
in an environmentally safe manner whenever feasible; and disposal or release
into the environment should be chosen only as a last resort and should be
conducted in an environmentally safe manner.

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), BOD5, 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
pollutants were set for metallo-organic PAIs containing arsenic, mercury,
cadmium, or copper.

            Several industry members challenged the BPT regulation in 1978 and
the U.S. Court of Appeals remanded them on two minor issues [BASF Wyandotte
Corp. v. Costle. 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,
                                     1-4

-------
the Agency indicated it was considering changing  its approach to developing
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 \Chemical 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
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.

Scope of the 1992 Proposed Rule

            The April 10,  1992 proposed regulations covered the 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 (Subcategory C) at a later date.  Under the Consent Decree in NRDC
                                      1-5

-------
et al v. Reilly referred to above, the Administrator is to sign final effluent
guidelines covering this industry by the end of August 1995.

            In the 1992 proposal, EPA proposed expanded 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 was proposed 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 proposed reserving the BCT, BAT, NSPS, PSES, and
PSNS effluent limitations for this subcategory.

            EPA proposed that the effluent limitations guidelines and
standards would be applicable to discharges generated during the manufacture
of PAIs from chemical reactions.  (For one PAI, the effluent guidelines
applied only to discharges of wastewater generated during the purification of
that PAI to a higher quality PAI product.)  The proposed regulations did 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 did the proposed 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 the separate rulemaking referred to previously.  The proposed
regulations also did not apply to the manufacture of "intermediate" chemicals,
which are not pesticides but which subsequently are converted by further
chemical reactions to pesticide active ingredients.  The "intermediates" may
be covered by other regulations, such as the Organic Chemicals, Plastics, and
Synthetic Fibers (OCPSF) effluent guidelines and standards (40 CFR Part 414)
when the intermediate is an organic chemical, or the Inorganic Chemicals
effluent guidelines and standards (40 CFR Part 415) when the intermediate is
an inorganic chemical.

            The BPT regulations promulgated in 1978,  which limit discharges
from the manufacture of certain specified PAIs, are not being changed.
However, EPA proposed extending the applicability of the existing Subcategory
A limitations to discharges from the manufacture of fifteen organic PAIs and
organo-tin PAIs, which were previously excluded or omitted from coverage by
the organic pesticides chemicals manufacturing subcategories.  Information
collected and developed on direct dischargers indicated that all manufacturers
of these 15 organic PAIs and organo-tin PAIs were already subject to permit
limitations equal to or more stringent than the BPT Subcategory A limitations;
the limitations in these permits were developed on a "best professional
judgment" basis, using the existing BPT limitations as guidance.
                                      1-6

-------
            EPA proposed BCT limits for conventional pollutants (pH, BOD5 and
TSS) equal to BPT limits for subcategory A.

            EPA proposed BAT limitations for subcategory A PAIs based on the
use of the following treatment technologies: hydrolysis, activated carbon,
chemical oxidation, resin adsorption, solvent extraction, distillation,
biological treatment and/or incineration to control the discharge of PAIs in
wastewater.  EPA has also based the proposed BAT limitations on pollution
prevention, including in-process recycling (recirculation), and
(out-of-process) recycle/reuse where possible.  For some PAIs, compliance with
the proposed BAT limitations would require implementation of pollution
prevention practices and/or improvements to treatment technologies currently
in place at facilities by enhancing the operations, such as increasing
retention time for hydrolysis or carbon adsorption treatment.  BAT effluent
limitations for all but one of the priority pollutants were proposed based on
the use of model control technologies identified in the OCPSF effluent
guidelines.  For total cyanide, long-term data from three pesticide chemical
industry facilities and five OCPSF facilities were used.

            EPA proposed NSPS limitations for subcategory A PAIs based on the
mass-based BAT limitations for the PAIs, but modified NSPS limitations for
certain PAIs to reflect a wastewater flow reduction of 28% to account for the
ability of new sources to utilize less water or to reuse water generated in
the chemical reactions.  The NSPS proposed for priority pollutants were
concentration based, and so were set equal to the BAT limitations for
subcategory A priority pollutants. For these pollutants, the flow reduction of
with 28% would be applied by permit writers in setting the mass limits for
each site.

            EPA proposed PSES for subcategory A equal to BAT limitations for
PAIs.  As with BAT, proposed PSES for the priority pollutants were primarily
based on a direct transfer of the OCPSF pretreatment standards. In addition,
two priority pollutants for which pretreatment standards were proposed were
deemed not to pass through or interfere with POTWs and therefore were not
proposed to be regulated by PSES.

            For PSNS for subcategory A, the following were proposed:  (1) the
same PAIs were proposed to be subject to regulation under PSNS for this
subcategory as were proposed for BAT and NSPS; and (2) the same priority
pollutants proposed for PSES regulations  were proposed for regulation by
PSNS.  PSNS limitations were proposed for PAIs in subcategory A as equal to
NSPS limitations.  For the priority pollutants,  PSNS limitations for priority
pollutants were proposed as equal to the PSES limitations. For PSES and PSNS,
the 28% flow reduction would be applied when calculating the site specific
mass limits.

Post-Proposal Notice of Data Availability

            On April 14, 1993,  EPA published a Notice of Data Availability
(NOA) (58 FR 19392), making available for public comment additional
                                      1-7

-------
information received since the time of the proposal and placing in the public
record information previously, but no longer,  claimed as confidential business
information (CBI).

            The new information consisted largely of additional long-term
treatment system performance data for control  of discharges of certain PAIs.
This new data provided information on treatment system performance over a
wider variety of conditions than was previously available.   In addition,
performance data were also submitted to EPA for new full-scale treatment
systems to be used as a basis for limitations  instead of transferring
technology information from pilot studies or full-scale treatment of similar
PAIs.   Data were also submitted on analytical  methods where the commenter
believed the methods in use differed from the  proposed method.

            The NOA also solicited comment on  certain information excluded
from public review at the time of proposal based on claims  of CBI by the
submitter of this information.  Based upon subsequent review of these claims,
some submitters withdrew their CBI claims, allowing for public review of the
information.  The information that was previously,  but no longer, claimed as
CBI included questionnaire responses from eleven facilities; reports (visits,
sampling, health and safety plans, analytical  results and correspondence) for
six of the eleven facilities visited and/or sampled;  long-term treatment
system performance data for five of the eleven facilities;  and information on
EPA's  development of limitations based on this data,  along with the analysis
of the cost impacts on these eleven facilities.

1.2         SCOPE OF TODAY'S RULE

            The regulation promulgated 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.

            In today's notice, EPA is promulgating expanded 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 promulgated equal to BPT for the organic pesticide
chemicals manufacturing subcategory.  Also, the coverage of the existing BPT
regulations has been expanded.
                                     1-8

-------
            For the metallo-organic pesticide chemicals manufacturing
subcategory, current BPT limitations require no discharge of process
wastewater pollutants.  EPA is reserving BCT, BAT, NSPS, PSES, and PSNS
effluent limitations for this subcategory.

            The final 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
chemicals ("intermediates") which are not pesticides but which subsequently
are converted by further chemical reactions to pesticide active ingredients.
The "intermediates" may be covered by other guidelines, such as the Organic
Chemicals,  Plastics,  and Synthetic Fibers (OCPSF) effluent guidelines (40 CFR
Parts 414 and 416) or the Inorganic Chemicals effluent guidelines (40 CFR Part
415).
                                     1-9

-------

-------
                                   SECTION 2

                                    SUMMARY

2.0         OVERVIEW OF THE INDUSTRY

            According to data collected by EPA during the development of this
rule, in 1986 the pesticide chemicals manufacturing industry included 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 commercial 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.

            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 no process wastewater because of recycle/reuse operations
or because they do not use water.

            Since proposal, there have been two major changes in the industry
that are relevant to this rulemaking.  First, EPA's latest information is that
there has been a decrease in the number of plants that manufacture pesticides
from 90 to 75 due to plant closures.  Second, a number of plants have
installed additional or improved wastewater treatment facilities since the
time of EPA's data collection for this rulemaking.   (See Section 5 of  this
document, describing the data EPA has received concerning these new treatment
facilities.)   Also as explained in that section, EPA has incorporated  these
new data into the development of the limitations in today's final rule where
possible.

            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,  BOD5,  and TSS), a
                                      2-1

-------
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 and
conventional pollutants.  The major physical-chemical treatment technologies
in use for PAI removal are activated carbon, chemical oxidation, and
hydrolysis.  More detail is provided in Section 7.

2.1         SUMMARY OF THE FINAL REGULATIONS

2.1.1       Applicability of the Final Regulations

            The final 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 formulators 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, BOD5,  TSS,  and pH.  The  organic  PAI
regulation also limited total pesticides in wastewaters resulting from the
manufacturing of 49 specific organic PAIs.  For metallo-organic PAIs, the BPT
limitations require that there be no discharge of process wastewater
pollutants.

            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.  In this final rule, EPA is
expanding the coverage of BPT limitations (for BOD5,  COD, TSS, and  pH)  to
include manufacture of three 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 three organic PAIs and
organo-tin PAIs.

            In addition, EPA is amending the BPT regulation to include 11 PAIs
which will now be subject to the existing BPT limitations for BODS,  TSS  and
pH, but will not be subject to the existing BPT limitations for COD. All
                                      2-2

-------
                                   Table 2-1

                               PAIs ADDED TO BPT
PAI CODE
025
058
060
138
142
157
192
211
211.05
223
224
226
239
256
257
PAI
Cyanazine
Ametryn
Atrazine
Glyphosate
Hexazinone
Methoprene*
Organo-tin Pesticides*
Phenylphenol*
Sodium Phenylphenate*
Prometon
Prometryn
Propazine
Simazine
Terbuthylaz ine
Terbutryn
*Limitations for BOD5>  TSS,  COD and pH apply to these PAIs only. For the
 other 11 PAIs, limitations for BODS,  TSS and pH apply, but the COD
 limitations do not apply.
                                      2-3

-------
manufacturers of these 11 PAIs are already subject to permit limitations for
BOD5,  TSS  and pH  that  are  at  least  as  stringent as the BPT  limitations but  the
facilities cannot achieve the BPT limitations for COD.

            In this final rule, the existing BPT limitations (i.e., those
promulgated in 1978) are not being changed. Additionally, there is no change
to the existing BPT effluent limitations guidelines  for metallo-organic PAIs.

2.1.3       BCT

            In this final regulation,  the Agency is  setting BCT equal to BPT
for conventional pollutants under the organic pesticide chemicals
manufacturing subcategory. The Agency is reserving 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 BOD5,  COD, and TSS.   Options for  further
removal of TSS and/or BOD5, initially  considered  for  evaluation as  BCT
candidate technologies, included multimedia filtration,  carbon adsorption,
membrane filtration, incineration,  evaporation,  additional biological
oxidation (above the level required to meet BPT), and clarification through
the use of settling ponds.  Of these options, multimedia filtration appeared
to be the most promising option for BCT.  However,  EPA determined that
multi-media filtration has not been demonstrated to  consistently achieve
additional removals of BOD5 and TSS in this industry.  Multimedia filtration
was then evaluated by the BCT cost test.  This technology also failed the BCT
cost test.  Since no other technologies were identified that would be expected
to enhance conventional pollutant removal above that provided by BPT
technologies, the Agency is setting 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

            The final BAT limitations for PAIs under the organic pesticide
chemicals manufacturing subcategory are based on the use of the following
treatment technologies:  hydrolysis, activated carbon,  chemical oxidation,
resin adsorption, biological treatment, solvent extraction, distillation,
and/or incineration.

            Limitations for PAIs were derived on a mass basis, using long-term
data where available.   Where long-term effluent and flow 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 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
                                      2-4

-------
                                   Table  2-2

                       BCT EFFLUENT LIMITATIONS FOR THE
             ORGANIC  PESTICIDE  CHEMICALS  MANUFACTURING  SUBCATEGORY
Effluent
Charact er I s t ic
BOD3
TSS
PH
Maximum for
Any One Day*
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.
                                     2-5

-------
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 are established for 28 priority
pollutants.  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 final 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 final BAT effluent limitations for organic PAIs and
classes of PAIs and priority pollutants under the organic pesticide chemicals
manufacturing subcategory are listed in Tables 2-3, 2-4, and 2-5.

            The Agency is reserving BAT for the metallo-organic pesticide
chemicals manufacturing subcategory.

            The BAT regulations in this rulemaking will be the basis for
limitations 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 is promulgating mass-based new source performance standards
(NSPS) for the organic pesticide chemicals manufacturing subcategory on the
basis of the BAT limitations plus a 28% achievable flow reduction for certain
PAIs.  NSPS are promulgated for conventional pollutants (BOD5, TSS,  and  pH)
and COD on the basis of BPT limitations and a 28% achievable flow reduction.
NSPS regulation of priority pollutants are based on BAT limitations 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 final NSPS limitations for
conventional pollutants and 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 is reserving NSPS for the metallo-organic pesticide
chemicals manufacturing subcategory.
                                      2-6

-------
                                   Table 2-3
           ORGANIC PESTICIDE ACTIVE INGREDIENT EFFLUENT LIMITATIONS
            BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)
            AND PRETREATMENT STANDARDS FOR EXISTING SOURCES  (PSES)
BAT/PSES Limitations*
Organic Pesticide Active
Ingredient (PAI)
2, 4-D
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb
Ametryn
Atrazine
Azinphos Methyl
Benfluralin
Benomyl and Carbendazim
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 40 [Potassium N-
hy dr oxyme thy 1 - N -
methyldi thiocarbamate ]
BAT/PSES effluent limitations
Daily Maximum Shall
Not Exceed
1.97 x ID'3
Honthly Average
Shall Not Exceed
6.40 x 10-4
Notes

No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
6.39 x 10-4
2.45
5.19 x lO'3
7.23 x 10-«
7.72 x 10°
5.12 x ID'3
2.74 x 10-2
3.22 x 10-1
3.50 x 10-2
1.69 x ID'2
1.97 x 10-»
9.3 x 10-'
1.54 x 10-3
3.12 x 10-1
2.53 x 10-3
1.72 x 10-3
1.41 x lO'2
1.09 x W-4
8.94 x lO'3
8.72 x ID'3







1
2

No discharge of process wastewater pollutants
3.83 x 10-'
3.95 x 10-3
3.95 x 10-3
5.74 x 10-3
1.16 x 10-1
1.27 x ID'3
1.27 x 10-3
1.87 x 10-3




                                      2-7

-------
 Table 2-3




(Continued)
Organic Pesticide Active
Ingredient (PA!)
Busan 85 [Potassium
dimethyldithiocarbamate ]
Butachlor
Captafol
Carbarn S [Sodium
dimethyldithiocarbamate ]
Carbaryl
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos
Cyanazine
Dazomet
DCPA
DEF
Diazinon
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
BAT/PSES effluent limitations
Daily Maximum Shall
Not Exceed
5.74 x 10-3
5.19 x lO"3
4.24 x 10-<
5.74 x lO'3
1.60 x lO'3
1.18 x lO*
8.16 x lO'2
1.51 x ID'3
8.25 x 10"
1.03 x 10-2
5.74 x lO'3
7.79 x ID'2
1.15 x lO'2
2.82 x lO'3
Monthly Average
Shall Not Exceed
1.87 x 10-3
1.54 x ID'3
1.31 x 10^
1.87 x lO'3
7.30 x 10-1
2.80 x 10"5
3.31 x lO'2
4.57 x 10^
2.43 x lO"
3.33 x ID'3
1.87 x ID'3
2.64 x lO'2
5.58 x 10°
1.12 x lO'3
Notes














No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x lO"2
7.33 x lO"3
3.15 x lO'2
2.95 x 10-*
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x 10-2





    2-8

-------
 Table 2-3




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Endothall, salts and
esters
Endrin
Ethalfluralin
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Heptachlor
Isopropalin
KN Methyl
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny 1
Methoxychlor
Metribuzin
Mevinphos
Nab am
BAT/PSES effluent limitations
Daily Maximum Shall
Not Exceed
Monthly Average
Shall Not Exceed
No discharge of process wastewater
pollutants
2.20 x 10-2
3.22 x 10*
5.51 x 10-3
1.02 x 10'1
1.48 x lO'2
1.83 x 10-2
5.40 x 10-3
8.80 x 10-3
7.06 x lO'3
5.74 x lO'3
2.69 x 10-3
2.35 x 10*
5.10 x 10-3
1.09 x 10*
1.57 x 10-3
3.61 x lO'2
7.64 x lO"3
9.45 x 10-3
2.08 x ID'3
2.90 x 10-3
2.49 x lO"3
1.87 x lO'3
1.94 x 10-3
9.55 x 10-3
Notes


1










No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.46 x lO'2
3.82 x lO'3
3.23 x lO'3
1.36 x lO'2
1.44 x 10*
5.74 x 10-3
5.58 x 10-3
7.53 x 10-3
1.76 x lO'3
1.31 x ID'3
7.04 x 10°
5.10 x 10's
1.87 x 10-3







    2-9

-------
 Table 2-3




(Continued)
Organic Pesticide Active
Ingredient (PAX>
Nabonate
Naled
Norflurazon
Organotins
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Permethrin
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I and
Pyrethrin II
Simazine
Stirofos
TCMTB
BAT/PSES effluent limitations
Daily Maximum Shall
Not Exceed
5.74 x 10-3
Monthly Average
Shall Not Exceed
1.87 x 10-3
Notes

No discharge of process wastewater pollutants
7.20 x 10-4
1.72 x lO'2
7.72 x 10-4
7.72 x 10-1
5.75 x 10-4
1.17 x 10-2
2.32 x 10-4
3.12 x 10-»
3.10 x W-4
7.42 x 10-3
3.43 x W-*
3.43 x 10-4
1.90 x W
3.62 x lO'3
6.06 x 10's
9.37 x 10's
No discharge of process wastewater
pollutants
7.72 x lO'3
7.72 x 10-3
6.64 x 10-4
5.19 x 1C'3
1.06 x 10-3
7.72 x lO'3
1.24 x 10-2
7.72 x lO'3
4.10 x 10-3
3.89 x lO'3
2.53 x lO'3
2.53 x ID'3
2.01 x 10-4
1.54 x 10-3
4.84 x 10-4
2.53 x 10-3
3.33 x lO'3
2.53 x lO'3
1.35 x lO'3
1.05 x 10-3

3






4










   2-10

-------
                                   Table 2-3

                                  (Continued)
Organic Pesticide Active
Ingredient (PAD
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin
Vapam [ Sodium
methyldithiocarbamate ]
Ziram [Zinc
dimethyldithiocarbamate ]
BAT/PSES effluent limitations
Daily Maximum Shall
Not Exceed
9.78 x 10-2
3.83 x 1C'1
4.92 x 10*
7.72 x ID'3
7.72 x 1C'3
1.02 x 10-2
6.52 x 10-2
3.22 x 10*
5.74 x lO'3
5.74 x lO'3
Monthly Average
Shall Not Exceed
3.40 x 10-2
1.16 x 10-'
1.26 x 10*
2.53 x lO'3
2.53 x lO'3
3.71 x ID'3
3.41 x 10-2
1.09 x 10*
1.87 x lO'3
1.87 x 10-3
Notes







1


 *Limitations are in Kg/kkg (lb/1,000 Ib) i. e., kilograms of pollutant per
  1,000 kilograms product (pounds of pollutant per 1,000 Ibs product).

'Monitor and report  as  total toluidine  PAIs,  as  Trifluralin.

2Pounds  of product include Benomyl and  any Carbendazim production not
 converted to Benomyl.

3Monitor and report  as  total tin.

'Applies to purification by  recrystallization portion of the process.
                                     2-11

-------
                                  Table 2-4

          BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS
FOR DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL TREATMENT
IlilililB
illiiiiiPlilPiliiiiP^^^I
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
Dlbromochlorome thane
Naphthalene
Phenol

IlilllBilililillllllli
IIBiliPiiiiliillill
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
380
794
380
794
59
26
lililiiii^ii^^liii
Iliii|iip:i:|||liitiii
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
142
196
142
196
22
15
;:-;';;: -:-:::^->-;: :'^^-^y ••''---']''.'•''•.
::;:;-x.;v;:;:;:;YXf;:;>:;:;:':'\:.; I.;.":'-
ilil;i;!iil!f^
||||j||iig||||
























                                    2-12

-------
                                  Table 2-4

                                  (Continued)


fiilliiiib^^
Tetrachloroethylene
Total Cyanide
Total Lead
m 	 W 	 Kas 	 ; 	 mz?™» 	 vmmwfm?* 	 Ki'mim 	 mttZ-ltim;
mlsj;£:^^
|ii|llllillilil:iilll^llli:l
lll|;li^lliiiili^||ii§;

56
640
690
Illliliiliiiliiiliilli


22
220
320




1
1
'Lead and  total cyanide limitations apply only to noncomplexed lead-bearing or
 cyanide-bearing waste streams.   Discharges of lead from complexed
 lead-bearing process wastewater or discharges of cyanide from complexed
 cyanide-bearing process  wastewater are not subject to these limitations.
                                     2-13

-------
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       Pesticide Product 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
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 Consideration

            At proposal, there were 270 PAIs or classes of PAIs that EPA
considered for regulation.  Since proposal, EPA has revoked the registration
of biphenyl for use as a pesticide.  Because biphenyl can no longer be used as
a pesticide, it is no longer considered for coverage under these regulations,
and, therefore, 269 PAIs or classes of PAIs are considered for regulation in
the final rule.  The initial basis for the list of covered PAIs 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 272 PAIs and classes of PAIs.  Because the consolidated
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 272 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 the 272 PAIs that were included in
the Pesticide Manufacturing Facility Census of 1986 (hereinafter referred to
as the "Facility Census").  Table 3-1 lists these 272 PAIs and classes of
PAIs, including the three PAIs -- biphenyl, ortho-dichlorobenzene, and
para-dichlorobenzene -- that were included in the Facility Census but are not
being considered for regulation in the final rule.

3.1.3       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.
                                     3-3

-------
                                     Figure 3-1


                FLOW  CHART FOR DETERMINING  INCLUSION  OF  PAI
           IN  PESTICIDE  MANUFACTURING  FACILITY CENSUS FOR 1986
                All salts or esters of PAIs addressed in 1985 Rule
                      (such as salts and esters of 2,4-0)
                       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 tor
  Regulation
 Was PAI
Beti«v«o to
   B«h
Production?
    S«vcn
EPA-OPP R
   for 198445
   Product!
                              606 PAIs condensed into
                             272 PAIs or classes of PAI
                                 included in OOP
                                                                            229 PAIs
                                                                            Excluded
                                                                            fromDCP
                                           3-4

-------
                 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
**
30001
**
30801
**
80811
mffim
miMm
i
2
3
4
5
6
6
7
8
9
10
11
12
13
14
14
15
15
16
16
17
17
18
litililllifllllH
l,l-Bis(chlorophenyl)-2,2,2- trichloro ethanol [Dicofol]
l,2-Dlhydro-3,6-pyrldazinedione[Malelc Hydrazide]
1,2-Ethylene dlbromlde [EDB]
1,3,5-Triethylhexahydro-s-Triazlne [Vanclde TH]
1 , 3 -Di chloropropene
Fhenarsazina Oxide
10 , 10 ' -Oxyblsphenoxarsine
[l-(3-Chloroallyl)-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 [Triadlmefon]
2,2'-Methylenebls(3,4,6- trlchlorophenol) [Hexachlorophene]
2,2'-Methylenebls(4,6-dichloro phenol) [Tetrachlozophene]
2,2'-MethyLenebls(4-chloro phenol) [Dlchlorophene]
2,2-Dichlorovlnyl dimethyl phosphate [Dichlorvos]
2,3,5-Trimethylphenylmethylcarbamate [Landrin-2]
2,3,6-Trichlorophenylacetic acid [Fenac]
2,3,6-Trichlotophenylacetic acid, salts and esters
2,4,5-Trichlorophenoxyacetic acid [2,4,5-1]
2,4,5-Irichlorophenoxyacetic acid, salts and esters
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- (o-chloroanilino)-s-Triazine [Anilazine]
|llll|i^lll|llli
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
**
00094-75-7
**
00094-82-6
**
00101-05-3
lllg5?3MS6fil^ili;_SSpft;:i*:S::;g
DDT
Bydrazide
EDB
s-Triazin*
EDB
Organoarsanlc
Organoarsenic
Amnonium
Triazine
Chlorophene
Chlorophene
Chlorophene
Phosphate
Carbamate
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
s-Triazine
lllllllselliillf.liflilllllll
Insecticide
Herbicide, growth regulator
Fumigant
Fungicide
Nematocide
Fungicide
Fungicide
Disinfectant
Fungicide
Disinfectant
Disinfectant
Disinfectant
Insecticide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide

-------
                                                    Table 3-1  (Continued)




                                         LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIs)

36001
31301
8707
15801
39001
84101
100101
19101
30501
**
99901
67703
31401
**
31501
**
60101
80815
21201
**
35603
99001
m$mm
Illllli
19
20
21
22
23
24
25
26
27
27
28
29
30
30
31
31
32
33
34
34
35
36
I^^^^^^^^^^^^^^^^^JiS^^^^^^^^^^^^^^^^
2, 4-Dinitro-6-octylphenyl crotonate,
2,6-Dinitro-4-octylphenylcrotonate, and Nltrooctylphenols
(Dlnocap) (The octyl's ace a mixture of 1-Methylheptyl ,
1-Ethylhexyl, and 1-Propylpentyl)
2,6-Dlchloro-4-nitcoanlllne [DichLoran]
2-Bromo-4-hydroxy acetophenone [Busan 90]
2-Carbomethoxy-l-methylvinyl dimethyl phosphate, and related
compounds [MevinphosJ
2-Chloroallyl diethyldlthlocarbamate [Sulfallate]
2-Chloro-l-(2,4-dlchlorophenyl)vlnyl dlethyl phosphate
[ChlorCenvlnphos ]
2-Chloro-4- ( 1-oyano-l-methylethyl ) amlno ) -6-ethylamino) -
s-Trlazlne [Cyanazina]
2-Chloro-N-isopropylacetanilide [Propachior]
2-MethyL-4-chlorophenoxyacetlc acid [MCFA]
2-Methyl-4-chlorophenoxyacatic acid, salts and esters
2-n-Octyl-4-isothiazolin-3-'one [Octhilinone]
2-Pivaly 1- 1 , 3- indandione [ Pindone ]
2-(2,4-Dichlorophenoxy) propionic acid [Dichlorprop]
2-(2,4-Dichlorophenoxy) propionio acid, salts and esters
2-(2-Methyl-4-chlorophenoxy) propionic acid [MCPP]
2-(2-Methyl-4-chlorophenoxy) propionic acid, salts and esters
2-(4-Thiazolyl)benziinidazole IThiabendazole]
2-(methylthio)-4-(ethylamino)-6-(l,2-dimethylamino)-s-Triazine
2-(m-Chlorophenoxy)propionic acid [Cloprop]
2-(m-Chlorophenoxy)propionic acid, salts and esters
2-(Thiocyanomethylthio)benzo thiazole [TCMTB]
2-((Hydroxyroethyl)an>ino) ethanol [HAE]

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
**
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
il:5:i1lj;§ttw|^^S^&^:|sii;:;;:|:::
Phenylcrot.onate
Arylhalido
Miscellaniious
Phosphate
Dithiocarbamate
Phosphate
s-Triazina
Acetanllide
Phenoxy acid
Phenoxy acid
Heterocyciic
Indandione
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
Heterocyciic
Triazine
Phenoxyacetic acid
Phenoxyacetic acid
Heterocyciic
Alcohol
:||||||||:|il|,|i||g;:;:SjSl|||lll;;:;
Insecticide
Fungicide
Slimicide
Insecticide
Herbicide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Rodenticide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Herbicide
Herbicide
Herbicide
Fungicide
Bacteriostat
w

-------
                                                     Table 3-1 (Continued)




                                          LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIs)

67707
102401
101701
100501
28201
107801
86001
**
37507
101101
19401
**
19201
**
44401
84701
55501
59804
103301
114401
**
90501
mtmm
37
38
39
40
41
42
43

44
45
46
46
47
47
48
49
50
51
52
53
53
54
llllllliilll!^
2-( (p-Chlorophanyl)phenyl acetyl)-!, 3-indandione
[Chlor ophac inone ]
3,4,5-trimethylphenyl methylcarbamate [Landrin-1]
3,5-Dichloro-N-(l,l-dimethyl-2-propynyl)benzan)ide [Fronamlde]
3,5-Dimethyl-4-(methylthio) phenyl dimethylcarbamate
[Methlocatb]
3 ' , 4 ' -Dichloropropionanillde [Propanil]
3-Iodo-2-propynyl butylcarbamaba
3-(a-Acetonylfur£uryl)-4-hydroxycoumarin [Coumafuryl]
3-(a-AcetonylfurfuryL)-4-hydroxycoumarin, salts and esters
4,6-Dlnitro-o-cresol tDHOC)
4-Aroino-6- ( 1 , l-dimethylethyl)-3- (methylthio ) -
l,2,4-triazin-5(4H)-one [Metrlbuzin]
4-chlorophenoxyacetlc acid [CPA]
4-chlorophenoxyacetic acid, salts and esters
4-(2-Methyl-4-chlorophenoxy)butyric acid [MCPB]
4-(2-Methyl-4-chlorophenoxy)butyric acid, salts and esters
4-(Dlmethylamlno)-m-tolyl methylcarbamate [Aminocarb]
5-Ethoxy-3-(trichloromethyl)-l,2,4-thiadiazole [Etrldlazole]
6-Ethoxy-1.2-dihydro-2,2,4-trimethyl qulnollne [Ethoxyquin]
8-Quinoliol sulfate [Qulnollol sulfate]
Acephate (0,S-Dlmethyl acetylphosphoramidothioate)
Acifluorfen (5-(2-Chloro-4-(trifluoromethyl)
phenoxy)-2-nitrobenzolc acid)
Acifluorfen, salts and esters
ALachlor (2-Chloro-2'6'~diethyl-N-(methoxymethyl)acetanilide
Ijllllfiil^lllll
03691-35-8
02655-15-4
23950-58-5
02032-65-7
00709-98-8
55406-53-6
00117-52-2
**
00534-52-1
21087-64-9
00122-88-3
**
00094-81-5
**
02032-59-9
02593-15-9
00091-53-2
00134-31-6
30560-19-1
50594-66-6
**
15972-60-8
IPSpftiiSfiaSffiilijMS^siiliif:
Indandioni!
Carbamate
Chloroben-.i amide
Carbamate
Chloropropionanilide
Carbamate
Hydroxycoumarin
Hydroxycoumarin
Phenol
Triazine
Phenoxy aoid
Phenoxy asld
Phenoxy acid
Phenoxy acid
Carbamate
Heterocyclic
Quinoline
Quinoline
Phosphor amidothioate
Benzole acid
Benzoic acid
Acetanilide
illillll-ifSl|i|ii^;;|f^|;;||:||f'
Rodenticide
Insecticide
Herbicide
Insecticide, Molluscide
Herbicide
Fungicide
Rodenticide
Rodenticide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Insecticide, Miticide,
Molluscide
Fungicide - soil
Fungicide, growth
regulator, antioxidant
Fungicide, bacteriostat
Insecticide
Herbicide
Herbicide
Herbicide
OJ



-vl

-------
                                                     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
35302
112301
101401
12501
**
iililt
35
56
57
58
59
60
61
62
63
64
65
66
67
68
68
69
69
70
71
72
72
!!sl!lK;;;|!^
Aldicarb (2-Methyl-2- (methylbhio )propionaldehyde
0- (mothylcarbamoyl )oxime )
[AlXyl* dimethyl benzyl Ammonium chloride * (SOX C14, 40% C12,
10* C16)]
Allefchrln (all isomers and allethrin coil)
Ametryn (2-(Ethylamino)-4-(isopropylamino)-
6-(methylthlo)-s-Triazine
Aroitraz (N'-2,4-Dimethylphenyl)-N-
( ( (2, 4-dimethylphenyl)imino)methyl)-N-methylroethanimidamide)
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-Thlocyanoethyl esters of mixed fatty acids containing from
10-18 carbons [Le thane 384]
Bifenox [Methyl-5-(2,4-dichloro phenoxy)-2-nitrobenzoate]
Biphenyl1
Bronacil [5-Brorao-3-sec-Butyl-6-methyluracil]
Bromacil, lithium salt
Bromoxynil (3,5-Dibromo-4-hydroxy benzonitrile]
Bromoxynil octanoate
Butachlor [N-(Butoxymethyl)-2-chloro-2' ,6'-diethylacetanilide]
• -Bromo- * -nitros tyr ene [ Giv-gard ]
Cacodylic acid [Dimethylarsenic acid)
Cacodylic acid, salts and esters

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
01689-99-2
23184-66-9
07166-19-0
00075-60-5
**
|||||||;S|||||B||j|l|S^;||:|:||
Carbamate
Ammonium
Cyclopropane carboxylic
acid
s-Trlazinn
Imidamido
s-Triazino
Carbamate
Carbamate
Arylhalidu
Ester
Thiocyana.e
Nitrobenzoate
Aryl
Uracil
Uracil
Benzonitrile
Benzonitrile
Acetanilide
Miscellaneous
Organoarsenic
Organoarsenic
9MS9t^&Mi:^'f^^^M^M!
Insecticide
Antimicrobial
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Fungicide - vegetables
Disinfectant
Repellent
Insecticide
Herbicide
Fungicide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Slimicide
Herbicide
Herbicide
oo

-------
                                                     Table  3-1  (Continued)


                                         LIST  OF  PESTICIDE ACTIVE INGREDIENTS (PAIs)

81701
81301
56801
90601
90602
29901
**
58201
27301
81501
81901
25501
83701
59102
59101
14504
24002
39105
109301
43401
•fill
73
74
75
76
77
78
78
79
80
81
82
83
84
85
86
87
88
89
90
91

Captafol [cis-N-( (1,1,2, 2-Tetrachloroethyl)thio)-
4-cyclohexene-l,2-dicarboxlmide]
Captan IN-Trichloromethylthio-4-cyclohexene-l, 2-carboxlmide]
Carbaryl [ 1-Naphthylmethylcarbamate]
Carbof uran ( 2 , 3-Dlhydro-2 , 2-dimethyl-7-benzof uranyl
methylcarbamate ]
Carbosulfan [2,2-Dihydro-2,2-dimethyl-7-benzo£uranyl
(dibutylamino)thio)methylcarbamate]
Chloraniben [3-Amino-2,5-dichlorobenzoic acid]
Chloramben, salts and asters
Chlordane [Octachloro-4,7-methanotetrahydroindane]
Chloroneb [l,4-Dlchloro-2,5-dlmethoxy benzene]
Chloropiorin [Irichloronltromethane]
Chlorothalonil [2,4 , 5,6-Tetraohloro-l, 3-dlcyanobenzene]
Chloroxuron t3~(4-(4-Chlorophenoxy)phenyl)-l, 1 -dime thy luraa)
Chloro-l-(2,4,5-trlchloro phenyDvinyl dimethylphosphate
[Stirofos]
Chlorpyrlfos methyl [0,0-Dlroethyl 0-(3,5,6-trichloro-
2-pyrldyl)phosphorothloate]
ChlorpyrifoB [0,0-Dlethyl 0-(3,5,6-trlcbloro-2-pyrldyl)
[phosphorothloate]
Coordination product of Manganses 16X, Zinc 21, and
Ethylanebiadlthlocarbamate 623E (Mancozeb)
Copper 8-hydroxyquinoline
Copper ethylenediamlnetetraacetate
Cyano(3-phenoxyphenyl)methyl 4-chloro-a-(l-methylethyl)
benzeneacetate (9CA) [Fenvalerate]
Cyclohexlmlde
[3-(2-(3,5-Dlmethyl-2-oxocyclohexyl)-2-hydroxyethyl)glutarlrolde]

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
00961-11-5
05598-13-0
02921-88-2
08018-01-7
10380-28-6
14951-91-8
51630-58-1
00066-81-9
:ll||||::Sllfi|S|i||^|^;|||il|
Fhthallmlde
Fhthallmlde
Carbamate
Carbamate
Carbamate
Benzole acid
Benzole acid
Multiring hallde
Arylhallde
Aliylhalide
Phthalonitrile
Urea
Phosphate
Fhosphorcthloate
Fhosphorc thloate
Dithiocaibamate
Organocopper
Organo- copper
Benzeneacetlc acid ester
Cyclic kotone
^i^^fiBtij^iiiii^Nii^ip
Fungicide
Fungicide
Insecticide
Insecticide
Insecticide
Herbicide
Herbicide
Insecticide
Fungicide
Fumigant
Fungicide
Herbicide
Insecticide
Insecticide
Insecticide
Fungicide
Fungicide
Slimicide
Insecticide
Growth regulator
CO
I

-------
  28901
    ^M^MV

    **


  27501


  57601




  104801


  14502


  11301


  29801
   ^V^M

    **
   m^^^^m

  29601
 "•"""•••^••^

 103401




  32101


 •"•*«™™»M™

  86501


 57801




 108201


	i i_ _

 69122




 35001




 53501


 35201




 58801
  95
101
 104



 105

«-^~^_
 106



 ipr

 108



 109
                                                                  Table  3-1  (Continued)


                                                   LIST  OF PESTICIDE  ACTIVE INGREDIENTS
                                                                                        (PAIs)
                it!
      	
     	           •  '   - •-	•-•-•-".-.-.-.-.v.-.-.v.v.-;???

   Dalapon (2.2-dichLoropropionic acid)

   Dalapon, salts and esters


   Decachloro-bis(2,4-cyelopenta diene-1-yl)

   Demeton CO.O-Diethyl 0-(and

   S-)<2-ethylthio)ethyl)phosphorothioate]

   Desmedipham [Ethyl m-hydroxycarbanilate  c.rbanilatel

   DiAmmonlum gait of ethylenebisdithiocarbamate

   Pibromo-3-chloropropane [DBCP]

   Dicamba [3,6-Dlchloro-o-aniaie  acid]

   Dicamba, salts  and esters


   Dichlone [2,3-Dichloro-l,4- naphthoquinone]


 IDiethyl «.4"o-phenylenebis<3-thioallophanate) [Thiophanate



 Uiethyl diphenyl dichloroethane and related compound, [P.rthane]



 IDiethyl dithiobis(thionoformate)


 IDiethyl 0-(2-isoprppryl-6- methyl-4-pyrimidinyl)
 I phosphorothloate [Diazinonl


 I Diflubenzuron [H-(((4-Chlorophenyl)amino)

 I carbonyl)-2,6-di£luorobenzamide]
  Dimethoate  [0,0-Dimethyl[S-((methylcarbamoyl)methyl)
  Phosphorothioate]


  Dimethyl 0-p-nitrophenyl Phosphorothioate [Parathion methvll
  n4m«.4.V..l >_t	^ _ *.        "     ^•-     mm,,   m
1    	•"-"•^^••^^^^•^^•.^^^^^_^_^_^^^_^^_	

 Dimethyl phosphate ester of a-methylbenzyl

\ 3-hydroxy-cis-crotonate [Crotoxyphos]
  I 00075-99-0


   **

  ^^•4^^

  1 02227-17-0


   08065-48-3




   13684-56-5
             _

   03566-10-7
             !•

  00096-12-6


 ] 01918-00-9
 IB««N
  **



  00117-80-6


 I 23564-06-9


 *^^^^^^™***l"*H^^^^^^

  00072-56-0




 | 00502-55-6


 00333-41-5
 i



 35367-38-5




 00121-54-0


            .1

 00060-51-5


 ———^»—n»^

 00298-00-0


| 00141-66-2




i 07700-17-6
                                                                                          lAUtylhaUda


                                                                                          I Arylhalide
                                                                                          I	
                                                                                           Phosphoro dithioate
                                                                                          Carbamate

                                                                                          	
                                                                                          Dithiocarbamate

                                                                                         lEDB
                                                                                         I Arylhalide

                                                                                         I Arylhalide
                                                                                         —	
                                                                                         | Quinone
                                                                                         r-~—-™^~—
                                                                                          Carbamate
                                                                                          DDT
                                                                                         [Dithiocarbamate
                                                                                                        —

                                                                                          Phosphorothioate



                                                                                         | Urea


                                                                                         ^*

                                                                                         I Ammonium


                                                                                         ,   —i"     ..       	

                                                                                         I Phosphoro dithioate


                                                                                        ,

                                                                                        | Phosphorothioate
                                                                                        ^^^^•"^^^^"••••H

                                                                                         Phosphate


                                                                                        ^^""•n-^^^^™»—

                                                                                         Phosphate

   Herbicide


  | Herbicide


  I Miticide
  ^""-"^•—^»™^M

   Insecticide

  .•.i.     i _ „

  i Herbicide
  *>

  ! Fungicide
  Nematocide
  ^^•••^•^^V^^^^IM

  Herbicide
  ^H^H^_.

  Herbicide
  ^^^^.WIBM

  Fungicide
  ^•-——

  Fungicide
  Insecticide



 1 Herbicide
 	"

  Insecticide


 •	

  Insecticide


 —

I Disinfectant


           ....

 Insecticide


1

 Insecticide
•

 Insecticide, Miticide


•

 Insecticide

-------
           Table 3-1 (Continued)




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIs)

78701
S7901
37505
37801
67701
36601
38501
47201
63301
35505
44303
44301
79401
38901
**
41601
113101
58401
41101
100601
28801
lilSlii;:
iiilli
110
111
112
113
114
115
116
117
118
119
120
121
122
123
123
124
125
126
127
128
129
^^^^^^^^^^^^^^^^^^j^^^^^^^^^S^^^^^^^:
Dimethyl 2,3,5,6-tetrachlorotetephthalate [DCPA]
Dimethyul (2,2,2-trichloro-l-hydroxyethyl) phosphonate
[TrlchloroCon]
Dlnoseb [2-sac-Butyl-4,6-dinitrophenol]
Dioxathion [2,3-p-Dioxanedlthiol S,S-bia(0,0-diethyL
[phosphorodithloate ) ]
Diphacinone [2-(Diphenylacetyl)-l,3-indandione]
Dlphenamid [N,N-Dimethyl-2,2-diphenyl acetamlde]
Diphenylamino
Dlpropyl isoclnchomeronate [MGK 326]
Dlsodlum cyanodlthioimidocarbonate [Nabonate]
Diuron (3-(3,4-Dlchlorophenyl)-l, 1-dimethylurea]
Dodacylguanldlne hydrochlorlde [Metasol DGH]
Dodlne [Dodecylquanidina acetate]
Endosulfan [Hexachlorohexahydeotnethano-
2,4,3-benzodioxathiepin-3-oxide]
Endothall [7-Oxablcyclo(2,2,l)heptane-2,3-dicarboxyllc acid]
Endothall, salts and esters
Endrln [Hexachloroepoxy octahydro-endo.endo-
dlmethanonaphthalene ]
Ethalfluralin [H-Ethyl-H-(2-methyl-2- propenyl)-
2,6-dinltro-4-(trl£luoromethyl)benzeneamlne]
Ethion tO,0,0',0'-Tetraethyl S , S • -methy lene
bisphosphorodithioate]
Ethoprop CO-Ethyl S,S-dipropyl phosphorodlthioate]
Ethyl 3-methyl-4-(raethylthio)phenyl l-(methylethyl)
phosphoramldate [Fenamiphos]
Ethyl 4 , 4 ' -dichlorobenzilate [Chlorobenzllate]
illliiijillii
01861-32-1
00052-68-6
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
22224-92-6
00510-15-6
lillllllil|ft|ilill:K|pll5|lll;:
Tetephthailc acid ester
Phosphonabe
Phenol
Phosphoro dithioate
Indandion*
Acetamide
Arylamine
Ester
Isocyanate
Urea
Ammonium
Ammonium
Multiring halide
Bicyclic
Bicyclic
Multiring halide
Toluidine
Phosphoro dithioate
Phosphoro dithioate
Phosphoro amidate
Arylhalide
ii.is^iSssSisiiSiliisSS^Sijisjis-
Herbicide
Insecticide
Herbicide
Insecticide
Rodenticide
Herbicide
Insecticide
Repellant
Slimicide
Herbicide
Fungicide
Fungicide
Insecticde
Herbicide
Herbicide
Insecticide
Herbicide
Insecticide
Insecticide
Nematocide
Miticide

-------
  41405
 •^•^^•^•IBV
  59901

 •••••••••••••I
 206600

 ••••••••MMM
  53301


  34801

  35503

  75002

 81601
 1 -     •!
 103601
  *••••••••
   **
  •••vtw
 103602

 44801

 115601


 107201


109401


100201

 47601

 97401


 9001

35506
 132
 133
142

143
                                                                  Table 3-1  (Continued)

                                                   LIST  OF  PESTICIDE ACTIVE INGREDIENTS
                                                                                        (PAIs)

        Ethyl diisobutyUhiocarbaniate [Butylate]
        Fenarimol [a-<2-Chlorophenyl)-a-
        (4-chlorophanyl)-5-pyrlniidinemethanol]
    _      .    	*».„.,,j. 0-(«-methylthio)-m-toluyl)
  | phosphorothioate]
   Ferbam tFerric dimethyldithiocarbamatel
   Fluometuron t          ————
  	'	'
  I Fluoroacetaraide
  I
   Folpet [H-((Trichloromethyl) thio)phthaUmidel
   Glyphoaate  [H-(Phosphonoaethyl)glycinel     ~"
   Glyphosate, salts and esters
 JGlyphosine  tH.H-bis(Phosphonomethyl) glycine]
  Heptachlor  [Hapt.chlorotetrahydro-4,7-methanoindenel
  Hexadecyl oyclopropanecarboxylate ICycloprateJ

  Hexazinone [3-Cyclohexyl-6-(dimethy
  lamino)-l-methyi-l,3,5-tria2ine-2.4-(lH.3H)-dionel
  Isofenpho. ll-Methylethyl 2-((.thoxy<(l-l»ethylethyl>
 I amino)phosphinothioyl)oxy)  benzoatel
 | Isopropalin  t2.6-Dinitro-H,H-dipropyl cumidine]
 I Isopropyl  H-phenyl carbamate  [Propham]
                   _	_	_	
                                 acid esterof3-(m-hydroxy
        	;ea]	
I Lindana  (ganma  isomer of Benzene hexachloride, 99* pure!

| Linuron  t3-(3,4-Dichlorophenyl)-l-mathexy-l-meThyT^aT
   02008-41-5
     • •    n i -i •
  j 00052-85-7

  '-•  " '•      •«•
   60168-88-9

   00055-38-9


 [14484-64-1
 | 02164-17-2

 I 00640-19-7
 [_p0133-07-3

 | 01071-83-r
 h^™~
  **
 [J2439-99-8
 | 00076-44-8
 :         	
  54460-46-7


 51235-04-2


| 25311-71-1


 33820-53-0

 00122-42-9~

] 04849-32-5


 00058-89-9
•^—^—
 00330-55-2
 I Thiocarbainate
 p——^——— ———_
  Phosphorothioate
 I Pyrimidin.j
 I	,.	.
 ! Phosphoroshioate
                                                                                           Dithiocacbamate
                                                                                          	
                                                                                          [Urea
                                                                                          | Acetaroida
                                                                                          ! PhthalimiJe
                                                                                           Fhosphoramldate
                                                                                          | Phosphorainldate
                                                                                          Fhosphoranidate
                                                                                         '"""""^""•••"••••••••••^—•^••••••^
                                                                                         I Multirlng hallde
 Cyclopropane oarboxylic
I acid
           .
I s-Triazine
                                                                                          Phosphoro amidothioate
                                                                                         '"•'      • —
                                                                                         [ToXuidtna
                                                                                         r™^™^""™1^™"
                                                                                         I Carbamate
                                                                                         r^—._
                                                                                          Carbaraate/Urea

                                                                                         [ArylhaUde
                                                                                         Urea
                                                                                                                        Herbicide
   Insecticide
   ^^—~
   Fungicide
                               Insecticide
                              ^^w™.^^^
                              I Fungicide
                                  —
                              | Herbicide
                              r—""^*™^^—
                               Rodenticide
                                                                                                                        Fungicide
                              Herbicide
                                                                                                                       Herbicide
                              Herbicide
                                                                                                                       Insecticide
  Insecticide

  •"
  Herbicide

 —•*———»——
  Insecticide

      -    .
! Herbicide
 •••  —i i   .•.
 Insecticide
	
I Herbicide

'--•   -   n—.
I Insecticide
—^-™HKBWIIBBBBB.^
 Herbicide

-------
                                                    Table  3-1  (Continued)




                                         LIST OF PESTICIDE ACTIVE  INGREDIENTS  (PAIs)

39504
57701
14505
34802
114001
**
101201
100301
90301
105401
34001
69134
53201
**
69129
68102
54101
108801
44201
iilllsi
ifllfl
149
150
151
152
153
153
154
155
156
157
158
159
160
161
162
163
164
165
166
tlllltllllllM
Malachite green [Amnoniun)(4-(p-(dlmethy
lamino)-alpha-phenylbenzylidine)-2, 5-cyclo hexadien-1-ylidene)-
dimethylchloride]
Malathion [0,0-Dlmathyl dlthiophosphate of dlathyl
[mercaptosucclnate]
Maneb [Manganese salt of ethylenebisdithiocarbamate]
Manganous dimethyldithiocarbamate
Mefluidide [N-(2,4-dimethyl-5-(((tri£luoro
methyl ) sulf ony L ) amino ) pheny 1 acetamide]
Mefluidide, salts and esters
Methamldophos (0,S-Dimethyl phosphor amidothioate]
Methldathlon [0,0-Dimethyl phosphorodlthloate, S-ester of
4-(mercaptomethyl)-2-inethoxy-delta 2-l,3,4-thiadlazolln-5-one]
Methomyl (S-Methyl N-((methylcarbainoyl)oxy)thlo acetimidate]
Methoprene [Isopropyl(E,E)-ll-methoxy-
3 , 7 , ll-tcimethyl-2, 4-dodecadienoate]
Mathoxychlor (2,2-bis(p-methoxyphenyl)-l, 1, 1-trichloroethane)
Methylbenzethonium chloride
Methylbromlde
Methylarsonlc acid, salts and esters
Methyldodecylbenzyl trimethyl Amnonium chloride BOX and
methyldodecylxylylene bis(trimethylamnoniuinchloride) 20X[HYAMINE
2389]
Methylene bisthiocyanate
Methyl-2,3-quinoxalinedithiol cyclic S,S-dithiocarbamate
[Quinmethionate]
Metolachlor l2-Chloro-H-(2-ethyl-6-methyl
phenyl ) -N- (2-roethoxy-l-roethylethyl) acetamide]
Mexacarbate [4-(Dimethylamino)-3,5-xylyl methylcarbamate]
?::;;i||ip:::|l|l|l
00569-64-2
00121-75-5
12427-38-2
15339-36-3
53780-34-0
**
10265-92-6
00950-37-8
16752-77-5
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
IBllllllSMllllllisBSpllllll
Amnonium
Fhosphoro dithioate
Dithiocarhamate
Dithiocarbamate
Acetamide
Acetamide
Fhosphoro amidothioate
Fhosphoro dithioate
Carbamate
Ester
DDT
R4H
AlkylhaliJe
Organoarsanic
Ammonium
Thiocyanate
Beterocycllc
Acetanilide
Carbamate
Wm^MtMf^MUK'ti^MzM^
Fungicide, Bacteriostat
Insecticide
Fungicide
Fungicide
Defoliant
Defoliant
Insecticide
Insecticide, Miticide
Insecticide
Regulator
Insecticide
Disinfectant
Fumigant
Herbicide
Disinfectant
Slimicide
Fungicide, Miticide
Herbicide
Insecticide
CO

-------
                                                    Table  3-1  (Continued)




                                         LIST OF PESTICIDE ACTIVE  INGREDIENTS  (PAIs)

14601
35502
35501
103001
80301
14503
34401
35801
105801
30701
30702
**
57001
84301
79501
79101
36501
32701
32501
105901
mriam
167
168
169
170
171
172
173
174
175
176
176
176
177
178
179
180
181
182
183
184
lillliilllllllliB
Mixture of 83.9* Ebhylenebis(dlthiocatbamato) zinc and 16. IX
Ethylenebisdithiocarbamate, bimolecular and trimolecular cyclic
anhydrosulfldes and disulfides [Matiram]
Monuron TCA • Monuron trichloroacetata
Monucon [3-(4-Chlorophenyl)-l,l- dimethylurea)
N,N~Diethyl-2-(l-naphathalenyloxy)propionamide [Napropamide]
N,N'Diethyl-meta-toluamide and other isomers [Deet]
Nabam [Disodium salt of ethylenebisdlthlocarbarnate]
Haled [l,2-Dibromo-2,2-dichloroethyl dimethyl phosphate]
Norea [3-Hexahydro-4,7-methano indan-5-yl-l,l-dimethylurea]
NorClurazon [ 4-Chloro-5- (methylamino ) -2-
( a , a , a-tr i f luoro-m-toly 1 ) -
3(2H)-pyridazinone]
N-1'Haphthylphthalimide
Haptalam (N-1-Naphthylphthalamic acid)
Naptalam, salts and esters
N-2-Ethylhexyl bicycloheptene dicarboximide [MGK 264]
H-Butyl-H-ethy L-a , a , a-tr if luoro- 2 , 6-dinitro-p-toluidine
[Benfluralin]
0,0,0,0-Ietraethyl dithiopyrophosphate [Sulfotepp]
0,0,0,0-Tetrapropyl dithiopyrophosphate [Aspon]
0,0-Diethyl 0-(3-chloro-4-methyl-2-oxo-2H-l-benzopyran-7-yl
[Coumaphos]
0,0-Diethyl 0-(p-(methylsulfinyl)phenyl) phosphorothioate
[Fensulfothion]
0,0-Diethyl S- (2- (ethylthio)ethyDphosphorodithioate
[Disulfoton]
0,0-Dimethyl 0-(4-nitro-m-tolyl)phosphoro thioate [Fenitrothion]
||l|||ii|l|||l!
09006-42-2
00140-41-0
00150-68-5
15299-99-7
00134-62-3
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
IjSjjijijjIP^
Dithiocarbamate
Urea
Urea
Amide
Toluamide
Dithiocarbamate
Phosphate
Urea
Heterocyclic
Fhthalamide
Fhthalamlde
Fhthalami le
Bicyclic
Toluidine
Dithiopyro phosphate
Dithiopyro phosphate
Fhosphorothioate
Phosphorothioate
Phosphoro dithioate
Fhosphorothioate
|:|||||||>i«S|,|8||f||^|;|p:l|v:;::
Fungicide
Herbicide
Herbicide
Herbicide
Repellent
Fungicide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Repellent
Herbicide
Insecticide
Insecticide, Miticide
Insecticide
Insecticide
Insecticide
Insecticide
U)

-------
                                                    Table 3-1 (Continued)




                                         LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIs)

59201
58001
S8702
**
**
**
**
**
S9401
104201
103801
111601
111501
219900
41801
41701
47802
61501
57501
108501
56502
iiislii
Illllii
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
^^^P^^^^^^^P^^^^H^^iBiipl^^^lsill^ill^^li^l
0,0-Dlmethyl S-(phthalimldomathyl) phosphorodithioate [Phosmet]
O,0-Dimethyl S-((4-oxo-l,2,3-benzotriazin- 3(4H)-yl)roethyl)
phoaphorodithioato [Azinphos Methyl]
0,0-Dimabhyl S-((ethylsulfinyl) ethyl) phosphorothioate
[Oxydemeton methyl]
Organo-arsenic pesticides (not otherwise listed)
Organo-cadmium pesticides
Organo-coppar pesticides
Organo-mercury pesticides
Organo-tin pesticides
ortho Dichlorobenzene1
Oryzalin t3,5-Dinitro-N«,N4-dipropylsulfanilaniide]
Oxamyl (Methyl H' ,H'-dimethyl-N-( (methyl
carbamoyl)oxy)-l-thiooxamidate]
Oxyfluorfen [2-Chloro-l-(3-ethoxy-4-nitro phenoxy)-
4-(tri£Luoromethyl)benzene]
0-Ethyl 0-(4-(methylthio)phenyl) S-propyl phosphorodithioate
[Sulprofos; Bolstar]
0-Ethyl 0-(4-(methylthio)phenyl) S-propyl phosphorothioate {9CA}
[Sulprofos Oxon]
0-Ethyl 0-(p-nltrophenyl)phenylphosphonothioate [Santox]
0-Ethyl S-phenyl ethylphosphonodithioate [Fonofos]
o-Isoproxyphenyl methylcarbamate [Propoxur]
para Dichlorobenzene1
Parathion [0,0-Diethyl O-(p-nitrophenyl)phosphorothioate]
Pendimethalin [H- ( 1-ethylpropyl) -3 , 4-dimethyl-
2,6-dinitrobenzenamine]
Pentachloronitrobenzene
iiiiiiiiiiiiiiii
00732-11-6
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
00114-26-1
00106-46-7
00056-38-2
40487-42-1
00082-68-8
|||||||;I^i||^i|*Mo^l:|lll:
Phosphoro dithioate
Fhosphoro dithioate
Phosphoro dithioate
Organoarsenic
Organocadioium
Organocopper
Organomercury
Tin atkyl
Aryl halide
Sulfanylimide
Carbamate
Miscellaneous
Phosphoro dithioate
Phosphorothioate
Phosphonothioate
Phosphono dithioate
Carbamate
Aryl halide
Phosphorothioate
Benzeneaniine
Aryl chloride
|||lill;;l$iMsili|^^llil|lll'
Insecticide
Insecticide
Insecticide
Coccidiostat

Fungicide
Disinfectant
Fungicide
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Insecticide
Insecticide, Miticide
Insecticide
Insecticide
Mothballs
Insecticide
Herbicide
Herbicide
U!

-------
           Table  3-1  (Continued)




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIs)

63001
**
108001
109701
98701
64501
64103
57201
97701
18201
5101
**
67501
69183
34803
102901
39002
101301
111401
80804
80805
tiiSlai
llHil
206
206
207
208
209
210
211
212
213
214
215
215
216
217
218
219
220
221
222
223
224
liililliliiliiiilllll^
Fenbachlorophenol
Fenbachlotophenol, salts and esters
Perf luldone [1,1, 1-Trlf luoro-N- ( 2-raethyl-
4-(phenylsulfonyl)phenyl) methanesulfonamide]
Permethrin {(3-Fhenoxyphenyl)methyl 3-(2,2-dichlorethenyl)-
2,2-dlmethylcyclopropane carboxylate]
Fhenmedlpham [Methyl m-hydtoxycatbanilate m-methyL carbaniLate]
Fhenothlazine
Phenylphenol
Fhorate [0,0-Diethyl S-((ethyLthio)methyl)phosphorodithioate]
Fhosalone [0,0-Diethyl S-((6-chloro-2-oxobenzoxazolin-3-yl)
methyl) phosphorothioate]
Fhosphamidon [2-Chloro-N,N-diethyl-3- hydroxycrotonamide ester
of dlmethylphosphate]
Picloram [4-Amino-3,5,6-trichloropioolinlc acid]
Flcloram, salts and esters
Fiperonyl butoxide [(Butylcarbityl)(6-propylpiperonyl)etherl
Poly ( oxyethy lene ( dime thy llmlno ) ethy lene ( dimethyllmlno ) ethy lene
di chloride [PBED (Bus an 77)]
Potassium dimethyldithiocarbamate [Bus an 85]
Potassium N-hydroxymethyl-N-methyldithiocarbamate [Busan 40]
KN Methyl [Potassium N-methyldithiocarbamate]
Potassium N-(alpha-(nitroethyl)benzyl)ethylenediamine [Metasol
J26]
Frofenofos [0-(4-Bromo-2-ohlorophenyl) 0-ethyl S-propyl
[phosphosothioate]
Prometon [2,4-bis(Isopropylamino)-6-methoxy-s-Triazine]
Prometryn [2, 4-bis(Isopropylamino)-6-(methylthio)-s-Triazine]

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
**
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
iiiiiiiiii«i^piiiliss^Jiiiii:
Phenol
Phenol
Sulfonamlde
Cyclopropane carboxilic
acid
Catbamate
Heterocyc Lie
Phenol
Phosphoro dithioate
Phosphoro dithioate
Phosphate
Pyridine
Pyridine
Ester
Ammonium
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Miscellaneous
Phosphorothioate
s-Triazine
s-Triazire
lll||lil^S|iiifct|^|;|llifflg;
Preservative
Preservative
Herbicide
Insecticide
Herbicide
Insecticide
Bacteriostat
Insecticide
Insecticide, Miticide
Insecticide
Herbicide
Herbicide
Synergist
Fungicide
Fungicide
Fungicide
Fungicide
Fungicide, Slimicide

Herbicide
Herbicide

-------
           Table 3-1 (Continued)




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIs)
:"'';'f£:£Sfc&
97601
80808
77702
119301
69004
69001
69002
69006
97801
58301
71003
74801
35509
82501
**
80807
103901
34804
75003
39003
mxtxm
225
226
227
228
229
230
231
232
233
234
235
236
237
238
238
239
240
241
242
243
|||l|f|f||f|||fc
Froparglte [2-(p-tert-Butylphenoxy) cyclohexyl-2-propynyl
sulfite]
Fropazine [ 2-Chloro-4 , 6- ( isopropylamino ) -s-Tr iazine ]
Froplonlc acid
Propyl (3-dlmethylamino)propyl carbamate hydrochloride
[Fropamocarb and Fropamocarb HC1)
Pyrethrln coils
Pyrethrin I
Pyrethrin II
Pyrethrum (synthetic pyrethrin)
Resmethrin ((5-Phenylinethyl)-3-furanyl)methyl 2 , 2-dimethy 1-
3-(2-methyl-l-propenyl) cyclopropanecarboxylate]
Ronnel [0,0-Dlmethyl 0-(2,4,5-trichlorophenyl) phosphor othioate!
Rotenone
S,S,S-Tributyl phosphorotrithioate [DEF]
Siduron {l-(2-Methylcyclohexyl)-3-phenylurea]
Silvax [2-(2,4,5-Trichlorophenoxy propionic acid)]
Silvex, salts and esters
Simazine [2-Chloro-4,6-bis(ethylamino) -s-Triazine]
Sodium bentazon [3-Isopropyl-lH-2,l,3-benzothiadiazin-
4(3H)-one-2,2-dioxide]
Sodium dimethyldithiocarbanate [Carbam-S]
Sodium monofluoroacetate
Sodium methyldithiocarbamate [Vapam]
lllliliililpi
02312-35-8
00139-40-2
00079-09-4
25606-41-1

00121-21-1
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
|||||||;3ipg||ifip|^^g||||:;||
Miscellaneous
s-Triazinci
Alkyl acid
Carbamate
Cyclopropane carboxylic
acid
Cyclopropane carboxylic
acid
Cyclopropun ecarboxylic
acid
Cyclopropane carboxylic
acid
Cyclopropane carboxylic
acid
Phosphoro Aioate
Miscellaneous
Phosphoro trithioate
Urea
Fhenoxy asid
Phenoxy acid
s-Triazine
Heterocylic N.S
Dithiocarbamate
Acetate salt
Dithiocarbamate
lIlli;liSfiSSiMii:Sfi^l§liiS-
Insecticide, Miticide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide
Insecticide
Insecticide v-
Insecticide
Insecticide
Insecticide
Defoliant
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Rodenticide
Fungicide

-------
                                                     Table 3-1 (Continued)



                                          LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIs)
SilllliiiS81|wS:
57101
41301
41401
41402
41403
41404
35604
9801
105501
59001
12701
105001
80814
80813
63004
**
35602
102001
79801
80501
m*mm
iiiiiii
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
258
259
260
261
262
^i^^il^^^^lMi^^l^ftl^^i^iii^i^i^^ilii^^^i^i^i^
Sulfoxide [l,2-Methylenedioxy-4-(2-(octylsulfidynyl) propyl)
benzene]
S-Ethyl cycLohexylethylthiocarbamate [Cycloate]
S-Ethyl dipropylthiocarbamate [EPIC]
S-Ethyl hexahydro-lH-azepine-1-oarbothioate [Molinate]
S-Propyl butylethylthiocaxbamate [Febulate]
S-Fxopyl dipzopylthiocatbaraate [Vernolate]
S-(2-Hydroxypropyl)thio methanesulfonate [HFIMS]
S-(0,0-Diisopropyl) phosphorodithioate ester of
N-(2-metcaptoethyl)benzenesul£onamide [Bensulide]
Tebuthiuron [N-(5-(l, 1-Dimethylethyl)-
l,3,4-thiadiazol-2-yl)-H,H'-ditnethylurea]
Temephos (0,0,0* ,O* -Ietramethyl-0,0' -thiodi-p-phenylenephosphoro
thioate]
Terbacil [3-tert-Butyl-5-chloro-6-methyl uracil]
Terbufos [S-(((l, l-Dimethylethyl)thio) methyl) 0,0-diethyl
phosphorodithioate]
Terbuthy lazine [ 2- ( ter t-Buty latnino ) -
4-chloro-6-(ethylaroino)-s-Triazine]
Terbutryn [2- ( tert-Butylamino ) -4- ( ethyl
amino ) -6- (methylthio ) - s -Tr iazine ]
Tetrachlorophenol
Tetrachlorophenol salts and esters
Tetrahydro-3,5-dimethyl-2H-l,3,5-thiadiazine-2-thione [Dazomet]
Thiophanate methyl [Dimethyl 4,4'-o-phenylenebis
(3-thioallophanate)]
Thiram [Tetramethylthiuram disulfide]
Toxaphene [technical chlorinated camphene (67-69X chlorine)]

00120-62-7
01134-23-2
00759-94-4
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
00137-26-8
08001-35-2
lltsBSwStiS
HeterocycJ.ic
Thiocarbaniate
Thiocarbaciate
Thiocarbatiate
Thiocarbariate
Thiocarbariate
Thiosulphonate
Phosphoro dithioate
Urea
Phosphoro';hioate
Uracil
Phosphoro dithioate
s-Triazina
s-Triazine
Phenol
Phenol
Heterocyclic
Carbamate
Dithiocarbamate
Hultiring hallde
lll|:i?||;;ltB|I|ils?Ssf«lllllll^
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Herbicide
Herbicide
Insecticide
Herbicide
Insecticide
Herbicide
Herbicide
Preservative
Preservative
Fungicide
Insecticide
Fungicide
Insecticide
I
I-1
00

-------
                                                              Table  3-1  (Continued)


                                                 LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIs)

74901
36101
86002
**
51705
14506
34805
78802
69005
69003
18301
lliSiiil
263
264
265
265
266
267
268
269
270
271
272

Tributyl phosphorotrithioate [Merphos]
Trifluralin [a,a,a-Trifluoro-
2 , 6-dinitro-N , N-dipropyl-p-toluidine J
Warfarin [3-(a-Acetonylbenzyl)-4-hydroxycoumarinJ
Warfarin salts and asters
Zinc 2-mercaptobenzothiazolate [Zinc MET]
Zineb [Zinc ethylenebisdithiocarbamate]
Ziram [Zinc dimethyldithiocarbamate]
S-<2,3,3-Trichloroallyl)diisapropylthiocarbamate
(3-Phenoxyphenyl)methyl d-cis and trans* 2 , 2-dimethy 1-
3-(2-methylpropenyl) cyclopropanecarboxylate *(Max. d-cis 25X;
Min. trans 75*) [Fhenothrin]
(4-Cyclohexene-l,2-dicarbojc imido )methyl 2, 2-dimethy 1-3-
( 2-methy Ipropenyl ) eye lopropanecarboxylate [ Tetr amathr in ]
Isopropyl N-(3-chlorophenyl) carbamate [Chloropropham]

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
JiiS;!;^
>-:vX:X;Xv'v::':°:'>x.v>X:Xj£'x':-x^^
Fhosphoro trithioate
Toluidine
Hydroxycoiunarin
Hydroxycoiunarin
Organozino
Dlthiocarbamate
Dithiocarbamate
Thiocarbamate
Cyclopropane carboxylic
acid
Cyclopropane carboxylic
acid
Carbamate
;|;||||||;W|||g|||;;:|p|^:|l:i|||;
Defoliant
Herbicide
Rodenticide
Rodenticide
Fungicide
Fungicide
Fungicide
Herbicide
Insecticide
Insecticide
Herbicide plant growth
regulator
CO
I
M
VO
   1 Deleted because the chemical is covered by OCFSF Effluent Limitations Guidelines and Standards


   1 No longer registered for use as a pesticide.

-------
            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
from those reviewers,  EPA determined that the draft questionnaire needed
extensive revision to better define and focus the questions and that the
pesticide formulator/packager segment of the industry was significantly
different from the manufacturing segment and should be covered by a separate
s tudy.

            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
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 Final Effluent Limitations Guidelines and Standards for the
Pesticide Manufacturing Industry" for information concerning the development
of the economic portion of the questionnaire.)

            Distribution of the 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 covered all manufacturing facilities that were operating in 1986.

            Under the authority of Section 308 of the Act, EPA distributed the
questionnaire entitled the "Pesticide Manufacturing Facility Census for 1986"
to all 247 facilities in EPA's database.  EPA received responses from all 247
                                     3-20

-------
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, and since
proposal EPA has determined  that  75 of the 90 facilities are still in
operation  (see Section 3.5 for a  discussion on changes in the industry).

            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 manutacturing operations at the facility); and (5) 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.  A summary of the information
obtained from the Facility Census, and from the follow-up telephone calls and
written requests for clarification of the information provided in the industry
responses,  is presented  in this technical development document.

3.1.4       Industry Self-Monitoring Data

            All facilities which  discharge wastewater directly to receiving
streams must have NPPES permits which establish effluent limitations and
monitoring  requirements.  Some POTWs also require indirect dischargers to
monitor their effluent.  To make use of these 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
two facilities at EPA's request provided needed long-term treatment system
performance data.

            Fifty-five (55) 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 (34) of the 55 facilities submitted priority pollutant data, and
                                     3-21

-------
49 facilities submitted data for PAIs.  However,  much of these data were not
useful in characterizing pesticide manufacturing 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 pesticide
process wastewaters.  However, industry-supplied data from 27 facilities
covering 55 PAIs were evaluated for use in determining treatment system
performance for PAI removal.

3.1.5       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
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 the final rule and are described in more
detail in Section 3.1.6.
                                     3-22

-------
                                   Table 3-2




                       TREATMENT UNIT OPERATIONS SAMPLED
Treatment Dnit 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
Sampled
7
1
11
0
1
7
3
7
0
4
1
1
1
3
1
1
0
2
0
1
Note:  Plants may operate more than one treatment unit.
                                     3-23

-------
            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: (1) the wastewater treatment
system was effective in removing PAIs, .and (2) the PAls manufactured appeared
to be representative of one or more PAI structural categories,  such as
organo-phosphate PAIs.  Wastewaters containing PAls in 21 structural groups
were analyzed during EPA sampling.

            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
identified any information in the draft report that the facility considered
confidential business information.

            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 evaluated for use in developing
limitations for these PAIs when it was demonstrated that the technology was
effective at PAI removal (these treatability studies are discussed in the next
section).

3.1.6       EPA Bench-Scale Treatabilitv Studies

            EPA conducted a number of bench-scale studies to evaluate the
treatability of PAIs by various wastewater treatment technologies, including:
                                     3-24

-------
hydrolysis, membrane filtration, chemical oxidation, and activated carbon
adsorption.  Treatability studies were conducted on both clean water to which
PAIs were  added  ("synthetic wastewaters") and on actual pesticide process
wastewater.

            The  hydrolysis, membrane filtration, and carbon isotherm
treatability studies used synthetic wastewaters.  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 in order to assess the
appropriateness  of the bench scale testing.  In other cases studies were
conducted  to obtain hydrolysis data not available in the literature.  All of
the PAIs selected were expected to hydrolyze under some conditions.

            In the hydrolysis treatability study, EPA conducted a series of
bench-scale tests to determine the hydrolysis rates of selected PAIs.
Thirty-eight (38) PAIs were selected for testing and separated into four
synthetic  test solutions.  The hydrolysis treatability study was conducted
under six  conditions using a matrix of three pH levels (2, 7, and 12) and two
different  temperatures (20°C and 60"C).

            The  carbon isotherm studies used PAIs selected from various
structural groups to determine which groups would be most amenable to
activated  carbon technology.   Manufacturers of PAIs in a few of those groups
were known to use activated carbon technology to treat the wastewater,  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.  Another factor in selecting the PAIs for these studies was
the ability to measure the PAI following the testing.  For example, too rapid
a hydrolysis rate could destroy the PAI before chemical analyses of the
samples are complete following activated carbon testing,  thus giving an
erroneously high removal value.  The results of the isotherm tests were
evaluated  using  the Freundlich isotherm equation.

            The  membrane filtration studies used PAIs selected to span the
molecular  weight range of the 269 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 three 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.
                                     3-25

-------
            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.

            In one series of tests EPA also conducted activated carbon
treatability studies to determine adsorption properties of selected PAIs.
These studies included carbon adsorption isotherm tests and accelerated column
tests which are used in estimating full scale carbon system designs and cost.

            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 manufacturing 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
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 Submitted After  Proposal

            EPA received comments on the April, 1992 proposed regulations from
34 interested parties.  A number  of the commenters submitted new information
to EPA,  including the following:

            1.     Additional long-term treatment system performance data for
                  control of discharges of PAIs.  These new data provide
                  information on  treatment system performance over a wider
                  variety of conditions than was previously available.

            2.     Long-term treatment system performance data for new
                  treatment systems to control discharges of PAIs.  These new
                  treatment systems were installed after the period for which
                  EPA collected information for the proposed rulemaking; they
                  replaced inadequate treatment or supplemented existing
                  treatment.  The new data allow more of the limitations to be
                                     3-26

-------
                  based  on demonstrated performance of full-scale treatment
                  systems instead of treatment system performance data
                  transferred from other PAIs or estimates from treatability
                  studies of the performance expected of full-scale treatment.

            3.    Analytical methods used by dischargers to monitor PAIs in
                  discharges, where the commenter believed the proposed EPA
                  methods were different from those currently in use.

            4.    Additional information identifying specific pollution
                  prevention practices and  "out-of-process" recycle/reuse.

3.1.8       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 manufacturers'
wastewaters.  In this final rule, EPA is promulgating direct discharge
limitations for these 28 priority pollutants and pretreatment standards for
all but 4 of these 28 pollutants, as described below.  For 23 of these 28
priority pollutants, EPA is relying on the OCPSF technical database to
promulgate limitations.  Limitations for one priority pollutant, cyanide, are
based on long-term data collected from the pesticide industry.  The other four
priority pollutants are volatile organic compounds, but they were not
regulated under the OCPSF guidelines and there are no treatment performance
data for these four specific pollutants.  EPA developed limitations for these
four priority pollutants by transferring limitations from other structurally
similar priority pollutants based on OCPSF technology (steam stripping).  This
is the same procedure that was used in developing OCPSF limitations (40 CFR
Part 414) when performance data were lacking for certain volatile priority
pollutants.

            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.   Forty-six
(46) of the 75 pesticide chemicals manufacturing facilities (55 of 90 at
proposal) also manufacture compounds regulated under the OCPSF category.
Based on these factors, EPA is transferring technical data from the OCPSF
category and effluent limitations for priority pollutants based on that data
to the pesticide chemicals manufacturing category as supporting data for the
limitations for the priority pollutants in this regulation.

            The 23 priority pollutants for which EPA is relying on the OCPSF
database to set BAT and NSPS limitations for the pesticide chemicals
manufacturing category are presented in Section 2 of this technical
development document.  The OCPSF limitations for volatile priority pollutants
were based on data from plants that exhibited efficient volatile pollutant
                                     3-27

-------
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 transferring PSES and PSNS standards and data
supporting those standards from the OCPSF category for the same 23 priority
pollutants.   EPA is relying on analyses conducted in support of the OCPSF
regulations to determine pass-through for these pollutants.  See Section 7.6
for a discussion of priority pollutant limitations development.

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; 8 other PAIs were produced before and after 1986, but not in 1986.
Since 1986,  15 of the 90 manufacturing facilities have closed, and these 15
facilities produced 22 of the 178 PAIs in 1986.  Currently, as in 1986, the
majority of the pesticide manufacturing facilities are located in the eastern
half of the United States and along the Gulf Coast.  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;
EPA Regions I, II, and III are included in the "Northeast" region on the
figure, EPA Region IV is included in the "Southeast" region, EPA Regions V,
VI, and VII are included in the "Midwest" region, and EPA Regions VIII, IX,
and X are included in the "West" region.

            Table 3-3 presents the geographic distribution of OCPSF
manufacturing facilities by EPA Region as surveyed in 1983, in relation to the
pesticide manufacturing facilities.  The distribution of the OCPSF
manufacturing facilities is similar to the distribution of the pesticide
chemicals manufacturing industry.  Of the 90 pesticide chemicals manufacturers
operating in 1986, 55 also manufactured products covered under the OCPSF
guidelines.   Forty-six (46) of the current 75 pesticide chemicals
manufacturers also manufacture OCPSF products.
                                     3-28

-------
                                                 Figure 3-2



                                     Distribution of Pesticide Manufacturing

                                           Facilities by EPA Region
u>
I
N>
VO
Northeast   Southeast    Midwest

                    Region
                                                                     West
                                                                                70%
                                                                                60%  .c
                                                                                50%  rt

                                                                                      13

                                                                                      03
                                                                                30%  £L
                                                                                      co
                                                                                      15
                                                                                10%  •&
                                                                                0%
# 1986 Facilities
                      # 1993 Facilities
                                                                   % PAI Mfg

-------
                                   Table 3-3

                   COMPARISON OF THE GEOGRAPHIC  DISTRIBUTION
                          OF THE OCPSF vs. PESTICIDE
                              INDUSTRY BY REGION
Itegion1
Northeast
Southeast
Midwest
West
TOTAL
No. of ;OCPSF
Manufacturing
Facilities
311
181
361
87
940
Uo. of
Pesticide
Manufacturing
Facilities
19S6
22
25
35
8
90
Current*
16
22
29
8
75
% Of OCPSF
Manuf actur ing
Facilities
33.1
19.3
38.4
9.2
100
% of
Pesticides
Manufacturing
Facilities
1986
24.4
27.8
38.9
8.9
100
Current2
21.3
29 .3
38.7
10.7
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.

2Accounts  for facility closures since 1986.
                                     3-30

-------
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.

            This industry is included within, but not limited to, SIC Major
Group 28, Chemical and Allied products.  More specifically, facilities
manufacturing PAIs 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

            Most of the  facilities which currently manufacture PAIs began
manufacturing operations in the 1950s and 1960s.   Most of the pesticide
manufacturing operations also began about this time and pesticide operations
start-ups continued at about the same rate into the 1970s.  The oldest
reported pesticide operation began in 1909, while the most recent operation
began in 1987.  Thirty-four (34) of the current 75 pesticide manufacturers
reported that pesticide  operations began at the same time that 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 pesticide chemicals
manufacturing facilities.  Approximately 18% of 1986 pesticide active
ingredient production was delivered to industry,  commerce, or U.S. government
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

            Fifty-five (55) of the 90 pesticide manufacturing facilities that
were operating in 1986 generated wastewater discharges from OCPSF operations,
and 46 of the 75 current pesticide manufacturers  generate OCPSF wastewaters.
Thirty-two (32) of the 75 current facilities co-treat OCPSF wastewater with
pesticide manufacturing wastewater.
                                     3-31

-------
                                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%
                              3-32

-------
                                   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
1986
15
6
9
16
20
12
8
4
90
'
Current1
12
3
8
16
20
8
8
0
75
Pesticides
Operations Began
1986
1
7
6
16
22
22
12
4
90

: Currentr
1
5
4
15
20
19
11
0
75
Last Major
Expansion of
Pesticides
Operations
1986
0
1
0
0
5
18
53
13
90
Current1
0
0
0
0
5
15
50
5
75
'Accounts  for  facility  closures  since  1986.
                                     3-33

-------
            Over half of the 75 pesticide manufacturing facilities also
conduct pesticide formulating and/or packaging (PFP) activities.  Nineteen
(19) 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
chemicals, and conducted PFP operations.

3.3         PESTICIDE PRODUCTION

            A wide variety of PAls or classes of PAIs are produced by Lhe
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.

Table 3-1 presents the 269 PAIs or classes of PAIs considered for regulation
by pesticide type.  One type of pesticide, the rodenticides, were not
manufactured in 1986.   Table 3-1 also includes three PAIs that have been
dropped from consideration: ortho- and para-dichlorobenzene and biphenyl.
Ortho- and para-dichlorobenzene were deleted prior to proposal because those
                                     3-34

-------
two chemicals are covered by the Organic Chemicals, Plastics and Synthetic
Fibers  (OCPSF) guidelines (40 CFR 414), and biphenyl has been dropped because
it is no longer a registered pesticide.

            The 269 PAIs or classes of PAIs may also be grouped into 70
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 (90 facilities), manufactured 129 of the 269
PAIs and classes of PAIs and 48 salts and esters of these PAIs (for a total of
177 PAIs).  These PAIs were manufactured by 223 separate pesticide production
processes.  In addition, there were eight other PAIs which were manufactured
either before or after 1986, but not during 1986.  The 15 pesticide
manufacturers that have closed since 1986 manufactured 22 of the 177 PAIs that
were manufactured 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 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 177 PAIs was
approximately 1.2 billion pounds with 55% of this total accounted for by
herbicides.   About 1.1 billion of the 1.2 billion pounds of total industry
production in 1986 was reported by the 75 pesticide manufacturing facilities
that are currently still in operation.  Table 3-5 presents the list of
individual PAIs manufactured in 1986 and the 8 PAIs manufactured before or
after 1986.
                                     3-35

-------
                    Table 3-5

PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 19861

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
27
28
29
30
31
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
17.17
17.27
17.32
20.00
21.00
22.00
25.00
26.00
27.01
27.16
27.17
27.29
28.00
Common Name
EDB
Vancide TH
Dichloropropene
Dowicil 75
Triadimefon
Dichlorophene
Dichlorvos
2,4-D
2,4-D; 2-Butoxyethyl ester
2,4-D; Butyl ester
2,4-D; Diethanolamine salt
2,4-D; Dimethylamine salt
2,4-D; 2-ethylhexyl ester
2,4-D; 2-octyl ester
2,4-D; Isopropylamine salt
2,4-D; Isopropyl ester
2,4-D; Triethanolamine salt
2,4-D; Triisopropanolamine salt
2,4-DB; Dimethylamine salt
2,4-DB; 2-Ethylhexyl ester
2,4-DB; Isopropyl ester
Dichloran or DCNA
Bus an 90
Mevinphos
Cyanazine or Bladex
Propachlor
MCPA; Sodium salt
MCPA; 2-Ethylhexyl ester
MCPA; Dimethylamine salt
MCPA; Isooctyl ester
Octhilinone
                      3-36

-------
              Table 3-5 (Continued)

PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 19861

32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
AI Code
30.17
30.27
30.29
31.13
31.17
31.27
31.29
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
66.00
68.00
68.02
69.00
69.03
70.00
71.00
73.00
Common Name
2,4-DP; Dimethylamine salt
2,4-DP; 2-Ethylhexyl ester
2,4-DP; Isooctyl ester
MCPP; Diethanolamine salt
MCPP; Dimethylamine salt
MCPP; 2-Ethylhexyl ester
MCPP; Isooctyl ester
Thiabendazole
TCMTB
HAE
Pronamide
Propanil
3-Iodo-2-propynyl butylcarbamate
Metribuzin
Etridiazole
Acephate or Orthene
Acifluorfen
Alachlor
Aldicarb
Hyamine 3500
Ametryn
Atrazine
Benomyl (and Carbendazim)
Bifenox
Bromacil
Bromacil; Lithium salt
Bromoxynil
Bromoxynil; Octanoic acid ester
Butachlor
Giv-gard
Captafol
                      3-37

-------
              Table 3-5 (Continued)

PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 19861

63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
AI Code
74.00
75.00
76.00
80.00
81.00
82.00
*84.00
86.00
88. OO2
*90.00
91.00
98.00
103.00
*107.00
110.00
112.00
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
Common Same
Cap tan
Sevin (Carbaryl)
Carbofuran
Chloroneb
Chloropi'*''"i'n
Chlorothalonil
Stirofos
Chlorpyrifos
Bioquin
Fenvalerate
Cycloheximide
Dicamba
Diazinon
Methyl Parathion
DCPA
Dinoseb
Dioxathion
Diphenamid
MGK 326
Nabonate
Diuron
Metasol DGH
Endothall
Endothall; N,N-Dimethylcocoamine salt
Endothall; Potassium salt
Endothall; Sodium salt
Endrin
Ethalfluralin
Ethion
Ethoprop
Chlorobenzilate or Acaraben
                       3-38

-------
              Table 3-5 (Continued)

PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 1986'

94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
AX Code
130.00
132.00
133.00
135.00
138.00
138.01
140 . 00
142 . 00
144.00
*148.00
150.00
154.00
156.00
157.00
158.00
160.00
161. Ol2
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. Ol2
Common Name
Butylate
Fenarimol
Fenthion or Baytex
Fluometuron
Glyphosate
Glyphosate; Isopropylamine salt
Heptachlor
Hexazinone
Isopropalin
Linuron
Malathion
Methamidophos
Methomyl
Methoprene
Methoxychlor
Methylbromide or Bromome thane
Monosodium methyl arsenate
Methylene Bisthiocyanate
Napropamide
Deet
Nabam
Naled
Norflurazon
N- 1 -Naphthylphthalimide
MGK 264
Benfluralin
Fensulfothion
Disulfoton
Phosmet
Azinphos Methyl
Copper naphthenate
                      3-39

-------
              Table 3-5 (Continued)

PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 19861

125
126
127
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
153
154
155
AI Code
190. 022
190. 032
191. Ol2
191. 022
191. 032
191. 052
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
215.03
216.00
Common Name
Copper octoate
Copper salt of fatty & resin acids
Phenyl mercuric dodecyl succinate
Phenyl mercuric acetate
Phenyl mercuric oxide
Chloromethoxy propyl mercuric acetate
Tributyltin neodecanoate
Tributyltin monopropylene glycol maleate
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 (PCP)
Pentachlorophenol ; Sodium salt
Permethrin
Phenothiazine
Phenylphenol
Phenylphenol ; Sodium salt
Phorate
Picloram
Picloram; Potassium salt
Picloram; Triisopropanolamine salt
Piperonyl butoxide
                      3-40

-------
              Table 3-5 (Continued)

PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 19861

156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
AI Code
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
255.00
256.00
257.00
259.00
*262.00
264.00
Common Name
Busan 85 Or Arylane
Bus an 40
KN Methyl
Metasol J26
Prometon or Caparol
Prometryn
Propazine or Milogard
Propanoic acid
Pyrethrin I
Pyrethrin II
DBF
Simazine
Carbarn- S or Sodam
Vapam
Cycloate or Ro-Neet
EPTC or Eptam
Molinate
Vernolate or Vernam
HPTMS
Bensulide or Betesan
Tebuthiuron
Temephos
Terbacil
Terbufos or Counter
Terbuthylazine
Terbutryn
Dazomet
Toxaphene
Trifluralin or Treflan
                      3-41

-------
                             Table 3-5 (Continued)

               PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
                     REPORTED  TO  BE MANUFACTURED IN 19861

165
186
iiiiii|illliiiii
268.00
272.00

Ziram
Chloropropham
'This  list also includes eight additional PAIs manufactured between 1985 and
 1990 (these PAIs are sarkecl with an asterisk).

2These PAIs are metallo-organic PAIs.
                                     3-42

-------
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, for both the 90 manufacturers in
operation in 1986 and for the 75 current manufacturers.  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, 143 of the 177 PAIs produced in 1986
were reported to be manufactured by only one facility in the United States;
the 75 current pesticide manufacturers produced 130 of the 177 PAIs.  As shown
in Table 3-7, about one-half of the pesticide manufacturing facilities
reported producing only one active ingredient in 1986;  47 of the 90 facilities
in operation in 1986 (52%) and 37 ot the 75 facilities that are still in
operation (49%).   The remaining facilities produced between 2 and 16 PAIs
each.  In 1986, each of the seven largest pesticide manufacturing facilities,
which are all still currently in operation, produced more than 45 million
pounds of active ingredient.  These 7 facilities together represented almost
half (47%) of all 1986 pesticide production for the 177 PAIs.  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 FAIs 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 also 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.

3.4         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
                                     3-43

-------
                   Table 3-6

NUMBER OF PESTICIDE ACTIVE INGREDIENTS PRODUCED
     BY NUMBER OF MANUFACTURING FACILITIES
AI Production At:
1986
143
25
7
1
1
177
No. of PAls
Current'
130
24
7
1
1
163bb


One Facility
Two Facilities
Three Facilities
Four Facilities
Five Facilities
Total
                   Table 3-7

NUMBER OF MANUFACTURING FACILITIES BY NUMBER OF
     PESTICIDE ACTIVE INGREDIENTS PRODUCED
No. of PAls Produced
1986
47
16
10
7
10
90
No. of facilities
Current*
37
13
8
7
10
75


One
Two
Three
Four
Five or More
Total
                      3-44

-------
                        Table 3-8




DISTRIBUTION OF FACILITIES BY QUANTITY OF PAI PRODUCTION
Number of Facilities
1986
7
19
38
18
8
90

Current*
7
17
32
14
5
75

Range of PAI Production
(1986 Ib/yr)
>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 (90 Facilities)
-1,086,645,000 (75 Facilities)
                          3-45

-------
compounds.  Pesticide active ingredients may also be used as raw materials in
manufacturing derivative PAIs typically through the formation of various salts
and esters.  This final rule is intended to control the discharge of
pollutants in wastewater generated during the manufacture of PAIs from raw
materials.  (For one PAI, the effluent limitations apply only to the discharge
of wastewater generated during the purification of that PAI to a higher
quality PAI product.)  The final regulations do not apply to the manufacturer
of chemicals ("intermediates") which are not pesticides but which subsequently
are converted by further chemical reactions to PAIs.  The "intermediates" may
be other effluent guidelines, such as covered by the OCPSF effluent guidelines
(40 CFR Parts 414 and 416) for organic intermediates or the inorganic
chemicals effluent guidelines (40 CFR Part 415) for inorganic intermediates.

            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.

            The PAI manufacturing processes used by facilities are highly
dependent upon the type of PAIs 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 223 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.
Forty-five (45) of the reported 223 manufacturing processes used to produce
pesticides in 1986 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 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.
                                     3-46

-------
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.

            b.    Carbamates

            The fundamental building block of carbamate pesticides is carbamic
acid, the monoamide of carbonic acid:

            0                                     0
            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:

                                                 O
                                                 II
                      R-OH + R'-N-C-O	> 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
                                     3-47

-------
                                                             Figure  3-4



                                    REACTION MECHANISMS FOR s-TRIAZINES  AND ATRAZINE AND AMETRYN


                                   UCN + CI2
                                                                                   s-TRIAZINES
u>

*-
00
a

I
I
it      I
          C2.I5NH2
a


"
                                                  a

                                                  I
                                                  /-»
                                               ATRAZINK
                                                                                                   9


                                                                                                   c
                                                                                                 V* Nw


                                                                                                "jj

                                                                                                f*
                                                                                                AMIilRYN
           Marshall  Sittig,  editor,  Pesticide  Manufacturing  and  Toxic Materials  Control  Encyclopedia.  Noyes  Data

           Corporation,  Park Ridge, NJ, 1980; p. 51, 63.

-------
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.


            Thiolcarbonic acid and dithiocarbonic 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

             Thiolcar.bamic acid             Dithiocarbamic acid
Dithiocarbamates are produced by the reaction of an alkyl amine and carbon
disulfide with sodium hydroxide, as shown:
                                    NaOH        | |
                          RNHZ + 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.
                                     3-49

-------
u>

Ui
o
                                                        Figure 3-5



                                      REACTION MECHANISMS FOR CARBOFURAN  AND NABAM
                                             + NaOII + CSj
                                         (CH3)2 +  CH3N=C=0
                                                                ETHER
                                                                            ClljNIICSNa
                                                                            CII2NIICSNa
                                                                                 S


                                                                              NABAM
                                                            TRIE^1^YLAMI^4E
                                                                             CARBOFURAN
    Marshall  Sittig,   editor,   Pesticide  Manufacturing  and  Toxic  Materials  Control  Encyclopedia.  Noyes  Data

    Corporation,  Park Ridge, NJ,  1980; p. 145,  545.

-------
            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 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
                                     3-51

-------
                                                       Figure 3-6


                                     REACTION MECHANISMS FOR PROPANIL AND ALACHLOR
OJ

Ln
NJ
                                    +   CH3CH2COOH
                                                          SOCI2
                                                                         NHCC2H5
                                                                         a
                                                                        PROPANIL
   H3C2
                                                         C1H2C
C2HS         H5C2

   CICH2COCI
H3COH2C
HC
  52
                                                                            NH3
C2H5
                                                                                         ALACHljOR
    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
Ui
LO
                                                                                    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.

-------
                 ONa
I
l_n
•P-
                                                       Figure 3-8



                                              REACTION MECHANISMS FOR 2,4-D
                                   ClCHCOONa
                                                                                        2,4-D ESTERS
                                                                                ROH
2,4 D AM1NE SALTS
                                                                               NaOH
                                                                                         2,4-D SODIUM SALTS
      Marshall  Sittlg,  editor,  Pesticide  Manufacturing  and Toxic  Materials  Control  Encyclopedia.  Noyes  Data

      Corporation, Park Ridge, NJ, 1980; p. 229.

-------
The phosphorothioates are derivatives of phosphorothioic acid, the sulfur
analog of phosphoric acid with the following structures:
                               O              S
                               II              II
                           RO- P - SR  and RO- P - OR

                              OR            OR
The phosphorodithioates are further sulfur-substituted as follows:

                               S             0
                               I!             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
                                  RO - P - NHR

                                     OR
            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.  A PAI intermediate,  as defined in the Facility
Census, is any "specific precursor compound formed in the process of
                                     3-55

-------
                                                   Figure 3-9


                                REACTION MECHANISMS FOR  PARATHION AND PHORATE
    P,S5 «• C,HjOH
                             — SH
                                    CI
S
It
                                                           ONa
                                                                  Aoctunc
                                                           NO,
                                                                                      PARATHJON
     P2S, + CII2II5OII
      S                         S
      jl         CH2=0           II           CalljSII
(C2HjO)2P —SH	   (C2H,O)2PCH2OII    	•
                                          —SCII2SC2H3

                                         PHORATE
Marshall  Sittig,  editor,  Pesticide  Manufacturing  and  Toxic  Materials  Control  Encyclopedia.  Noyes  Data
Corporation,  Park Ridge, NJ,  1980; p. 584,  611.

-------
                                                       Figure  3-10


                                            REACTION MECHANISM FOR GLYPHOSATE
w                            O                                               O
01                            H                                NaOH           II
                         (HO)2PCH2C1   +   NH2CH2COOtI      ...... 1JOi *    (HO)2PCH2NHCH2COOH

                                                                             GLYPHOSATE
         Marshall Sittig,  editor,  Pesticide  Manufacturing  and  Toxic Materials Control  Encyclopedia.  Noyes  Data
         Corporation,  Park Ridge, NJ,  1980; p. 441.

-------
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,
and two of these 11 facilities are now closed.  As discussed in Section 3.4,
the manufacturers of PAI intermediates are not subject to this regulation.

            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 (15) by-products at 17 facilities were reported to be produced and
sold in 1986, and 14 of these 17 facilities are still currently in operation.

3.5         CHANGES IN THE INDUSTRY

            Data compiled from the Facility Census provides 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.

            The 1986 Facility Census identified 90 pesticide manufacturing
facilities --.8 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 15 facility closings;
three metallo-organic and 13 organic pesticide manufacturers (one of the
facility closures manufactured both organic and metallo-organic PAIs).

            One hundred seventy-seven (177) PAIs and salts and esters of PAIs
were identified in the Facility Census as being manufactured that year from
223 production processes, and eight PAIs were produced before or after 1986,
but not in 1986.  The Agency believes that 42 PAI production processes have
closed since 1986 --38 organic PAIs and 4 metallo-organic PAIs -- and 20 of
these PAI processes were in operation at the 15 facilities that have closed
since 1986.  However, these 42 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.
                                     3-58

-------
                                   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.

            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.
                                     4-1

-------
            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.
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).

            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
                                     4-2

-------
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
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 FJ. 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.

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 in 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.
                                      4-3

-------
            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
Information.  The primary factors for subcategorizing plants in the industry
were dominant product type, manufacturing processes,  and raw materials used.
As discussed in Section 1.1.4, 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
                                    Manufacturing

            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.

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
                                     4-4

-------
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
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.

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
                                     4-5

-------
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
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
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 could 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
                                      4-6

-------
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.  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 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         FINAL 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.

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 otherwise fit the definition of a metallo-organic active
ingredient given in the BPT  regulation (see Section 455.31(a)), organo-tin
pesticides were not included in the metallo-organic pesticide chemicals
subcategory (see Section 455.30) during the 1978 rulemaking because
wastewaters from their manufacture have significantly different wastewater
characteristics from wastewaters from the manufacture of metallo-organic
pesticides containing arsenic, cadmium,  copper,  and mercury.  EPA does not
                                      4-7

-------
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 is
regulating a broad range of pollutants in this subcategory:  conventional
pollutants, nonconventional pollutants (including COD and the PAIs),  and
priority pollutants.

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 two existing indirect
dischargers in this subcategory.
                                     4-8

-------
                                   SECTION 5

                   WATER USE AND WASTEWATER CHARACTERIZATION

5.0         INTRODUCTION

            In 1988, under the authority of Section 308 of  the Clean Water
Act, EPA distributed the Facility Census to 247 facilities  that EPA had
previously identified as possible pesticide chemicals manufacturers.
Responses to the Facility Census by these 247 facilities indicated that 90
facilities manufactured pesticides in 1986.  This section presents information
on water use at these 90 facilities, and at the 75 of the 90 manufacturing
facilities that are still currently in operation.  This section also presents
information on process wastewater characteristics for those PAI manufacturing
processes that were sampled by EPA and for those PAI manufacturing processes
that provided self-monitoring data.

5.1         WATER USE AND SOURCES OF WASTEWATER

            As described in Section 3, 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
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 usually 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.
In addition,  some chemical compounds may leave the manufacturing process in
the form of air emissions.
                                      5-1

-------
                                                                  Figure 5-1

                                       EXAMPLE OF PESTICIDE ACTIVE INGREDIENT MANUFACTURING PROCESS
i
M
Water
Water
Water
1 Other Reactants ' '
1
*
Raw Materials — + React|Qn
Solvent — *•
— > Intermediate — i
1
1
i
t
Wastewater
1
t
th, Rpflpfion

i
i
i
t
Wastewater
I
i
^ Purification

1
1
i
t
Wastewater
(e.g., Carrier/Reaction Media) (e.g., Water of Reaction) (a 9- Process
Stream Wash)
T







r- ^
Further processing
and/or sales.
May also be a
source of wastewater.

^ >
















Water
1
1
|


I
1
i
t
Wastewater
(e.g., Product Wash)



Types of Process Wafer
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

-------
            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; and

            •     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 are often combined with other sources of process
                  wastewaters that are being 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." For this
final rule, process wastewater flow is defined to mean the sum of the average
daily flows from the following wastewater streams: process stream and product
washes,  equipment and floor washes, water used as solvent for raw materials,
water used as reaction medium,  spent acids, spent bases, contact cooling
water,  water of reaction,  air pollution  control blowdown,  steam jet blowdown,
vacuum pump water, pump seal water, safety equipment cleaning water, shipping
container cleanout,  safety shower water,   contaminated storm water, and
product/process laboratory quality control wastewater.  See section 455.21(d).

            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;

            •     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;
                                     5-3

-------
            •     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;

            •     Product/process Laboratory Quality Control Wastewater: water
                  from laboratories used to determine product and/or process
                  quality; and

            •     Safety Shower Water:    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 is
                  process wastewater.  Because of the infrequent use, the
                  amount of water is minuscule compared to other sources of
                  process wastewater.

            Most of the above sources are present in manufacturing almost all
FAIs.  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
                  control fumes from reaction vessels, storage tanks, and
                  other process equipment;

            •     Equipment and floor  washes:   water used to clean process
                  equipment and floors during unit shutdowns;
                                     5-4

-------
            •     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;

            •     Shipping Container Cleanout: water used to clean out
                  shipping containers for reuse;

            •     Contact Cooling Water:  water used to cool steam and other
                  emissions from evaporating water from products; and

            •     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 in 1986 was 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 bv 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
                  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;
                                     5-5

-------
                                   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
₯aste Volume

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.

2Total contaminated stormwater is presented here.   See Table 5-2 for the
 average daily contaminated stormwater flow per plant.
                                      5-6

-------
            •     Cleaning safety equipment used in pesticide production.
                  Equipment  includes goggles, respirators, and boots.  These
                  must be cleaned after every use so they will be free of
                  contaminants when next needed.  Cleaning is usually done
                  with solvents followed by a soap and water wash; and

            •     Contaminated stormwater.  Accidents, leaks, spills, shipping
                  losses, and fugitive emissions can all lead to PAls 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 "other" sources, and no facility reported
monitoring flows for these sources (except for stormwater).  The number of
plants that reported these sources is presented in Table 5-2, both for the 90
facilities that were operating in 1986 and for the 75 of the 90 facilities
that are still currently in  operation.  For example, 56 of the 67 facilities
that reported shower water in 1986 are still currently in operation.
Table 5-2 also presents the  average estimated flows reported for employee
showers, laundries, safety equipment cleaning, and contaminated stormwater.
The flows for 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). The flows for
employee showers and laundries were excluded from the definition of process
wastewater flow (section 455.21(d)) and were excluded from consideration in
developing the regulatory limitations.

5.1.3       Other Facility Wastewater Co-Treated with Pesticide Wastewate

            Often, a facility which manufactures pesticides also manufactures
other products.  Wastewaters generated from other operations may be co-treated
with wastewaters from pesticide chemicals manufacturing.  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 269 PAIs and classes of PAIs
                  considered for regulation);

            •     Organic Chemicals,  Plastics, Synthetic Fibers (OCPSF);

            •     Inorganic  Chemicals;

            •     Pharmaceuticals;
                                      5-7

-------
                                   Table 5-2

     WASTEWATER GENERATED IN 1986  FROM OTHER  PESTICIDES  WASTEWATER SOURCES
# Facilities
1986
67
21
47
47
Current2
56
19
39
39
Average Wastewater
Generated
(gal/day)
1986
3,070
1,210
1,352
177,000
Current2
2,300
1,330
1,414
210,211
Source

Showers
Laundry
Safety Equipment
Contaminated
Stormwater1
'The  average  daily contaminated stormwater  flow per plant  is  presented here.
 See Table 5-1 for total contaminated stormwater flow.

2Seventy-five (75)  of  the  90  facilities  in  operation  in 1986  are still
 currently in operation, and 15 of the 90 facilities have closed.  The numbers
 in this column are based on the Facility Census responses from the 75
 facilities still currently in operation.
                                      5-8

-------
            •     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 percentage of the total flow co-treated for
each wastewater source in 1986.  This information is presented separately for
all 90 pesticide manufacturers operating that were operating in 1986 and for
the 75 of the 90 manufacturers that are still currently in operation.  For
example, 19 of the current 75 PAI manufacturers reported that, in 1986, they
co-treated PFP wastewaters with pesticide manufacturing wastewaters.

            OCPSF operations contributed the largest percentage of the
co-treated wastewater, and the largest number of facilities.  On average, 50%
of the total wastewater volume from treatment systems that co-treat pesticide
and OCPSF manufacturing wastewaters is due to OCPSF processes, and 32 of the
current 75 PAI manufacturers reported co-treating pesticide and OCPSF
manufacturing wastewaters in 1986.  In contrast, only 4% of the total
wastewater volume from treatment systems that co-treat pesticide manufacturing
and PFP wastewaters is due to PFP processes.  Other facility wastewater, such
as sanitary wastewater, was commingled with pesticide wastewater at 27 of the
90 facilities operating in 1986; 23 of these 27 facilities are still currently
in operation.

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
that does not result in a discharge to waters of the United States.
                                      5-9

-------
                                   Table 5-3

 OTHER FACILITY WASTEWATER GENERATED IN 1986  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 Wastewater3
# Facilities1
1986
19
39
14
9
17
27
Current2
19
32
12
8
13
23
Average % of Total
Flow Co-Treated
1986
4
50
23
28
28
34
Current*
4
48
18
21
32
39
'A  facility  is  double  counted  if  it  co-treated more  than one  source of water
 with pesticide manufacturing wastewater.

2Seventy-five  (75)  of  the  90 facilities  in  operation in  1986  are  still
 currently in operation, and 15 of the 90 facilities have closed.  The numbers
 in this column are based on the Facility Census responses from the 75
 facilities still currently in operation.

30ther wastewater includes, for example,  sanitary water.
                                     5-10

-------
5.2.2       Discharge Status of Pesticide Manufacturing Facilities

            Twenty-eight (28) of the 75 current manufacturing facilities are
direct dischargers and 28 are indirect dischargers.  One facility discharges
wastewater both directly and indirectly; therefore, there are 55 current
dischargers.  Of the remaining 20 facilities, 13 facilities dispose of their
wastewater by on- or off-site deep well injection, incineration, or
evaporation and 7 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 generated in 1986 by
pesticide manufacturing facilities was 1.45 billion gallons, and approximately
1.30 billion gallons were discharged either directly or indirectly to surface
waters of the United States.  The 75 current pesticide manufacturers generated
approximately 1.36 billion of the 1.45 billon gallons of total wastewater
generated in 1986.  These 75 facilities discharged, either directly or
indirectly, 1.22 billion of the 1.30 billion gallons of wastewater that was
discharged by all pesticide manufacturers in 1986.

            In 1986, about 83% of all process wastewater generated by the 75
current pesticide manufacturers was discharged directly (1.134 billion
gallons), while 6% was discharged indirectly (0.087 billion gallons).
Similarly, about 82% of the total wastewater volume generated by all 90
facilities operating in 1986 was discharged directly and 8% was discharged
indirectly.  Most of the wastewater not discharged in 1986 was disposed of by
deep well injection (DWI).   Table 5-4 presents the volumes of pesticide
process wastewater discharged or disposed in 1986, for both the 90
manufacturers operating in 1986 and the 75 manufacturers still currently in
operation.

            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) facilities.
Over 99% of the wastewater generated and discharged in the pesticide
manufacturing industry is due to the manufacturing of Subcategory A PAIs.  In
1986, the 75 current pesticide manufacturers generated 1.36 billion of the
1.44 billion gallons of Subcategory A wastewater, or about 94 percent.  The 15
pesticide -manufacturers that have closed since 1986 generated only 6% of the
total Subcategory A wastewater.   However,  the 15 now-closed manufacturers were
responsible for a significant portion of the Subcategory B wastewater that was
discharged indirectly in 1986.   These 15 facilities discharged 525,000 gallons
of the 621,000 gallons of Subcategory B wastewater that was discharged
indirectly in 1986.
                                     5-11

-------
                                   Table 5-4
          TOTAL PROCESS WASTEWATER FLOW IN 1986 BY TYPE OF DISCHARGE
                              (Gallons per Year)

                       All Facilities Operating in 1986
Discharge
Status
Direct
Indirect
No Discharge1
TOTAL
Number of
facilities
32
36
23
912
Percent of
Facilities
36
40
« r
£O
102
Total
Flow (gal)
1,179,246,000
117,938,000
148,370,000
1,445,554,000
                   Facilities Still Currently in Operation3
Discharge
Status
Direct
Indirect
No Discharge1
TOTAL
Number of
Facilities
28
28
20
762
.P**e6ttt of
Facilities
37
37
26
100
Total
Floir (gal)
1,133,784,000
87,365,000
142,197,000
1,363,346,000
'"No  discharge"  facilities  dispose of their wastewater through deep well
 injection (DWI), incineration (on or off-site), or evaporation. Although
 incineration was reported as a "no discharge" technology, there is a
 potential for a residual discharge of scrubber blowdown water.  Incineration
 was not considered to be a fully zero-discharge technology for purposes of
 setting the final limitations.

2The  number of facilities is  greater  than 90 and greater than 75 and the
 percent is greater than 100 due to one facility that discharges both directly
 and indirectly.

3Seventy-five  (75)  of  the 90  facilities  in operation in 1986  are still
 currently in operation.  The numbers in this column are based on  the Facility
 Census responses from the 75 facilities still currently in operation.
                                     5-12

-------
                                   Table 5-5
               PESTICIDE PROCESS WASTEWATER FLOW IN 1986 FOR THE
              ORGANIC PESTICIDE  SUBCATEGORY  (SUBCATEGORY A) AND
           THE METALLO-ORGANIC PESTICIDE SUBCATEGORY (SUBCATEGORY B)

                       All Facilities Operating in 1986
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
                   Facilities  Still Currently in Operation2
Discharge Status
Direct
Indirect
No Discharge1
TOTAL
Total Subcategory A
₯iOV (gat)
1,133,784,000
87,269,000
140,145,000
1^361, 198, 000
Total Subcategory B
Flow (g«l)
0
96,000
2,052,000
2,148,000
'"No  discharge"  facilities dispose of their wastewater through deep well
 injection (DWI),  incineration (on or off-site), or evaporation. Although
 incineration was reported as a 'no discharge* technology, there is a
 potential for a residual discharge of scrubber blowdown water.  Incineration
 was not considered to be a fully zero-discharge technology for purposes of
 setting the final limitations.

2Seventy-five  (75)  of the 90  facilities  in operation in 1986  are still
 currently in operation.  The numbers in this column are based on the Facility
 Census responses from the 75 facilities still currently in operation.
                                     5-13

-------
5.3         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,  data
obtained from EPA sampling at pesticide manufacturing facilities, and
self-monitoring data submitted after the proposal for new or improved
treatment systems.  Results of these data gathering efforts are described in
more detail below.

5.3.1       Industry-Supplied Self-Monitoring Data

            As part of the Facility Census,  EPA requested that peaLieida
manufacturing facilities submit any available wastewater monitoring data and
requested that these data be submitted as individual data points (as opposed
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.

            In comments to the proposed regulations, some facilities submitted
new or additional self-monitoring data.  These data are generally PAI
concentrations in effluents from new or improved treatment systems, and do not
provide additional information on raw wastewater characterization.  However,
the PAI self-monitoring data submitted before and after proposal are often
quite detailed and were useful in developing the final PAI limitations and
standards.  Self-monitoring data submitted by 27 facilities for 55 PAIs were
of sufficient quality to develop effluent limitations and standards as part of
the final rule.  Development of the final limitations are discussed in more
detail in Section 7.

            Priority pollutant data submitted by facilities were not quite as
useful as the PAI data.  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 total of 49 priority pollutants, only 11 facilities
reported these concentration data for raw pesticide process wastewaters.
                                     5-14

-------
            The conventional and non-conventional (other than the PAIs)
pollutant data were submitted for both in-plant and end-of-pipe sampling
locations.  At sampling points following commingling of other industry-related
wastewaters, it was not possible to attribute these pollutants solely to the
pesticide processes.  These data were useful, however, in evaluating the
overall performance of the end-of-pipe BPT treatment systems.

5.3.2       EPA Pesticide Manufacturers Sampling Program

            As described above in Section 5.3.1, 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 23 pesticide manufacturing facilities
between 1988 arid 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.

            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.
These fractions included analyses for: Group I (BODj, 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
                                     5-15

-------
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.).

5.4         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
the pollutant characterization of raw pesticide process wastewaters.  This
database was compiled from the data gathering efforts previously described in
Section 5.3.  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.

5.4.1       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 (BODS) .   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
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
                                     5-16

-------
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
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
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
                                     5-17

-------
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.

            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.  However, industry data for end-of-pipe sampling
locations show that wastewater treatment systems are reducing conventional
pollutant concentrations to levels consistent with the long term average BPT
concentrations.

            The industry-submitted BOD5 data  characterizing  end-of-pipe
discharges are summarized in Figure 5-2.  The figure displays the number of
BODj  results  reported in ranges  of 100  mg/L (i.e.,  0-100  mg/L,  100-200 mg/L,
etc.) and compares these self-monitoring data to the BPT long term average
concentration of 24 mg/L.  Figure 5-2 shows that BOD5  concentrations  in
end-of-pipe discharges are typically in the 0-100 mg/L range, which is
consistent with the BPT long term average concentration.   The
industry-submitted TSS data characterizing end-of-pipe discharge are
summarized in Figure 5-3, along with the BPT long term average concentration
of 28 mg/L.  Similar to BOD5,  the  table shows  that  TSS concentrations  in
end-of-pipe discharges are typically in the 0-100 mg/L concentration range,
which is consistent with the BPT long term average concentration for TSS (28
mg/L).   The industry-submitted pH data characterizing end-of-pipe discharges
are summarized in Figure 5-4.  BPT limitations require pesticide manufacturers
to maintain the pH of their effluent discharges between 6 and 9.  Figure 5-4
shows that the majority of the reported results are within this pH range.
                                     5-18

-------
                         Figure 5-2

INDUSTRY SELF-MONITORING BOD LEVELS IN FINAL EFFLUENT DISCHARGE
                                 BPT Long Term Average Concentration
                                             24 mg/L
    0-100   100-200  200-300  300-400   400-500   500-600
                     BOD Concentration (mg/L)
>600

-------
                                                    Figure  5-3




                                INDUSTRY SELF-MONITORING TSS  LEVELS IN FINAL DISCHARGE
                               -4936
Ul


to

o
                      5000



                   O


                   1
                   c  4000
                   o
                   o
.12  3000-

                      2000-
                       1000-
                                                            BPT Long Term Average Concentration

                                                                      28 mg/L
                              0-100     100-200   200-300    300-400    400-500


                                              TSS Concentration (mg/L)
                                                                 >500

-------
                                                    Figure 5-4

                                INDUSTRY SELF-MONITORING pH LEVELS IN FINAL DISCHARGE
i
N3
      BPT Limit Range
          6-9
                          0-2   2-4   4-6   6-7
7-8   8-9  9-10  10-11  11-12 12-13 13-14
  pH Ranges

-------
5.4.2       Priority Pollutants

            Data characterizing pesticide process wastewaters 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 episodes.   In addition, the EPA Toxic
Release Inventory System (TRIS) was used to confirm the presence of priority
pollutants in pesticide process 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 process 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
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 5-6
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 5-6
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 5-6 also shows
whether or not at least one of the facilities submitting data for each
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.
                                     5-22

-------
                   Table 5-6




PRIORITY POLLUTANT DATA-FACILITY SELF MONITORING

Tetrachlorome thane
Hexachloroethane
2,4, 6 -Tr ichlorophenol
Chloroform
2-Chlorophenol
2,4-Dichlorophenol
2 , 4 - D ime thy Ipheno 1
Methylene Chloride
Chlorome thane
Phenol
Toluene
Cyanide

21
2
10
32
12
6
5
30
8
5
6
235

11
2
10
28
12
6
2
24
4
4
6
235
^^^^^^^^^^^^^^^^^^B

0.5
260
590
0.5
7
13,350
2,300
0.5
3
100
2,200
180

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
-
Known
Known
Believed
Known
-
Known
Known

Known
Known
                      5-23

-------
            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 23 pesticide
manufacturing facilities.  At three of the 23 facilities, sampling was
conducted to collect wastewater for bench-scale studies.  For the other 20
episodes,  samples were collected for three days at locations throughout the
wastewater generation, treatment, and discharge path.  A report that there was
a detection of a priority pollutant in at least two daily samples at the same
location indicates high probability that the priority pollutant was in fact
present.  A reported detection of a priority pollutant in only one sample 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 LaaL
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 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.

            Seventy (70) priority pollutants were detected in pesticide
manufacturing wastewaters during EPA sampling at the 20 facilities.  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 5-7 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 5-7 also shows whether or not at least one of the
facilities where each priority pollutant was confirmed present either knew or
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.
                                     5-24

-------
                Table 5-7

 PRIORITY POLLUTANT DATA - EPA SAMPLING
ORGANIC PESTICIDE CHEMICALS MANUFACTURING
Polltttant;
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1 -Trichloroethane
Hexachloroethane
Chloroform
2 - Chlorophenol
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
1 , 1-Dichloroethene
Trans -1 , 2-Dichloroethene
2 , 4-Dichlorophenol
Ethylbenzene
Methylene Chloride
Chlorome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Nitrobenzene
Phenol
Tetrachloroethene
Toluene
Concentration
C**A)
CTllfrxflttlffl
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
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
Knows or Believed
Present
Believed
Known
	
Known
	
	
Known
Believed
	
	
	
	
Believed
Known
Known
—
Known
Known
Known
	
	
Believed
Believed
Known
                  5-25

-------
 Table 5-7




(Continued)
Pollutant
Trichloroethene
Cyanide
Lead
Concentration
<**A}
Minimum
19
50
930
Mayftmnn
38
2,740,000
1,600
Known or Believed
Present
—
Known
	
   5-26

-------
            As discussed in Section 6, not all of the priority pollutants in
Table 5-7 are regulated in the final rule.  Three pollutants shown in the
table -- hexachloroethane, nitrobenzene, and trichloroethene -- are excluded
from regulation because they are either cotreated with regulated pollutants or
unique to a small number of sources.   Also, four regulated pollutants - -
1,2-dichloropropane, 1,3-dichloropropene, bromomethane, and 2,4-dimethylphenol
-- are not shown in Table 5-7.  One of the pollutants, 2,4-dimethylphenol, was
reported in industry self-monitoring samples (see Table 5-6), and the other
three pollutants are manufactured for use as PAIs and were all reported as
known to be present in pesticide process wastewaters.

            EPA also collected samples at three metallo-organic pesticide
manufacturing (Subcategory B) facilities. Two of the plants were indirect
dischargers and one plant was a "direct" discharger subject to the zero
discharge BPT regulation. The direct discharger achieves compliance by
off-site disposal. Two plants (one the direct discharger) also manufacture
organic PAIs. During two of the sampling episodes (one the direct discharger),
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 above, 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.
Both of the indirect dischargers sampled have ceased manufacturing pesticides.

            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 to regulate.   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.  However,
most of the priority pollutants shown in Table 5-7 are being regulated as
discussed in Section 6.

5.4.3       Pesticide Active Ingredients

            Raw wastewater data for PAIs are available from both industry
self-monitoring and EPA sampling.  The industry self-monitoring data as EPA
sampling data submitted both before and after proposal 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, however,  PAIs detected in commingled
wastewaters can be attributed to the pesticide processes since PAIs should not
be present in wastewaters generated by non-pesticide processes.   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
                                     5-27

-------
wastewaters.  Fifteen  (15) 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.  EPA conducted three-day sampling episodes at 20 pesticide
manufacturing facilities, and these sampling episodes were used to
characterize pesticide process 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.

5.4.4       Non-conventional Pollutants (other than Pesticide Active
            Ingredients)

            Non-conventional pollutants (other than PAIs) and pollutant
parameters include chemical oxygen demand (COD),  total organic carbon (TOG),
and non-priority organic pollutants (and any other non-priority,
non-conventional pollutants).  COD is a measure of the pollutants in a
wastewater stream that can be oxidized 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 BOD5 values
for the same sample.  The COD test cannot be substituted directly for the BOD3
test because the COD/BOD5 ratio  is  a  factor  that  is extremely variable and is
dependent on the specific chemical constituents in the wastewater.  However, a
COD/BOD5  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
was derived and cannot be utilized to estimate the BOD5 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.

            TOC 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 TOC
value will be less than the actual amount.  The promulgated BPT limitations do
                                     5-28

-------
not include a limit for TOG.  TOC is a parameter which is controlled under the
BOD5 and COD regulations.   In addition,  the most highly toxic TOC 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% of the
samples collected include 2-propanone, 2-butanone, 1,4-dioxane, and xylenes.
However, many of the compounds discussed above were detected in 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 regulated under BPT (aside
from the PAIs) is COD.  Self-monitoring data submitted by pesticide
manufacturers included substantial amounts of COD analytical results, and
these COD results are summarized in Figure 5-5.  The figure  shows the number
of reported COD detections in concentration ranges of 200 mg/L (i.e., 0-200
mg/L, 200-400 mg/L, etc.) and compares the reported detections with the long
term average BPT concentration (160 mg/L) for pesticide manufacturing
facilities.

5.5         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 non-conventional pollutants (including
the PAIs) are discussed below.  The performance of the treatment technologies
in-place at pesticide manufacturing facilities is 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 BODS
and TSS and 7.2 million pounds per year of the non-conventional pollutant COD
are discharged directly by organic pesticide chemical manufacturing
facilities.  Because the BODj  and TSS  discharged by this  industry are
compatible with POTWs, these parameters are not currently monitored by any of
the 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.
                                     5-29

-------
                                                     Figure 5-5



                                 INDUSTRY SELF-MONITORING COD LEVELS IN  FINAL DISCHARGE
u>
o
                    0>
                    o
                        iooo-
                        aoo-
8

i
2   600-
                        400
                        200-
                    3
                           0
                                906
                                       BPT Long Term Average Concentration


                                                  160 mg/L
                               0-200     200-400    400-600    600-800   800-1000

                                               COD Concentration (mg/L)
                                                                >1000

-------
            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.  At proposal, EPA estimated that
approximately 310,00 pounds per year (Ib/yr) of PAIs and 46,000 Ib/yr of
priority pollutants were being discharged (direct plus indirect discharges) by
Subcategory A plants after in-place treatment.  Since proposal, EPA has
learned of 15 plant closures,  and some facilities reported that they have
upgraded existing treatment systems or installed new treatment systems.
Taking these changes into account, EPA estimates that current PAI discharges
total 204,000 Ib/yr and priority pollutant discharges total 38,000 Ib/yr.  In
addition, it is estimated that about 6 million pounds per year of volatile
organic priority pollutants are present in PAI wastewaters with considerable
potential for volatilization to the atmosphere.  The incremental PAI and
priority pollutant removals achieved by the final rule are discussed in
Sections 10 and 12 of this technical development document.
                                     5-31

-------

-------
                                   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 waste-waters.  Using this information, EPA selected specific pollutants
for regulation.  This section presents the criteria used in the selection
process and identifies those pollutants regulated under BPT, BAT, PSES, NSPS,
and PSNS for the organic pesticides chemicals manufacturing subcategory
(Subcategory A).  No new limitations and standards are being promulgated 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 decisions 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
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 14 organic PAIs within the group of 25 PAIs and classes of
PAIs, and BPT is amended to include these PAIs.   These 14 PAIs are presented
below.

                  Ametryn                 Simazine
                  Prometon                Terbuthylazine
                  Prometryn               Glyphosate
                  Terbutryn               Phenylphenol
                  Cyanazine               Hexazinone
                  Atrazine                Sodium Phenylphenate
                  Propazine               Methoprene

EPA has also developed analytical methods and collected effluent data to
support BPT coverage of organo-tin pesticides. Therefore, EPA is extending the
applicability of BPT to cover BOD5, TSS and  pH discharges from the manufacture
of these 14 previously excluded organic PAIs and classes of PAIs and the
organo-tin pesticides. For the reasons explained in Section 7,  the COD
limitations apply to discharges from the manufacture of Phenylphenol, Sodium
Phenylphenate,  Methoprene  and the organo-tin pesticides, but not to
discharges from manufacture of the other 11 PAIs in the above list.
                                      6-1

-------
            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
wastewaters.  For these reasons, oil and grease and fecal coliform are not
being selected for regulation.

6.2         PRIORITY POLLUTANTS

            Prior to this rulemaking, there were no effluent guideline
regulations covering the discharge of individual 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 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 5-6 or 5-7, are
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.
                                     6-2

-------
            Not all of the priority pollutants shown in Tables 5-6 and 5-7 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 (non-complexed),
and cyanide (non-complexed).   The 28 priority pollutants selected for
regulation are presented in Table 6-1.  The development of limitations for
these priority pollutants is discussed in Section 7.
                                     6-3

-------
                 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
086
Pollutant:
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2 -Dichloroe thane
1,1, 1-Trichloroethane
Chloroform
2 - Chlorophenol
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
1 , 1- Dichloroe thene
Trans -1 , 2-Dichloroethene
2 , 4-Dichlorophenol
1 , 2-Dichloropropane
1 , 2-Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Methylene Chloride
Chlorome thane
Br omome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Te trachloroe thene
Toluene
                    6-4

-------
 Table 6-1




(Continued)
Pollutant Ntnnber
121
122
Pollutant:
Cyanide
Lead
   6-5

-------
            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-Dinitroto luene
4, 6-Dinitro-o-cresol
Bis (2-Chloroisopropyl) ether
Bis (2-Chloroethoxy) methane
N-Nitrosodimethylamine
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' -ODD
alpha - Endosulf an
beta-Endosulfan
Endosulfan sulfate
alpha -BHC
beta-BHC
gamma -BHC
delta-BHC
PCS -1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
2,3,7 , 8-Tetrachlorodibenzo-p-dioxin

                  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.
                                     6-6

-------
2 - Chloronaphthalene
1, 3-Dichlorobenzene
2 , 4 - D ini tr o to luene
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
Hexachlorobenzene
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
The pollutant will be effectively controlled by the
technologies which are the basis for controlling certain
                    6-7

-------
                  pesticide active ingredients in the 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 and may not be
                  manufactured in the future.
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 for COD discharged by the organic pesticides manufacturers are not
being amended although EPA is extending the applicability of BPT to cover COD.
resulting from the manufacture of 3 previously excluded organic PAIs
(phenylphenol,  sodium phenylphenate,  and methoprene) and the organo-tin
pesticides.

            Under Subcategory A, 169 individual PAIs were manufactured in
1986; and 8 PAIs were manufactured from 1985-1989,  but were not manufactured
in 1986.  Therefore, a total of 177 individual PAIs were considered for
                                      6-8

-------
potential regulation.  Of these, 120 individual PAIs were selected by the
Agency for regulation under either BAT, NSPS,  PSES, or PSNS.  EPA is not
promulgating regulations for 57 individual PAIs.  Of the 57 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 17 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 to demonstrate what technology would be
effective and there are no structurally similar PAIs with treatment data which
could be transferred.  Available toxicity data indicates that these 17 PAIs
are less toxic than most of the 120 PAIs for which PAI effluent limitations
are proposed.
                                     6-9

-------

-------
                                   SECTION 7

                  TECHNOLOGY SELECTION AND LIMITS DEVELOPMENT

7.0         INTRODUCTION

            This section describes the wastewater treatment technologies
currently used to reduce or remove conventional pollutants, PAIs and other
non-conventional pollutants, and priority pollutants in process wastewaters
discharged by pesticide chemicals manufacturing facilities.  A summary of the
treatment performance achievable by different technologies is presented based
on industry submissions and treatability test results.  This section also
discusses the development of effluent limitations guidelines and standards for
PAIs and priority pollutants and identifies how the pollution prevention and
recycling practices currently being employed in the industry are incorporated
into the final PAI limitations.

            Section 7.1 presents a discussion of the pollution prevention and
recycle/reuse practices identified in the pesticide chemicals manufacturing
industry.  This section identifies current pollution prevention and recycling
practices for wastewater and non-wastewater streams and discusses how these
current practices are incorporated into the final rule.

            Section 7.2 presents a summary of the treatment performance
databases available to EPA on wastewater control.  EPA has compiled three
databases; one from industry-submitted data,  one from wastewater sampling
conducted by EPA, and a third from treatability studies conducted on actual
facility wastewaters or synthetic wastewaters containing PAIs.

            Section 7.3 presents a description of the in-plant and end-of-pipe
technologies used in the pesticide chemicals manufacturing industry to treat
wastewaters containing conventional pollutants, PAIs and other non-
conventional pollutants, and priority pollutants.  This section also discusses
the disposal of solid residues that are generated during wastewater treatment.

            Section 7.4 presents treatment performance data for BAT
technologies and Section 7.5 presents the methodologies used to develop the
effluent limitations and standards for the Subcategory A facilities in the
pesticide chemicals manufacturing industry.  Section 7.5 also presents those
cases where limitations require no discharge of process wastewater pollutants
and discusses options available for compliance with the zero-discharge
standards.  Considerations related to the effluent limitations guidelines and
standards for Subcategory B PAIs are discussed in Section 14.

7.1         POLLUTION PREVENTION AND RECYCLING PRACTICES

            This section addresses how pollution prevention and recycling
practices are used in the pesticide chemicals manufacturing industry,  and
specifically for those PAIs covered by this regulation,  by:

            •     Discussing pollution prevention and recycling practices used
                  in the pesticide chemicals manufacturing industry and
                  describing how these practices were identified;


                                      7-1

-------
            •     Identifying which facilities incorporate these practices;

            •     Discussing how these practices are incorporated into the
                  final rule;

            •     Discussing how strict mass-based limitations may promote the
                  implementation of pollution prevention and recycling
                  practices; and

            •     Discussing why it may not be feasible for all pesticide
                  manufacturing plants to incorporate these practices.

Under Section 6602(b) of the Pollution Prevention Act of 1990, Congress
established a national policy stating that:

            •     Pollution should be prevented or reduced at the source
                  whenever feasible;

            •     Pollution that cannot be prevented should be recycled in an
                  environmentally safe manner whenever feasible;

            •     Pollution that cannot be prevented or recycled should be
                  treated in an environmentally safe manner whenever feasible;
                  and

            •     Disposal or other release into the environment should be
                  employed only as a last resort and should be conducted in an
                  environmentally safe manner.

            This policy is a formal embodiment of the Agency's working
definition of pollution prevention.  It makes clear that prevention is EPA's
first priority within the following environmental management hierarchy:  1)
prevention, 2) recycling, 3) treatment, and 4) disposal or release.
"Prevention" includes in-process recycling, which will be referred to as
"recirculation",  but does not include out-of-process reuse, which will be
referred to as "recycling."   For example, a wastewater stream generated in a
PAI process may be recycled to the same process step in which it was
generated, and this operation is defined as "recirculation."  If this same
wastewater stream is reused outside the PAI process (e.g., in the
formulating/packaging process), this operation is defined as "recycling."

            Another important aspect of pollution prevention that will be
discussed is the concept of source reduction.  Source reduction, as defined by
the Pollution Prevention Act of 1990, reduces the generation and release of
hazardous substances, pollutants, wastes, releases or residuals at the source,
usually within a process.  The term includes equipment or technology
modifications, process or procedure modifications, reformulation or redesign
of products, substitution of raw materials, and improvements in housekeeping,
maintenance, training, or inventory control.  The term "source reduction" does
not include any practice which alters the physical, chemical, or biological
characteristics or the volume of a substance, pollutant, or contaminant
through a process or activity which itself is not integral to and necessary
for the production of a product or the providing of a service.  The source


                                      7-2

-------
reduction activities discussed in this section are recirculation and recycle
of water, wastewater, and non-wastewater streams.

            Section 7.1.1 provides an overview of the recirculation and
recycle practices used in the pesticide chemicals manufacturing industry.
Section 7.1.2 discusses recirculation and recycling practices for non-
water/was tewater streams.  Section 7.1.3 focuses on wastewater sources in the
pesticide chemicals manufacturing industry and on current water/wastewater
recirculation and recycle practices.  Section 7.1.4 discusses how pollution
prevention practices have been incorporated into the proposed pesticide
chemicals manufacturing rule, and Section 7.1.5 discusses the limitations of
applying recirculation and recycling steps being practiced by one facility to
other facilities.

7.1.1       Overview of Pollution Prevention and Recycling Practices

            The Section 308 pesticide manufacturers' questionnaires (1986
operations), site visit and sampling trip reports, industry comments to the
proposed rulemaking, and additional information submitted before or after
proposal were reviewed to identify the pollution prevention practices
currently employed in the pesticide chemicals manufacturing industry.  In the
Section 308 questionnaires, facilities were required to identify the pollution
prevention and recycling practices employed in their PAI manufacturing
processes.  In addition, the Agency conducted sampling episodes at 20 PAI
manufacturing facilities, conducted site visits to 9 PAI manufacturers which
were not sampled, and collected wastewater for treatability studies from 3 PAI
manufacturers that were not part of the sampling visits or site visits.
During each of these activities, industry personnel were questioned by the
Agency concerning the pollution prevention and recycling opportunities
applicable to their processes and the status of implementing these practices.

            Non-water/wastewater streams currently recirculated or recycled by
one or more pesticide chemicals manufacturers include solvents,  other organic
streams, acids, bases, alcohols, and product recovery streams.  EPA has relied
on the recirculation and recycle practices for these non-water/wastewater
streams as the full or partial technology basis for the limitations for 80 of
the 120 regulated PAIs; this count includes 24 PAIs (of the 30 PAIs) with
zero-discharge limitations.  The extensive recycle of these non-
water/wastewater streams represents source reduction of potential waste
streams/contaminants and reuse of valuable raw materials.  If these streams
were not recirculated and recycled, large amounts of highly contaminated
wastewaters would be generated, and these wastewaters would require extensive
treatment prior to discharge.

            Typical waters and wastewaters generated from the manufacture of
PAIs include:  carrier/reaction media, water of reaction, process stream
washes, product washes, equipment washes, pump seal wastewater,  steam jet and
vacuum pump wastewater, and blowdown from air pollution control scrubbers.
EPA has relied on recirculation and recycle practices for these
water/wastewater streams as the full or partial technology basis for the
limitations for 58 of the 120 regulated PAIs; this count includes 28 PAIs (of
the 30 PAIs) with zero-discharge limitations.
                                     7-3

-------
            There is overlap in the recirculation/recycle counts discussed
above.  That is, for some PAIs,  EPA has relied on the recirculation and
recycle practices employed for both wastewater and non-wastewater streams as
the full or partial technology basis for the limitations.  Either wastewater
or non-wastewater recirculation or recycle practices are being relied on by
EPA as the full or partial basis for the limitations for 96 of the 120
regulated PAIs; this count includes all 28 PAIs with zero-discharge
limitations based on complete recirculation or reuse of all wastewaters. (Two
other PAIs have zero discharge based on no water use.)

            Although many PAI manufacturing facilities have implemented
recirculation, recycle, and source reduction practices, the Agency concluded,
in general, that there is no support for generically transferring these
practices as the basis for BAT limitations from one PAI process to other,
dissimilar PAI processes.  However, the final rulemaking implicitly
incorporates these pollution prevention and recycling practices where mass
limitations are transferred directly from the BAT manufacturer of a PAI to the
non-BAT manufacturers of the same PAI or similar PAIs ("BAT manufacturers")
are those facilities that have reduced.mass discharges to BAT levels through
BAT treatment and wastewater flow reduction, where applicable).  Where mass
limitations were not transferred directly, the mass limitations are expected
to influence facilities to implement pollution prevention and recycling
practices to the fullest possible extent in their processes.  Although process
reviews and on-site testing will be required to implement these practices, the
utilization of pollution prevention and recycling techniques should enable
many facilities to more cost-effectively comply with the limitations in the
final rule.

7.1.2       Recirculation and Recycle Practices for Non-Water/Wastewater
            Streams

            The purpose of this section is to identify the types of non-
water/was tewater streams being recirculated and recycled in the industry and
the plants and PAI processes where these practices are being employed.  EPA
grouped the non-water/wastewater streams generated during PAI manufacturing
into the following categories:

            PAI Product:  crude PAI product, generally recirculated to the
            reaction step or to a purification step.

            Reactant:  non-water stream involved in the reaction process and
            converted to a PAI product; reactant streams are generally
            recirculated to the reaction step or to a purification step.

            Catalyst:  non-water stream involved in the reaction process to
            form a PAI product,  without undergoing a change in chemical
            structure itself; catalysts are generally recirculated to the
            reaction step or to a purification step.

            Acid/Base:  acidic or basic process stream, generally used in PAI
            processes to maintain pH control during reaction and purification
            steps (acid/base streams are considered non-water streams for the
                                      7-4

-------
            purpose of this  report even though water may constitute the major
            portion of these streams).

            Carrier/Reaction Medium:  non-water stream used to transport or
            support the chemicals involved in the reaction process, usually
            removed from  the PAI product during subsequent purification steps.

            Extraction Medium:  non-water stream used to remove impurities
            from process  streams, including process streams containing the PAI
            product.

            Miscellaneous Process Solvent:  includes non-water streams that
            could not be placed into one of the above categories due to a lack
            of detail in  the process diagrams.

            The recycle of non-water/wastewater streams represents source
reduction of potential pollutants in the pesticide chemicals manufacturing
industry.  A review of the manufacturers' questionnaires (1986 operations),
sampling trip reports, and other applicable industry-submitted data identified
37 plants as practicing recirculation and recycle of non-water/wastewater
streams during the manufacture of 80 PAIs.  The non-water/wastewater streams
most often recirculated in the PAI processes or recycled-into other, non-PAI
processes are reactants and  streams serving as carriers or the reaction
medium.  Table 7-1 presents  a breakdown of the types of non-water/wastewater
streams being recirculated or recycled.  The number of streams shown in Table
7-1 is greater than 80 because some PAI manufacturing processes recirculate or
recycle more than one type of non-water/wastewater stream.

            Recovery and recirculation of solvents minimizes the purchase of
new solvent and reduces the  volume of spent solvent that must be disposed.
The frequency of solvent recirculation/recycle in PAI manufacturing processes
was expected as it represents good engineering design by reducing solvent
costs and potential shortages and because solvent disposal  may be subject to
air, water, or land pollution regulations (Reference 1).  Due to a lack of
detail on some of the manufacturers' process diagrams, however, it was not
possible to categorize all of the recirculated/recycled solvent streams into
one of the specific non-water/wastewater types (e.g., carrier, reaction
medium, etc.).  For these streams, where sufficient detail  was not available,
a general category was developed and is listed as "miscellaneous process
solvent" in Table 7-1.

            Table 7-2 presents the regulated PAIs where non-water/wastewater
recirculation and/or recycle  is currently being practiced.   The PAIs are
divided into two groups depending on whether the recycle/recirculation
practices are closed-loop (100% recycle/recirculation) or non closed-loop
(less than 100% recycle/recirculation); zero-discharge limitations are being
promulgated for those PAIs in the first group - closed-loop
recycle/recirculation.  The  table also identifies whether the non-
water/wastewaters are being  recirculated,  recycled or both.  Table 7-3
presents a list of the plants that manufacture the regulated PAIs listed in
Table 7-2 and currently recirculate or recycle non-water/wastewater streams.
                                      7-5

-------
                                  Table  7-1

                     TYPES OF NON-WATER  STREAMS THAT ARE
                          RECIRCULATED AND RECYCLED
Non-Water/Wa&tewater Type
Product
Reactant
Catalyst
Acid/Base
Carrier/Reaction Medium
Extraction Medium
Miscellaneous Process Solvent **
TOTAL
Number of Streams
4
21
2
13
47
11
25
123
Percent of
Recirculated
and/or Recycled
Streams*
3
17
2
11
38
9
20
100
 *For example Carrier/Reaction Medium represents 11 streams out of the 123.
  Therefore the percent of all recycle streams is 11 -s- 123 x 100 = 9 percent.

**Includes recirculated or recycled non-water/wastewater streams that could
  not be more specifically categorized due to insufficient detail in the
  manufacturers'  process diagrams.
                                      7-6

-------
                  Table 7-2

  PAIS WHOSE MANUFACTURE CURRENTLY INCLUDES
RECIRCULATION OR RECYCLE OF NON-WATER STREAMS
PAI
Code
Pesticide Name
Recirculation
Recycle
Regulated PAIs Whose Manufacture Includes 100% Non-Water/Wastewater
Recirculation and/or Recycle (Closed-Loop)
016
017
027
030
031
2,4-D salts and esters (10 S&Es)
2,4-DB salts and esters (3 S&Es)
MCPA salts and esters (4 S&Es)
Dichlorprop salts and esters (3
S&Es)
MCPP salts and esters (4 S&Es)
X
X
X
X
X





Regulated PAIs Whose Manufacture Includes Non-Water/Wastewater
Recirculation and/or Recycle (Non Closed-Loop)
008
016
025
026
035
041
052
053
054
058
060
062
068
069
070
073
075
082
Triadimefon
2,4-D
Cyanazine
Propachlor
TCMTB
Propanil
Acephate
Acifluorfen
Alachlor
Ametryn
Atrazine
Benomyl
Bromacil
Bromoxynil/Bromoxynil octonate
Butachlor
Captafol
Carbaryl
Chlorothalonil
X
X
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X





X





X






                     7-7

-------
 Table 7-2




(Continued)
PAI
Code
103
110
112
113
125
126
132
133
140
150
154
156
175
178
182
183
186
192
197
203
204
208
212
223
224
226
230
Pesticide Name
Diazinon
DCPA
Dinoseb
Dioxathion
Ethalfluralin
Ethion
Fenarimol
Fenthion
Heptachlor
Malathion
Methamidophos
Me thorny 1
Norfluorazon
Benfluralin
Fensulfothion
Disulfoton
Azinphos methyl
Or gano - t ins ( 3 )
Bo Is tar
Parathion
P endime thai in
Permethrin
Phorate
Prometon
Prometryn
Propazine
Pyrethrin I
Recirculation
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Recycle






X




X





X









    7-8

-------
 Table 7-2




(Continued)
PAI
Code
231
236
239
252
254
255
256
257
264
Pesticide Name
Pyrethrin II
DEF
Simazine
Tebuthiuron
Terbacil
Terbufos
Terbuthy laz ine
Terbutryn
Trifluralin
Recirculation
X
X
X
X
X
X
X
X
X
Recycle








X
   7-9

-------
                     Table 7-3

PLANTS THAT MANUFACTURE PAIS  WHOSE PROCESS INCLUDES
   RECIRCULATION AND RECYCLE  OF NON-WATER STREAMS
Plant Name
Ciba Geigy
duPont
ICI
Monsanto
Cedar
Chevron
Anrvac
Monsanto
Eli Lilly
M&T
Ciba Geigy
FMC
Dow Chemicals
MGK
American Cyanamid
Monsanto
Mobay
Albaugh
Hercules
Cedar
American Cyanamid
Troy
Witco- Argus
Rhone Poulenc
Rhone Poulenc
Rohm & Haas
Velsicol
City
Mclntosh
Axis
Bucks
Anniston
West Helena
Richmond
Los Angeles
Muscatine
Lafayette
Carrollton
St. Gabriel
Baltimore
Midland
Minneapolis
Hannibal
St. Louis
Kansas City
St. Joseph
Hattiesburg
Vicksburg
Linden
Newark
Brooklyn
Portland
Mt. Pleasant
Knoxville
Memphis
State
AL
AL
AL
AL
AR
CA
CA
IA
IN
KY
LA
MD
MI
MN
MO
MO
MO
MO
MS
MS
NJ
NJ
NY
OR
TN
TN
TN
                        7-10

-------
 Table 7-3




(Continued)
Plant Name
Buckman
duPont
Rohm & Haas
duPont
. Rhone Poulenc
ISK Biotech
Cosan
Cumberland
Sandoz
Riverdale
City
Memphis
LaPorte
LaPorte
Belle
Institute
Houston
Carlstadt
Houston
Charlotte
Chicago
State
TN
TX
TX
WV
WV
TX
NJ
TX
NC
IL
   7-11

-------
7.1.3       Recirculation and Recycle Practices for Water/Wastewater Streams

            The purpose of this section is to identify the types of
waters/wastewaters being recirculated and recycled in the industry and the
plants and PAI processes where these practices are being employed.  Section 5
of this Technical Development Document describes in detail water use and
wastewater generation in this industry.  EPA grouped water/wastewaters
generated from the manufacture of PAIs into the following categories:

            Carrier/Reaction Media:  water used to transport or support the
            chemicals involved in the reaction process, usually removed from
            the process through a separation stage.

            Water of Reaction:  water formed during the chemical reaction,
            such as from the reaction of an acid with a base.

            Process Stream Washes:  water added to the carrier, spent acid, or
            spent base which has been separated from the reaction mixture, to
            purify the stream by washing away the impurities.

            Product Washes:  water added to the reaction medium to wash away
            impurities in the intermediate or PAI product, this water is then
            removed through a separation stage; or water used to wash the
            crude product after it has been removed from the reaction medium.

            Equipment Washes:  water used to clean process equipment (e.g.,
            during unit shutdowns).

            Pump Seal Wastewater:  water used to cool packing and lubricate
            pumps, which may contact pesticide-containing water through
            leakage and therefore becomes a pesticide-containing wastewater.

            Steam Jet/Vacuum Pump Wastewater:  water which contacts the
            reaction mixture or water stripped from the reaction mixture
            through the operation of a venturi or vacuum pump.

            Air Pollution Control Scrubber Slowdown:  water, or acidic or
            basic solutions, used in air emission control scrubbers to control
            fumes from reaction vessels,  storage tanks, and other process
            equipment.

Other pesticide wastewater sources include:  wastewater from cleaning safety
equipment used in pesticide production, laboratory wastewater,  and
contaminated stormwater.

            During the review of available data, 20 plants were identified as
practicing recirculation and recycle of process water/wastewater in the
manufacture of 51 PAIs.  Each water or wastewater recirculation/recycle stream
was labelled according to the wastewater categories presented above, and
Table 7-4 shows the water/wastewater recirculation and recycle streams broken
down by category  (Note: the number of streams is greater than 51 because some
PAI manufacturing processes recirculate or recycle more than one type of
wastewater stream).  Based on this categorization, the majority (75%) of


                                     7-12

-------
                                   Table  7-4

         TYPES OF WATER/WASTEWATER THAT ARE RECIRCULATED AND RECYCLED
Water/ffastewater Type
Carrier/Reaction Media
Water of Reaction
Process Stream Wash
Product Wash
Equipment Wash
Scrubber Water
Steam/Vacuum Jet Condensate
Miscellaneous
TOTAL
Number of Streams
2
11
2
24
12
5
2
5
63
Percent of
Re circulated
and/or Recycled
Streams*
3
18
3
38
19
8
3
8
100
*For example Carrier/Reaction Media represents 2 streams out of the 63.
 Therefore the percent of all recycle streams is 2 * 63 x 100 - 3 percent.
                                     7-13

-------
water/wastewater streams recirculated or recycled are product washes,
equipment washes, and water of reaction.

            Table 7-5 lists the regulated PAIs whose manufacture currently
includes water/wastewater recirculation and/or recycle.   The PAIs are divided
into two groups depending on whether the recycle/recirculation practices are
closed-loop (100% recycle/recirculation) or non closed-loop (less than 100%
recycle/recirculation);  zero discharge limitations are being promulgated for
those PAIs in the first group - closed-loop recycle/recirculation.   The table
also identifies whether the water/wastewaters are being recirculated,  recycled
or both.  Table 7-6 presents a list of the plants that manufacture  the PAIs
listed in Table 7-5 and have incorporated water or wastewater
recycle/recirculation operations.

7.1.4       Incorporation of Pollution Prevention and Recycling Practices Into
            the Final Rule

            The final effluent limitations guidelines and standards for the
pesticide chemicals manufacturing industry incorporate pollution prevention
and recycling practices in the following ways:

            1.    The flow and concentration data used to develop the numeric,
                  non-zero limitations and standards account for plant-
                  specific water,  wastewater, and non-wastewater recirculation
                  and recycle practices.

            2.    Zero-discharge limitations are being promulgated for 28 PAIs
                  based on closed-loop recirculation and recycle practices and
                  in the case of two PAIs, based on no water use in the
                  manufacturing process.

            3.    The NSPS and PSNS are based on improved,  more efficient
                  designs of production processes which include increased
                  recirculation, recycle, and other source reduction
                  techniques.  These improvements result in a 28% reduction in
                  the PAI mass discharge standards and guidelines for new
                  facilities, compared to the BAT limitations and PSES.

Additionally,  the numerical limitations and standards established in this rule
should promote additional source reduction through the incorporation of
recirculation and recycle practices.  This topic is discussed in detail in
Section 7.1.5.

            BAT Flow and Concentration Data

            BAT limitations for PAIs regulated by this rulemaking were
developed using:

            •     Long-term full-scale BAT treatment performance data
                  submitted by pesticide chemical manufacturers; and
                                     7-14

-------
                      Table  7-5

PAIs WHOSE MANUFACTURE INCLUDES WATER OR WASTEWATER
              RECIRCULATION  AND  RECYCLE
PAI
Code
Pesticide Name
Re circulat ion
Recycle
Regulated PAIs Whose Manufacture Includes 100% Water/Was tewater
Recirculation and/or Recycle (Closed-Loop)
016
17
027
030
031
2,4-D salts and esters (10 S&Es)
2,4-DB salts and esters (3 S&Es)
MCPA salts and esters (4 S&Es)
Dichlorprop salts and esters
(3 S&Es)
MCPP salts and esters (4 S&Es)
X
X
X
X
X





Regulated PAIs Whose Manufacture Includes Water/Was tewater
Recirculation and/or Recycle (Non Closed-Loop)
016
041
045
053
060
069
075
080
103
112
125
150
158
178
192
212
226
239
2,4-D
Propanfl
Metribuzin
Acifluorfen
Atrazine
Bromoxynil/Bromoxynil octanoate
Carbaryl
Chloroneb
Diazinon
Dinoseb
Ethalfluralin
Malathion
Methoxychlor
Benfluralin
Organo-tins (2)
Phorate
Propazine
Simazine
X

X
X
X
X

X
X
X
X
X
X
X
X
X
X
X

X




X



X


X




                        7-15

-------
 Table 7-5




(Continued)
PAI
Code
241
243
252
255
256
259
264
268
Pesticide Name
Carbarn- S
Vapam
Tebuthiuron
Terbufos
Terbuthylazine
Dazomet
Trifluralin
Ziram
Recirculation
X
X
X
X
X
X
X
X
Recycle






X

   7-16

-------
                     Table  7-6
PLANTS THAT MANUFACTURE PAIs WHOSE PROCESS INCLUDES
  RECIRCULATION AND/OR RECYCLE OF WATER/WASTEWATER
Plant Identification
Ciba Geigy
Cedar Chemicals
ICI Americas
Vinings
Eli Lilly
Vanderbilt Chemical
Ciba Geigy
Dow Chemicals
American Cyanamid
Mobay
Cedar Chemical
American Cyanamid
Rhone Poulenc
Rhone Poulenc
Witco- Argus
Kincaid
Cosan
Riverdale Chemical
Rohm & Haas
Rhone -Poulenc
City
Mclntosh
West Helena
Richmond
Marietta
Lafayette
Murray
St. Gabriel
Midland
Hannibal
Kansas City
Vicksburg
Linden
Portland
Mt . Pleasant
Brooklyn
Nitro
Carlstadt
Chicago
LaPorte
Charleston
State
AL
AR
CA
GA
IN
KY
LA
MI
MO
MO
MS
NJ
OR
TN
NY
WV
NJ
IL
TX
WV
                        7-17

-------
            •     The transfer of statistical data from the PAIs for which BAT
                  performance data are available to PAIs for which no BAT
                  treatment performance data are available, in combination
                  with the results of treatability studies for the non-BAT
                  PAIs.

The following discussion on BAT limitations development is subdivided into
four sections.  The first section identifies the PAI processes that have
achieved BAT-level mass discharges through treatment and wastewater flow
reduction, where applicable, and quantifies how many of these "BAT PAIs"
currently employ recirculation and recycling practices in their processes.
The next two sections discuss limitations development for the "non-BAT PAIs".
The fourth section summarizes the extent to which pollution prevention and
recycling practices have been relied on in setting limitations for the
regulated PAIs.

            BAT PAIs (Group A) --  EPA evaluated long-term effluent data to
identify PAI processes that have reduced mass discharges through BAT-level
treatment and flow reduction, where applicable, and these data were used as
the basis for limitations development.  This subsection discusses the
pollution prevention and recycling practices implemented by these "BAT PAIs,"
which will be referred to as the Group A PAIs in this section.   Twenty-eight
plants manufacturing PAIs regulated under this rulemaking submitted BAT data,
and these data were used to develop mass limitations for 86 of the 120 PAIs
covered by this rulemaking.  These 86 BAT PAIs are listed in Table 7-7.  Table
7-7 also indicates which of these BAT PAIs employ recirculation and recycle
practices and whether or not zero-discharge limitations are being promulgated.

            According to the data, 21 of the 28 BAT plants (75%) have
implemented non-water/wastewater recirculation and recycle practices for 56 of
the BAT PAIs, including 24 zero discharge PAIs.  Fifteen of the 28 BAT plants
(54%) are known by the Agency to have implemented water/wastewater
recirculation or recycle for 37 of the BAT PAIs, including 24 zero-discharge
PAIs.  The total count of BAT plants which have implemented pollution
prevention and recycling of non-water/wastewater and water/wastewater streams,
including zero discharge, is 23 of 28 plants, or 82 percent.   EPA has relied
on these practices as the basis for limitations for 59 of the 86 BAT PAIs, or
69 percent.  There is some overlap in these counts since many of the BAT
plants recirculate or recycle both water/wastewater and non-water/wastewater
streams.  In addition, some of these plants manufacture multiple PAIs and do
not incorporate recirculation or recycle practices for every PAI.

            Twenty-seven of the 86 BAT PAIs listed in Table 7-7 do not
recirculate or recycle water/wastewater or non-water/wastewater streams
according to the process diagrams and other information presented in the
Section 308 questionnaires.  However, the process diagrams and questionnaires
often did not contain sufficient detail for the Agency to identify whether
pollution prevention and recycling practices had been incorporated.  To
prepare the counts discussed above and presented in Table 7-7, it was assumed
that these practices were not in use, unless other information (e.g., a site
visit report) was available to indicate otherwise.
                                     7-18

-------
     Table  7-7




BAT PAIs (GROUP A)
PAI.
Code
16
16SE
17SE
53
54
55
60
186
62
197
68S
69
76
80
82
86
25
110
236
103
30SE
12
112
113
183
PAI
Name
2,4-D
2,4-D S&E (10)
2,4-DB S&E (3)
Acifluorfen
Alachlor
Aldicarb
Atrazine
Azinphos Methyl
Benomyl
Bolstar
Bromacil Salt
Bromoxynil
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos
Cy anaz ine
DCPA
DEF
Diazinon
Dichlorprop S&E
(3)
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Water/
Vastewater
Rec ircttlat ion/
Recycle
yes
yes
yes
yes
no
no
no
no
no
no
no
yes
no
yes
no
no
no
no
no
yes
yes
no
yes
no
no
Non-Water/
Waste-water
Re cirettlat ion/
Recycle
yes
yes
yes
yes
yes
no
yes
yes
yes
yes
no
yes
no
no
yes
no
yes
yes
yes
yes
yes
no
yes
yes
yes
Zero-
Discharge
PAI
no
yes
yes
no
no
no
no
no
no
no
yes
no
no
no
no
no
no
no
no
no
yes
no
no
no
no
       7-19

-------
 Table 7-7




(Continued)
PAI
Code
119
123SE
124
126
203
132
182
133
90
140
144
148
27SE
31SE
154
156
158
45
22
173
192
205
204
208
212
PAI
Name .
Diuron
Endothall S&E
(3)
Endrin
Ethion
Ethyl Parathion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Heptachlor
Isopropalin
Linuron
MCPA S&E (4)
MCPP S&E (4)
Methamidophos
Me thorny 1
Methoxychlor
Metribuzin
Mevinphos
Naled
Organo-tins (8)
PCNB
Pendimethalin
Permethrin
Phorate
Water/
Wastewater
Recirculation/
Recycle
no
no
no
no
no
no
no
no
no
no
no
no
yes
yes
no
no
yes
yes
no
no
no
no
no
no
yes
Non-Water/
ffastewater
Re circttlat ion/
Recycle
no
no
no
yes
yes
yes
yes
yes
no
yes
no
no
yes
yes
yes
yes
no
no
no
no
no
no
yes
yes
yes
Zero-
Discharge
PAI
no
yes
no
no
no
no
no
no
no
no
no
no
yes
yes
no
no
no
no
no
yes
no
no
no
no
no
   7-20

-------
 Table 7-7




(Continued)
PAI,
Code
185
41
84
252
255
262
8
264
PAI
Name
Phosmet,
recrystallized
Prop anil
Stirofos
Tebuthiuron
Terbufos
Toxaphene
Triadimefon
Trifluralin
Water/
Wastewater
Recirculation/
Recycle
no
yes
no
yes
yes
no
no
yes
Non-Water/
Waste-water
Recirculation/
Recycle
no
yes
no
yes
yes
no
yes
yes
Zero-
Discharge
PAI
yes
no
no
no
no
no
no
no
   7-21

-------
            PAI Mass Limitations Based on Direct Transfers
            (Group B) --  Production-based mass limitations were calculated
for the BAT PAIs using their average daily flows and production rates and the
effluent concentrations determined to be acheivable after BAT-level treatment.
These mass limitations are in the form of pounds of PAI allowable discharge
per one thousand pounds of PAI production (lb/1,000 Ibs PAI production).
Because these limitations are mass-based, they incorporate the reductions in
wastewater volumes and PAI mass loadings achieved through pollution prevention
and recycling practices and the reductions in PAI effluent concentrations
achieved by in-plant or end-of-pipe (EOP) BAT treatment technologies.
Wastewater flow reductions are accounted for in the mass limitations because
these flows, in gallons/1,000 Ibs PAI production, are multiplied by the
achievable effluent concentrations to calculate the allowable PAI mass
discharge.  Therefore, wastewater flow reductions acheived through the
implementation of pollution prevention and recycling practices are reflected
in a reduced production-based mass limitation.

            In a number of cases, EPA directly transferred mass limitations
developed for BAT PAIs to structurally similar non-BAT PAIs.  For example,
data are available for alachlor showing that BAT-level mass discharges are
being achieved through pollution prevention, recycling and effective EOP
treatment.  The numerical limitations developed for alachlor were transferred
directly to butachlor and propachlor; that is, the same daily and monthly
limitations apply to all three PAIs.  By directly transferring mass
limitations, the pollution prevention and recycling practices used to reduce
PAI discharges by the BAT facilities are implicitly incorporated as the basis
for the limitations for the structurally similar, non-BAT facilities.  In
addition, 13 BAT PAIs are also produced at facilities that are not currently
achieving BAT levels established in this rulemaking ("non-BAT" facilities).
(for example, atrazine is produced at BAT and non-BAT facilities), and the
mass limitations developed for these PAIs apply to both the BAT and non-BAT
facilities.  In this section, the non-BAT PAIs with limitations transferred
directly from BAT PAIs are denoted as Group B PAIs.

            Limitations could not be directly transferred between PAIs that
have dissimilar chemical structures and manufacturing processes.  These
differences significantly impact wastewater generation and content and the
pollution prevention and recycling opportunities that are available.
Limitations development for these PAIs (Group C PAIs),  where limitations are
not directly transferred from BAT PAIs, are discussed later in this section.

            EPA was able to directly transfer the mass limitations developed
for 7 of the BAT PAIs to 14 structurally similar non-BAT PAIs.  Therefore, 100
of the total 120 PAI limitations are based on either data from BAT PAIs (86
PAIs) or on the direct transfers of mass limitations from BAT PAIs to non-BAT
PAIs (14 PAIs).  Because these mass limitations are being transferred directly
(i.e., the same numerical limitations apply to both the BAT and non-BAT PAIs),
they implicitly incorporate the pollution prevention and recycling practices
discussed above for the BAT PAIs.  However, to estimate the economic impacts
on the non-BAT facilities, the Agency conservatively assumed that the
limitations would be met solely through the operation of BAT treatment
technologies, and costs were estimated using the flow rates reported by the
non-BAT facilities.  The Agency believes, though, that many of the non-BAT


                                     7-22

-------
facilities will be able to meet the  limitations more cost-effectively by
integrating the pollution prevention and recycling practices being employed at
their counterpart BAT facilities.  For  this  reason, the direct transfer of
mass limitations should influence the non-BAT  facilities to implement these
practices to the extent possible in  their processes.

            PAI Mass Limitations Not Based on  Direct Transfers
            (Group C) --  As discussed  above,  mass limitations could not be
directly transferred between dissimilar PAIs due  to differences in their
chemical processes.  When BAT mass limitations could not be directly
transferred, the PAI limitations were based  on the performance of BAT
treatment technologies.  Limitations for 20  of the 120 regulated PAIs were
based on BAT treatment performance rather than direct mass limitation
transfers, and these PAIs are denoted as Group C  PAIs in this section.

            To illustrate the difference between  direct and non-direct
transfers, assume that the mass limitation developed for BAT PAI "A" is 1.0 x
10'3 lb/1000 Ib PAI production.  Also assume that  PAIs "B" and "C" are
structurally similar to PAI "A" and  are produced  by similar chemical
processes, while PAI "D" is a dissimilar PAI produced by a dissimilar chemical
process.  If the mass limitation for PAI "A" is directly transferred to PAIs
"B" and "C" , then these PAIs must meet  the 1.0 x  10'3 lb/1,000 Ib limitation,
regardless of their current wastewater  discharge  flow and PAI effluent
concentration.  If PAIs "B" and "C"  are treating  to the same PAI effluent
concentration as PAI "A" but generate more wastewater, their PAI mass
discharges will be greater than the  mass discharge at PAI "A" and, therefore,
PAIs "B" and "C" would have to reduce their  flows or treat their wastewater
more effectively to comply with the  1.0 x 10'3  lb/1,000 Ib mass limitation.

            In this example, because PAI "D" is produced by a dissimilar
chemical process, the mass limitation for PAI  "A" (1.0 x 10"3 lb/1,000 Ib)
cannot be directly transferred to PAI "D".  The same flow reduction
opportunities through pollution prevention and recycling may not be available
to the process producing PAI "D" and, therefore,  the PAI "D" process may
generate more wastewater, in gallons/1,000 Ib  of  production.  However, PAIs
"A" and "D" may be amenable to the same BAT  treatment technology, such as
activated carbon or hydrolysis.  In  these cases,  EPA evaluated the achievable
effluent concentration and treatment system variability in the treatment of
PAI "A" and applied this BAT treatment  performance to non-BAT PAIs like PAI
"D."  Unlike the direct limitation transfers,  however, the discharge flow and
production rate at PAI "D" (rather than PAI  "A")  were used in conjunction with
the BAT effluent concentration (demonstrated by PAI "A") to develop the
limitation for PAI "D".

            As discussed above, when limitations  could not be transferred
directly,  EPA relied on BAT treatment performance as the basis for limitations
development.   Through review of the  long-term  data submitted by PAI
manufacturing facilities, EPA determined that  properly operated BAT
technologies will,  in most cases,  reduce PAI wastewater concentrations to at
or near their analytical detection limits.  This  treatment performance was
applied to the non-BAT PAIs, and compliance costs were estimated for upgrading
or installing the applicable treatment  system  so  that the BAT-level effluent
concentrations could be achieved.   However,  due to a lack of data, a


                                     7-23

-------
methodology could not be developed to directly transfer the flow reductions
achieved by the the BAT PAIs (Group A) to the non-BAT PAIs (Group C).   The
process diagrams in the questionnaires were helpful in identifying whether
pollution prevention and recyling practices had been integrated into the BAT
PAI processes.  However, sufficient data are not available from the
questionnaires and other information sources to quantify the wastewater flow
reduction achieved through these practices on a PAI-by-PAI basis for existing
facilities.   To quantify these reductions, EPA would have needed detailed
information on flows and pollutant loadings both before and after the
implementation of the pollution prevention and recycling practices.   The
required historical data needed to quantify the impact of these practices are
seldom available unless the changes were made recently, since only recently
have plants begun to track and maintain this information more closely.

            Another complication inhibiting the transfer of flow reduction
techniques for this industry is the uniqueness of dissimilar PAI processes.
Unlike the similar PAI processes involved in the direct limitation transfers,
flow reduction techniques available to one PAI process are often not available
to an entirely different PAI process.  The differences in the chemical
processes between dissimilar PAIs can have a significant impact on waste
generation and on the pollution prevention and recycling opportunities
available for implementation.  This process complexity, which is a
characteristic of the PAI manufacturing industry, is discussed in more detail
in Section 7.1.5.

            Although flow reduction techniques were not transferred as part of
the technology basis for the BAT mass limitations for the 20 Group C PAIs, the
manufacturers of these non-BAT PAIs are expected to implement these
techniques,  if possible, due to the limitations being established by this
rule.  Process analysis and testing to evaluate potential pollution prevention
and recycling opportunities may 'help facilities to more cost-effectively meet
the regulations for the 20 Group C PAIs.  However, EPA does not have
sufficient data to quantify the precise flow reductions acheivable by each of
these 20 PAI processes.
  •
            Regulated PAIs  --  As discussed earlier in this section,  120 PAIs
are being regulated by this rulemaking.  Of these 120 PAIs: Group A -  the BAT
PAIs - includes 86 PAIs, 30 PAIs with zero-discharge limitations and 56 PAIs
with numeric, non-zero limitations; Group B, where limitations are based on
the direct transfer of mass limitations from BAT to non-BAT PAIs, includes 14
PAIs; and Group C, where limitations are based on BAT treatment performance,
includes 20 PAIs.  Table 7-8 lists the 120 regulated PAIs and identifies
whether the PAIs are in Group A, B, or C.

            Table 7-8 also identifies whether pollution prevention and
recycling practices are currently being practiced by the regulated PAIs or if
the mass limitations are being directly transferred from BAT PAIs that
currently employ pollution prevention and recycling practices.  EPA has relied
on recirculation and recycle practices for non-wastewater streams as the full
or partial technology basis for the limitations for 80 of the 120 regulated
PAIs; this count includes 24 PAIs (of the 30 PAIs) with zero-discharge
limitations.  EPA has relied on recirculation and recycle practices for
wastewater streams as the full or partial technology basis for the limitations

                                     7-24

-------
   Table  7-8




REGULATED PAIs
PAI
Code
16
16SE
17SE
52
53
54
55
58
60
186
178
62
197
68
68S
69
69
219
218
70
73
241
75
76
80
PAI
Name
2,4-D
2,4-D S&E (10)
2,4-DB S&E (3)
Acephate
Acifluorfen
Alachlor
Aldicarb
Ametryn
Atrazine
Azinphos Methyl
Benfluralin
Benomyl
Bolstar
Bromacil
Bromacil Salt
Bromoxynil
Bromoxynil
Octanoate
Bus an 40
Bus an 85
Butachlor
Captafol
Carbarn- S
Carbaryl
Carbofuran
Chloroneb
Group
A
A
A
C
A
A
A
B
A
A
B
A
A
C
A
A
B
C
C
B
C
C
C
A
A
Wastewater
Recirculation
and/or
Recycle
yes
yes
yes
no
yes
no
no
no
no
no
yes
no
no
no
yes
yes
yes
yes
yes
no
no
yes
yes
no
yes
Uon-₯as tewa ter
Recirculation
and/or
Recycle
yes
yes
yes
yes
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
no
yes
yes
no
no
yes
yes
no
yes
no
no
Zero-
Discharge
PAI
no
yes
yes
no
no
no
no
no
no
no
no
no
no
no
yes
no
no
no
no
no
no
no
no
no
no
     7-25

-------
 Table 7-8




(Continued)
PAI
Code
82
86
25
110
236
259
103
30SE
12
112
113
183
119
123SE
124
125
126
203
132
182
133
90
140
144
220
PAI
Name
Chlorothalonil
Chlorpyrifos
Cyanazine
DCPA
DEF
Dazomet
Diazinon
Dichlorprop S&E
(3)
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall
S&E (3)
Endrin
Ethalfluralin
Ethion
Ethyl Parathion
Fenarimol
Fensulfdthion
Fenthion
Fenvalerate
Heptachlor
Isopropalin
KN Methyl
Group
A
A
A
A
A
C
A
A
A
.A
A
A
A
A
A
B
A
A
A
A
A
A
A
A
C
ffastewater
Recirculation
and/or
Recycle
no
no
no
no
no
yes
yes
yes
no
yes
no
no
no
yes
no
yes
no
no
no
no
no
no
no
no
yes
Non-Wastewater
Re cir culat Ion.
and/or
Recycle
yes
no
yes
yes
yes
no
yes
yes
no
yes
yes
yes
no
no
no
yes
yes
yes
yes
yes
yes
no
yes
no
no
Zero-
Discharge
PAI
no
no
no
no
no
no
no
yes
no
no
no
no
no
yes
no
no
no
no
no
no
no
no
no
no
no
   7-26

-------
 Table 7-8




(Continued)
PAI
Code
140
27SE
31SE
150
263
154
243
156
158
45
22
172
118
173
175
192
205
107
204
208
212
185
223
224
PAI
Name
Linuron
MCPA S&E (4)
MCPP S&E (4)
Malathion
Merphos
He thami dopho s
Metham Sodium/
Vapam
Methomyl
Methoxychlor
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norflurazon
Or gano - t ins ( 8 )
PCNB
Parathion
Methyl
Pendimethalin
Permethrin
Phorate
Phosmet,
recrys .
Prometon
Prometryn
Group
A
A
A
C
B
A
C
A
A
A
A
C
C
A
C
A
A
B
A
A
A
A
B
B
Wastewater
Re circulation
and/or
Recycle
no
yes
yes
yes
no
no
yes
no
yes
yes
no
yes
yes
no
no
no
no
no
no
no
yes
no
no
no
Non- tfas tewater
Recirculation
and/or
Recycle
no
yes
yes
yes
yes
yes
no
yes
no
no
no
no
no
no
yes
no
no
yes
yes
yes
yes
no
yes
yes
Zero-
Discharge
PAI
no
yes
yes
no
no
no
no
no
no
no
no
no
no
yes
yes
no
no
no
no
no
no
yes
no
no
   7-27

-------
 Table 7-8




(Continued)
PAI
Code
39
26
41
226
230
231
239
84
35
252
254
255
256
257
262
8
264
268
PAI
Name
Pronamide
Propachlor
Propanil
Propazine
Pyrethrins I
Pyrethrins II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin
Ziram
Group
C
B
A
B
C
C
B
A
C
A
C
A
B
B
A
A
A
C
ffastewater
Recirculation
and/or
Recycle
no
no
yes
yes
no
no
yes
no
no
yes
no
yes
yes
no
no
no
yes
yes
Non~ Wa.s tewa ter
Recirculation
and/or
Recycle
no
yes
yes
yes
yes
yes
yes
no
yes
yes
yes
yes
yes
yes
no
yes
yes
no
Zero-
Discharge
PAI
no
no
no
no
no
no
no
no
no
no
no
no
no
no
no
no
no
no
   7-28

-------
for 54 of the 120 regulated PAIs; this count includes 24 PAIs (of the 30 PAIs)
with zero-discharge limitations.  Either wastewater or non-wastewater
recirculation or recycle practices are being relied on by EPA as the full or
partial basis for the limitations for 96 of the 120 regulated PAIs; this count
includes all 28 PAIs with zero-discharge limitations based on complete
recycle/reuse of wastewater.

            Zero Discharge Limitations

            Zero-discharge limits are being promulgated in this rule for PAIs
where compliance can be demonstrated through zero discharge of process
wastewaters using a pollution prevention technology such as:  closed loop
recirculation of process wastewater, 100% recycle of process wastewater to
another operation such as pesticide formulation, or zero water addition or
generation during manufacture of a PAI.   Zero-discharge limitations were set
for 30 PAIs under this rulemaking.  As discussed earlier, many of the PAIs
with numeric, non-zero limitations have been based at least in part on
recirculation and recycling practices, but these practices do not represent
closed loop recirculation or 100% recycling and so do not eliminate all
wastewater discharges.  Zero-discharge limitations were not set unless these
practices have resulted in no discharge of process waters.

            Of the 30 PAIs with zero-discharge limitations, 2 PAIs fall into
the category of zero water addition or generation during manufacture,  and the
remaining 28 zero-discharge PAIs are salts and esters including phenoxy acid
salts and esters.  The salt and ester PAIs are good examples of how pollution
prevention has been incorporated into this rule.  There are four plants in the
industry which manufacture phenoxy acid salts and esters.  Three of these four
plants currently are achieving zero discharge by recycling the water generated
during the esterification reaction as make-up water for the salt formation
process.   When production schedules do not allow for immediate use of the
esterification process wastewater for salt formation, this wastewater is
typically stored until needed.  These plants also recover reactants used in
the esterification reaction and recycle these reactants into subsequent
batches of the same ester.  The zero-discharge limitations set for the phenoxy
salt and ester PAIs are based on the three plants that currently employ the
pollution prevention and recycling practices discussed above.  The fourth
plant will be subject to the same zero-discharge limitation and will likely
need to implement similar pollution prevention and recycling techniques to
comply with this limitation.

            NSPS and PSNS

            NSPS and PSNS regulations for this rulemaking are based the final
BAT limitations plus 28% flow reduction.   New plants have the opportunity to
install the best and most efficient production processes, source reduction
techniques, and wastewater treatment technologies.  As a result, NSPS and PSNS
incorporate the flow reductions demonstrated by newer PAI processes.  More
detailed discussions of NSPS and PSNS are provided in Sections 7.5.3 and
7.5.5, respectively, and Section V of the preamble to the final rule.
                                     7-29

-------
7.1.5       Process Complexity in the Pesticide Chemicals Manufacturing
            Industry

            As discussed in Section 7.1.4, EPA does not believe that the
identified pollution prevention and recycling practices can be directly
transferred between manufacturers of dissimilar PAIs.  For example, it may be
possible to recirculate a large portion of a product wash water stream in one
PAI process whereas a. different PAI process might tolerate very little recycle
of the same type of stream without significantly impacting process control or
product quality.  This is due to the complexity of the processes in the
pesticide chemicals manufacturing industry.

            For some industries, such as the pesticide formulating, packaging,
and repackaging (PFP) industry, there is little diversity in the process
operations or the water use and wastewater generation characteristics among
different facilities.  This is not true, however, for PAI manufacturing
facilities.  PAIs are complicated organic molecules, and their production
requires the operation of sophisticated chemical processes.  These processes
often involve the addition of multiple reactants and the use of catalysts to
promote the formation of the desired PAI product.  In addition, a variety of
different unit operations are employed to purify the PAI product, recover raw
materials and separate wastes from process streams.  These operational steps
can differ significantly among different PAI manufacturing processes due to
the different types of reactants and solvents used and the range of
byproducts, coproducts and waste products formed during PAI synthesis.

            Contaminants enter into PAI processes or are generated within the
PAI processes themselves through a number of mechanisms.  Impurities can enter
the process in reactants, solvents, and catalysts; commercially available
feedstocks and solvents typically contain 0.5% or more impurities (Reference
4).   Waste constituents are generated in the process because PAI reaction
steps are not 100% efficient.  In most all reaction processes, multiple
reactions occur; the desired reaction which forms the product PAI and other,
usually undesired reactions which account for the formation of byproducts,
coproducts, and waste products, such as water of reaction.  Stringent process
control and the proper use of catalysts can decrease, but not eliminate, the
formation of unwanted compounds.  Water of reaction, however, cannot be
eliminated without changing the process chemistry, since this water is formed
due to the combination of the reactants used in the process.

            Contaminants, byproducts, coproducts and waste products that enter
or are generated in the reaction step are separated from the desired PAI
product during downstream processing.  Depending on the difficulty of
separation, a multitude of processing steps may be required.   Water of
reaction is sometimes volatilized from the reaction medium using evaporators
or separated in centrifuges or decanters based on density differences.  This
water of reaction, once separated, can be recycled to the reaction step in
some but not all processes, depending on the reaction chemistry and the water
solubility of the reactants and PAI product.  Without very detailed knowledge
of the process kinetics, and testing, it is not possible to predict if or how
much of this water can be recycled.
                                     7-30

-------
            Water is also used during downstream processing to remove waste
constituents from the PAI product stream or from other process streams so that
these process streams can be recycled.  Water is effective in these steps
because the waste constituents, such as dissolved salts, are more water
soluble than the PAI product or the organic constituents in the process
stream.  However, during these wash steps, some PAI product and organics from
the process stream are removed with the wash water.  For this reason, these
wash waters are often reused in the wash step to minimize the loss of product
and desired raw materials.  However, as recirculation of wash water increases,
there is also an increase in the concentration of waste constituents in the
wash water since less clean makeup water is being used.  As a result the wash
step becomes less efficient and more of the waste constituents may leave with
the product or process stream.  Operational problems may also occur if the
magnitude of the blowdown, or discharge stream, is not sufficient to prevent
critical buildup of the waste constituents in the recycled wash water.  For
example, some waste constituents may precipitate from the wash water stream if
their concentration becomes too elevated.  Without on-site testing it is not
possible to estimate when critical buildup of these constituents will occur
due to the range of waste constituents that may be present from one PAI
process to another.  One PAI process may allow recycle of 25 to 30% of a wash
water stream while another PAI process may encounter operational and product
quality problems at 10% recycle.

            Due to the individuality of each PAI manufacturing process and the
impact of these differences on the chemical content and other characteristics
of the wastewaters generated, the Agency did not propose generic transfers of
recirculation, recycle, and source reduction practices from one PAI process to
another.  That is, the Agency did not set one generic wastewater discharge
rate, in gallons per thousand pounds of PAI production, for all PAI processes.
Because of the differences in wastewater generation, recirculation, and
recycle capabilities between different PAI processes, no one flow rate was
considered applicable to all PAIs.

            Facilities not in compliance with the PAI mass limitations have
various options to acheive compliance, such as: reduce waste loads from the
process; optimize existing in-plant and/or EOP treatment;  install additional
in-plant and/or EOP treatment; or implement some combination of the above.
EPA believes that facilities will choose to integrate recirculation,  recycle,
and source reduction practices if possible to lessen the economic burden of
the effluent limitations and standards.   For example, in evaluating a
pollution prevention project, a facility may have concluded in the past that
the cost of pollution prevention equipment exceeds the benefits of product
recovery.  Due to the mass limitations,  however, the facility must now compare
these pollution prevention costs with the cost of upgrading or adding new
treatment, and this comparison shows the economic benefits of pollution
prevention more clearly.  Since wastewater recirculation or recycling may
allow a plant to reap the economic benefits of product recovery,  the facility
would be more apt to invest in the project.  In addition,  facilities might not
consistently meet permit limitations without decreasing the waste load to
treatment since the mass limitations will require much smoother wastewater
treatment plant operation.  One way to decrease this waste load from some
processes is to increase product and raw material recovery through the
                                     7-31

-------
recirculation and recycle of wastewater streams,  such as product or process
stream washes.

7.2         TREATMENT PERFORMANCE DATABASES

            The sources of treatment performance data available for the
pesticide chemicals manufacturing industry include:  self-monitoring data
submitted with the Pesticide Manufacturing Facility Census for 1986; data
collected during EPA short-term sampling at pesticide chemicals manufacturing
facilities between 1988 and 1991; data generated during EPA sponsored bench-
scale treatability tests on selected PAIs; data submitted following the April
10, 1992 proposal of effluent limitations guidelines and standards; and
evaluations of existing treatment performance databases, including databases
compiled to support other effluent guidelines.

            The database on PAI treatment performance was developed primarily
from information collected since 1986 as part of this rulemaking effort.  The
treatment performance database for the conventional pollutant parameters,
cyanide, and COD was compiled during the previous rulemaking efforts for the
pesticide chemicals industry supplemented by new BOD5, TSS  and COD  data
submitted by 10 plants in response to the questionnaire.  The treatment
performance database for all of the priority pollutants, except cyanide, was
compiled during the development of regulations for the OCPSF point source
category.  All of the treatment performance databases identified above are
discussed in more detail in Sections 7.2.1 through 7.2.4.

7.2.1       Analytical Data Submitted with the Pesticide Manufacturing
            Facility Census for 1986

            The Pesticide Manufacturing Facility Census for 1986,   as
described in Section 3.1.3, requested engineering and economic data regarding
pesticide manufacturing processes, wastewater generation, treatment, and
handling procedures from each plant that received the questionnaire.  In
addition, the questionnaire requested submittal of all wastewater monitoring
data collected in 1986, in the form of individual data points rather than
monthly aggregates.  The intent of this request was to obtain a full year of
daily monitoring data from each respondent, specifically for wastewater
streams leaving manufacturing processes and entering and exiting treatment
systems.  The questionnaire further requested that the respondents identify
the sampling points in relation to the process and treatment diagrams
submitted with their completed questionnaires.

            When the data submitted by a plant were found to be insufficient
or required further explanation, EPA requested additional information from
the plant.  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.

            The industry-submitted long-term data contained mostly PAI data,
and these data were entered into EPA's treatment performance database.  Of the
90 pesticide manufacturing plants that responded to the 1986 survey, data from
27 facilities covering 55 PAIs were evaluated for use in determining treatment
                                     7-32

-------
system performance.  EPA relied on these data extensively in the course of
developing limitations, as discussed in Section 7.5.

7.2.2       Sampling and Analytical Programs

            Between 1988 and 1991, EPA visited 32 of the 90 manufacturing
facilities.  During each visit, EPA gathered production process information
and waste and wastewater generation, treatment and disposal information.
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 wastewater for bench-scale treatability studies at 7 of the 32
facilities.  Four of these seven were among the 20 facilities sampled in order
to characterize process discharges and treatment system performance.
Therefore, overall, 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 intimately commingled with wastewater 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. (The ninth plant did
provide long-term self-monitoring data, however.)

            During the sampling activities, raw wastewater 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.  EPA initially selected faclities for sampling
based on data which indicated that: (1) the wastewater treatment system was
effective in removing PAIs, and (2) 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
sampled.

7.2.3       Treatabilitv Test Data

            As part of this rulemaking effort for the pesticide chemicals
manufacturing industry, EPA conducted numerous bench-scale treatability
studies on both clean water to which PAIs were added ("synthetic wastewaters")
and on actual pesticide process wastewaters.  Through the treatability
studies, EPA analyzed the efficacy of activated carbon adsorption, membrane
filtration, hydrolysis and chemical oxidation (alkaline chlorination and UV
ozonation) for control of 76 PAIs in synthetic wastewaters.  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 final rule.

            Activated Carbon Adsorption

            Activated carbon adsorption isotherm tests were performed on
synthetic wastewaters containing 29 selected organic PAIs, chosen from the
list of 260 organic PAIs considered for regulation.  The carbon isotherm


                                     7-33

-------
                  EPA collected information for the  proposed rulemaking;  they
                  replaced inadequate treatment or supplemented existing
                  treatment.   The new data allow more  of the limitations  to  be
                  based on demonstrated performance  of full-scale treatment
                  systems instead of treatment system  performance data
                  transferred from other PAIs  or estimates from treatability
                  studies of the performance expected  of full-scale treatment.

            3.     Analytical methods used by dischargers to monitor PAIs  in
                  discharges, where the commenter believed the proposed EPA
                  methods were different from those  currently in use.

            4.     Additional information identifying specific pollution
                  prevention practices and  "out-of-process" recycle/reuse.

In addition, EPA conducted hydrolysis rate studies of  pyrethrin I and
pyrethrin II as part of its study of the.formulator/packager industry.  The
hydrolysis showed that pyrethrin I and pyrethrin II  hydrolyze rapidly under
alkaline conditions.   EPA has added that data to its database in response to
comments.

7.2.5       Existing Treatment Performance Databases

            The treatment performance databases used in the analysis of
treatment of conventional pollutants (BOD5,  TSS  and  pH)  and COD,  include  the
data submitted in response to the questionnaire, and the pesticide chemicals
industry BPT database.  The OCPSF database was used  for priority pollutants.
These databases are not repeated here but can be found in the following
documents:

            •     Development Document for Final Effluent Limitations
                  Guidelines for the Pesticide Chemicals Manufacturing Point
                  Source Category.   [EPA 440/1-85/079  (BAT) and EPA 440/1-
                  78/060-e]

            •     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.

The BODj,  TSS and COD data from the questionnaire are  presented in Section 5.

7.3         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.  EPA found
that pesticide chemicals manufacturing facilities primarily select in-plant
physical/chemical treatment, in addition to the pollution prevention and
recycle/reuse practices, for the removal of highly concentrated pollutants


                                     7-36

-------
from process wastewaters.   [These in-plant controls are then often followed by
biological treatment usually after these streams are combined with other
facility wastewaters].  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.  In a few cases, activated carbon is
used as an end-of-pipe treatment step to polish commingled facility
wastewaters prior to discharge.

            Table 7-9 summarizes the in-plant and end-of-pipe treatment
technologies used to control pollutant discharges in pesticide industry
process wastewaters.  Table 7-9 also presents the number of facilities that
reported using each of the technologies according to the Facility Census for
1986 and the number of facilities currently using the technologies.  The
number of treatment systems currently operating takes into account the new
treatment systems that have been installed since  1986, as well as the
manufacturing facilities that have closed.  It should be noted that many
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
PAIs, 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:

            •     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 in the following
paragraphs.
                                     7-37

-------
                                   Table 7-9

               TREATMENT TECHNOLOGIES USED BY FACILITIES IN THE
                  PESTICIDE CHEMICALS MANUFACTURING INDUSTRY
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 (1986)
25
14
7
11
8
1
1
6
3
2
3
4
2
Total Number
of Facilities
(Current1)
24
12
5
9
6
2
0
4
3
2
3
6
2
'Accounts  for  facility closures since 1986.
                                     7-38

-------
7.3.1       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
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
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
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

                                     7-39

-------
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,
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.

7.3.2       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
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)~


                                     7-40

-------
            Carbamate hydrolysis occurs by the following reaction:
                  0
                  I
                  C
                /   \             OH-
            R,-N     0 -  Rj + HjO  ---- > RjOH + RrNH + C02
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.

            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 of malathion at 60°C and pH 12 is less
than one minute) and methomyl (half-life less than 5 minutes), the half-life
is much less than 30 minutes .

            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 .


                                     7-41

-------
            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.

7.3.3       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
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 ran 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
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


                                     7-42

-------
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.

7.3.4       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.

            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, chlorobenzenes,  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 of the pollutant
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.
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
                                     7-43

-------
no recovery value.  For this reason, resins have generally been restricted to
application where few other treatment options have proven useful.

7.3.5       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, increase the solubility of constituents in the
solvent or decrease the solubility of constituents in water.

            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

            •     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.

7.3.6       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.  The alcohol is then condensed.
                                     7-44

-------
            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.

7.3.7       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
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
typically capable of rejecting molecules having diameters greater than 0.001
micron (3.94 x 10"8 inches)  or nominal molecular weights  greater than 2000.
The systems operate at feed pressures of 50-200 psig.  Some pretreatment may


                                     7-45

-------
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.

            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.

            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


                                     7-46

-------
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.

7.3.8       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
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
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.
                                     7-47

-------
7.3.9       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
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.

7.3.10      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.
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;
                                     7-48

-------
            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
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.

7.3.11      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.

            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).

7.3.12      Coagulation/Flocculation

            Coagulation and flocculation are commonly used in conjunction to
enhance settling of suspended particles ranging in size from those particles


                                     7-49

-------
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.

            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.

7.3.13      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 of 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
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.
                                     7-50

-------
7.3.14      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
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
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.  (For a further description of steam
stripping technology, see the final OCPSF rule, 52 FR 42540, and Section 7 of
the OCPSF Technical Development Document, EPA 440/1-87/009,  October 1987).

7.3.15      Pre- or Post-Treatment

            The pesticide chemicals manufacturing industry uses equalization,
neutralization, and/or filtration to pre- or post-treat process wastewaters.
                                     7-51

-------
            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.

            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).

            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);
                                     7-52

-------
            •     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).

7.3.16      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,
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
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).
                                     7-53

-------
            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.

7.4         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.

7.4.1       Carbon Adsorption

            In the pesticide manufacturing industry, activated carbon
adsorption is or has been used to treat PAIs in the following structural
groups:  acetanilides, 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 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 to
establish limitations.

            Based on long-term concentration data achieved using activated
carbon adsorption, final limitations are based on activated carbon adsorption
technology for individual PAIs in the following structural groups:
acetanilides, aryl halides, benzonitrils,  bicyclics, phenols,
phosphorothioates, phosphorodithioates,  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 loadings from
their discharges.  These systems currently account for the prevention of the
discharge of approximately 430,000 pounds of pesticide active ingredient per
year.

            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 average to detection limit (LTA/MDL) ratio
varies from 3.19 to 26.0 (i.e., for these compounds, the average concentration
following treatment ranged from 3.19 to 26 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

                                     7-54

-------
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 synthetic pyrethrins.

            In addition to the PAI being treated, a number of factors can
affect 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 adsorption step 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.  However,  while the
calculated efficiency of removing PAIs from less contaminated streams
decreases, for those PAIs using carbon as a polishing step very low effluent
concentrations were achieved in the carbon effluent.

            Using an activated carbon system dedicated to removal of a
specific PAI from the undiluted process discharge will also improve
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


                                     7-55

-------
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.

7.4.2       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.  These systems proved capable of reducing the amount of PAI in
wastewater to the extent that the average of the LTA effluent concentrations
for facilities using hydrolysis as a PAI treatment technology was 2.69 times
the minimum detection limit for the individual PAI.  At many of the
facilities,  no PAI was measured above 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.  The EPA sponsored treatability studies at more
uniformly controlled conditions on PAIs for which hydrolysis appeared to be a
potential BAT technology.  Hydrolysis proved highly effective in destroying
most of 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 were 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.

            EPA is using hydrolysis as the technology basis for a number of
PAIs which are not currently treated using this technology, but for which
treatability studies have demonstrated excellent destruction of the PAIs.

7.4.3       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.

            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.  Based on the EPA treatability studies that


                                     7-56

-------
were conducted, the dithiocarbamate PAIs do not appear to be uniformly
treatable through the use of activated carbon adsorption.  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 this gas.

            The EPA performed treatability studies on a number of actual
process wastewater samples containing dithiocarbamate PAIs using alkaline
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 found 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.  EPA also conducted treatability studies on
technologies which are not currently used in the pesticide manufacturing
industry using ozonation and ultraviolet light 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 indicate that ozone can
achieve about the same degree of PAI reduction as chlorine.

7.4.4       Resin Adsorption

            Resin adsorption is currently used to treat specific pesticide
active ingredients which have not proved amenable to other treatment
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 and achieve very
low discharge concentrations ranging from 3 to 32 ppb PAI in the treated
effluent.  BAT is being promulgated 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.

7.4.5       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


                                     7-57

-------
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 where necessary for
those facilities expected to comply with BAT/PSES guidelines through the use
of existing solvent extraction systems.

            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 promulgating 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.

7.4.6       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 salts
of other PAIs where any possible residual of the phenoxy PAI would not
interfere with the maketability of the other PAI, 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 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


                                     7-58

-------
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.

7.4.7       Biological Treatment

            In the case of one pesticide active ingredient, biological
treatment has been demonstrated to achieve PAI removals of greater than 98%
PAI during biological oxidation.  EPA does not have data demonstrating that
activated carbon, hydrolysis or other physical-chemical treatment will achieve
significant additional removals of that PAI.  Therefore, EPA selected
biological treatment as BAT technology for that PAI.  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.

7.4.8       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 organo-tin compounds, this can be achieved through
reacting the organo-tin 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 organo-tins 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 organo-tin compounds.
Removal efficiencies of up to 99.5% have been achieved on a long-term basis
using this technology.

7.4.9       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 99.99% destruction of the PAI in wastewater streams.
While the PAIs and other pollutants of concern are virtually destroyed, an
                                     7-59

-------
effluent stream is generated from the scrubber on the incinerator overheads.
Trace amounts of PAIs remain in the scrubber discharges.

7.5         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 are
contained in the final rule and discusses options available for compliance
with these zero-discharge standards.

            EPA identified two regulatory options for consideration to reduce
the discharge of PAIs by organic pesticide chemicals manufacturers.  Option 1
would base BAT, NSPS,  PSES and PSNS limitations on the efficacy of hydrolysis,
activated 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.   Also, certain PAIs would be subject to zero-discharge
limitations based on closed-loop recycling or on no water use or generation in
the process.   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.

            The Agency is promulgating the BAT and PSES limitations for
Subcategory A plants based upon Option 1.  Option 1 will greatly reduce
pollutants discharged into the environment while avoiding cross-media transfer
of pollutants that might occur under Option 2 and incorporating recycle/reuse
technologies where possible.  The pollutants that are removed under this
option (and that are not recycled or reused) will be removed or destroyed by
the BAT treatment technologies.   This option will have minimal economic
impacts and is deemed to be economically achievable.

            The Agency rejected Option 2 because it was determined not to be
economically achievable and because of the cross-media implications of the
transfer of pollutants for off-site disposal that might occur through
industry's efforts to meet a zero discharge limitation for all PAIs.  However,
a zero discharge requirement is promulgated for certain PAIs under Option 1
where zero discharge has been demonstrated to be achievable through water
recycle/reuse or the lack of water use.

            The new source performance standards (NSPS and PSNS) are based on
Option 1 as is BAT and PSES, however, the limitations are also based on a 28%
flow reduction for most PAIs.  The Agency found that an average wastewater
volume flow reduction of 28% has been demonstrated at newer facilities for
similar production processes (see Section 7.5.3).

            Sections 7.5.1 through 7.5.6 provide a detailed discussion of the
steps followed in the determination of effluent limitations guidelines and
standards for PAIs.  These steps include:
                                     7-60

-------
            •     Statistical analysis of long-term self-monitoring data
                  (Section 7.5.1);

            •     Calculation of  effluent limitations guidelines under BAT
                  (Section 7.5.2);

            •     Calculation of  effluent limitations guidelines under NSPS
                  (Section 7.5.3);

            •     Analysis of POTW pass-through for PAIs (Section 7.5.4); and

            •     Calculation of  effluent limitations guidelines under PSES
                  and PSNS (Section 7.5.5).

            •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 assumed
weekly (four times per month) monitoring to demonstrate compliance.  These
procedures are discussed in the following section.

7.5.1       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 PAIs 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.
     '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.

                                     7-61

-------
            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
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 fj,
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.

The equation of the cumulative distribution function is as follows:
(D
           F(c) = P(C*c) = 8l(c-D)  +  (1-*)-=!= i
                                             *
            The expected value E(C)  of the concentration under this
distribution function is given by
                                            H)-
(2)
                                     7-62

-------
and the variance V(C) is given by the following expression:


                                                                   2       (3)
        V(C)  =  (1-5) exp (2n + a2) [exp (o2)-(l-6)] + 6 (l-5)£[I?-2exp (n + i-)].
The 99th percentile of the distribution can be expressed in terms of n, a, and
the inverse normal cumulative distribution function  ($"'), as follows:
                                                L-5
Finally, the daily variability factor VF(1) is defined as the 99th percentile
divided by the mean:
                                 VF(1) =
            To estimate daily variability factors for each plant-PAI dataset,
the following calculations were performed.  The estimate, fi, 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
£, divided by the number of detects minus one.  The estimated probability of a
nondetect, B, 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 Cw 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,
            In developing limitations, EPA used statistical estimates of upper
percentiles of the distributions fit to the concentration data sets.2 For the
daily maximum limitation, EPA used the product of the estimated 99th
percentile of the distribution of the daily concentration data, and the
average daily flow, divided by the average daily production.  For the monthly
average limitation, EPA used the product of the 95th percentile of the
distribution 4-day averages of the concentration data, and the average daily
flow, divided by the average daily production.  [The variability factor is not
used in determining the limitation.  However, in these cases, it is possible
     2  For two  Pals,  EPA estimated the production-normalized mass limitations
using the daily mass data reported by  the facilities.  The percentiles of the
mass data were estimated using the same statistical methodology as was used
for the concentration data for the other PAIs.  The limitations were estimated
by dividing the percentiles by the production.

                                     7-63

-------
to compute variability factors for the pesticides effluent data by merely
dividing the limitations by the long term average for a particular PAI.  For
example, if the limitation has a value of 15 mg/1 and the long term  average
has a value of 5 mg/1, the variability factor is 3.]

            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 /z4 and <74,
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 54, 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 54 if the daily nondetect  probability is S.

            The following equations therefore hold:


                        4)  = E(C) =
                                 (exp(a42)-(l-84))+84(l-84).D(Z?-2exp(^4+44-)),
and

                      C95(4) =
            Equations  (6) and  (7) can be algebraically solved for 04 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:
                                    (E(C)-8'D)2  E(O-t>'D
To derive an estimate, a^,  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 ^(C),  and B
by 3.  Next, the estimated o4 together with S  and E(C)  were substituted into
(6), which was solved to yield an estimate £„  of ^J.^.   Finally, /i4 and a^  in (8)


                                     7-64

-------
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 £(C) to give the estimated variability factor vT(4).

            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
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
(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.

7.5.2       Calculation of Effluent Limitations 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
                                     7-65

-------
            •     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
then compared for applicability.

            EPA segregated the 260 PAIs into 69 structural groups.  These
groups and the PAIs in them are listed in Table 7-10.  The final rule contains
numerical or zero-discharge limitations for 120 organic (Subcategory A) PAIs
in 32 of the structural groups, including 105 PAIs that were left unregulated
by the 1978 BPT effluent limitations.  Fifteen PAIs of the 120 PAIs are part
of the 49 PAIs already regulated under BPT as total pesticides.  These are:
endrin, heptachlor, methoxychlor,  PCNB, toxaphene, trifluralin, azinphos
methyl, diazinon, disulfoton, malathion,  parathion methyl, carbaryl, diuron,
linuron, and 2,4-D.  A list of the 120 PAIs being regulated and the basis for
their limitations is contained in Table 7-11.

            The final BAT limitations and costs for organic PAIs are based on
the same BAT technologies as were identified in the proposal--i.e.,
hydrolysis, activated carbon, chemical oxidation, resin adsorption, biological
treatment, solvent extraction and/orincineration treatment systems.  In
addition, pollution prevention and recycle/reuse practices are incorporated
into many of the PAI limitations as previously discussed in Section 7.1

            At each stage of BAT limitations development,  the Agency attempted
to obtain data from pesticide chemicals manufacturing plants with treatment
systems representing BAT performance to provide coverage as complete as
possible for the PAIs and priority pollutants discharged by the pesticide
chemicals manufacturing industry.   The final PAI numeric limitations are
based, wherever possible, on actual industry monitoring data on the
concentrations of PAIs in wastewaters treated by the full-scale BAT treatment
systems.  Where actual full-scale data are not available,  the final BAT
limitations are based on a transfer of treatment system performance data
between structurally similar PAIs, supported by data from EPA or industry
bench-scale treatability studies.   In some cases, the final BAT limitations
might require that existing PAI treatment technologies currently in place at
facilities be improved by enhanced operations, such as hydrolysis with
increased retention time, carbon adsorption with increased retention time, and
additional PAI monitoring.

            For 55 PAIs the mass limitations are based on full-scale BAT data
(including 5 PAIs for which incinerator scrubber water data were used),
submitted by the manufacturers; for 30 PAIs the limitations are set at zero
discharge based on recirculation,  recycle/reuse and/or no water use or excess
from the process; for one PAI the limitations take into consideration the
discharge from the production of an intermediate which is measured by the same
analytical method; and for 34 PAIs limitations are based on technology
transfer.  The 55 PAIs with limitations based on full-scale data reflecting
                                     7-66

-------
     Table 7-10




PAI STRUCTURAL GROUPS
Structural Group
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Phenoxy Acid
Acetamide
Acetamide
Acetate salt
Acetanilide
Acetanilide
Acetanilide
Acetanilide
Alcohol
Alkyl Acid
Alkyl Halide
Alkyl Halide
Alkyl Halide
Aryl Amine
Aryl Halide
Aryl Halide
Aryl Halide
Terephathalic acid
ester
Aryl Halide
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
116
20
80
98
110
129
PAI Name
2,3,6-T, S&E
2,4, 5-T
2,4,5-T, S&E
2,4-D, S&E (10)*
2,4-D
2,4-DB, S&E (3)*
MCPA, S&E (4)*
Dichlorprop, S&E (3)*
MCPP, S&E (4)*
Chlorprop , S&E
CPA, S&E
MCPB, S&E
Silvex
Diphenamide
Fluoroacetamide
Sodium mono-
fluoroacetate
Propachlor
Alachlor
Butachlor
Metolachlor
HAE
Propionic acid
Chloropicrin
Dalapon
Methyl bromide
Diphenylamine
Dichloran
Chloroneb
Dicamba
DCPA
Chlorobenzilate
Limit Type
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
No Discharge (Closed Loop)
Numerical
No Discharge (Closed Loop)
No Discharge (Closed Loop)
No Discharge (Closed Loop)
No Discharge (Closed Loop)
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 No Data
Reserved No Data
Reserved No Data
Reserved - Not Mfg in 1986
Reserved - (Regulated as a
Priority Pollutant)
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Numerical
Reserved - Deep Well
Numerical
Reserved - (Not mfg. since
1986)
        7-67

-------
Table 7-10




(Continued)
Structural Group
Aryl Chloride
Benzeneamine
Benzoic Acid
Benzoic Acid
Benzonitrile
Benzonitrile
Bicyclic
Bicyclic
Bicyclic
Multiring Halide
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Amide
Carbamate
Carbamate
Carbamate
Carbamate/Urea
Chlorobenz amide
Chlorophene
Chlorophene
PAI #
205
204
53
78
69
69
123
123
177
262
13
38
40
42
48
55
61
62
75
76
77
95
100
145
156
166
170
195
260
272
146
39
9
10
PAI Name
PCNB
Pendimethalin
Acifluorfen
Chloramben
Bromoxynil
Bromoxynil octanoate
Endothall
Endothall, S&E (3)*
MGK 264
Toxaphene
Landrin 2
Landrin 1
Methiocarb
3-Iodo-2-propanyl
butylcarbamate
Aminocarb
Aldicarb
Bendiocarb
Benomyl
Carbaryl
Carbofuran
Carbosulfan
Desmedipham
Thiophanate ethyl
Propham
Me thorny 1
Mexacarbate
Napropamide
Oxamyl
Thiophanate methyl
Chloropropham
Karbutilate
Pronamide
Hexachlorophene
Tetrachlorophene
Limit Type
Numerical
Numerical
Numerical
Reserved - Not Mfg in 1986
Numerical
Numerical
Reserved - No Data
No Discharge - (Closed Loop)
Reserved - No Data
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - No Data
Reserved - Not Mfg in 1986
Numerical
Reserved - Not Mfg in 1986
Numerical
Numerical
Numerical
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 - Not Mfg since 1986
Reserved - Not Mfg in 1986
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
   7-68

-------
Table 7-10




(Continued)
Structural Group
Chlorophene
Chloropropionanilide
Phthalonitrile
Hydroxycoumarin
Hydroxycoumarin
Cyclic Ketone
DDT
DDT
DDT
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
EDB
EDB
EDB
Ester
Ester
Ester
Ester
Aryl Halide
PAI #
11
41
82
43
265
91
1
101
158
23
87
102
134
151
152
167
172
218
219
220
241
243
261
267
268
3
5
97
64
117
157
216
93
PAI Name
Dichlorophene
Propanil
Chlorothalonil
Coumafuryl
Warfarin
Cycloheximide
Dicofol
Perthane
Methoxychlor
Sulfallate
Mancozeb
EXD
Ferbam
Maneb
Manganous
dimethyldithiocarbamate
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
Limit Type
Reserved - Not Mfg since 1986
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
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
Numerical
Reserved - Deep Well
Reserved - (Regulated as
Priority Pollutant)
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - No Data
Reserved - Deep Well
Reserved - No Data
Reserved - Not Mfg in 1986
   7-69

-------
Table 7-10




(Continued)
Structural Group
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic N,S
Heterocyclic
Hydrazide
Imidamide
Indandione
Isocyanate
Aryl Halide
Aryl Halide
Miscellaneous
Indandione
Indandione
Miscellaneous
Benzeneacetic Acid
Ester
Dithiocarbamate
Acetamide
Heterocyclic
Miscellaneous
Carbamate
Carbamate
Phosphate
Miscellaneous
Miscellaneous
Carbamate
Miscellaneous
Heterocyclic
Thiocarbamate
FAX *
28
32
35
49
175
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
269
FAX Name
Octhilinone
Thiabendazole
TCMTB
Etridiazole
Norflurazon
Phenothiazine
Sodium bentazon
Dazomet
Maleic Hydrazide
Amitraz
Diphacinone
Nabonate
Benzene Hexachloride
Lindane
Bus an 90
Pindone
Chlorophac inone
Giv-gard
Fenvalerate
Amobam
Mefluidide
Quinomethionate
Oxyfluorfen
Propoxur
Phenme dipham
Phosphamidon
Metasol J26
Propargite
Promamocarb and
Promamocarb HC1
Rotenone (Mexide)
Sulfoxide
Triallate
Limit Type
Reserved - No Data
Reserved - No Data
Numerical
Reserved - No Data
Numerical
Reserved - No mfg. currently
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 - No Data
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - No Data
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - No Data
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - No Data
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
   7-70

-------
Table 7-10




(Continued)
Structural Group
Cyclopropane
carboxylic Acid
Ammonium
Ammonium
Ammonium
Ammonium
Ammonium
Ammonium
R4N
Ammonium
Ammonium
Nitrobenzoate
Organoarsenic
Organoarsenic
Organoarsenic
Or gano ar s eni c
Organocadmium
Organocopper
Organocopper
Organocopper
Organomercury
Tin alkyl
Or gano -zinc
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenylcrotonate
Phophorodithioate
Phosphate
PAI- #
270
7
56
105
120
121
149
159
162
217
66
6
72
161
188
189
88
89
190
191
192
266
44
112
206
206
211
258
19
94
12
PAI Name
Phenothrin
Dowicil 75
Hyamine 3500
Benzethonium chloride
Metasol DGH
Dodine
Malachite Green
Methyl benzethonium
chloride
Hyamine 2389
PBED (Busan 77)
Bifenox
Phenarsazine Oxide
Cacodylic acid
Methylarsonic acid,
salts and esters
Organo- Arsenic
Or gano - Cadmium
Copper 8-
hydr oxyquino 1 ine
Copper EDTA
Organo -Copper
Organo -Mercury
Organo -Tins (8)*
Zinc MBT
DNOC
Dinoseb
PCP; sodium salt
PCP
Phenylphenol
Tetrachlorophenol
Dinocap
Demeton
Dichlorvos
Limit Type
Reserved - Not Mfg in 1986
Reserved - No Data
Reserved - No Data
Reserved - Not Mfg in 1986
Reserved - No Data
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 - No Data
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Subcategory B
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Subcategory B
Reserved - Not Mfg in 1986
Reserved - Subcategory B
Reserved - Subcategory B
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Numerical
Reserved
Reserved - Deep Well
Reserved - No Data
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Numerical
   7-71

-------
Table 7-10




(Continued)
Structural Group
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphonate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphonothioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
PAI *
22
24
84
108
109
173
111
128
138
138
139
52
143
154
106
113
126
127
150
155
183
185
185
186
197
199
200
212
213
251
255
85
86
103
FAX Name
Mevinphos
Chlorfenvinfos
Stirofos
Dicrotophos
Crotoxyphos
Naled
Trichlorofon
Fenamiphos
Glyphosate , S&E
Glyphosate
Glyphosine
Acephate
Isofenphos
Methamidophos
Dimethoate
Dioxathion
Ethion
Ethoprop
Malathion
Methidathion
Disulfoton
Phosmet, recrystallized
Phosmet
Azinphos Methyl
(Guthion)
Bolstar
Santox (EPN)
Fonofos
Phorate
Phosalone
Bensulide
Terbufos
Chlorpyrifos methyl
Chlorpyrifos
Diazinon
Limit Type
Numerical
Reserved - Not Mfg in 1986
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
No Discharge - No Water Use
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - No Data
Reserved - No Data
Reserved - No Data
Numerical
Reserved - Not Mfg in 1986
Numerical
Reserved - Not Mfg in 1986
Numerical
Numerical
Reserved - Deep Well
Numerical
Reserved - Not Mfg in 1986
Numerical
No Discharge - No Water Use
Reserved - Deep Well
Numerical
Numerical
Reserved - Not Mfg in 1986
Reserved - Deep Well
Numerical
Reserved - Not Mfg in 1986
Reserved - No Data
Numerical
Reserved - Not Mfg in 1986
Numerical
Numerical
   7-72

-------
Table 7-10




(Continued)
Structural Group
Phosphorothioate
Phosphorothioate
Phosphorothioate
Dithiopyrophosphate
Dithiopyrophosphate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorotrithioate
Phosphorotrithioate
Phthalamide
Phthalimide
Phthalimide
Phthalimide
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
Cyclopropane
carboxylic Acid
PAI #
107
131
133
179
180
181
182
184
187
198
203
222
234
253
236
263
176
73
74
137
57
208
229
230
231
232
233
271
PAI Name
Parathion methyl
Famphur
Fenthion
Sulfotepp
Aspon
Coumaphos
Fensulfothion
Fenitrothion
Oxydemeton methyl
Suprofos oxon
Parathion ethyl
Profenofos
Ronnel
Temephos
DEF
Merphos
Naptalam
Captafol
Cap tan
Folpet
Allethrin
Permethrin
Pyrethrin coils
Pyrethrum I
Pyrethrum II
Pyrethrins
Resmethrin
Tetramethrin
Limit Type
Numerical
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 - Not Mfg in 1986
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Deep Well
Numerical
Numerical
Reserved - No Data
Numerical
Reserved - Deep Well
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Numerical
Reserved - Not Mfg in 1986
Numerical
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
   7-73

-------
Table 7-10




(Continued)
Structural Group
Pyridine
Pyridine
Pyrimidine
Quinolin
Quinolin
Quinone
Sulfanilamide
Sulfonamide
Thiocarbamate
Cyclopropane
carboxylic Acid
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocyanate
Thiocyanate
Thiosulphonate
Toluamide
Toluidine
Toluidine
Toluidine
Toluidine
Triazine
Multiring Halide
Multiring Halide
Multiring Halide
Multiring Halide
Uracil
Uracil
Uracil
Urea
Urea
PAI #
215
215
132
50
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
254
83
104
PAI Name
Picloram
Picloram, S+E
Fenarimol
Ethoxyquin
Quinolinol sulfate
Dichlone
Oryzalin
Perfluidone
Butylate
Cycloprate
Cycloate
EPTC
Molinate
Pebulate
Vernolate
Le thane 60
Methylene
bisthiocyanate
HPTMS
Deet
Ethalfluralin
Isopropalin
Benfluralin
Trifluralin
Metribuzin
Chlordane
Endosulfan
Endrin
Heptachlor
Bromacil; lithium salt
Bromacil
Terbacil
Chloroxuron
Diflubenzuron
Limit Type
Reserved - No Data
Reserved - No Data
Numerical
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 - Deep Well
Reserved - Not Mfg in 1986
Reserved - Deep Well
Reserved - Deep Well
Reserved - Not Mfg since 1986
Reserved - Not Mfg in 1986
Reserved - Deep Well
Reserved - Not Mfg in 1986
Reserved - No Data
Reserved - No Data
Reserved - No Data
Numerical
Numerical
Numerical
Numerical
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
Numerical
Numerical
No Discharge (closed loop)
Numerical
Numerical
Reserved - Not Mfg in 1986
Reserved - Not Mfg in 1986
   7-74

-------
Table 7-10




(Continued)
Structural Group
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
s-Triazine
Triazine
s-Triazine
s-Triazine
Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
PAI *
119
135
148
168
169
174
237
252
4
8
18
25
33
58
60
142
223
224
226
239
256
257
FAI Name
Diuron
Fluometuron
Linuron
Monuron TCA
Monuron
Norea
Siduron
Tebuthiuron
Vancide TH
Triadimefon
Anilazine
Cyanazine
Belclene 310
Ametryn
Atrazine
Hexazinone
Prometon
Prometryn
Propazine
Simazine
Terbuthy laz ine
Terbutryn
Limit Type
Numerical
Reserved - No Data
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 - No Data
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
   7-75

-------
                              Table 7-11




PAIs AND PAI STRUCTURAL GROUPS WITH PAI LIMIT DEVELOPMENT METHODOLOGIES
Structural Group
2,4-D
2,4-D
Phenoxy acid
Phenoxy acid
Phenoxy acid
Phenoxy acid
Acetanilide
Acetanilide
Acetanilide
Aryl Halide
Terephthalic acid
esters
Aryl Chloride
Benzeneamine
Benzoic Acid
Benzonitrile
Benzonitrile
Bicyclic
Multiring Halon
Carbamate
PAI #
16
16
17
27
30
31
26
54
70
80
110
205
204
53
69
69
123
262
55
PAI Name
2,4-D
2,4-D, S&E
(10)
2,4-DB, S&E
(3)
MCPA, S&E
(4)
Dichlorprop ,
S&E (3)
MCPP, S&E
(4)
Propachlor
Alachlor
Butachlor
Chloroneb
DCPA
PCNB
Pendimethalin
Acifluorfen
Bromoxynil
Bromoxynil
octanoate
Endothall , S&E
(3)
Toxaphene
Aldicarb
Limit Basis
Full -Scale
Data
No
Discharge
No
Discharge
No
Discharge
No
Discharge
No
Discharge
Technology
Transfer
Full -Scale
Data
Technology
Transfer
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
Technology
Transfer
No
Discharge
Full -Scale
Data
Full -Scale
Data
BAT
Technology
SE, CO
DIS/REC/ND
DIS/REC/ND
DIS/REC/ND
ND
DIS/REC/ND
/
AC
AC
AC
CO
AC, BO
AC
IN
SE
AC
AC
ND
AC
HD
Notes
1
2, 8
2, 8
2, 8
2, 8
2, 8
12
1
12
4
4
4
1
1
4
9
2, 8
4
4
                                 7-76

-------
Table 7-11




(Continued)
Structural Group
Carbamate
Carbamate
Carbamate
Carbamate
Chlorobenz amide
Chloropropionanilide
Phthalonitrilic
DDT
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Heterocyclic
Heterocyclic
Heterocyclic
Isocyanate
PAI #
62
75
76
156
39
41
82
158
172
218
219
220
241
243
268
35
175
259
118
FAX Name
Benomyl
Carbaryl
Carbofuran
Me thorny 1
Pronamide
Propanil
Chlorothalonil
Methoxychlor
Nab am
Bus an 85
Bus an 40
KN Methyl
Carbarn- S
Vapam (Metham
Sodium)
Ziram/Cynate
TCMTB
Norflurazon
Dazomet
Nabonate
Limit Basis
Full -Scale
Data
Technology
Transfer
Full -Scale
Data
Full -Scale
Data
Technology
Transfer
Full -Scale
Data
Full-Scale
Data
Full -Scale
Data
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer '
BAT
Technology
HD
HD
HD
HD
AC
BO
BO
CO
CO
CO
CO
CO
CO
CO
CO
HD
AC
CO
CO
Notes
6
13
4
4
7
4
4
4 -
11
11
11
11
11
11
11
10
7
11
11
   7-77

-------
Table 7-11




(Continued)
Structural Group
Benzeneacetic acid
ester
Organo-tin
Phenol
Phosphate
Phosphate
Phosphate
Phosphate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
PAI #
90
192
112
12
22
84
173
52
154
113
126
150
183
185
186
197
212
255
86
PAI Name
Fenvalerate
Organo-Tins
(8)
Dinoseb
Dichlorvos
Mevinphos
Stirofos
Naled
Acephate
Me thami dopho s
Dioxathion
Ethion
Malathion
Disulfoton
Phosmet ,
recrystallized
Azinphos
Methyl
(Guthion)
Bolstar
Phorate
Terbufos
Chlorpyrifos
Limit Basis
Full -Scale
Data
Full-Scale
Data
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
No
Discharge
Technology
Transfer
Full -Scale
Data
Full-Scale
Data
Full- Scale
Data
Technology
Transfer
Full -Scale
Data
No
Discharge
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
BAT
Technology
HD, BO, SE
CO, CL
AC
HD
HD
HD
ND
IN
HD, AC
HD, AC
AC
HD
HD, BO, AC
ND
HD, BO, AC
HD, BO, AC
IN
IN
CO
Notes
4
4
4
4
4
4
16
3
4
4
1
14
4
16
4
4
1
1
1
   7-78

-------
Table 7-11




(Continued)
Structural Group
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorotrithioate
Phosphorotrithioate
Phthalimide
Cyclopropane
Carboxylic Acid
Cyclopropane
Carboxylic Acid
Cyclopropane
Carboxylic Acid
Toluidine
Toluidine
Toluidine
Toluidine
Triazathione
Multiring Halide
Mul tiring Halide
Uracil
PAI #
103
107
133
182
203
236
263
73
208
230,
231
132
125
144
178
264
45
124
140
68
PAI Name
Diazinon
Parathion
methyl
Fenthion
Fensul f o th i on
Parathion
ethyl
DEF
Merphos
Captafol
Permethrin
Pyre thrum I
and II
Fenarimol
Ethalfluralin
Isopropalin
Benfluralin
Trifluralin
Metribuzin
Endrin
Heptachlor
Bromacil
Limit Basis
Full -Scale
Data
Technology
Transfer
Full -Scale
Data
Full -Scale
Data
Full -Scale
Data
Full-Scale
Data
Technology
Transfer
Technology
Transfer
Full -Scale
Data
Technology
Transfer
Full-Scale
Data
Technology
Transfer
Full-Scale
Data
Technology
Transfer
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
Technology
Transfer
BAT
Technology
AC
HD, BO
HD, BO, AC
HD, BO, AC
HD, BO
HD, BO, AC
HD, BO, AC
IN
AC, RA
HD
IN
AC
IN
AC
AC
HD, AC
RA
RA
AC
Notes
4
17
4
4
4
4
15
3
4
10
4
18
4
18
4
4
4
4
7
   7-79'

-------
                                        Table 7-11

                                        (Continued)
Structural Group
Uracil
Uracil
Urea
Urea
Urea
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
FAI Name
Bromacil;
lithium salt
Terbacil
Diuron
Linuron
Tebuthiuron
Triadimefon
Cyanazine
Ametryn
Atrazine
Prometon
Prometryn
Propazine
Simazine
Terbuthylaz ine
Terbutryn
Limit Basis
No
Discharge
Technology
Transfer
Full -Scale
Data
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
Full-Scale
Data
Technology
Transfer
Full-Scale
Data
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
Technology
Transfer
BAT
Technology
ND
AC
AC, BO
AC, BO
IN
HD, AC
HD, BO
AC
HD, BO
AC
AC
AC
AC
AC
AC
Notes
8
7
4
4
4
4
1
5
1
5
5
5
5
5
5
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
                                           7-80

-------
                                        Table 7-11

                                        (Continued)

SE = Solvent Extraction

1.          Mass discharge limitations based on BAT data submitted by the manufacturer.
            Limitations were revised following proposal using new BAT data submitted by
            the manufacturer of this PAI.

2.          Zero discharge achieved through closed loop recycle/recirculation of all
            process wastewater.

3.          Mass discharge limitations developed using the manufacturer's detection limit
            for this PAI and by transferring the average variability factors from
            pendimethalin, phorate, terbufos, tebuthiuron, and fenarimol (Incineration
            Transfer).

4.          Mass discharge limitations based on BAT data submitted by the manufacturer.
            Final mass  discharge limitations equal the proposed mass discharge
            limitations.

5.          Direct transfer of average of atrazine and cyanazine mass discharge
            limitations.

6.          Mass discharge limitations revised following proposal to include carbendazim
            production  rates.

7.          Mass discharge limitations developed using the manufacturer's detection limit
            for this PAI and by transferring the average LTA/MDL ratio and average
            variability factors from ethion, permethrin, alachlor,  diazinon, dinoseb,
            toxaphene,  bromoxynil,  trifluralin (SP5,  monitoring point following the
            activated carbon unit), and PCNB (Activated Carbon Transfer).

8.          Zero-discharge PAI, all water added during manufacture remains with the salt
            product.

9.          Direct transfer of bromoxynil mass discharge limitations.

10.         Mass discharge limitations developed using the manufacturer's detection limit
            for this PAI and by transferring the LTA/MDL ratio and variability factors
            from benomyl (Hydrolysis Transfer).

11.         Direct transfer of average of nabam,  carbarn-S, and dazomet mass discharge
            limitations (Dithlocarbamate Chemical Oxidation Transfer).

12.         Direct transfer of alachlor mass discharge limitations.

13.         Mass discharge limitations developed using a treatability study LTA and by
            transferring the average LTA/MDL ratio and average variability factors from
            aldicarb and methomyl.
                                           7-81

-------
                                        Table 7-11

                                        (Continued)

14.          Mass discharge limitations developed using the manufacturer's detection limit
            for this PAI and by transferring the average LTA/MDL ratio and average
            variability factors from stirofos,  ethyl parathion,  dioxathion, and DBF
            (Structural Group Transfer).

15.          Direct transfer of DEF mass discharge limitations.

16.          Zero discharge achieved through zero water addition or generation during the
            manufacturing processes for this PAI.

17.          Direct transfer of parathion ethyl mass discharge limitations.

18.          Direct transfer of trifluralin mass discharge limitations.
                                           7-82

-------
their BAT treatment  (and  in some cases planned improvements to that treatment)
are: 2,4-D, cyanazine, acifluorfen, alachlor, atrazine, chlorpyrifos,  ethion,
pendemethalin, phorate, terbufos,  triadimefon, dichlorvos, mevinphos,
propanil, metribuzin, aldicarb, bromoxynil, carbofuran, chloroneb,
chlorothalonil, stirofos, fenvalerate, diazinon, DCPA, dinoseb, dioxathion,
diuron, endrin, fenarimol, fenthion, heptachlor, isopropalin, linuron,
methamidophos, methomyl,  methoxychlor, fensulfothion, disulfoton, azinphos-
methyl, the 8 organo-tins, bolstar, parathion-ethyl, PCNB, permethrin, DEF,
tebuthiuron, toxaphene, and trifluralin.

            For another 30 PAIs, zero-discharge BAT limitations have been set.
For 28 of these 30,  zero  discharge is based on either closed loop
recycle/reuse or recirculation of all process wastewater or on the fact that
all water added to the process remains with the salt product.  These 28 (of
the 30) PAIs are: the 10  salts and esters of 2,4-D, 3 salts and esters of 2,4-
DB, 3 salts and esters of dichlorprop, 4 salts and esters of MCPA, 4 salts and
esters of MCPP, 3 salts and esters of endothall, and the lithium salt of
bromocil.  For one PAI, naled, zero-discharge limitations are set based on no
water use in the manufacturing process.  Also, the purification of the PAI
phosmet, by either single or double recrystalization, involves no water use,
and that part of the manufacturing process only is regulated at zero
discharge.

            For one  PAI,  benomyl, the BAT limitations are based on full-scale
data that include carbendazim's production (ie., pounds of PAIs per 1,000
pounds of benomyl and carbendazim produced) since the analytical method does
not differentiate between the two;  data that eliminate the loadings from the
formulating and packaging operations at the facility; and data that account
for additional removals by the end-of-pipe biological treatment system
following hydrolysis.  The remaining 34 PAIs with limitations in the final
rule have their limitations based on technology transfer.  Fourteen of these
34 PAIs received mass limitations by "direct transfer" of mass limitations
(i.e., the numeric production-based mass limitations for one PAI, such as "1 x
10'3 pound of pollutants per 1,000 pounds of product produced," are also
established for a second  PAI based on a direct transfer based on similar
chemical structure and treatability).   These PAIs are: ametryn, prometon,
prometryn, propazine, simazine,  terbuthylazine, and terbutryn from the average
of the mass limitations for atrazine and cyanazine; bromoxymil octanoate from
bromoxynil; propachlor and butachor from alachlor;   merphos from DEF;
parathion methyl from parathion ethyl; and ethalflurin and benfluralin from
trifluralin.

            The remaining 20 (of the 34) PAIs have limitations based on
technology transfer  using data from other PAIs with full-scale BAT treatment
system information but not "directly"  transferring the mass limitations.  For
these 20 PAIs, direct transfers of mass limits were not made because in
general there were no other PAIs that were sufficiently similar structurally
and for which data were available.  EPA did,  however, have information on
which technologies were effective in removing these PAIs.  Therefore,  EPA in
effect transferred data on the level of treatment system performance that
these technologies achieve with respect to other PAIs.  These other PAIs are
not necessarily structurally similar to these 20 PAIs but are susceptible to
treatment by the same types of technologies.   Specifically, the limitations


                                     7-83

-------
for these PAIs were generated by: (1) setting achievable long-term average
(LTA) concentrations for each PAI based on the demonstrated performance for
other PAIs using the same BAT technology; (2) applying average variability
factors for each group by the associated BAT treatment technology; and (3)
determining the production-based mass limitations for each plant and PAI
combination by multiplying the long-term average (annual) flow by the
concentration-based limitation value determined under Parts (1) and (2) and
dividing this quantity by the average production for the specific PAI.

            In evaluating data for PAIs with treatment system performance
data, the Agency noted that those PAIs subjected to similar treatment systems
achieved similar ratios of long-term average effluent concentrations to their
respective analytical method detection limit (the LTA/MDL ratio) .   EPA also
noted that the technology in use at plants with long-term data typically
reduced the PAI concentration to average levels close to the detection limit.
Accordingly, EPA limitations based on transfer of the LTA/MDL ratio require
the same degree of treatment for PAIs with similar treatment systems.   By
knowing the hydrolysis rate, chemical oxidation rate or carbon adsorption
ratio (carbon usage per pound of PAI removed),  the cost for full-scale
treatment can be determined.

            The following describes in more detail the procedure used by the
Agency to determine limitations for PAIs without sufficient full-scale
treatment data.

            The Agency calculated the ratio of the LTA to the MDL for each PAI
with long-term full-scale treatment system performance data.   These data were
also used to determine daily and monthly variability fa cors for each PAI. The
Agency then calculated the average LTA/MDL ratio and average variability
factors for each set of PAIs that use the same treatment technology.  For PAIs
with no full-scale or bench-scale treatability data the long-term mean
effluent concentration level achievable was estimated by the product of the
average LTA/MDL ratio for the set of PAIs and the MDL for the PAI.  The daily
and monthly limitation concentration values for the PAI were then calculated
by the product of the estimated LTM for the PAI and the average variability
factors for each structural group related to the appropriate BAT treatment
technology.

            For a few PAIs subjected to hydrolysis treatment where data were
used to transfer limitations to PAIs without similar chemical structures the
PAI with the highest LTA/MDL ratio and variability of that PAI were used.
Finally, the production-based mass limitations were determined by multiplying
the long-term average flow from the PAI manufacturing process by the
transferred concentration-based limitation value and dividing this quantity by
the average daily production of the PAI.

            For 2 of the 20 PAIs that have limitations based on this
technology transfer methodology, acephate and captafol, the limitations were
based on using the concentration at the  minimum detection level (i.e.,
LTA/MDL ratio = 1),  and transferring the average variability factors based on
full-scale incinerator scrubber water data for the incineration of
pendimethalin, phorate, terbufos, tebuthiuron,  and fenarimol because all
available data from incineration treatment of acephate and captafol were


                                     7-84

-------
reported as not detected.  For four PAIs, norflurazon, pronamide, bromacil,
and terbacil, the BAT limitations are based on using their MDL and multiplying
the average LTA/MDL data and average variability factors from activated carbon
treatment of ethion, permethrin, alachlor, diazinon, dinoseb, toxaphene,
bromoxymil, trifluralin, and PCNB.  For three PAIs, TCMTB, pyrethrin I, and
pyrethrin II, BAT limitations are based on their MDL in conjunction with the
LTA/MDL ratio and variability factors from hydrolysis treatment of benomyl
which has a slower hydrolysis rate than any of these other three PAIs.  (Other
PAIs subjected to hydrolysis treatment hydrolyze either faster than or at
about the same rate as TCMTB, pyrethrin I and pyrethrin II.  Therefore,
transfer of the average LTA/MDL ratio and average variability factors could
overestimate the effectiveness of hydrolysis technology for TCMTB, pyretherin
I and pyrethrin II.)  For one PAI, carbaryl, limitations were transferred from
aldicarb and methomyl using full-scale hydrolysis treatment average LTA/MDL
data and average variability factors.  For nine PAIs (nabonate, nabam, busan
85, busan 40, KN methyl, carbam-S, vapam, dazomet, and ziram),  BAT limitations
are based on transfer of variability factors using full-scale performance data
from one facility and bench-scale treatability test results to demonstrate the
BAT level LTA for all of these nine (dithiocarbamates) PAIs.  For the last of
the 20 PAIs using this technology transfer methodology, malathion, the
limitations were based on its MDL and transferring the average LTA/MDL ratio
and average variability factors from a similar structural group of PAIs,
stirofos, parathion-ethyl, dioxathion, triadimefom, and DEF treated using
hydrolysis.

            A number of PAI limitations were revised for the final rule,  based
on new data received by the Agency.  Specifically, a number of pesticide
manufacturing facilities indicated to EPA in their comments that they are
using treatment systems that are new and improved compared to the systems on
which EPA's proposed regulations were based.  These commenters  provided
additional and supplemental full-scale treatment system data giving updated
results for the pollutant levels that could be achieved using their new or
improved treatment systems.

            The limitations in the final rule were revised for 29 PAIs overall
since proposal.  The 29 PAIs with revised limitations in the final rule are:
2,4-D; cyanazine; acifluorfen; alachlor; atrazine; chlorpyrifos;  ethion;
pendemethalin; phorate; terbufos; acephate; captofol; ametryn;  prometon;
promotryn; propazine; simazine; terbuthylazine; terbutryn; benomyl; pronamide;
bromacil; terbacil; TCMTB; pyrethrin I;  pyrethrin II; propachlor; butachlor;
and norflurazon.

            The bases for the revised limitations for the 29 PAIs are as
follows:  For 7 PAIs (the first 7 the of 29 listed above--2,4-D through
ethion) limitations were revised as a result of new full-scale  data submitted
by manufacturers.  More specifically the limitations, for acifluorfen have been
revised to take into account changes in the production rate and to base
limitations more on additional source reduction rather than solely on
additional treatment.

            Limitations for atrazine and cyanazine are revised based on new
full-scale data supplied by a manufacturer of atrazine and cyanazine for  a
much longer period of time than was previously available (six years versus one


                                     7-85

-------
year).  Those new data show that the treatment system experiences more
variability than was apparent from the earlier data.  Thus, the final
limitations have been increased from the proposed limitations to account for
this higher variability.

            Limitations for 2,4-D are revised based on full-scale data
reflecting the use of a solvent recovery system.  Limitations are revised for
alachlor based on long-term full-scale data submitted after the proposal by a
manufacturer.  These full-scale data replace the treatability study data used
at proposal.  Limitations for ethion were also revised based on the submittal
of full-scale BAT treatment data following the proposal.  At proposal, EPA
lacked full-scale long-term data and therefore had proposed limitations for
ethion based on a transfer of the limitations set for other pollutants.  The
final limitations for ethion are based on these new data and not on BAT
technology transfer as was proposed.  The final limitations are greater than
the limitations that were proposed for ethion.

            The average LTA/MDL ratio and average variability factors used to
calculate the proposed transferred limitations for ethion were based on both
full-scale and bench-scale data for PAIs that are treated by activated carbon.
EPA notes that when these values are recalculated to consider only cases in
which full-scale treatment data are available, the recalculated limitations
are approximately equal to the final limitations for ethion, which are based
on full-scale data.  The agreement of these values serves to validate this
methodology for deriving transferred limitations in the other cases in which
it was  used (e.g., in the cases of bromacil and terbacil, for which data from
structurally similar PAIs were not available).  Limitations for pendimethalin
have been revised to reflect the higher flows based on treatment by two
incinerators because both can and do operate at the same time. Limitations for
phorate and terbufos are revised to account for higher flows per production
unit than originally considered1.  The limitations for chlorpyrifos are revised
based on submittal of longer term full-scale treatment data.

            For seven PAIs, ametryn, prometon, prometryn, terbutryn,
propazine, simazine, and terbuthylazine, EPA transferred data on BAT level
removals  from PAIs atrazine and cyanazine.   These technology transfers, at
the time of proposal, were supported by EPA and industry treatability tests.
Limitations in the final rule are revised based on using the new full-scale
data for atrazine and cyanazine discussed above.

            The limitations for benomyl are revised to account for the fact
that much of the benomyl-containing wastewater not currently treated in the
in-plant hydrolysis treatment system is formulating/packaging process
wastewater rather than manufacturing process wastewater; to account for more
of the  production of the the intermediate, carbendazim, which is treated by
the in-plant hydrolysis treatment and cannot be distinguished from benomyl by
the current analytical methods; and to include additional removals by the end-
of- pipe biological treatment system that were not considered in the proposed
regulations.  Limitations for TCMTB, pyrethrin I, and pyrethrin II were also
revised based on transfer of the BAT treatment data on hydrolysis from benomyl
and using the LTA/MDL ratio and variability factors data.  Two PAIs, butachlor
and propachlor, have limitations revised based on new full-scale data
submitted on alachlor.


                                     7-86

-------
            At proposal, EPA derived achievable concentration levels by using
bench-scale treatability study data for activated carbon treatment for three
PAIs, (alachor, butachlor, and propachlor).  The new full-scale data submitted
on the BAT treatment of alachlor  (discussed above) have also been used to set
limits for these two other,  structurally similar PAIs manufactured at the
same plant and treated in the same treatment system (those two PAIs, butachlor
and propachlor were not at full production during the time the new data were
collected, so performance data for those PAIs could not be obtained).   In
addition, the Agency deferred establishing final limitations for one PAI,
glyphosate salt.

            The proposed limitation for glyphosate salt, which is a product
manufactured from another PAI, glyphosate, was zero discharge.   At proposal,
there were insufficient data to establish limitations for glyphosate,  however,
the portion of the manufacturing process which gave glyphosate salt had no
discharge.  Thus zero-discharge limitations were proposed for that portion of
the process.  Since proposal, the manufacturer has significantly changed the
manufacturing process in order to reduce overall pollutant releases to all
media.  However, unlike the previous process, the new process that produces
glyphosate salt has a water discharge.   New information was submitted
following the proposal, reflecting effluent levels following biological
treatment of the total process wastewaters.  After reviewing the effluent
data, EPA cannot determine whether the data represent BAT level treatment or
whether other control technologies should be identified as BAT.  Because there
was insufficient time to conduct additional treatment studies, and because
this PAI (and its salt) has low toxicity, regulation is being deferred at this
time.

            Based on the reevaluation of the data set for use in transferring
variability factors for ethion, discussed above, EPA revised the limitations
transfer procedure to eliminate using variability data from treatability
studies for activated carbon.  This revised procedure resulted in final
limitations for four PAIs (bromacil, terbacil, norflurazon, and pronamide)
that are higher than the proposed limitations for those four PAIs.

            In addition, the Agency proposed effluent limitations requiring
zero discharge of process wastewater pollutants for 37 pesticide active
ingredients (PAIs) based on total recycle and reuse of all process wastewater
for 29 PAIs, no water use for 1 PAI, all data reported as "not detected" for 2
PAIs, no current discharge for 2 PAIs (one of which was biphenyl) ,  and EPA' s
estimated lowest cost treatment of off-site disposal by incineration for 2
PAIs.   Also,  the Agency proposed requiring zero discharge of process
wastewater pollutants for the purification of phosmet by re-crystallization
based on recycle/reuse of all water, which was the only part of the phosmet
manufacturing process for which the Agency proposed any limitations.

            Commenters stated that the data reported as "not detected" were
measured by current analytical methods,  and show only that the pollutant
levels were below the detection limit;  the data do not necessarily show "zero
discharge."  Further, today's methods may eventually be replaced by methods
with lower detection limits, and so a "non-detect" value today may show up as
a detectable (measured) value in the future.   The Agency agrees with these
comments.  Commenters also stated that achieving zero discharge to surface


                                     7-87

-------
waters involves an increase in total plant discharges to other  media,  such as
air emissions or solid waste disposal if the process wastewater cannot be
reused effectively.  The Agency generally agrees that this could be the case
in some circumstances.

            Therefore, EPA has revised its determination of the PAIs that
should be subject to a zero-discharge limitation.   As proposed, the final rule
promulgates zero-discharge limitations for the 28  PAIs as to which zero
discharge was based on total recycle and reuse of  all process wastewater and
for the one PAI that is manufactured without water and a no water use portion
of the process for one other PAI.   For 5 PAIs (of  the 29 PAIs with revised
limitations), acephate, captafol,  norflurazon, pyrethrin I, pyrethrin II for
which EPA proposed a "zero discharge" requirement  based either on data that
were below the current detection limit,  no current discharge, or off-site
disposal, EPA is promulgating numeric limitations  in response to comments.  To
derive these limitations, EPA used the technology  transfer procedures
described above (utilizing LTA/MDL ratios and average variability factors)
since performance data were unavailable (all data  were below the current
detection limit or there was no treatment or there was no treated effluent
because the wastewaters were transported off-site  for disposal).

            Norflurazon was discussed previously as having revised limitations
based on transfer of data from other PAIs treated  with activated carbon;
pyrethrin I and pyrethrin II, discussed earlier, have limitations based on
hydrolysis treatment of benomyl;  and acephate and  captafol have revised
limitations based on the transfer of full-scale incinerator scrubber
wastewater discharge data.  As discussed previously, regulation of glyphosate
salt has been deferred and the last of the proposed zero-discharge PAIs,
biphenyl, as discussed previously, has been dropped from coverage of this
rule.

7.5.3       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 achievability of costs to implement the best treatment
technologies for new plants is considered when setting NSPS limitations.  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 will 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 limitations for new PAIs.  However, EPA
is setting NSPS limitations for all the PAIs which are covered by BAT
limitations.

            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
                                     7-88

-------
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 and PSNS,  the
Agency investigated trends in reduction of contaminated wastewater discharges
by newer manufacturing facilities.  The Agency compared wastewater generation
and discharge practices at these more recently built (i.e., newer) pesticide
manufacturing plants with those at older plants.  Specifically, EPA looked at
the practices for manufacturing PAIs for which BAT regulations are being
promulgated, most of which are produced at the older plants.  The Agency
compared the practices at the older plants to those practices used for similar
production processes at the more modern plants.   That is,  the comparison
involved a similar production process at the newer plant but not necessarily
production of the same PAI.  In many cases, the comparison was to the
production of a PAI that is not covered by the final regulations due to lack
of an analytical method for the new PAI and lack of BAT treatment performance
data.  The Agency found that an average wastewater volume flow reduction of
28% has been demonstrated at the newer facilities for similar production
processes.  This flow reduction has been achieved by increased recycle/reuse
of wastewater and, in many cases, specific identifiable source reduction
steps, such as increased source segregation of process streams to allow for
more direct recycle within the process, and increased use of closed loop
recovery systems with or without treatment.

            The flow reduction evaluation consisted of reviewing the
questionnaire responses to determine contaminated wastewater' discharge flow
rates and process age; comparing process wastewater discharge rates for each
facility with their pesticide process starting and last modification dates for
the PAI production process; and normalizing the discharge volume by dividing
it by the annual PAI production volume.  Although this analysis revealed a
flow reduction trend, the dates reflected plant level startup or modification
rather than startup of individual processes;  these data were therefore too
general to be used.  A second evaluation looked at overall industry data
comparing the 1977 and 1986 Manufacturers' Census.  However, this method of
evaluation also proved to be too general to be satisfactory since there was
not sufficient process identification with respect to changes reflected in the
different flow levels.  The final evaluation method consisted of identifying
which PAI manufacturing processes were in operation in 1986 that were  not in
operation during 1977, using the Manufacturers'  Census for both years.
Metallo-organic pesticides processes were excluded since they were required to
meet zero discharge by the 1978 BPT rules and their process water needs are
significantly different from those of organic pesticides processes.

            Certain PAI processes (for organic pesticides) were also excluded
from the analysis because they are associated with unique  wastewater
generation characteristics.  Excluded were those processes which manufacture
PAIs from other registered PAIs,  either through the amination or
esterification of 2,4-D compounds, bromacil,  bromoxomyl, pentachlorophenol,
endothall, or glyphosate,  or through the purification of hexazinone, phosmet
or malathion.  Also excluded were instances where process  wastewater was
disposed of primarily by deepwell injection or incineration since deepwell
disposal does not provide much of an incentive to reduce flows,  and the
                                     7-89

-------
incinerator flows represent scrubber water flows which cannot be further
reduced on a daily discharge basis.

            Out of a total of 36 processes (at 29 facilities) that were
started-up since 1977, 25 processes (at 23 facilities) were identified in the
flow per unit production analysis as "new plants".  Two analyses of flow per
unit production were made: first, all wastewater discharge volumes to
treatment for each process were totaled to determine flow rates per process;
and second, those wastewater discharges which resulted from specifically
identified and quantified contact process streams (excluding scrubber
blowdowns, stripper or distillation overheads, and contaminated stormwater)
were totaled to estimate total discharge volumes from segregated, PAI-
contaminated streams.  While contaminated stormwater may also contain PAIs, it
was excluded from the second analysis because control of stormwater reflects
housekeeping and facility design more than process design.

            Between the "Old" and "New" plants, there is a difference in total
wastewater discharges of 0.44 (from 1.55 to 1.11) gallons per pound of PAI
produced, representing a 28% reduction in flow.  The difference between
discharges of contact wastewater are even greater - - this analysis suggests
that in newer processes only 52% of all wastewater discharged results from
unsegregated process streams, as opposed to 70% in older facilities.  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.  However, not included in this analysis was a determination of the
degree of segregation between contact streams resulting from pre-PAI formation
steps and post-PAI formation steps in the processes, a practice which is also
more common in the newer facilities.  Selective treatment, using PAI
destruction/removal technologies of only contaminated wastewater streams could
also reduce the flow to and therefore the cost of PAI treatment processes.

            Based on these flow reduction data, it is evident that newer
facilities have redesigned their processes and minimized their flows in
significant ways compared to older facilities.  Moreover, a number of
manufacturers have provided evidence that even since the time of EPA's
information collection for this rulemaking, plants have been doing more to
achieve a reduction in effluent flow volume.   Specifically, in their comments
on the proposed regulations, two companies provided information on flow
reduction measures (resulting from source reduction practices) that have been
implemented at three existing plants since 1990.  Four other commenters gave
details of their intentions to implement further source reduction measures to
achieve flow reduction in t;he near future at four facilities.

            EPA's finding that a 28% average flow reduction has been achieved
at newer plants is based not just on reducing the volume of water used in the
production process, but also on source reduction techniques that reduce the
mass of pollutants in the effluent.  These source reduction techniques reduce
both the volume of effluent and the mass of pollutants discharged.  There are
a number of different ways in which the newer generation of plants are already
achieving source reduction.  Some examples are presented below (these examples
reflect techniques that have actually been employed at one or more of the
                                     7-90

-------
newer generation of existing plants, as reflected in the record for this
rulemaking):

            - Redesign  (reordering) of the steps undertaken to manufacture
            PAIs can reduce the overall amount of solvents and water needed in
            the production process as reaction and carrier media.  This leads
            to a lower  amount of spent solvents and wastewaters that need to
            be disposed of;

            - New facilities can be designed to reduce the amount of piping
            between chemical process reactors and other equipment, such as
            storage tanks.  Newer plants have the opportunity to locate
            pesticide chemical reactor vessels and other equipment closer
            together to reduce the amount of piping.  Because there is a
            smaller amount of piping to wash periodically, there is a smaller
            volume of effluent generated due to equipment washing and a
            smaller mass  of pollutants in the effluent;

            - Solvents  rather than water can be used to perform equipment
            washing.  Generally, solvents are much more effective than water
            at washing  because they absorb much greater levels of impurities
            (the solubility levels of pollutants in solvents are usually much
            higher than they are in water).  Therefore, lower volumes of
            solvents can be used for equipment washes compared to water, and
            the solvents  can be reused to a much greater degree than wash
            water can.  Further, solvent washes that are no longer usable may
            be burned (i.e., used as a fuel).  Contaminated water from
            equipment washes, however, has very little fuel value and can be
            incinerated only at a high cost.  Equipment wash water therefore
            is more likely to have been discharged by older plants.   (Because
            older plants may not have been designed and equipped to cope with
            flammability  and explosion concerns that may be present when using
            solvent washes, they may have no choice but to use water rather
            than solvent washes.); and

            - The manufacturing equipment can be designed and configured at
            newer plants  to lead to greater recovery of equipment wash water
            and spills  of reaction materials before they are contaminated,
            either through contact with the ground or through commingling with
            other wastestreams.   Therefore, a greater portion of these flows
            can be reused rather than discharged (impurities introduced into
            these flows from ground contact or from commingling can render
            them unfit  for reuse).

            Moreover, even without employing source reduction practices,
reducing the volume of water itself will lead to a related reduction in the
mass of pollutants discharged because of more efficient wastewater treatment.
It may well be that some water (or even source) reduction will,  in some cases,
lead to an increase in  the pollutant concentration in wastewaters (for
example, where process wastewater streams are segregated from non-contact
streams, reducing dilution of the process wastewater streams).   However, in
such cases, because the volume of wastewater has been reduced,  the treatment
systems can be operated more efficiently and will ultimately remove  a larger


                                     7-91

-------
overall portion (mass) of the pollutants in the wastewaters than was removed
prior to flow reduction.  The data in fact show that the BAT control
technologies, when properly operated, will generally reduce the level of
pollutants to similar concentrations both before and after flow reduction.
This phenomenon holds true for all of the control technologies identified in
this rule as BAT technologies (i.e., hydrolysis, activated carbon, chemical
oxidation, and biological treatment).

            For example, assume that a unit of PAI production generates 1,000
gallons of wastewater with 100 ppb of pollutant, and that the control
technology will reduce this level of pollutant to 1 ppb in the effluent.  If
the flow were reduced to 750 gallons of wastewater and the mass of pollutants
were not reduced,  the concentration of pollutants in the influent would
increase to 133 ppb.  The data show, though,  that after treatment, a level of
approximately 1 ppb can still be achieved in the effluent due to more
efficient operation of the treatment system.   As a result, a greater mass of
pollutants has been removed by treatment in the latter case.

            Therefore, to set NSPS limitations for PAIs, EPA used the BAT
limitations and applied a 28% wastewater flow reduction to arrive at the mass-
based NSPS (except as described below for three PAIs).   This flow reduction
was applied where  BAT limitations are based on the flows at older facilities
(of course, where  the BAT is a zero-discharge limitation, NSPS is also set at
zero discharge) .   At proposal there were two PAIs (carbofuran and DEF) with
non-zero BAT limitations that were being produced at the more modern plants
(also, limits for  a third PAI, merphos, were based on technology transfer from
DEF, one of the other two).  Because these are newer plants,  EPA assumes that
they have both achieved flow reductions of at least 28% compared to older
plants.  Because there were insufficient data to quantify further flow
reductions that might be possible, EPA proposed to set the NSPS limits for
these three PAIs equal to the BAT limits.   EPA received no further
information from commenters on this approach for these three PAIs, and
therefore the final NSPS limits for these PAIs are being promulgated as
proposed.

7.5.4       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
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 27,000 pounds of PAIs and
22,000 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


                                     7-92

-------
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
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.

            As described in more detail below with respect to the priority
pollutants, two OCPSF rulemaking notices describe additional pass through
considerations that were recently evaluated by EPA with respect to the OCPSF
pollutants (57 FR 56883, December 1, 1992, and 58 FR 36872, July 9, 1993).  As
explained there, EPA initially found that removals  of two OCPSF priority
pollutants were greater at BAT plants than at POTWs.  Subsequently, EPA
determined that this conclusion was strictly an artifact of lower influent
levels at the POTWs -- i.e., the removals from these low levels down to the
analytical minimum level appeared to be less than the removals by BAT plants,
even though the actual removals by POTWs and BAT plants might be about the
same.  In light of this artifact of the removal calculations, and a chemical
and engineering analysis focusing on the high biodegradability of these two
priority pollutants, the Agency concluded that these two priority pollutants
do not actually pass through POTWs.

            Even under these additional pass through considerations,  EPA
continues to conclude that all of the 120 PAIs being regulated in this
rulemaking do pass  through POTWs.   As described above,  to compare removals at
well-operated POTWs versus BAT-level plants, EPA relied on laboratory data to
estimate the removal of POTWs.  These were controlled experiments that were
not subject to the  low influent concentrations that may be present in the case
of actual full-scale data at POTWs.  In fact,  as noted,  EPA believes that
these laboratory data were optimistic in that they tended to overestimate the
removals of the PAIs at well-operated POTWs.  Therefore,  there is no basis for
altering EPA's findings under the traditional pass through methodology that
these PAIs do pass  through POTWs.

            In addition to pass-through, may 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


                                     7-93

-------
operational problems at the POTWs (a more detailed analysis is presented in
the public record - DCN 4002).

7.5.5       Calculation of Effluent Limitations Guidelines Under PSES and PSNS

            Based on the results of the pass-through analysis, EPA is
promulgating 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
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.  In the final rule, PSES limitations are 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,
and zero discharge for selected PAIs.  This option is economically achievable
and greatly reduces pollutants discharged into the environment, since
pollutants not recycled or reused are destroyed by treatment.   As with BAT and
NSPS, Option 2 is rejected because of its economic unachievability and the
significant cross-media implications of the transfer of pollutants off-site
for treatment of the total wastewater volumes.

            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 for PAIs 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 discussed previously for BAT, NSPS, and PSES are
available as the basis for PSNS.  PSNS for Subcategory A are based on the PSES
technologies,  modified to reflect the flow reduction capable at most new
facilities.  EPA also considered the zero-discharge option, but it was
rejected for the same reasons as under NSPS (i.e., its economic
unachievability and the cross-media pollution impacts).

7.6         EFFLUENT LIMITATIONS DEVELOPMENT FOR PRIORITY POLLUTANTS

            This section discusses the development of effluent limitations
guidelines and standards for priority pollutants discharged in Subcategory A
wastewaters of the pesticide chemicals manufacturing industry.  As discussed
in Section 14, EPA is reserving further regulations for priority pollutants in
Subcategory B wastewaters.

            The final rule contains effluent limitations for 28 priority
pollutants.  For 23 of these 28 priority pollutants,  EPA is relying on the


                                     7-94

-------
OCPSF database to set limitations that are identical to the limitations set
for these pollutants in the OCPSF guidelines.  For four other priority
pollutants, which are the brominated priority pollutants, and were not
regulated under the OCPSF guidelines, there are no treatment performance data.
Thus EPA is using limitations set in the OCPSF guidelines for other priority
pollutants that are deemed to have similar "strippabilities".   Final
limitations for these pollutants are based on the average data for each
subgroup of volatile organic priority pollutants, with respect to
"strippability."  This is the same procedure used in the OCPSF rulemaking for
developing limitations when performance data were lacking for certain priority
pollutants.  Final limitations for one priority pollutant, cyanide, are based
on actual long-term full-scale data from pesticide and organic chemicals
manufacturing facilities.

            For the 23 priority pollutants for which the Agency is
transferring BAT limitations from the OCPSF category, the basis for this
transfer is the similarity in wastewaters, other than the PAIs which are
usually removed from the wastewaters prior to treatment for the priority
pollutants.  As discussed earlier in Section 3, at least 46 of the 75
pesticide chemicals manufacturing facilities also manufacture compounds
regulated under the OCPSF category.  Typically, wastewaters from the pesticide
manufacturing processes are commingled with OCPSF wastewaters generated at the
site and treated in the same end-of-pipe 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.

7.6.1       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 pesticide
chemicals manufacturing,  and that these streams are commingled and treated
with OCPSF wastewaters.  Therefore, the BAT limitations for these 23
pollutants are being directly transferred to the pesticide chemicals
manufacturing category as BAT effluent limitations guidelines.  Four priority
pollutants (bromomethane,  tribromomethane, bromodichlormethane, and
dibromochloromethane),  detected at significant concentrations  in pesticide
manufacturing wastewaters, were not regulated under the BAT limitations for
the OCPSF category.  The final rule sets BAT effluent limitations for those
four pollutants by transferring OCPSF limitations reflecting the average data
within the grouping of volatile pollutants that have similar strippabilities.
BAT limitations for cyanide are based on treatment data from pesticide and
OCPSF manufacturing facilities.

            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.   In the OCPSF rulemaking, for


                                     7-95

-------
the volatiles limited in 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
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, and the OCPSF Technical Development Document, EPA 440/1-87/009, 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.

            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 setting limitations for BAT  and
NSPS 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 set in the


                                     7-96

-------
final rule for pesticide chemicals 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.

            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 promulgated for volatile pollutants.

            As explained above, the final 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 "Subpart J"
                                     7-97

-------
limitations) and a different, generally more stringent set of limitations for
those plants that do (the OCPSF "Subpart I" limitations).

            This methodology for setting limitations was challenged in the
OCPSF litigation, and the court remanded the issue to EPA.  EPA's recent
response to the OCPSF remand explains in detail the Agency's reasons for
adopting this approach (58 FR 36881-85 and supporting record).  The Agency
explained there that it is not feasible, necessary or desirable to eliminate
or limit the applicability of the non-EOP biological treatment limitations for
priority pollutants.  EPA stated its belief that the Clean Water Act does not
require the Agency to develop a scheme that is not technically defensible and
which would create undesirable treatment incentives within the regulated
community.

            EPA also discussed three alternatives to EPA's scheme that were
suggested in the litigation.  The first suggested alternative was to develop a
BOD5  "floor"  (i.e.,  a minimum BOD5 level) to limit the applicability of the
non-EOP biotreatment limitations.  EPA found,  however, that the development of
a floor would be technically infeasible due to the lack of a theoretical
minimum BODS  level  for  sustaining biological treatment and the  great
variability of OCPSF production and wastewater characteristics.  These reasons
generally hold true with respect to the pesticides manufacturing industry as
well.  Although a given pesticides manufacturing plant may be able to operate
a biological system at a certain long-term average BOD3 level,  that does  not
assure that another plant with the same long-term average BODj  level, but with
a different waste stream composition or varying BOD5  levels, will  also be able
to operate a biological system.  In addition,  plants that need to achieve
significant BOD5  reductions  will  generally  be motivated by economic
considerations to install biotreatment systems over the more costly
alternatives.  Moreover,  as explained in the OCPSF preamble, EPA believes that
a BOD5  floor  would  be undesirable in that it would  likely result  in irrational
and undesirable wastewater treatment and waste management decisions (i.e., it
would create incentives to maximize BOD3 loads  at the end-of-pipe).

            The second alternative suggested was that EPA limit the
applicability of the non-EOP biotreatment limitations to those processes for
which there has been an adequate showing of low-BOD5  wastewater.   In  fact,  low
BODj  wastewater seldom  occurs in  the pesticides manufacturing  industry.    In
any event, as noted, there are only two direct discharger plants that do not
have EOF biological treatment and therefore will be subject to the non-EOP
biological treatment limitations on priority pollutants, and EPA expects few
new sources to be built that will manufacture the regulated PAIs.

            The third alternative was that EPA could eliminate the non-EOP
biotreatment limitations and address low-BOD5 situations through  fundamentally
different factors ("FDF") variances (or maintain the limitations but apply
them only where a site-specific showing of necessity is made).  (FDF variances
are not available to new sources.)  As discussed in the OCPSF preamble,
however, maintaining the option of non-EOP biotreatment limitations is
desirable in that it encourages source control and other in-plant waste
management techniques.   EPA's decision to provide two sets of limitations
instead of accounting for low BOD5  through  the  FDF  process is  a rational
exercise of, its discretion under the Act.


                                     7-98

-------
            EPA notes that setting less stringent limitations in these
regulations for plants without EOF biological treatment will result in
virtually no actual increase in priority pollutant discharges to surface
waters.  There are only two direct discharging pesticide chemicals
manufacturing plants that will be subject to the non-EOP biological treatment
limitations.  One of these plants incinerates all of its wastewaters; since
only scrubber wastewater remains, there would be nothing left to treat in a
biological treatment system.  The second plant has very low loadings of
priority pollutants after applying BAT physical/chemical treatment
technologies.  Both of these facilities also perform some recycling/reuse of
either non-wastewater streams or wastewater streams.  Together,  EPA estimates
that these two plants will discharge less than one pound per year of priority
pollutants to surface waters after meeting the non-EOP biological treatment
limitations on priority pollutants.   Imposing limitations on the second plant
based on EOP biological treatment would remove only a trivial additional
amount of priority pollutants.

            The final 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
limitations, one for plants that use end-of-pipe biological treatment and one
for plants that do not.  Some pesticide chemicals manufacturers  fall into each
category.  The final rule contains this approach in order to be  consistent
with what was promulgated (and now recently reaffirmed) for the  OCPSF point
source category.  Moreover, consistency with the OCPSF regulations is
necessary in some cases to avoid having two different sets of limitations (and
regulatory approaches) applicable to the same pollutant being discharged by a
single combined OCPSF/pesticides plant.

            EPA notes that there are two priority pollutants (2-chlorophenol
and 2,4-dichlorophenol) for which limitations are included for plants that use
end-of-pipe biological treatment but for which limitations are not included
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 included for plants without end-of-pipe
biological treatment because of a lack of treatability data and  because a
transfer of limitations was not possible (see the OCPSF Technical Development
Document, Section 7).

            In this final rule for pesticide 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 limitations.

            EPA concluded in the December, 1991 OCPSF re-proposal and in the
July 9,1993 final amendments 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


                                     7-99

-------
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
final rule .

            Brominated Organic Pollutants

            Four priority pollutants (bromomethane ,  tribromomethane ,
bromodichlorme thane ,  and dibromochlorome thane ), detected at significant
concentrations in pesticide manufacturing wastewaters, were not regulated for
BAT under the OCPSF category.  This final rule contains BAT effluent
limitations for those four pollutants using as a basis the transfer of OCPSF
limitations based on the average data within groups  of volatile pollutants
that have similar strippabilities.

            Of the four brominated organic compounds found in pesticide
manufacturing process wastewaters, 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 one or more were detected in 7 of 23 EPA sampling episodes
between 1988 and 1990.

            Under the OCPSF methodology, volatile priority pollutants were
divided into high and medium strippabilty groups based on the Henry's Law
Constants.  For each strippability group, a LTA concentration was developed
based on the volatile priority pollutants where steam stripping effluent data
were available.  The LTA concentration for pollutants with no data in each
strippability group was determined by the highest of the LTAs within each of
the strippability groups, based on the 15 pollutants for which the Agency had
data.  Following this methodology, the Agency obtained a high strippability
LTA of 64.5 Mg/L and a medium strippability LTA of 64.7
            For the purpose of transferring variability factors (VFs) ,  the
Agency maintained the separation of volatile priority pollutants into the high
and medium strippabilty groups.  For each subgroup, the Agency averaged the
VFs for those pollutants with data in that subgroup and transferred these
average VFs to the volatile priority pollutants without data in that subgroup .
The average VFs are 5.88383 (daily max VF) and 2.18759 (monthly max avg VF)
for the high strippability group and 12.2662 (daily max VF) and 3.02524
(monthly max avg) for the medium strippability group.

            Based on comparisons of Henry's Law coefficients for the
brominated priority pollutants with other volatile priority pollutants which
were regulated under OCPSF, it appears that all of the brominated priority
pollutants may be removed by steam stripping.  Two of them, bromomethane and
bromodichloromethane, are identified as "highly strippable" under the criteria
utilized during OCPSF compliance costing, while the other two,
dibromochoromethane and tribromomethane ,  are identified as "medium
strippable."  Following the OCPSF methodology for transferring the average LTA

                                     7-100

-------
concentration and average VFs to pollutants within the same strippabilty
subgroups, limitations were developed for the four brominated priority
pollutants:
Brominated Priority
Pollutant
Bromome thane
Bromodichlorome thane
Tribromome thane
Dibromochlorome thane
Henry's
Law
Constant
8.21
0.10
0.023
0.041
Strippatillty
Group
High
High
Medium
Medium
Effluent Limitations
Daily
Max
380
380
794
794
Monthly
Max Avg
142
142
196
196
            Lead

            The final rule applies only to non-complexed lead-bearing
wastewaters generated by organic pesticide chemical manufacturing processes.
The OCPSF rule set a concentration-based limitation on lead, to be applied
only to the flows discharged from metals-bearing process wastewaters (see 58
FR 36872).  Compliance could be monitored in-plant or, after accounting for
dilution by nonmetal-bearing process wastewater and non-process 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 final 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
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,
                                     7-101

-------
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 generally 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).

            Cyanide

            The final limitations for cyanide apply only to non-complexed
cyanide-bearing wastewaters generated by organic pesticide chemical
manufacturing processes.  For cyanide,  the discharge quantity (mass) shall be
determined by multiplying the concentrations listed in the applicable tables
in this subpart times the flow from non-complexed cyanide-bearing waste
streams for total cyanide.  Discharges of cyanide in cyanide-bearing waste
streams are not subject to the cyanide limitation and standards if the permit
writer or control authority determines that the cyanide limitations and
standards are not achievable due to elevated levels of non-amenable cyanide
(i.e., cyanide that is not oxidized by chlorine treatment) that result from
the unavoidable complexing of cyanide at the process source of the cyanide-
bearing waste stream and establishes an alternative total cyanide or amenable
cyanide limitation that reflects the best available technology economically
achievable.  The determination must be based upon a review of relevant
engineering, production, and sampling and analysis information, including
measurements of both total and amenable cyanide in the waste stream, based on
the foregoing information, and its impact on cyanide treatability shall be set
forth in writing and, for direct dischargers, be contained in the fact sheet
required by 40 CFR 124.8.

            These final limitations 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 manufacturing facilities,
along with effluent data from one pesticides manufacturing facility with
biological treatment only.  The effluent data are:
                                     7-102

-------
Plant Type
A
A
A
B
B
B
B
B

Treatment
BO .
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
GO/BO

# Analyses (# > MDL)
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
B - Organic Chemical Manufacturing Plant  CO
                                 - Biological Oxidation
                                 - Chemical Oxidation
7.6.2
Calculation of Effluent Limitations Guidelines Under NSPS
            The final rule contains NSPS limitations set 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.
7.6.3
Calculation of Effluent Limitations Guidelines Under PSES
            To evaluate the need for PSES for the priority pollutants,  EPA is
relying on the methodology and analysis originally done to support the OCPSF
regulations and the revised pass through analysis completed for the amendments
to the OCPSF regulations as a result of the remand.  (See Section 6 of the
October 1987 OCPSF Technical Development Document, Section III of the May 1993
Supplement to the Technical Development Document, and 58 FR 36872, July 9,
1993).

              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
                                     7-103

-------
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
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 originally showed
that 21 of those 23 priority pollutants pass through; the only priority
pollutants of those 23 that were determined not to pass through were
2-chlorophenol and 2,4-dichlorophenol. As described below,  and in more detail
in a later OCPSF rulemaking (58 FR 36872),  EPA has now determined that two
more priority pollutants, phenol and 2,4-dimethylphenol, also do not pass
through a POTW.

            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.

            The number of priority pollutants that are covered by the final
PSES regulations is based on EPA's pass-through methodology as described in
two OCPSF rulemaking notices published on December 1, 1992 (57 FR 56883) and
July 9, 1993 (58 FR 36872) (the "OCPSF notices").  A detailed description of
this methodology is contained in the OCPSF notices (at 57 FR 56886-87 and
58 FR 36885-88).

            Those notices explain the following:  In general, EPA is
continuing to apply its traditional pass-through methodology, which considers
the median percent removals of a pollutant by direct dischargers and by POTWs
to determine pass through.  This approach has been upheld in litigation as an
appropriate, conservative means of determining pass through (CMA v. EPA. 870
F.2d 177, 243-48 (5th Cir. 1989)) and EPA continues to believe it is the
correct approach as a general matter.  However, the traditional approach is
overly conservative for two priority pollutants, phenol and 2,4-
dimethylphenol.  EPA's analysis focused first on the data relating to phenol
removals.  A comparison of median removals by BAT technologies and at POTWs
indicated that phenol and 2,4-dimethylphenol do pass through POTWs.  It became
apparent, however, that the pass-through conclusion was strictly an artifact
of the higher influent concentrations for direct dischargers in EPA's
database.  (Specifically, the calculated removals from lower influent
concentrations at POTWs down to the analytical minimum level are less than the
calculated removals from the higher influent concentrations for direct
dischargers down to the analytical minimum level, even though the POTWs and
direct dischargers might actually be achieving about the same removals.)  The


                                     7-104

-------
OCPSF notices state that viewing the data as a whole, EPA found that POTWs
appear to achieve removals of the phenols that are essentially equivalent to
those achieved by direct dischargers.

            As also explained in the OCPSF notices, a chemical and engineering
analysis indicates that the two phenols are highly biodegradable due to their
simple chemical structures, and EPA finds that a pollutant's estimated
biodegradation rate is the best theoretical indicator of whether it will pass
through POTW biological treatment systems.  Under all the above
considerations, EPA concluded that phenol and 2,4-dimethylphenol do not pass
through POTWs.  EPA's decision to modify its traditional pass-through
methodology for phenol and 2,4-dimethylphenol was based on the Agency's
conclusion that both the data available for these two pollutants and the
chemical and engineering analysis performed by EPA indicate that the
traditional pass-through methodology is overly conservative for these
pollutants.

            For the pesticides manufacturers' rulemaking, EPA had proposed to
set categorical pretreatment standards for 26 priority pollutants,  including
phenol and 2,4-dimethylphenol, based on a determination that they pass through
POTWs.  However, in the notice published on December 1, 1992,  EPA indicated
that for both the OCPSF and pesticides manufacturers rulemakings,  the Agency
was considering not setting pretreatment standards for phenol and 2,4-
dimethylphenol for the above reasons.  In the notice published on July 9,
1993, EPA finalized its decision not to set pretreatment standards for phenol
and 2,4-dimethylphenol in the OCPSF rulemaking.  In today's final pesticides
manufacturers' rule, consistent with the OCPSF rule, EPA has similarly deleted
these two pollutants from the list of pollutants that are covered by
pretreatment standards.  For the reasons articulated more fully in the
December 1, 1992 and July 9, 1993 notices, EPA has determined for today's
final rule that phenol and 2,4-dimethylphenol do not pass through POTWs.

            Therefore, the final rule sets pretreatment standards for 24
priority pollutants instead of 26 pollutants as proposed.  As the proposal
indicated, EPA has determined under its traditional pass-through methodology
that these 24 pollutants do pass through POTWs.  Further, even under the
additional pass-through considerations described above, EPA still finds that
these 24 pollutants do pass through.  Of these 24 priority pollutants,  17 are
volatile organics as to which EPA would have applied the "volatile override"
to determine that they pass through if the percent removal analysis had not
shown pass through.  (The 17 pollutants in question are all of the 24
pollutants listed in Table 6 of the regulations except for naphthalene,
cyanide, lead, and the four brominated compounds: bromomethane,
tribromomethane, dibromochloromethene,  and bromodichloromethane.)   These
pollutants have overall volatilization rates comparable to the rates for which
EPA has applied the volatile override in the past (see, e.g.,  OCPSF rule,
58 FR 36886-88, July 9, 1993).  Based on their Henry's Law constants, these
are all highly volatile compounds.   Because much of the "removal"  of these
pollutants prior to and during POTW biological treatment is likely the result
of volatilization, EPA continues to conclude, based on its traditional
methodology, that these 17 pollutants pass through POTWs.
                                     7-105

-------
            One of the remaining pollutants,  naphthalene,  is also a volatile
organic pollutant as to which EPA would have applied the "volatile override"
to determine that it passes through if the percent removal analysis had not
shown pass through.  EPA is mentioning naphthalene separately because, unlike
the case of the 17 pollxitants discussed above, biological treatment has been
identified in this rulemaking as part of the BAT basis for naphthalene
limitations.  This indicated that naphthalene's biodegradability might be
important for pass through purposes.  However, EPA continues to conclude, as
stated in the OCPSF rulemaking, that naphthalene is chemically more complex
than the phenols and therefore less readily biodegradable in POTWs.  The
volatile override would control EPA's finding of pass through in any event for
naphthalene.  (See 58 FR 36887 - determination in the OCPSF remand notice that
naphthalene does pass through POTWs).

            As stated in the proposal, there is very little data to determine
POTW removals for the four brominated priority pollutants: bromomethane,
bromoform (tribromomethane),  dibromochloromethane, 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 of these
pollutants occurs in sewers rather than removal via treatment, and the Agency
expects that similar volitilization would 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,  EPA has determined that pass-
through does occur for these four brominated priority pollutants.

            The 2 remaining priority pollutants out of 24 are cyanide and
lead.  The determination of pass through for cyanide is based on actual full-
scale data showing very high removals for cyanide at BAT-level plants (over
99%), compared to an average removal level for cyanide of 54% at well-operated
POTWs, as determined in the 50-plant study.  For lead, as the proposal
explained, the BAT concentration limits were based on the use of hydroxide
precipitation technology.  EPA transferred data for this technology from the
Metal Finishing industry for purposes of both the OCPSF and pesticides
manufacturers' rulemakings.  It is clear that the data, which show much
greater removals of cyanide and lead by BAT technologies than by POTWs, are
not merely an artifact of different influent levels.  Cyanide and lead also
are not readily biodegradable compounds.  EPA therefore continues to conclude
that cyanide and lead do pass through POTWs.

            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, 2,4-dichlorophenol, phenol, and
2,4-dimethyIphenol.

7.6.4       Calculation of Effluent Limitations Guidelines Under PSNS

            The Agency is setting PSNS limitations for 24 of the 28 priority
pollutants addressed under NSPS.  As discussed under PSES, four priority
pollutants, 2-chlorophenol 2,4-dichlorophenol, phenol, and 2,4-dimethyIphenol
have not been shown to pass through a POTW and, therefore, are not being


                                     7-106

-------
regulated under PSNS. The final rule contains concentration-based PSNS
limitations equal to the PSES limitations.

7.7         EFFLUENT LIMITATIONS DEVELOPMENT FOR CONVENTIONAL POLLUTANTS AND
            COD

            BPT limitations set in 1978 for Subcategory A PAIs control the
discharge of COD, BODj,  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 amending the BPT applicability provision for
Subcategory A PAIs to include 14 of these 25 previously excluded PAIs, as well
as the organo-tin pesticides.  As part of the industry study for the
development of this final rule, the Agency collected effluent data on 15
organic PAIs within the group of 25 PAIs and classes of PAIs that were
exempted from BPT.  These data were originally collected by the manufacturing
facilities themselves in order to monitor their discharges.   The 15 organic
PAIs for which EPA now has treatment data are:  ametryn, prometon, prometryn,
terbutryn, cyanazine, atrazine, propazine, simazine, terbuthylazine,
glyphosate, phenylphenol, hexazinone, sodium phenylphenate,  biphenyl, and
methoprene.  EPA has also developed analytical methods and collected effluent
data for organo-tin pesticides, which were not covered in BPT guidelines.  EPA
stated in the proposal that the available treatment data demonstrated that
dischargers manufacturing these PAIs are meeting NPDES permit limitations
equivalent to the current BPT guidelines.  Therefore, EPA proposed to extend
the applicability of the BPT effluent guidelines to cover all of these PAIs.

            The effect of this revision, as proposed, would have been to set
the BPT limitations at the performance level currently being achieved at
facilities under their NPDES permits and to establish a baseline on which to
evaluate incremental costs of candidate BCT technologies.  At proposal, EPA
believed that the manufacturing facilities were in compliance with their NPDES
BPT permit limitations for pH, BOD5,  TSS  and  COD.   Thus,  EPA projected in the
proposal that there would be no costs incurred by any of these facilities in
connection with the proposed extension of BPT applicability in the national
effluent guidelines.

            In the final rule, EPA is amending the BPT applicability provision
as proposed,  with certain changes.  First, for 3 of these 15 PAIs
(phenylphenol, sodium phenylphenate,  and methoprene), the BPT limitations for
BODj, TSS, pH, and COD are being promulgated  in  today's final rule as
proposed.
            Second, for 11 of the remaining 12  PAIs (i.e., all except
biphenyl), EPA is promulgating BPT limitations  as proposed for BOD5, TSS,  and
pH, but is not promulgating COD limitations.   The 11 PAIs at issue are
ametryn,  prometon, prometryn, terbutryn, cyanazine, atrazine,  propazine,
simazine, terbuthylazine, glyphosate and hexazinone.  Manufacturers of these
PAIs submitted comments and explanatory data  demonstrating  that,  although
their discharges do meet the existing BPT limitations for pH,  BOD5,  and TSS,
they do not and cannot meet the BPT guidelines  for COD because of high COD
loadings and high salt contents of their wastewaters.

            EPA agrees with these comments.   The wastewater  treatment
technologies installed at the facilities manufacturing these 11 PAIs are


                                     7-107

-------
equivalent to the BPT technology, i.e., the technologies include both in-plant
treatment to control PAIs and end-of-pipe biological treatment to control BOD5
and TSS.  Because these manufacturers are meeting the BPT-level limitations on
BODj,  TSS and pH,  it appears that these technologies  are being well-operated.
The data show, however, that the production of these 11 PAIs generates
wastestreams with significantly higher COD loadings  (and higher salt content)
than are contained  in the wastestreams of the facilities on which the BPT
regulations were based.    The higher salt content reduces the ability of the
BPT treatment technologies to remove COD.  Therefore, there is no basis on
which to make the existing BPT regulations on COD applicable to the
manufacture of these 11 compounds.

            In addition, EPA does not have data on which COD limitations could
be derived for facilities that manufacture these 11 compounds.  To derive COD
limitations, EPA would require treatment technology performance data and/or
process source reduction information related to reductions in COD in the
discharges from the production of these compounds.  This information was not
available to support this rulemaking.   These 11 PAIs represent  a small
number of PAIs manufactured at a small number of facilities.   In the absence
of a national regulation, COD loading from the manufacturing of these 11 PAIs
may be regulated  by permit writers on a technology basis using best
professional judgment (BPJ)  or as necessary to meet water quality standards.
Moreover, compliance by manufacturers with the individual PAI and priority
pollutant limitations established in today's rule may result in additional COD
reductions over what these manufacturers are currently achieving.
Accordingly, the final regulations require the manufacturers of these 11 PAIs
to comply with the existing BPT limitations on BOD3,  TSS and pH but  not  the
COD limitations.

            The remaining pollutant from the group of 15 is biphenyl.  Since
the time of the proposal of this rule, EPA has revoked the registration of
biphenyl as a pesticide. (Letter from Linda J. Fisher, Assistant
Administrator, Office of Pesticides and Toxic Substances for EPA, "Notice of
Cancellation", November 12, 1992, Product Registration #005412-00005).
Therefore, because biphenyl can no longer be used as a pesticide, it is not
covered by the pesticide chemical effluent limitations guidelines and
standards, and EPA is not promulgating any regulations today covering
biphenyl.  See 40 CFR 455.10 and 455.21 (regulations cover "pesticides,"
defined as substances intended to prevent, destroy, repel or mitigate pests).
Instead, biphenyl is subject to the OCPSF effluent limitations guidelines and
standards at 40 CFR Part 414, Subpart H (Specialty Organic Chemicals).  (Note
that biphenyl manufacturing is classified under SIC Code 2869.)  EPA also
notes that all existing manufacturers of biphenyl already have NPDES permits
covering biphenyl (among other organic chemical manufacturing operations)
based on the OCPSF effluent guidelines.

            As discussed in Section 13, no BCT treatment technologies were
identified that passed the BCT cost test.  As a result, the Agency is setting
the BCT limitations for Subcategory A PAIs equal to the BPT limitations.

            NSPS limitations for conventional pollutants and COD are based on
the BPT limitations but adjusted to reflect the 28% reduction in wastewater
flow at newer facilities (as described above for PAIs).


                                     7-108

-------
                                   SECTION 8

                              ENGINEERING COSTS

8.0         INTRODUCTION

            This section discusses the treatment technology costs for the
pesticide chemicals manufacturing industry  for compliance with the final 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 final
effluent limitations guidelines are based.  The costing approach and
methodology used are the same as those used to determine the costs for the
1992 proposal.

8.1.1       Cost Methodologies

            First, the processes of each plant were evaluated to determine the
level of pollutant discharges based on current treatment (if any).  These
levels were then compared with the effluent concentration levels that would
result in the case of each of the two regulatory options considered:  Option
1, numeric effluent concentration levels identified based on the use of the
best available treatment technologies; and  Option 2, no discharge of process
wastewater pollutants.  Then, the specific  treatment technology additions or
treatment technology sequence upon which the 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 based on
the concentration reductions required and volumes of wastewater to be treated.

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, the methodology
                                      8-1

-------
                                     Figure  8-1

      FLOWCHART USED  TO DETERMINE  TREATMENT COSTS FOR  PAIS
       Is PAI
   to be regulated
       under
       BAT?
       It plant
   currently meeting
  BAT performance in
    PAI treatment?
       Do any
   other PAt» made
 at plant require same
     BAT tech?
        Can
    astewateni limn
different PAIa be treated
     same system7
No PAI BAT Coats.
   Proceed to
 Priority PoHutant
    Analyses
                                     Determine flow and
                                      concemraton of
                                      PAI contaminated
                                     Profect Combined
                                     Treatment System.
                                     Determine flow and
                                       concentration
                                  Run Cost
                                   Model
                                   tor PAI
                                  Treatment
                                 Technology
                    No
       Have
    all PAI* made
at Plant been analyzed
     compliance
   Allocate PAI
 Treatment Costs
by Row. Prod Days
                                          Proceed to
                                        Priority PoHutant
                                           Analyses
                                        8-2

-------
                                        Figure  8-2


FLOWCHART  USED  TO  DETERMINE  TREATMENT COSTS FOR  PRIORITY  POLLUTANTS
                         (denary Prfariy
                       Palhiuna Produced
                       by PAJ rrrlg Prrjceee,
                        ordumgPAIBAT
                           treatment.
                      Project Concentration
                      of Priority Pollutant in

                      jnd Plant Oteenerae
    No BAT coat    Yea
    (or group of
  piMly poNutantt
                                                           No BAT ooil
                                                           tor Analyzed
                                                          Priority Pollutant
                                                   bat Pnomy PoNuana tor
                                                    All PA) Manufacurmg
                                                    Pn
                                                                              Oetermne (tow and
                                                                          Priority Pollutant concentrations
                                                                               for comOMMM BAT
                                                                               treatment tvnem
                                                 Priority PoVutrnmeoneentnaon
                                                   for pmeeea epeetle BAT
                                                      treatment ayatem
                                            8-3

-------
assumes the design of one or more treatment trains as required.  PAI
-contaminated wastewaters requiring the same type of treatment (such as
activated carbon) are assumed to be commingled and put through the same
system.  This train is then sized based on the wastewater flow rate through
the system and the PAI removal efficiencies required to meet the limitations,
and costs are calculated for the resulting design.  The cost estimates are
based on a computer-based cost model containing independent modules which
represent the individual treatment processes.   The model links the individual
treatment units  (modules) together to represent an entire wastewater treatment
system.  The modules represent treatment technologies in use in the pesticide
chemicals manufacturing industry, and are useful and credible in providing
accurate costs.

            This design and cost process is repeated for any other FAIs 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 that does not currently monitor for a PAI or
priority pollutant.  These monitoring costs will be incurred regardless of
whether a plant will require additional treatment.  EPA included monitoring
costs for those plants not currently monitoring for which the final
regulations impose additional PAI and priority pollutant limitations.

            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.  Because the priority pollutant limitations are transferred from the
regulations established for OCPSF manufacturers, the methodology assumes that
plants will apply the BAT technologies identified in the OCPSF rulemaking as
the bases for these limitations.  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 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.
                                      8-4

-------
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, 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
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 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.
                                     8-5

-------
            EPA supplemented this cost model with Lotus 1-2-3 spreadsheets
designed 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 they are either
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 base year for costs calculated in the model be
                  changed?

            (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
                                      8-6

-------
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
engineering principles historically used for wastewater treatment system
design.  The user may link the modules into trains which represent entire
treatment systems.  The model then designs and costs various treatment trains
and ranks them with respect to present worth, capital, operating, or energy
cost.

            Several of the modules within CAPDET (carbon adsorption,
biological treatment, clarification) represent treatment processes in use in
the p.esticide 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
feedstocks) 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.

            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
                                      8-7

-------
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
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
information using this building block approach.  Although EPA followed this
approach for the pesticide industry cost model, EPA did not use the individual
cost 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
                                      8-8

-------
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.

            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.

            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
developing 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
                                      8-9

-------
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.

            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 ia.uk
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.

            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
                                     8-10

-------
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
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
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
                                     8-11

-------
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.
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."

            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.
                                     8-12

-------
(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.

(3)   Title card:  The user may select a title lor iiiu.ivid.ual
      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.

(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.
                         8-13

-------
             Table 8-1




CAPDET LARGE FACILITY UNIT PROCESSES
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.
27.
Flotation thickening
Secondary clarification (activated sludge)
Aerated lagoon
Aerobic digestion
Anaerobic digestion
Anion exchange
Attached growth denitrification
Belt filter for sludge
dewatering
Carbon adsorption
Cation exchange
Centrifugation
Chlorination
Secondary clarification
(user- specified)
Coagulation
Comminution
Complete mix activated
sludge
Contact stabilization activated sludge
User-specified costs for unit processes
Counter current ammonia
stripping
Cross current ammonia stripping
Denitrification (suspended growth)
Secondary clarification
(suspended growth denitrification)
Drying beds
User- specified liquid process
Equalization
Extended aeration activated sludge
Filtration
                8-14

-------
       Table  8-1  (Continued)




CAPDET LARGE FACILITY UNIT PROCESSES
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.
53.
54.
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 (suspended growth nitrification)
Neutralization
Nitrification (suspended growth)
Nitrification (rotating biological contactor)
Nitrification (trickling filter)
Secondary clarification (oxidation ditch)
Overland flow land treatment
Oxidation ditch
Plug flow activated sludge
Postaeration
Primary clarification
Secondary clarification (pure oxygen)
Intermediate pumping
Pure oxygen activated sludge
                8-15

-------
        Table  8-1  (Continued)




CAPDET LARGE FACILITY UNIT PROCESSES
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
Rapid infiltration land
treatment
Raw sewage pumping
Rotating biological contactor
Recarbonation
Secondary clarification
(RBC)
Screening
Second stage recarbonation (lime treatment)
Slow infiltration land
treatment
Sludge drying lagoons
Step aeration activated
Secondary clarification
sludge
(trickling filters)
Trickling filtration
User- specified sludge process
Vacuum filtration
Wet oxidation
                8-16

-------
              Table  8-2




CAPDET SMALL FACILITY UNIT PROCESSES
I.
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.
27.
Activated sludge
Aerated lagoon
Bar screens
Chlorination
Coagulation
User- specified costs for unit processes
Drying beds
User-specified liquid process
Equalization
Filtration
Flotation
Intermittent sand filtration
Lagoons
Secondary clarification (oxidation ditch)
Overland flow land treatment
Oxidation ditch
Postaeration
Primary clarification
Intermediate pumping
Rapid infiltration land treatment
Raw sewage pumping
Secondary clarification (trickling filter)
Septic tanks and tile fields
Slow infiltration land treatment
Sludge drying lagoons
Trickling filtration
User-specified sludge process
                8-17

-------
                                  Table 8-3

                        WASTE INFLUENT CHARACTERISTICS
Characteristics
Minimum Flow
Average Flow
Final/Initial
Maximum Flow
Temperature
Summer/Winter
Suspended Solids
Volatile Solids
Settleable Solids
BOD5
SBODj (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.
                                     8-18

-------
   Table  8-4




UNIT COST DATA

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.
Chit Cost
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 Noncons true t ion Cost
Administrative/Legal Cost
201 Planning Cost
Inspection Cost
198 $ 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%
2.00%
     8-19

-------
                             Table  8-4  (Continued)

                                UNIT COST DATA

27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
Unit 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)
1986 Value
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
  wastewater treatment modules.
                                     8-20

-------
            (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
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 7 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
disposal cost estimates for each technology are included for the following
technologies:

                  Activated carbon;
                  Biological treatment;
                  Chemical oxidation;
                  Contract hauling and incineration;
                  Distillation;
                  Equalization;
                                     8-21

-------
           Table  8-5




PROGRAM CONTROL/OUTPUT SELECTION

Analyze
List Total
Present Worth
Construction
Proj ect
Energy
Operation and Maintenance
Output Quantities
Summary
GO

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 .
              8-22

-------
            •     Filtration;
            •     Hydrolysis;
            •     Hydroxide precipitation;
            •     Resin adsorption; and
            •     Steam stripping.

This section also discusses how EPA estimated monitoring costs for compliance.

            Individual plant treatment costs associated with the final rule
are listed in Table 8-6.  The table lists the treatment costs estimated for
each  plant, broken down by capital, operating and maintenance (including
monitoring costs), land, and residual waste disposal costs.

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 PAls and priority pollutants.

            Physical Equipment

            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
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.
                                     8-23

-------
                Table 8-6




PESTICIDES OPTION 1 -  TOTAL COSTS BY PLANT
Plant ID
0028'
0046
0064*
0180
0288
0402
0448
0563
0705
1063
1189"
1287k
1562
1606
1624
1820b
1848"-"
1848M
1900
2008'
2080
2160*
2302"
2446
Total
Capital
Cost($)
2,866,451
0
0
0
0
468,626
0
0
0
450,379
1,020,201
0
0
0
0
0
0
16,000,000
0
0
0
0
486,875
0
Total O&M
Cost ($/yr)
2,506,648
40,730
11,439
31,785
13,680
57,470
83,690
47 , 200
4,760
35,193
1,119,656
0
55,550
1,180
6,540
0
0
5,000,000
34,860
85 , 540
25,880
55,220
39,337
35,580
Total Land
Cost <§/yr>
8,250
0
s\
u
0
0
17,176
0
0
0
7,695
1,134
0
0
0
0
0
0
0
0
0
0
0
2,592
0
Residual
Waste
Disposal
Cost <§/yr>
481,762
0
f\
\J
0
0
134,534
0
0
0
26,000
102 , 200
0
0
0
0
0
0
0
0
0
0
0
7,028
0
                   8-24

-------
           Table  8-6  (Continued)




PESTICIDES OPTION 1 - TOTAL COSTS BY PLANT
Plant IB
2507
2543
2561
2605"
2767
2847
2865
3043
3061"
3141"
3169"
3187"
3285"
3560
3329*
3560
3668
3828
3864
3908"
3944
3962
4024
4060
Total
Capital

-------
                             Table 8-6 (Continued)

                  PESTICIDES OPTION 1 - TOTAL COSTS BY PLANT
Plant IB
4168"
4220
42 544
446 2a
4505'
4863
4881'
4989
5005
5247
5461
5504
5522
Total
Capital
Cost($)
0
925,987
r f* *\ f\ r f\
ouu ,uou
1,420,219
3,305
0
555,136
175,015
45 , 734
2,346,222
0
0
0
Total O&tt
Cost C$/yr)
0
300,262
158,012
2,771,624
39,555
1,180
40 ,180
62,351
82,413
367,481
27 , 340
10,620
31,605
Total Land
Cost <§/yr>
0
4,050
4,133
5,115
0
0
0
2,403
3,856
1,492
0
0
0
Residual
Waste
Disposal
Cost <$/yr)
0
6,169
120,888
0
0
0
0
0
75,189
0
0
0
0
•Compliance  cost were  revised following proposal based on new information
 applicable to the PAIs manufactured at this plan.

bPlant  or PAI  product  line  closure  identified following proposal.   Compliance
 costs for the closed PAI product lines set equal to zero.

'Compliance  costs  reflect Agency  estimates  using revised wastewater flow and
 PAI loading information.

'Plant  estimate submitted following proposal.   A revised economic  impact
 analysis for this plant using the plant cost estimates indicates no
 significant adverse economic impact.
                                     8-26

-------
            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
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 FAI 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
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
                                     8-27

-------
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 (6005),  Chemical  Oxygen Demand  (COD),  suspended  solids,  volatile
suspended solids, non-biodegradable fraction of volatile suspended solids, pH,
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 BOD5 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.

            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;
                                     8-28

-------
                   Table  8-7

DESIGN PARAMETERS FOR THE BIOLOGICAL TREATMENT
                  COST MODULE
Design Parameter
Reaction rate contant
Fraction BOD, synthesized
Fraction BOD3 oxidized
Air requirement
Endogenous respiration rate
(sludge basis)
Endogenous respiration rate
(oxygen basis)
Nonbiodegradabe fraction of volatile
suspended solids in influent
Oxygen transfer ratio
Oxygen saturation ratio
Horsepower
Food/microorganism ratio
Standard transfer efficiency
Units
L/mg/hr


scfsa/1,000 gal
L/day
L/day


hp/1,000 gal
Ib BOD5/lb MLVSS
Ig 02/hp hr

Default Values
0.00135
0.73
0.52
20
0.057
0.15
0-5
0.53
0.9
0.9
0.5
6
                     8-29

-------
            •     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.

            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.

            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
                                     8-30

-------
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.

            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.

            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.
                                     8-31

-------
            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 Hi 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.

            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.

            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
                                     8-32

-------
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
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
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
                                     8-33

-------
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 iiisLall Lhe
equipment.  Operation and maintenance costs include energy, electricity for
power supply, thermal oil for heating, labor, and supplies.  Land costs are
negligible.

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.

            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.
                                     8-34

-------
             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.

             Desien 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
 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.

            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
                                     8-35

-------
concentrations.  A more detailed discussion of hydrolysis is presented in
Section 7.0.

            Input and 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.

            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
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.
                                     8-36

-------
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
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.
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
                                     8-37

-------
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
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
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
                                     8-38

-------
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.


                       o _KV _    Henry's Law Constant
                          T   Tower Operating Pressure
            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
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
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
                                     8-39

-------
                                   Table  8-8

             PRIORITY POLLUTANTS DIVIDED INTO GROUPS ACCORDING TO
                          HENRY'S  LAW CONSTANT VALUES
High
3 x 10* to 1Q-*
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
Fluorene
Naphthalene
Phenanthrene
Dimethyl Nitrosamine
Diphenyl Nitrosamine
Medium
10* to ifr3
Acenaphthene
Acrylonitrile
1 , 2 -Dichloroethane
Hexachloroethane
1,1, 2 -Trichloroethane
1,1,2 , 2-Tetrachloroethane
Methylene Chloride
1 , 2 -Dichloropropane
1, 3-Dichloropropene
1,1,1- Tr ibromoethane
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





Henry's Law constant units are mg/mVmg/m3.
                                     8-40

-------
                              Table 8-9




STEAM STRIPPING DESIGN PARAMETERS FOR HENRY'S LAW CONSTANT PARAMETERS
;'>X':v:-:-:-:-X:ly:-::!vX::-:'tVj^-jiii^'-''» '• V:Xxtt^>4^^«ia^3fe:^:i.^:Xy:::-:-::::X::;>:.:-v.v-X'
iSBISffliSBSSiS^
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
PR - Operating pressure of
column
REFLUX = Reflux ratio
RHOG - Vapor density
RHOL - Liquid density
SAFE - Safety factor for Vm
SIGL - Liquid surface
tension


cal/g-°K
ftVhr
ft»/hr
mg/1
MGD
unitless
unitless
mg/1
atm/atm
MGD
cal/g
Ib/ft-hr
mole/mole
atm
unitless
Ib./ft3
Ib.yft3
unitless
dyne/cm
iPi^iilliiiiilili^i^ii
Hexachlorobenzene
1.0
9.918 x 10"s
0.311
Option I - 1.0
Option II - 0.01
0.10 x L
1.0
3.775 x 10«
390
37.3
0.01-1.00
542.0
294.3 x 10-3
0.008
1.0
0.0
0.037
60
0.75
58.9
lillliii^iiiiiii
Illliilllilii;;;
Benzene
1.0
1.623 x W-4
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
1.0
0.0
0.037
60
0.75
58.9
                                8-41

-------
 Table 8-9




(Continued)
Design Parameter
TB - Boiling point of
aqueous reflux
TR - Reflux temperature
XPRF - Tray construction
indicator
Units
°C
"C
unitless
Medium
Strippaljiiity
100
9
Perforated
High
Strippability
100
9
Perforated
   8-42

-------
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 coses include
operation and maintenance labor; maintenance materials; steam energy;
electricity; and steam stripper overhead disposal costs.

            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
(>50,000gpd), 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
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.
                                     8-43

-------
8.3.12      Monitoring for Compliance

            To ensure compliance with the regulations,  plants will be required
to sample effluent from their wastewater treatment systems and analyze these
samples for the regulated pollutants.  Analytical test methods have been
developed and promulgated for all PAIs covered by the final rule.  The
monitoring costs incurred by facilities depend on the method employed to
analyze their effluent wastewaters and the number of times monitoring occurs
annually.  The analytical methods listed in Section 16 for each regulated PAI
were used to estimate monitoring costs.  Costs for analytical methods for
individual PAIs do not vary significantly; thus,  in cases where a choice of
several analytical methods is available, 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, Method 200.7 is assumed to be used for lead, and
Method 335 is assumed to be used for cyanide.  EPA assumed that the permitting
authority would require monitoring of regulated PAIs and limited priority
pollutants at least once per week of production.   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.
                                     8-44

-------
                                   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.  EPA has also developed analytical methods and
collected effluent data for organo-tin pesticides, which were not covered in
BPT guidelines.  At the time of proposal, the Agency intended to amend the
applicability of BPT to include these 15 organic PAIs and organo-tin PAIs.
However, for the final rule, EPA is amending the BPT applicability as
proposed, but with certain changes.  EPA is dropping BPT coverage that was
proposed for one of the 15 PAIs (biphenyl) because it is no longer
manufactured as a pesticide chemical.  Also, EPA is not promulgating COD
limitations for facilities that manufacture 11 of the 14 remaining PAIs
because EPA concluded that the data do not support setting such limitations,
as pointed out by commenters.

9.1         BPT APPLICABILITY

9.1.1       Revisions to BPT

            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
methoprene.   As previously stated, EPA has also developed analytical methods
and data for organo-tin pesticides, which were not covered in the BPT
guidelines.   This section discusses the rationale behind the revisions to the
proposed BPT limitation for the above PAIs.

            First,  for three of these 15 PAIs (phenylphenol, sodium
phenylphenate,  and methoprene), the BPT limitations for BOD5, TSS, pH,  and COD
are being promulgated in today's final rule as proposed.  Plants manufacturing
two of these PAIs (sodium phenylphenate and methoprene) are currently meeting
BFT limitations through no discharge of process wastewater.  Both plants use
water,  but do not discharge any wastewater generated to waters of the United
States.  The third plant is currently meeting these limitations with
biological treatment.
                                      9-1

-------
            Second, for 11 of the remaining 12 PAIs (i.e., all except
biphenyl),  EPA is promulgating BPT limitations as proposed for BOD5,  TSS,  and
pH, but is not promulgating COD limitations.  The 11 PAIs at issue are
ametryn, prometon, prometryn, terbutryn, cyanazine, atrazine, propazine,
simazine, terbuthylazine, glyphosate and hexazinone.  Manufacturers of these
PAIs submitted comments and explanatory data  demonstrating  that, although
their discharges do meet the existing BPT limitations for pH, BOD5,  and TSS,
they do not and cannot meet the BPT guidelines for COD because of high COD
loadings and high salt contents of their waste-waters.

            EPA agreed with these comments.  The wastewater treatment
technologies installed at the facilities manufacturing these 11 PAIs are
equivalent to the BPT technology, i.e., the technologies include both in-plant
treatment to control PAIs and end-of-pipe biological treatment to control EGD5
and TSS.  Because these manufacturers are meeting the BPT-level limitations on
BOD5, TSS and pH,  it appears  that these technologies are  being well-operated.
The data show,  however, that the production of these 11 PAIs generates
wastestreams with significantly higher COD loadings (and higher salt content)
than are contained in the wastestreams of the facilities on which the BPT
regulations were based.    The higher salt content reduces the ability of the
BPT treatment technologies to remove COD.  Therefore, there is no basis on
which to make the existing BPT regulations on COD applicable to the
manufacture of these 11 compounds.

            In addition, EPA does not have data on which COD limitations could
be derived for facilities that manufacture these 11 compounds.  To derive COD
limitations, EPA would require treatment technology performance data and/or
process source reduction information related to reductions in COD in the
discharges from the production of these compounds.  This information was not
available to support this rulemaking.   These 11 PAIs represent  a small
number of PAIs manufactured at a small number of facilities.   In the absence
of a national regulation, COD loading from the manufacturing of these 11 PAIs
may be regulated  by permit writers on a technology basis using best
professional judgment (BPJ)  or as necessary to meet water quality standards.
Moreover, compliance by manufacturers with the individual PAI and priority
pollutant limitations established in this final rule may result in additional
COD reductions over what these manufacturers are currently achieving.
Accordingly, the final regulations require the manufacturers of these 11 PAIs
to comply with the existing BPT limitations on BOD5,  TSS  and pH  but  not the
COD limitations.

            The remaining pollutant from the group of 15 is biphenyl.  Since
the time of the proposal of this rule, EPA has revoked the registration of
biphenyl as a pesticide. (Letter from Linda J. Fisher, Assistant
Administrator,  Office of Pesticides and Toxic Substances for EPA, "Notice of
Cancellation",  November 12, 1992, Product Registration #005412-00005).
Therefore,  because biphenyl can no longer be used as a pesticide, it is not
covered by the pesticide chemical effluent limitations guidelines and
standards,  and EPA is not promulgating any regulations today covering
biphenyl.  See 40 CFR 455.10, 455.21 (regulations cover  "pesticides," defined
                                     9-4

-------
as substances intended to prevent, destroy, repel or mitigate pests).
Instead, biphenyl is subject to the OCPSF effluent limitations guidelines and
standards at 40 CFR Part 414, Subpart H  (Specialty Organic Chemicals). (Note
that biphenyl manufacturing is classified under SIC Code 2869.)  EPA also
notes that all existing manufacturers of biphenyl already have NPDES permits
covering biphenyl (among other organic chemical manufacturing operations)
based on the OCPSF effluent guidelines.

9.1.2       Applicability of Final BPT Limitations

            EPA believes that 14 of the 15 organic PAIs discussed for BPT
coverage in the proposal and the organo-tin pesticides should be covered by
BPT, as discussed above, because the NPDES permits for these facilities
reflect a BPTlevel of treatment; and the data and engineering judgement
indicate the facilities are capable of achieving the limitations.

            EPA is therefore amending the BPT applicability provision for
Subcategory A to include 14 previously excluded PAIs listed in Section 9.0 and
the organo-tin pesticides.  Table 9-3 presents these 14 PAIs and the
organo-tin PAIs.

            In the final rule, as in the proposal, EPA is not making 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.
                                      9-5

-------
                                   Table 9-3




              ADDITIONAL 14 PAIs INCLUDED IN FINAL RULE UNDER BPT
PAI Code
025
058
060
138
142
157
192
211
211.05
223
224
226
239
256
257
PAI
Cyanazine *
Ametryn *
Atrazine *
Glyphosate *
Hexazinone *
Methoprene
Organo-tin Pesticides
Phenylphenol
Sodium Phenylphenate
Prometon *
Prometryn *
Propazine *
Simazine *
Terbuthylazine *
Terbutryn *
* Under BPT, these PAIs do not have COD limitations, only BOD5,  TSS and pH.
                                      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 final 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        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.  Of the PAIs and classes of PAIs considered
for regulation, EPA is promulgating limitations for 120 individual PAIs and 28
priority pollutants.  (Note, however, that the limitations on priority
pollutant discharges apply to the manufacturing of all 177 PAIs (biphenyl is
no longer considered a pesticide chemical - see section 9.1).

            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, biological treatment,
solvent extraction 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.
                                     10-1

-------
            As described in Section 8, the Agency estimated the engineering
cost of compliance with the proposed BAT effluent limitations guidelines
options and the associated pollutant reduction benefits.   For Option 1, which
has been chosen by the Agency for promulgation, EPA estimates that the BAT
regulation will result in the incremental removal (beyond that achieved by
BPT) of 147,000 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 $24.9 million and annualized costs
of $18.2 million (in 1986 dollars).  There are no plant closures anticipated
as a result of the BAT regulation.  Two facilities are projected to close
product lines as a result of the regulation,  with job losses equivalent to 31
full-time employees.  (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 BAT effluent limitations guidelines for organic PAIs are
mass-based limitations.  Facilities that manufacture PAIs that have a
limitation of zero discharge have achieved zero by using a closed-loop
recycle/reuse process and must be able to demonstrate compliance through
inspection by the local permitting authority.  In some instances where
facilities provide employee showers and laundry facilities,  which are not
covered by this 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, and 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 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 (EOP) as determined by the permit writer or
local control authority.  In 40 CFR 122.45(h) permit writers are given the
authority to impose internal monitoring and compliance locations in NPDES
permits when limitations imposed at the point of dicharge are impractical or
infeasible.  See also 40 CFR 403.6 concerning pretreaters.  EPA notes that the
clarification in the final regulation of which streams are considered to be
"process wastewater flow" should be helpful to permit writers in their
determination of appropriate monitoring locations (See 455.21(d) of the final
regulation).   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 final 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
                                     10-2

-------
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.

            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
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.

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 final
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.

10.3        BAT EFFLUENT LIMITATIONS GUIDELINES

10.3.1      Revisions to BAT Limitations

            The limitations in the final rule were revised for 29 PAIs overall
since proposal.  The 29 PAIs with revised limitations in the final rule are:
2,4-D, cyanazine, acifluorfen, alachlor, atrazine,  chlorpyrifos,  ethion,
pendemethalin, phorate, terbufos, acephate,  captofol, ametryn,  prometon,
promotryn, propazine, simazine, terbuthylazine, terbutryn,  benomyl, pronamide,
bromacil,  terbacil, TCMTB, pyrethrin I,  pyrethrin II, propachlor,  butachlor,
and norflurazon.

            The bases for the revised limitations for the 29 PAIs are as
follows:   For 7 PAIs (the first 7 the of 29  listed above--2,4-D through
ethion) limitations were revised as a result of new full-scale data submitted
by manufacturers.  More specifically the limitations for acifluorfen have  been
                                     10-3

-------
revised to take into account changes in the production rate and to base
limitations more on additional source reduction rather than solely on
additional treatment.

            Limitations for atrazine and cyanazine are revised based on new
full-scale data supplied by a manufacturer of atrazine and cyanazine for a
much longer period of time than was previously available (six years versus one
year).   Those new data show that the treatment systems experience more
variability than was apparent from the earlier data.   Thus, the final
limitations have been increased from the proposed limitations to account for
this higher variability.

            Limitations for 2,4-D are revised based on full-scale data
reflecting the use of a solvent recovery system.  Limitations are revised for
alachlor based on long-term full scale data submitted after the proposal by a
manufacturer.  These full-scale data replace the treatability study data used
at proposal.  Limitations for ethion were also revised based on the submittal
of full-scale BAT treatment data following the proposal.  At proposal, EPA
lacked full-scale long-term data and therefore had proposed limitations for
ethion based on a transfer of the limitations set for other pollutants.  The
final limitations for ethion are based on these new data and not on BAT
technology transfer as was proposed.  The final limitations are greater than
the limitations that were proposed for ethion.

            The average LTA/MDL ratio and average variability factors used to
calculate the proposed transferred limitations for ethion were based on both
full-scale and bench-scale data for PAIs that are treated by activated carbon.
EPA notes that when these values are recalculated to consider only cases in
which full-scale treatment data are available, the recalculated limitations
are approximately equal to the final limitations for ethion, which are based
on full-scale data.  The agreement of these values serves to validate this
methodology for deriving transferred limitations in the other cases in which
it was used (e.g., in the cases of bromacil and terbacil, for which data from
structurally similar PAIs were not available).  Limitations for pendimethalin
have been revised to reflect the higher flows based on treatment by two
incinerators because both can and do operate at the same time.  Limitations
for phorate and terbufos are revised to account for higher flows per
production unit than originally considered.  The limitations for chlorpyrifos
are revised based on submittal of longer term full-scale treatment data.

            For 7 PAIs, ametryn, prometon, prometryn, terbutryn, propazine,
simazine, and terbuthylazine, EPA transferred data on BAT level removals from
PAIs atrazine and cyanazine.   These technology transfers,  at the time of
proposal, were supported by EPA and industry treatability tests.  Limitations
in the final rule are revised based on using the new full-scale (variability)
data for atrazine and cyanazine discussed above.

            The limitations for benomyl are revised to account for the fact
that much of the benomyl-containing wastewater not currently treated in the
in-plant hydrolysis treatment system is formulating/packaging process
                                     10-4

-------
wastewater rather than manufacturing process wastewater; to account for more
of the production of the the intermediate, carbendazim, which is treated by
the in-plant hydrolysis treatment and cannot be distinguished from benomyl by
the current analytical methods; and to include additional removals by the
end-of-pipe biological treatment system that were not considered in the
proposed regulations.  Limitations for TCMTB, pyrethrin I, and pyrethrin II
were also revised based on transfer of the BAT treatment data on hydrolysis
from benomyl and using the LTA/MDL ratio and variability factors data.  Two
PAIs, butachlor and propachlor, have limitations revised based on new
full-scale data submitted on alachlor.

            At proposal, EPA derived achievable concentration levels by using
performance data, including bench-scale treatability study data for activated
carbon treatment for three PAIs, (alachlor, butachlor, and propachlor).  The
full-scale data submitted on the BAT treatment of alachlor (discussed above)
have also been used to set limits for these two other,  structurally similar
PAIs manufactured at the same plant and treated in the same treatment system
(those two PAIs, butachlor and propachlor were not at full production during
the time the new data were collected, so performance data for those PAIs could
not be obtained).

            The Agency deferred establishing final limitations for one PAI,
glyphosate salt.  The proposed limitation for glyphosate salt, which is a
product manufactured from another PAI, glyphosate, was zero discharge.   At
proposal, there were insufficient data to establish limitations for
glyphosate, however, the portion of the manufacturing process which produces
glyphosate salt had no discharge.  Thus zero discharge limitations were
proposed for that portion of the process.  Since proposal, the manufacturer
has significantly changed the manufacturing process in order to reduce overall
pollutant releases to all media.  However, unlike the previous process, the
new process that produces glyphosate salt has a water discharge.   New
information was submitted following the proposal, reflecting effluent levels
following biological treatment of the total process wastewaters.   After
reviewing the effluent data,  EPA cannot determine whether the data represent
BAT level treatment or whether other control technologies should be identified
as BAT.  Because there was insufficient time to conduct additional treatment
studies, and because this PAI  (and its salt) has "low toxicity, regulation is
being deferred at this time.

            Based on the reevaluation of the data set for use in transferring
variability factors for ethion, discussed above, EPA revised the limitations
transfer procedure to eliminate using variability data from treatability
studies for activated carbon.  This revised procedure resulted in final
limitations for four PAIs (bromacil,  terbacil, norflurazon, and pronamide)
that are higher than the proposed limitations for those four PAIs.

            In addition, the Agency proposed effluent limitations requiring
zero discharge of process wastewater pollutants for 37 PAIs based on total
recycle and reuse of all process wastewater for 29 PAIs, no water use for one
PAI, all data reported as "not detected" for 2 PAIs, no current discharge for
                                     10-5

-------
two PAIs (one of which was biphenyl),  and EPA's estimated lowest cost
treatment of off-site disposal by incineration for 2 PAIs.   Also, the Agency
proposed requiring zero discharge of process wastewater pollutants for the
purification of phosmet by re-crystallization based on recycle/reuse of all
water, which was the only part of the phosmet manufacturing process for which
the Agency proposed any limitations.

            Commenters stated that the data reported as "not detected" were
measured by current analytical methods,  and show only that the pollutant
levels were below the detection limit; the data do not necessarily show "zero
discharge."  Further, today's methods may eventually be replaced by methods
with lower detection limits, and so a "non-detect" value today may show up as
a detectable (measured) value in the future.  The Agency agrees with these
comments.  Commenters also stated that achieving zero discharge to surface
waters involves an increase in total plant discharges to other media, such as
air emissions or solid waste disposal if the process wastewater cannot be
reused effectively.  The Agency generally agrees that this could be the case
in some circumstances.

            Therefore, EPA has revised its determination of the PAIs that
should be subject to a zero discharge limitation.  As proposed, the final rule
promulgates zero discharge limitations for the 28 PAIs as to which zero
discharge was based on total recycle and reuse of all process wastewater and
for the one PAI that is manufactured without water and a no water use portion
of the process for one other PAI. For five PAIs (of the 29 PAIs with revised
limitations), acephate, captafol, norflurazon, pyrethrin I, pyrethrin II for
which EPA proposed a "zero discharge" requirement based either on data that
were below the current detection limit,  no current discharge, or off-site
disposal, EPA is promulgating numeric limitations in response to comments.  To
derive these limitations,  EPA used the technology transfer procedures
described above (utilizing LTA/MDL ratios and average variability factors)
since performance data were unavailable (all data were below the current
detection limit or there was no treated effluent because the wastewaters were
transported off-site for disposal).

            Norflurazon was discussed previously as having revised limitations
based on transfer of data from ethion; pyrethrin I and pyrethrin II, discussed
earlier, have limitations based on hydrolysis treatment of benomyl; and
acephate and captafol have revised limitations based on the transfer of
full-scale incinerator scrubber wastewater discharge data.   As discussed
previously, regulation of glyphosate salt has been deferred and the last of
the proposed zero discharge PAIs, biphenyl, as discussed previously, has been
dropped from coverage of this rule.

            The final 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.

            The Agency is reserving BAT for the metallo-organic pesticide
chemicals manufacturing subcategory (Subcategory B).
                                     10-6

-------
                                  Table 10-1
           ORGANIC PESTICIDE ACTIVE INGREDIENT EFFLUENT LIMITATIONS
            BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE  (BAT)
BAT Limitations*
Organic Pesticide Active
Ingredient (PAI)
2, 4-D
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb
Ametryn
Atrazine
Azinphos Methyl
Benfluralin
Benomyl and Carbendazim
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 40 [Potassium N-
hy dr oxyme thy 1 - N -
methyldithiocarbamate ]
BAT/JSES effluent limitations
Daily Maximum Shall
Not Exceed
1.97 x 1C'3
Monthly Average
Shall Not Exceed
6.40 x lO"
Notes

No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
6.39 x 10"
2.45
5.19 x 10-3
7.23 x 10"
7.72 x 10-3
5.12 x 10-3
2.74 x 1C'2
3.22 x 10-*
3.50 x lO'2
1.69 x lO'2
1.97 x 10"
9.3 x 10-'
1.54 x 10-3
3.12 x 10"
2.53 x ID'3
1.72 x ID'3
1.41 x 10-2
1.09 x 10"
8 . 94 x 10-3
8.72 x lO'3







1
2

No discharge of process wastewater pollutants
3.83 x 1C'1
3.95 x lO'3
3.95 x lO'3
5.74 x 10-3
1.16 x 10-1
1.27 x 1C'3
1.27 x lO"3
1.87 x 10-3




                                     10-7

-------
Table 10-1




(Continued)
Organic Pesticide Active
Ingredient (PAD
Busan 85 [Potassium
dimethyldithiocarbamate ]
Butachlor
Captafol
Carbarn S [Sodium
dimethyldithiocarbamate ]
Carbaryl
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos
Cyanazine
Dazomet
DCPA
DBF
Diazinon
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Muron
BAT/PSES effluent limitations
Daily Maximum Shall
Not Exceed
5.74 x 10-3
5.19 x ID'3
4.24 x 10-«
5.74 x ID'3
1.60 x 10-3
1.18 x 10-4
8.16 x lO'2
1.51 x 10-3
8.25 x 10-*
1.03 x lO'2
5.74 x lO'3
7.79 x 10-2
1.15 x ID'2
2.82 x lO'3
Monthly Average
Shall Not Exceed
1.87 x 10-3
1.54 x lO"3
1.31 x 10-6
1.87 x lO'3
7.30 x 10"
2.80 x ID'5
3.31 x 10-2
4.57 x 10"
2.43 x 10"
3.33 x 1C'3
1.87 x lO'3
2.64 x 10-2
5.58 x lO'3
1.12 x 10-3
Notes





_








No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x 10-2
7.33 x lO'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 10-2

•



    10-8

-------
Table 10-1




(Continued)
Organic Pesticide Active
Ingredient (PAX)
Endothall, salts and
esters
Endrin
Ethalfluralin
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Heptachlor
Isopropalin
KN Methyl
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny 1
Methoxychlor
Metribuzin
Mevinphos
Nab am
BAT/PSES effluent: limitations
Daily Maximum Shall
Not Exceed
Monthly Average
Shall Sot Exceed
No discharge of process wastewater
pollutants
2.20 x 10-2
3.22 x 10-»
5.51 x 10-3
1.02 x 10-1
1.48 x lO'2
1.83 x 10-2
5.40 x lO'3
8.80 x 10-3
7.06 x 10-3
5.74 x 10-3
2.69 x lO'3
2.35 x 10-»
5.10 x 10-3
1.09 x 10-4
1.57 x 10-3
3.61 x lO'2
7.64 x 10-3
9.45 x 10-3
2.08 x 10-3
2.90 x 10-3
2.49 x 10-3
1.87 x 10-3
1.94 x lO'3
9.55 x 10-5
Notes


1










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 ID'3
1.36 x 1C'2
1.44 x 10-*
5.74 x lO'3
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
5.10 x 10-5
1.87 x 1C'3







   10-9

-------
Table 10-1




(Continued)
vX:>::;;:-::;:::'::: •x^x^^-'^x^/'x'xv^x^x
•:::::::::xVv:;;:::::::::::i:x''::';"::::::::::::^^
Ilillilliil^lISill^iill
^iSipi^iiiiiiiiiiiiiiiiiiiii

Nabonate
Naled
Norflurazon
Organotins
Parathion Ethyl
Parathion Methyl
PCNB
Pendime thai in
Permethrin
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I and
Pyrethrin II
Simazine
Stirofos
TCMTB
llillllll^
•:•:•:•:•:•:•: I-1-:-:.:.;.:-:-:-:-:---:-: :::•:•:: >:-:^-:-:-x :•::•:•: :•::••.•: :••:: :•;:••:•:•:-:-•• ;-•»/•:•:> •.••:•:•:•:;:•: :-:•:•:.:•:.:•:-:•.•.•:-:-.-:•:•.-.-:-:-:•:•:•:•:•.•:•.•/.:.:.:.:.:.-.: .;-:.:-:-:.:.:.:.:.:.:.v/.:.:.:.':
iissss^S^^
sgvayna^yaiMa^^
miijiij^^
5.74 x 1C'3


1.87 x lO'3
Ililllilll
Iliiiliiii

No discharge of process wastewater pollutants
7.20 x 10"1
1.72 x 10-2
7.72 x 10-«
7.72 x 10-4
5.75 x 10-1
1.17 x lO'2
2.32 x 10-1
3.12 x 104 .
3.10 x 10-4
7.42 x 10-3
3.43 x 10-*
3.43 x 10*
1.90 x lO-4
3.62 x 10-J
6.06 x 10-5
9.37 x 10'J
No discharge of process wastewater
pollutants
7.72 x 10-3
7.72 x lO'3
6.64 x 10-1
5.19 x 10-3
1.06 x 10-3
7.72 x 10-3
1.24 x ID'2
7.72 x 10-3
4.10 x lO'3
3.89 x lO'3
2.53 x ID'3
2.53 x ID'3
2.01 x 10^
1.54 x lO'3
4.84 x 10"
2.53 x ID'3
3.33 x ID'3
2.53 x lO'3
1.35 x 10-3
1.05 x lO'3

3






4










   10-10

-------
                                  Table  10-1

                                  (Continued)
Organic Pesticide Active
Ingredient (PAI)
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin
Vapam [Sodium
methyldithiocarbamate ]
Ziram [Zinc
dimethyldithiocarbamate ]
BAT/FSES effluent limitations
Daily Maximum Shall
Not Exceed
9.78 x 10-2
3.83 x lO"1
4.92 x 10-4
7.72 x 10-3
7.72 x 10-3
1.02 x lO'2
6.52 x 10-2
3.22 x 10-1
5.74 x lO'3
5.74 x ID'3
Monthly Average
Shall Hot Exceed
3.40 x 10-2
1.16 x 10-1
1.26 x 10^
2.53 x lO'3
2.53 x 10-3
3.71 x lO'3
3.41 x lO'2
1.09 x 104
1.87 x 10-3
1.87 x lO'3
Notes







1


 limitations are in Kg/kkg  (lb/1,000 Ib) i. e., kilograms of pollutant per
  1,000 kilograms product (pounds of pollutant per 1,000 Ibs product).

'Monitor and report  as  total toluidine PAIs,  as Trifluralin.

2Pounds  of product include Benomyl and any Carbendazim production not
 converted to Benomyl.

'Monitor and report  as  total tin.

4Applies to purification by recrystallization portion of the  process.
                                     10-11

-------
                                -Table  10-2

BAT EFFLUENT LIMITATIONS 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
Trichloromethane .
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- Dime thy Iphenol
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT effluent limitation*
Mift'X'i.Tnisnn r or *
toy One Bay
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
380
794
380
794
59
26
Maximum for
Honthly
Average-
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
142
196
142
196
22
15
Notes
























                                   10-12

-------
                                  Table 10-2

                                  (Continued)
. Priority $oUta&4H&'
Tetrachloroethylene
Total Cyanide
Total Lead
BAT effluent limitations

Any One Bay
56
640
690
Wg-TimqTft for
Monfcfciy
Average
22
220
320
Notes

1
1
'Lead  and total  cyanide  limitations apply only  to noncomplexed  lead-bearing or
 cyanide-bearing waste streams.  Discharges of lead from complexed
 lead-bearing process wastewater or discharges of cyanide from complexed
 cyanide-bearing process wastewater are not subject to these limitations.
                                    10-13

-------
                                 Table  10-3

BAT EFFLUENT LIMITATIONS 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 - Dichloroe thy lene
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 limitations

| Aaxy On* Bay
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
380
794
380
794
47
47
Maxiwwu. fox :
Monthly
. • Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
142
196
142
196
19
19
Botes






















                                   10-14

-------
                                  Table 10-3

                                  (Continued)
Priority toiluta-nt-
Tetrachloroethylene
Toluene
Total Cyanide
Total Lead
BAT effluent Hmfctatiotts

Any One Bay
164
74
640
690
Maximum for:
MonfcMy
Y. Average
52
28
220
320
. Note*


1
1
'Lead and  total  cyanide  limitations  apply  only  to noncomplexed lead-bearing or
 cyanide-bearing waste streams.  Discharges of lead from complexed
 lead-bearing process wastewater or discharges of cyanide from complexed
 cyanide-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 for existing plants can be
achieved and are justified in some cases; in the remaining cases, NSPS is set
equal to BAT.  BAT limits were modified to reflect the capability for
wastewater flow reduction at new facilities.  The Agency is promulgating the
organic pesticide chemicals manufacturing subcategory NSPS for 23 priority
pollutants by transferring them from the OCPSF point source category and has
developed 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.  EPA is promulagating Option 1 for NSPS effluent limitations
guidelines, as was proposed (although the final rule includes changes to some
of the individual PAI limitations as discussed below).  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.

11.1.1      Revisions to New Source Performance Standards

            For most PAIs, the basis for the final NSPS is not changed from
the proposal.  However, PAIs benfluralin, ethalfuralin, trifluralin,
pendimethalin, phorate, terbufos, acephate, and captafol, have final BAT
limitations based on incineration.  The only discharge from the PAI
manufacturing process at these facilities is the incinerator scrubber water
used to clean the incinerator gases prior to emission to the atmosphere.
Comments received from manufacturers correctly pointed out that a reduction in
                                     11-1

-------
the process wastewater volume will not reduce the need for or the amount of
scubber water used to clean the incinerator gases.  Therefore, EPA has revised
NSPS to be equal to the BAT limitations for these eight PAIs.

            The proposed NSPS limitations for pyrethrin I and pyrethrin II,
like the proposed BAT limitations,  were set at zero discharge.  The final BAT
limitations for those two PAIs are based on hydrolysis technology transfer,
and therefore, the final NSPS limitations for those two PAIs are based on
hydrolysis and a 28 percent reduction of process wastewater flow.  The
proposed BAT limitations for norflurazon were set at zero discharge; however,
the final limitations are numeric limitations based on technology transfer
from activated carbon treatment systems.  The norflurazon plant did not begin
operations until 1986 and is therefore a new plant, and EPA has information
that this plant has already incorporated source reduction.  Therefore, the
final NSPS for norflurazon are set equal to the final BAT limitations.

11.2        IMPLEMENTATION OF THE NSPS EFFLUENT LIMITATIONS GUIDELINES

11.2.1      National Pollutant Discharge Elimination System (NPDES) Permit
            Limitations

            The NSPS for conventional pollutant parameters, COD, and organic
PAIs are mass-based limitations and the 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).

            At the time of promulgation these NSPS 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 non-
process 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, this final
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.
                                     11-2

-------
11.3        NEW SOURCE PERFORMANCE STANDARDS (NSPS)

            The NSPS for conventional pollutants, organic PAIs and classes of
PAIs, and priority pollutants under the organic pesticide chemicals
manufacturing subcategory (Subcategory A) are listed in Tables 11-1, 11-2,
11-3, and 11-4.

            The Agency is reserving NSPS for the metallo-organic pesticide
chemicals manufacturing subcategory (Subcategory B).
                                     11-3

-------
                                  Table 11-1

         NSPS  EFFLUENT LIMITATIONS  FOR CONVENTIONAL POLLUTANTS AND  COD
Effluent
Character is t Ic
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.
                                     11-4

-------
                                  Table 11-2
               FOR ORGANIC

NSPS Effluent Limitations*
NSPS EFFLUENT LIMITATIONS
 PESTICIDES  ACTIVE INGREDIENTS  (PAIs)
Organic Pesticide
Active Ingredient
2, 4-D
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb
Ametryn
Atrazine
Benfluralin
Benomyl and Carbendazim
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil bctanoate
Bus an 40
Bus an 85
Butachlor
Captafol
Carbarn S
Carbaryl
NSPS .Effluent Limitations
Dally Maximum Shall
Not Exceed
1.42 x ID'3
Monthly Average
Shall Not Exceed
4.61 x 10-*
Notes

No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
6.39 x 10-*
1.77
3.74 x 10-3
5.21 x 10-4
5.56 x 10-3
3.69 x lO'3
3.22 x 10-1
2.52 x 10-2
1.22 x 10-2
1.97 x 10-"
6.69 x 10-1
1.11 x.lO-3
2.25 x 10-»
1.82 x 10-3
1.24 x 10-3
1.09 x 10-*
6.44 x 10-3
6.28 x 10-3






1
2

No discharge of process wastewater pollutants
2.76 x ID'1
2.84 x 10-3
2.84 x lO"3
4.14 x ID'3
4.14 x lO'3
3.74 x ID'3
4.24 x W*
4.14 x ID'3
1.18 x lO'3
8.36 x lO"2
9.14 x 10-4
9.14 x 10"1
1.35 x 10-3
1.35 x ID"3
1.11 x lO'3
1.31 x 10*
1.35 x 10-3
5.24 x 10-1









                                     11-5

-------
Table 11-2




(Continued)
Organic Pesticide
Active Ingredient
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos
Cyanazine
Dazomet
DCPA
DBF [S,S,S-Tributyl
phosphorotrithioate]
Diazinon
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin
Ethion
Fenarimol
Fensulfothion
NSPS Effluent Limitations
Bally Maximum Shall
Hot Exceed
1.18 x 10"
5.87 x 10-2
1.09 x 10-3
5.94 x 10"
7.42 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 Not Exceed
2.80 x 10-3
2.39 x 10-2
3.29 x 10"
1.75 x 10"
2.40 x ID'3
1.35 x lO'3
1.90 x lO'2
5.58 x lO'3
8.13 x 10"
Wotes









No discharge of process wastewater pollutants
6.88 x 10-4
3.41
2 . 54 x 10-2 .
5.28 x 10-3
2.27 x 10-2
2.13 x lO-5
1.03
9.31 x lO'3
2.72 x lO'3
1.01 x 10-2





No discharge of process wastewater pollutants
1.57 x 10-2
3.22 x 10"
3.97 x 10-3
1.02 x 10-'
1.06 x ID'2
3.69 x 10-3
1.09 x 10"
1.33 x lO'3
3.61 x lO'2
5.50 x ID"3





   11-6

-------
Table 11-2



(Continued)
Organic Pesticide
Active Ingredient
Fenthion
Fenvalerate
Guthion
Heptachlor
Isopropalin
KN Methyl
Linuron
Malathion
MCFA salts and esters
MCPP salts and esters
Merphos
Me thami dopho s
Me thorny 1
Methoxychlor
Metribuzin
Mevinphos
Nabam
Nabonate
Naled
Norflurazon
Organotins
Parathion Ethyl
Parathion Methyl
. . NSPS Effluent Limitations
Daily Maximum Shall
Kot Exceed
1.32 x ID'2
3.91 x 10-3
1.97 x ID'2
6.31 x lO'3
5.07 x ID"3
4.14 x 1C'3
1.94 x ID'3
1.69 x 10-1
Monthly Average
Shall Hot Exceed
6.79 x 10-3
1.50 x lO'3
1.02 x lO'2
2.06 x 10-3
1.82 x 10*
1.35 x 10-3
1.40 x 10-3
6.88 x 10-5
Notes








No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x lO'2
1.05 x lO'2
2.75 x lO'3
2.34 x lO'3
9.80 x 10-3
1.03 x 10-1
4.14 x 10-3
4.14 x ID'3
5.58 x 10-3
5.42 x ID'3
1.27 x 10*
9.25 x 10-»
5.06 x lO'3
3.69 x 10-5
1.35 x 10-3
1.35 x 10-3








No discharge of process wastewater pollutants
7.20 x 10-*
1.25 x 10-2
5.56 x 10"
5.56 x lO"
3.10 x 10-1
5.36 x 10-3
2.45 x 10"
2.45 x 10-*

3


   11-7

-------
Table 11-2




(Continued)
Organic Pesticide
Active Ingredient
PCNB
Pendimethalin
Permethrin
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I and
Pyrethrin II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
NSPS Effluent Limitations
Daily Maximum Shall
Not Exceed
4.16 x ID"4
1.17 x 10'2
1.68 x 10"4
3.12 x 10"4.
Monthly Average
Shall Not Exceed
1.38 x lO"4
3.62 x 10'3
4.39 x 10'5
9.37 x ICT5
No discharge of process wastewater
pollutants
5.56 x 10'3
5.56 x 1CT3
4.78 x ID"4
3.74 x 10'3
7.63 x Id"4
5.56 x 10°
8.91 x 10'3
5.56 x 10°
2.95 x 10'3
2.80 x 10'3
9.78 x 10'2
2.76 x 10"'
4.92 x ID"4
5.56 x ICT3
5.56 x 10'3
7.35 x 10'3
4.69 x 10'-
1.82 x 10'3
1.82 x 10'3
1.45 x ID"4
1.11 x ID'3
3.48 x ID"4
1.82 x 10'3
2.40 x 10'3
1.82 x 10'3
9.72 x 10-4
7.54 x ID"4
3.41 x 10'2
8.36 x 10'2
1.26 x 10-4
1.82 x 10'3
1.82 x ID"3
2.67 x 10'3
2.46 x 10'2
Notes




4

















   11-8

-------
                                  Table  11-2

                                  (Continued)
Organic Pesticide
Active Ingredient
Trifluralin
Vapam [ Sodium
me thyldithiocarbamate ]
Ziram [Zinc dime thyl-
dithiocarbamate]
NSFS Effluent Limitations
Dally Maximum Shall
{lot . Exceed
3.22 x W
4.14 x 10-3
4.14 x 10-3
Monthly Average
Shall Not Exceed
1.09 x 10-«
1.35 x ID'3
1.35 x lO'3
Notes
1
 limitations are in Kg/kfcg  (lb/1,000 Ib) i.e., kilograms of pollutant per
  1,000 kilograms product (pounds of pollutant per 1,000 Ibs product).

Notes

'Monitor  and report  as  total  Trifluralin.
2Pounds of product shall include Benomyl and any Carbendazim production not
 converted to Benomyl.
3Monitor  and report  as  total  tin.
4Applies  to purification by recrystallization portion of the process.
                                     11-9

-------
                                  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- Dime thy Iphenol
Ethylbenzene
D i chl o rome thane
Chlorome thane
Br omome thane
Tribromome thane
Bromodichlorome thane
Dibromochloromethane
Naphthalene
Phenol
NSPS effluent limitations
Maximum for
Any One Day

136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
380
794
380
794
59
26
Maximum for
Monthly
Average
(US/I.)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
142
196
142
196
22
15
Notes
























                                     11-10

-------
                                  Table 11-3

                                  (Continued)
Priority Bsllutant
Tetrachloroethylene
Total Cyanide
Total Lead
NSPS effluent limitations
Mayftniim for
Any One Day

56
640
690
Maximum for
Monthly
Average

22
220
320
Notes

]_
1
'Lead and total cyanide  limitations  apply  only  to noncomplexed lead-bearing  or
 cyanide-bearing waste streams.  Discharges of lead from complexed
 lead-bearing process wastewater or discharges of cyanide from complexed
 cyanide-bearing process wastewater are not subject to these limitations.
                                    11-11

-------
                       Table 11-4

NSPS FOR PRIORITY POLLUTANTS FOR PLANTS THAT DO NOT HAVE
           END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Te tr achlo r ome 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
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
BAT effluent limitations
Maximum for
Any One Bay

134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
380
794
380
794
47
Hay*"*"1" for
Monthly
Average
(*£/*•>
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
142
196
142
196
19
Notes





















                         11-12

-------
                                  Table 11-4

                                  (Continued)
•x:₯:₯:X:₯:₯:₯:₯:x:x;X;X;X;X:₯:₯:x^^
;x₯:₯:₯:₯:₯:₯:₯:₯:₯SX:₯x₯:₯ 	 : 	 ₯:₯: 	 x₯x₯x₯:₯ 	 : 	 x:::₯x::₯:₯x₯:₯:X:X:₯: 	 : 	 :x: 	 x;₯:x
xH:₯:₯xx;:S:;;xM:Xx₯xX^ :x₯x₯x₯x₯x'₯x₯;₯;₯xx₯3^
₯x₯:x:₯x 	 W:₯:X::x₯x₯:₯x₯:::₯:₯xX:₯: 	 W : 	 ₯:₯:₯:₯:₯:₯:::₯xXx₯:₯ 	 W 	 x 	 :₯: 	 :x'x:₯:x 	 ₯:
	 ftXxXvX 	 ₯x:;:;:;::xx:::;::::::x:x::x:xx:x::>xXx₯ x:Xx₯:₯x₯:₯:₯ 	 : 	 ₯x₯:₯x₯x₯:₯: 	 xXx₯x:x₯:X;:::x 	 tiff:
:™₯;₯X₯xX;x₯:::₯:;j₯:X;₯;S;^::^ ;xXx₯:;:;x;>xXx₯:;:₯x₯:;x;x:xXx;:₯:X:;:™x;xj
:iX:X:::₯x:;:::;Xv:o:::;:::;:-:;:;:::;Xv:x:::xX^XvX:X;Xx₯x' ₯:₯:₯:₯:₯:₯:₯:X:X;X:::Xv:v:;:xx:::X;:v:v:v:xX;:;:xXxX;>Xx:;X;Xv:v
SiSix':;*'::!:^^ SSSSSjigiSHHSJiSisSiSiggS
Phenol
Tetrachioroethylene
Toluene
Total Cyanide
Total Lead
:xx:::::;:H:₯;Bj^:^i6I:f Iitl61it:::::::l.
::;x:::::::::::>:₯:::.:::.::::::::::X:::::::::X-:v:::>-:-:::::::-:::::'::-:::x-::vX:x.-.-
:i::::XX:::::::|:i:|:;:i:j:₯:Xx::i^^^^^^^
^lllli|||:l||||i^lplplll!

47
164
74
640
690

^iiiiiiiiiiiipi
iiiililiili^iiii

19
52
28
220
320







1
1
'Lead  and total  cyanide  limitations  apply only  to noncomplexed lead-bearing or
 cyanide-bearing waste streams.  Discharges of lead from complexed
 lead-bearing process wastewater or discharges of cyanide from complexed
 cyanide-bearing process wastewater are not subject to these limitations.
                                    11-13

-------

-------
                                  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 is
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.

            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
27,000 pounds of PAIs and 22,000 pounds  of priority pollutants to POTWs.

            This section summarizes the  final 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).

12.1        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 has developed PSES and PSNS for
24 of the 28 priority pollutants and for the same 91 PAIs and classes of PAIs
being promulgated under BAT and NSPS. At proposal,  the OCPSF pass through

                                     12-1

-------
analysis showed that only two priority pollutants do not pass through
(2-chlorophenol and 2,4-dichlorophenol).     However, as described in detail in
the preamble to the OCPSF final rule (58 FR 36872),  EPA has since determined
that two more priority pollutants, phenol and 2,4-dimethylphenol, also do not
pass through a POTW.  Therefore, PSES and PSNS are not being set for these
four 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 BODj  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.

12.1.1      Revisions to PSES and PSNS

            In setting PSES and PSNS limitations for PAIs, EPA made the same
changes from proposal previously described for PAI limitations under BAT and
NSPS (including flow reduction).  See Sections 10 and 11 of this document for
revisions to BAT and NSPS.  Also, as stated above, EPA is excluding two
additional priority pollutants from promulgation of PSES and PSNS that were
included in the proposal.

            EPA estimates that the PSES regulation will result in the
incremental removal of 25,000 pounds per year of pesticide active ingredients,
and 21,000 pounds per year of priority pollutants.  EPA estimates that cost
for compliance with the proposed PSES are capital costs of $8.7 million and
annualized costs of just over $5.1 million (1986 dollars).  There are no plant
closures or line closures anticipated as a result of the PSES regulation.  No
additional firms are expected to experience significant financial impacts as a
result of compliance with PSES.  (See "Economic Impact Analysis of Effluent
Limitations and Standards of the Pesticide Manufacturers".)

12.2        PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)

            The 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 and 12-3.  The Agency is reserving PSES and PSNS
for Subcategory B.

12.3        COMPLIANCE DATE

            EPA is establishing a deadline for compliance with PSES to be as
soon as possible, but no later than three years after the date of publication
of the final rule in the Federal Register.
                                     12-2

-------
                                  Table 12-1
           ORGANIC PESTICIDE ACTIVE INGREDIENT EFFLUENT LIMITATIONS
              PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES)
PSES Limitations*
Ofcgatlie Pesticide Active
Ingredient (PAI)
2, 4-D
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb
Ametryn
Atrazine
Azinphos Methyl
Benfluralin
Benomyl and Carbendazim
Bolstar
Bromacil , lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 40 [Potassium N-
hy dr oxyme thy 1 - N -
methyldithiocarbamate ]
FSES effluent limitations
Daily Maximaia Shall
Not Exceed
1.97 x 10-3
Monthly Average
Shall Not Exceed
6.40 x 10-4
Notes

No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
6.39 x 10-4
2.45
5.19 x lO'3
7.23 x 10"4
7.72 x 10-3
5.12 x ID'3
2.74 x 10"2
3.22 x 10^
3.50 x lO'2
1.69 x lO'2
1.97 x 10^
9.3 x lO'1
1.54 x 10-3
3.12 x 10-4
2.53 x 10-3
1.72 x ID'3
1.41 x ID'2
1.09 x 10^
8.94 x 10-3
8.72 x 10-3







1
2

No discharge of process wastewater pollutants
3.83 x 10-1
3.95 x 10-3
3.95 x lO'3
5.74 x 10-3
1.16 x 10-1
1.27 x 10-3
1.27 x 10-3
1.87 x 10-3




                                     12-3

-------
Table 12-1




(Continued)
Organic Pesticide Active
Ingredient (MI)
Busan 85 [Potassium
dimethyldithiocarbamate ]
Butachlor
Captafol
Carbarn S [Sodium
dimethyldithiocarbamate ]
Carbaryl
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos
Cyanazine
Dazomet
DCPA
DEF
Diazinon
Dichlorprop , salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
PSES effluent limitations
Daily Majcisra» Shall
Not Exceed
5.74 x 1C'3
5.19 x lO'3
4.24 x 10-6
5.74 x 10-3
1.60 x ID'3
1.18 x 10^
8.16 x ID'2
1.51 x 10-3
8.25 x 10-1
1.03 x lO'2
5.74 x lO'3
7.79 x 10-2
1.15 x 10-2
2.82 x 10-3
Monthly Average
Shall Not Exceed
1.87 x lO'3
1.54 x 10-3
1.31 x lO*
1.87 x 10-3
7.30 x 10-4
2.80 x 10-5
3.31 x 10-2
4.57 x 10-*
2.43 x 10^
3.33 x 10-3
1.87 x 10-3
2.64 x lO'2
5.58 x lO'3
1.12 x 10-3
Notes














No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x 10-2
7.33 x 10-3
3.15 x 10-2
2.95 x 10-5
1.43
1.29 x ID'2
3.79 x ID'3
1.40 x lO'2





   12-4

-------
Table 12-1




(Continued)
Organic Pesticide Active
Ingredient (MI)
Endothall , salts and
esters
Endrin
Ethalfluralin
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Heptachlor
Isopropalin
KN Methyl
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny 1
Methoxychlor
Metribuzin
Mevinphos
Nab am
PSES exfltietit limitations
Daily Maxiimstt Shall
Not Exceed
Monthly Average
Shall Not Exceed
No discharge of process wastewater
pollutants
2.20 x ID'2
3.22 x 10*
5.51 x 10-3
1.02 x 10'1
1.48 x lO'2
1.83 x 10-2
5.40 x ID'3
8.80 x ID'3
7.06 x 10-3
5.74 x 10-3
2.69 x lO'3
2.35 x W-*
5.10 x 10-3
1.09 x W*
1.57 x 10-3
3.61 x 10-2
7.64 x 10-3
9.45 x 10-3
2.08 x 10-3
2.90 x 10-3
2.49 x 10-3
1.87 x lO'3
1.94 x 10-3
9.55 x lO'5
Notes


1










No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.46 x lO'2
3.82 x 10-3
3.23 x lO'3
1.36 x ID'2
1.44 x 10-4
5.74 x 10-3
5.58 x lO'3
7.53 x ID'3
1.76 x 10-3
1.31 x 10-3
7.04 x 10-3
5.10 x 10-5
1.87 x 10-3







   12-5

-------
Table 12-1




(Continued)
Organic Pesticide Active
Ingredient (PAI>
Nabonate
Naled
Norflurazon
Organotins
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Permethrin
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I and
Pyrethrin II
Simazine
Stirofos
TCMTB
PSES effluent limitations
Daily Maximum Shall
Sot Exceed
5.74 x lO'3
Honthly Average
Shall Not Exceed
1.87 x 10-3
Notes

No discharge of process wastewater pollutants
7.20 x 10"
1.72 x lO'2
7.72 x 10"
7.72 x 10-*
5.75 x 10"
1.17 x 10-2
2.32 x 10"
3.12 x 10"
3.10 x 10"
7.42 x 10-3
3.43 x 10"
3.43 x 10"
1.90 x 10"
3.62 x 10-3
6.06 x 10-5
9.37 x 10-5
No discharge of process wastewater
pollutants
7.72 x lO'3
7.72 x ID"3
6.64 x 10"
5.19 x 10-3
1.06 x 10-3
7.72 x 10-3
1.24 x 10-2
7.72 x 10-3
4.10 x lO'3
3.89 x 10-3
2.53 x lO'3
2.53 x 10-3
2.01 x 10"
1.54 x 10-3
4.84 x 10"
2.53 x lO'3
3.33 x 10-3
2.53 x 10-3
1.35 x 10-3
1.05 x lO'3

3






4










   12-6

-------
                                  Table 12-1

                                  (Continued)
Organic Pesticide Active
Ingredient (PAI)
Tebuthiuron
Terbacil
Terbufos
Terbuthy laz ine
Terbutryn
Toxaphene
Triadimefon
Trifluralin
Vapam [Sodium
me thyldithiocarbamate ]
Ziram [Zinc
dime thyldithiocarbamate ]
PSES effluent limitations
Daily Maximum Shall
Not Exceed
9.78 x 10-2
3.83 x 10-'
4.92 x 10-4
7.72 x 10-3
7.72 x 10-3
1.02 x ID'2
6.52 x 1C'2
3.22 x lO"4
5.74 x lO'3
5.74 x ID'3
Monthly Average
Shall Hot Exceed
3.40 x 1C'2
1.16 x 10-1
1.26 x lO"1
2.53 x lO'3
2.53 x lO'3
3.71 x ID"3
3.41 x ID'2
1.09 x lO-4
1.87 x 10-3
1.87 x lO'3
Notes .







1


 limitations are in Kg/kkg (lb/1,000 Ib) i. e., kilograms of pollutant per
  1,000 kilograms product (pounds of pollutant per 1,000 Ibs product).

'Monitor and report  as  total  toluidine  PAIs,  as  Trifluralin.

2Pounds of product include Benomyl and  any Carbendazim production not
 converted to Benomyl.

3Monitor and report  as  total  tin.

4Applies to purification by recrystallization portion of  the process.
                                     12-7

-------
                                  Table 12-2

                     PSES AND PSNS 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
Ethylbenzene
D i chl o r ome thane
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Tetrachloroethylene
Toluene
Total Cyanide
Total Lead
PSES/PSNS Effluent Limitations

Maximum foe Any
One Day C^g/L)
134
380
380
574
59
325
794
380
60
66
794
794
380
170
295
380
794
380
794
47
164
74
640
690
Maximum for
Monthly Average
C«g/L)
57
142
142
180
22
111
196
142
22
25
196
196
142
36
110
142
196
142
196
19
52
28
220
320



Notes






















1
1
'Lead and  total cyanide  limitations apply only to noncomplexed  lead-bearing  or
 cyanide-bearing waste streams.   Discharges of lead from complexed
 lead-bearing process wastewater or discharges of cyanide from complexed
 cyanide-bearing process wastewater are not subject to these limitations.
                                     12-8

-------
                                  Table 12-3
               FOR ORGANIC

PSNS Effluent Limitations*
PSNS EFFLUENT LIMITATIONS
PESTICIDES ACTIVE  INGREDIENTS  (PAIs)
Organic Pesticide
Active Ingredient
2, 4-D
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb
Ametryn
Atrazine
Benfluralin
Benomyl and Carbendazim
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 40
Bus an 85
Butachlor
Captafol
Carbarn S
Carbaryl
PSNS Effluent Limitations
Daily Maximuto Shall
Not Exceed
1.42 x ID'3
Monthly Average
Shall Not Exceed
4.61 x 10"
Notes

No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
6.39 x 10"
1.77
3.74 x lO'3
5.21 x 10"
5.56 x 10-3
3.69 x 10-3
3.22 x 10-4
2.52 x 10-2
1.22 x 10-2
1.97 x 10*
6.69 x 10-'
1.11 x 1C"3
2.25 x 10"
1.82 x lO"3
1.24 x 10-3
1.09 x 10"
6.44 x lO'3
6.28 x 10'3






1
2

No discharge of process wastewater pollutants
2.76 x 10-1
2.84 x lO'3
2.84 x 10-3
4.14 x ID'3
4.14 x 10-3
3.74 x lO'3
4.24 x 10^
4.14 x lO'3
1.18 x 10-3
8.36 x 10-2
9.14 x 10"
9.14 x 10"
1.35 x 10-3
1.35 x ID'3
1.11 x 10-3
1.31 x 10^
1.35 x 10-3
5.24 x 10"









                                     12-9

-------
Table 12-3




(Continued)
Organic Pesticide
Active Ingredient
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos
Cyanazine
Dazomet
DCPA
DEF [S,S,S-Tributyl
phosphorotrithioate ]
Diazinon
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin
Ethion
Fenarimol
Fensulfothion
PSNS Effluent Limitations
Daily Maximum Shall
Not Exceed
1.18 x 10-4
5.87 x 10-2
1.09 x lO'3
5.94 x lO-4
7.42 x 10-3
4.14 x 10-3
5.61 x ID'2
1.15 x lO'2
2.05 x 10-3
Monthly Average
Shall Not Exceed
2.80 x 10-5
2.39 x lO'2
3.29 x W-4
1.75 x lO-4
2.40 x 10-3
1.35 x 1C'3
1.90 x 10-2
5.58 x 10-3
8.13 x 10-4
Notes









No discharge of process wastewater pollutants
6.88 x lO'5
3.41
2.54 x ID'2
5.28 x 10-3
2.27 x 10-2
2.13 x 10's
1.03
9.31 x 10-3
2.72 x 10-3
1.01 x 10-2





No discharge of process wastewater pollutants
1.57 x 10-2
3.22 x IO-4
3.97 x 10-3
1.02 x ID'1
1.06 x ID'2
3.69 x 10-3
1.09 x 10-4
1.33 x 10-3
3.61 x lO'2
5.50 x 10-3





   12-10

-------
Table 12-3




(Continued)
Organic Pesticide
Active Ingredient
Fenthion
Fenvalerate
Guthion
Heptachlor
Isopropalin
KN Methyl
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Me thami dopho s
Methomyl
Methoxychlor
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norflurazon
Organotins
Parathion Ethyl
Parathion Methyl
PSNS Effluent Limitations
Daily Maximum Shall
Not Exceed
1.32 x 10-2
3.91 x 10-3
1.97 x 10-2
6.31 x 1C'3
5.07 x 10-3
4.14 x 10-3
1.94 x 1C'3
1.69 x 10-4
Monthly Average
Shall Not Exceed
6.79 x ID'3
1.50 x 10-3
1.02 x 10-2
2.06 x 10-3
1.82 x 10-3
1.35 x ID'3
1.40 x 10-3
6.88 x lO"5
Notes








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
4.14 x 1C'3
4.14 x 1C'3
5.58 x 10-3
5.42 x 10-3
1.27 x 10-3
9.25 x 10-4
5.06 x 10-3
3.69 x ID'5
1.35 x 10-3
1.35 x lO'3








No discharge of process wastewater pollutants
7.20 x 10^
1.25 x 10-2
5.56 x 10-*
5.56 x 10-1
3.10 x lO-4
5.36 x lO'3
2.45 x 10-4
2.45 x W*

3


  12-11

-------
Table 12-3




(Continued)
Organic Pesticide
Active Ingredient
PCNB
Pendimethalin
Permethrin
Phorate
Phosmet
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I and
Pyrethrin II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
PSNS Effluent Limitations
Daily Maximum Shall
Not Exceed
4.16 x 10"
1.17 x lO'2
1.68 x 10"
3.12 x 10"
Monthly Average
Shall Not Exceed
1.38 x ID"4
3.62 x 10'3
4.39 x 10'5
9.37 x 10'5
No discharge of process wastewater
pollutants
5.56 x 10'3
5.56 x ID'3
4.78 x ID"4
3.74 x 10'3
7.63 x 10-4
5.56 x 10'3
8.91 x Id'3
5.56 x 10°
2.95 x 10'3
2.80 x 10'3
9.78 x 10'2
2.76 x 10"'
4.92 x 10"
5.56 x 10'3
5.56 x 10'3
7.35 x 10'3
4.69 x 10'2
1.82 x 10'3
1.82 x 10'3
1.45 x 10"
1.11 x 10'3
3.48 x ID"4
1.82 x lO'3
2.40 x 10"3
1.82 x 10'3
9.72 x lO"
7.54 x 10"4
3.41 x 10'2
8.36 x lO'2
1.26 x 10"
1.82 x 10'3
1.82 x 10°
2.67 x 10°
2.46 x 10'2
Notes




4

















  12-12

-------
                                  Table 12-3

                                  (Continued)
Organic Pesticide
Active Ingredient
Trifluralin
Vapam [Sodium
me thy Idi thiocarbamate ]
Ziram [Zinc dimethyl -
dithiocarbamate ]
PSHS Effluent Limitations
Daily Maximum Shall
Not Exceed
3.22 x 10-4
4.14 x 10-3
4.14 x ID'3
Monthly Average
Shall Not Exceed
1.09 x lO"1
1.35 x 10-3
1.35 x ID'3
Notes
1
 limitations are in Kg/kkg (lb/1,000 Ib) i.e., kilograms of pollutant per
  1,000 kilograms product (pounds of pollutant per 1,000 Ibs product).

Notes

'Monitor  and report  as  total Trifluralin.
2Pounds of product shall  include  Benomyl  and any Carbendazim production not
 converted to Benomyl.
'Monitor  and report  as  total tin.
4Applies  to purification  by recrystallization portion of the process.
                                    12-13

-------

-------
                                  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:  BODJ(  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
v. 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
                                     13-1

-------
the POTW benchmark of $0.25 per pound in 1976 dollars for industries whose
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
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 BOD5  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
                                     13-2

-------
in removing specific compounds from wastewater, they may not be particularly
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.

13.3        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 BOD5 and TSS  removed,  due  to  the upgrade.
Conventionals considered in the total include BODS  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.
                                     13-3

-------
13.3.2      Application to the Organic Pesticide Chemicals Manufacturing
            Subcategorv

            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 BOD5  and TSS  concentrations;  and
            •     Effluent BOD5  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 BODj  and TSS were used to  determine  the
influent BOD5  and TSS concentrations to  the multi-media  filter.   Since  these
BOD5  and TSS data are mass based (i.e. 1.12 Ib. BOD5/1000 Ibs. of production
and 1.31 Ib. TSS/1000 Ibs. of production), the high flow and low flow
production values and flows were used with the mass-based long-term data to
determine BOD5 and TSS influent  concentrations.

            To determine the effluent BOD5 and TSS  concentrations for the
CAPDET module, BODS 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 BOD5 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 BOD5  and TSS
removals from the combined sand filter/settling pond system during sampling
were 48 percent BOD5 removal  and 53 percent TSS removal.

            Using the flows and the influent and effluent BOD5 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 BODS and TSS.
                                     13-4

-------
            Finally, a removal cost  ($/lbs. of conventional pollutants
removed) was determined by dividing  the incremental annual cost by the BOD5
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), BOD5 and
TSS removals (Ib/yr),  and removal costs ($/lb), are presented in Table 13-1.

13.4        CONCLUSIONS

            As seen in Table 13-1 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
setting BCT equal to BPT for this subcategory.

            EPA is reserving BCT for the metallo-organic pesticide chemicals
manufacturing subcategory.
                                     13-5

-------
                                  Table 13-1
                        POTW COST TEST RESULTS FOR THE
             ORGANIC  PESTICIDE CHEMICALS MANUFACTURING  SUBCATEGORY
Facility
Type
High Flow
Low Flow
C?/yx)
Animal Cost:
1976 ?
87,622
45,116
avyr)
BOD, & TSS
Removal
200,800
23,061
C$/D>)
Removal
Cost
0.44
1.96
POTff
Test Pass/
Tall*
Fail
Fail
*The removal costs ($/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.
                                     13-6

-------
                                   SECTION 14

         METALLO-ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY

            The Agency  is  reserving 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.  Since 1986, three
facilities producing pesticides  in this subcategory have ceased manufacturing
metallo-organic active  ingredients. 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 5,000 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 0.3 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.)

            For Subcategory B plants, EPA considered imposing PSES equal to
the existing BPT (i.e., requiring no discharge of process wastewater
pollutants), but determined that the only way the facilities could achieve
this standard is by off-site disposal (incineration).  Off-site disposal was
determined not to be economically achievable because one of the two facilities
in this subcategory  is 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 subject to
locally imposed pretreatment limits which EPA believes provide adequate
protection for the POTW and the environment.   The two existing facilities are
treating their discharges  in accordance with these limits and together are
discharging only 0.3 pounds of priority pollutants and PAIs annually.
Furthef,  imposing the control technologies that are the bases for the BAT
limitations being proposed today (i.e.,  Option 1,  physical/chemical treatment)
would result in the additional removal of only less than 0.3 pounds annually
of priority pollutants and PAIs from these two facilities.  In light of the
small amount of pollutants being discharged, as well as the economic
unachievability of off-site disposal, EPA is not establishing regulations for
existing indirect dischargers in the metallo-organic pesticides manufacturing
subcategory.

            One commenter  asserts that EPA should have  set PSES limitations
for Subcategory B,  because local limits are not within EPA's control and might
be relaxed by local authorities.  EPA does not agree that PSES limitations
should be set.   Current discharges subject to current local limits are
                                     14-1

-------
insignificant (only about 0.3 pounds per year),  and imposing PSES limits is
projected to remove only de minimis additional amounts of pollutants (less
than 0.27 pound per year).  Information concerning the two POTWs involved
indicates that they had previous problems with pesticide discharges,  and
because of that are unlikely to relax their local requirements.  Moreover,
three of the five  Subcategory B facilities that EPA identified at proposal as
indirect dischargers have closed.  Finally, even if the two POTWs removed
their local limits on these pollutants entirely, the total annual discharge
from the two plants would only be about 14 pounds per year, which is an
insignificant amount.  Accordingly, EPA is not setting PSES limitations for
Subcategory B.

            Under Subcategory B, the Agency is reserving PSNS.  The Agency
believes it is unlikely that there will be any new manufacturers of the
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.  Unlike organic pesticide chemicals, where
new producers of currently manufactured pesticides are possible, EPA believes
that new producers are unlikely, because there have been no new plants in the
me tallo-organic pesticide industry for more than 20 years and because the
current PAIs produced are the same as those produced over the past 20 years
(i.e., there have been no new me tallo-organic PAIs in 20 years).  In addition,
three of the eight organo-metallic pesticide manufacturing plants that were
operating in 1986 have closed and no new plants have begun operating.
Therefore, the Agency does not believe there will be any new sources, and
there is no need for PSNS for Subcategory B.
                                     14-2

-------
                                  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 effluent limitations guidelines and standards.
Accordingly, EPA has considered the effect of these regulations on air
pollution, solid waste generation, and energy consumption.

            The non-water quality environmental impacts associated with these
regulations 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 Act Amendments
(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
volatilization of both volatile organic compounds (VOC),  which contribute to
the formation of ambient ozone, and HAP from the wastewater.

            VOCs and HAPs are emitted from wastewater beginning at the first
air/water interface.   Thus, VOCs and HAPs 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 steam strippers lacking air emission control devices,  and any other units
where the wastewater is in contact with the air.

            Today's final 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 included in conjunction with
chemical oxidation systems as a combined BAT-level technology to prevent air
emissions of chlorinated priority pollutants from the chemical oxidation
effluent.

            Some increased air emissions could result from  generation of the
additional energy necessary to operate steam strippers, and from the
incineration of the small volumes of wastewater or residuals from treatment
systems (spent activated carbon, steam stripper overheads, wastewater
treatment solids).  However, the overall amounts of the air emissions are
expected to  significantly decrease due to compliance by pesticide
                                     15-1

-------
manufacturers with the final rule. Based on raw wastewater loading estimates,
air emissions of volatile priority pollutants would decrease by up to six
million pounds per year due to the use of steam stripping.  The final
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 pesticide manufacturing plants that currently use stripping are
using steam strippers and not air strippers.)  Also,  there are activities
underway under the Clean Air Act to address emissions of VOCs from industrial
wastewaters.  Specifically, the Agency plans to issue a Control Techniques
Guideline (CTG) for Industrial Wastewater (IWW) under Section 110 of the CAA
pursuant to Title I of the 1990 Clean Air Act Amendments (CAM) .   The
pesticide industry is one of several industries that would be covered by this
CTG.  The CTG will provide guidance to States recommending reasonably
available control technology (RACT) for VOC emissions from industrial
wastewater at (pesticide manufacturing) facilities located in areas failing to
attain the National Ambient Air Quality Standards for ozone.

            The Agency also plans to issue a National Emission Standards for
Hazardous Air Pollutants (NESHAP) under Section 112 of the CAA to address air
emissions of the HAPs listed in Title III of the 1990 CAAA.  This list
contains 20 of the 28 priority pollutants and 8 of the 120 PAI pollutants with
limitations in this rule.  The NESHAP will define maximum achievable control
technology (MACT).  The 1990 CAAA set maximum technology control requirements
on which MACT standards can be based for new and 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 these final pesticide effluent
guidelines, such as using steam stripping instead of air stripping.  Combining
compliance with the effluent guidelines and upcoming CAA regulations will be
more economical than individual compliance with each rule.
                                     15-2

-------
15.2        SOLID WASTE

            Wastewaters from  the production of the following PAIs are
regulated as RCRA listed hazardous wastes:

            K033  -     Wastewater and scrub water from the chlorination of
                        cyclopentadiene in the production of chlordane;

            K038  -     Wastewater from the washing and stripping of phorate
                        production;

            K098  -     Untreated process wastewater from the production of
                        toxaphene;

            K099  -     Untreated wastewater from the production of 2,4-D;

            K123  -     Process wastewater (including supernates, filtrates,
                        and washwaters) from the production of
                        ethylenebisdithiocarbamic acid and its salts;

            K124  -     Reactor vent scrubber water from the production of
                        ethylenebisdithiocarbamic acid and its salts; and

            K131  -     Wastewater from reactor and spent sulfuric acid from
                        the acid dryer from the production of methyl bromide.

The Agency is currently conducting additional hazardous waste listing
determinations for waters produced from the manufacture of carbamate,
carbamoyl oxime, thiocarbamate, and dithiocarbamate chemicals, which are
largely used as pesticides.   The Agency expects to propose its hazardous waste
listing determination by December 31, 1993, for these carbamate pesticides.

            Under Section 3004(n) of RCRA, standards controlling organic
emissions from process vents  and equipment leaks at facilities which treat,
store, or dispose of hazardous wastes (TSDF) have been enacted (55 FR 25454).
Additional standards to control air emissions at TSDFs from open tanks,
surface impoundments, and landfills were proposed July 22, 1991 (56 FR 33490),
and have not yet been promulgated by the Agency.  Wastewater treatment units
subject to regulation under either Section 402 or 307(b) of the Clean Water
Act would be exempt from these regulations under 40 CFR 264.1(g)(6) and 40 CFR
265(c)<10).

            Solid waste would be generated due to the following technologies,
if implemented to meet these  final regulations: steam stripping,  hydroxide
precipitation, and biological treatment.  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.
                                     15-3

-------
            The overhead stream from steam stripping will generally contain
organic waste.  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 at 16
facilities.

            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 31,000
pounds per year of precipitated solids would be generated due to the
implementation of hydroxide precipitation at one facility.

            Biotreatment is the model 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 would be generated due to these final
regulations.  For comparison, EPA estimates that all POTW's combined generate
more than 7.7 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

            EPA estimates that the attainment of BAT,  NSPS, PSES,  and PSNS
will increase energy consumption by a small increment over present industry
use.  The main energy requirement in  the final rule is to generate steam used
by steam strippers.  Steam provides the heat energy necessary to separate
volatile pollutants from wastewater streams treated by this technology.  It is
estimated that about 800 million pounds per year of steam would be required by
steam strippers operating at 16 facilities.  This would require approximately
187,000 barrels of oil annually; the United States currently consumes about 19
million barrels per day.  Energy requirements will also increase minimally due
to pumping needs associated with the proposed technologies.
                                     15-4

-------
                                  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 (BOD5) ,  (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)(1) of the CWA.are the list of 65 compounds and classes of compounds
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
                                     16-1

-------
used by EPA in its sampling of pesticide manufacturing industry wastewaters.
All of the PAI pollutant data EPA is relying on for the final effluent
limitations used analytical methods employing the latest in analytical
technology.  EPA is today requiring that compliance monitoring of PAIs in
effluent from the manufacture of the 120 PAIs with limitations in this rule
must employ methods listed in Table 16-1, and will not be permitted to use the
methods promulgated at 40CFR Part 136 (except where the Part 136 method is
identical to the 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 -
Supplementl" (July 1990).  EPA is including many of these drinking water
methods for monitoring pesticide active  ingredients in pesticide industry
wastewaters.

16.2        PROMULGATED 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, EPA
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.
                                     16-2

-------
                  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-Dichiorophenoxyacetic
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-Dichloropheno'xy)
propionic acid]
MCPP; MCPP Salts and Esters
[2- (2-Methyl-4-chlorophenoxy)
propionic acid]
TCMTB [ 2 - (Thiocyanomethyl thio )
benzothiazole ]
Pronamide
Propanil
Metribuzin
Acephate
Acifluorfen
Alachlor
GAS 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 Utonber (s)
507/633/525.1/1656
1657/507/622/525.1
1658/515. 1/615/
515.2/555
1658/515. 1/615/
515.2/555
1657/507/622/525.1
629/507
1656/508/608.1/525.1
1658/615/555
1658/515. 1/615/
515.2/555
1658/615/555
637
525.1/507/633.1
632.1/1656
507/633/525.1/1656
1656/1657
515.1/515.2/555
505/507/645/525. I/
1656
                    16-3

-------
Table 16-1




(Continued)
EPA
Survey
Code
55
58
60
62
68
69
69
70
73
75
76
80
82
84
86
90
103
107
110
112
113
Pesticide Name
Aldicarb
Ametryn
Atrazine
Benomyl
Bromacil; firomacil Salts and
Esters
Bromoxynil
Bromoxynil octanoate
Butachlor
Captafol
Carbaryl [Sevin]
Carbofuran
Chloroneb
Chlorothalonil
Stirofos
Chlorpyrifos
Fenvalerate
Diazinon
Parathion methyl
DCPA [Dimethyl 2,3,5,6-
tetrachloroterephthalate ]
Dinoseb
Dioxathion
CAS Number
00116-06-3
00834-12-8
01912-24-9
17804-35-2
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
EPA, Analytical
Method Number 
-------
Table 16-1




(Continued)
EFA
Survey
Code
118
119
123
124
125
126
127
132
133
138
140
144
148
150
154
156
158
172
173
175
178
.Pesticide Waae
Nabonate [Disodium
cyanodithioimidocarbonate ]
Diuron
Endothall
Endrin
Ethalfluralin
Ethion
Ethoprop
Fenarimol
Fenthion
Glyphosate [N- (Phosphonomethyl)
glycine]
Heptachlor
Isopropalin
Linuron
Malathion
Methamidophos
Me thorny 1
Methoxychlor
Nab am
Naled
Norflurazon
Benfluralin
CAS Number
00138-93-2
00330-54-1
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
EFA Analytical
Method NtunberO)
630.1
632/553
548/548 . 1
1656/505/508/608/
617/525.1
1656*/627*
1657/614/614.1
1657/507/622/525.1
507/633.1/525.1/1656
1657/622
547
1656/505/508/608/
617/525.1
1656/627
553/632
1657/614
1657
531.1/632
1656/505/508/608. 2/
617/525.1
630/630.1
1657/622
507/645/525.1/1656
1656*/627*
   16-5

-------
Table 16-1




(Continued)
EPA
.Survey
Code
182
183
185
186
192
197
203
204
205
206
208
212
218
219
220
223
224
226
230
232
Pesticide Name
Fensulfothion
Disulfoton
Phosmet
Azinphos Methyl
Organo-tin pesticides
Bolstar
Parathion
Pendimethalin
Pentachloronitrobenzene
Pentachlorophenol
Permethrin
Phorate
Busan 85 [Potassium
dimethyldithiocarbamate ]
Busan 40 [Potassium
N-hydroxymethyl -N-methyldithioc
arbamate ]
KN Methyl [Potassium
N-methyldithiocarbamate ]
Prometon
Prometryn
Propazine
Pyrethrin I
Pyrethrin II
GAS Number
00115-90-2
00298-04-4
00732-11-6
00086-50-0
12379-54-3
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
EPA Analytical
Hethod Number{s)
1657/622
1657/507/614/622/
525.1
^ r *• ••» / s f\ « t
LQ3 //0££. i.
1657/614/622
Ind- 01/200. 7/200. 9
1657/622
1657/614
1656
1656/608.1/617
625/1625/515. 2/5S5/
515. I/ 525.1
608. 2/508/525. I/
1656/1660
1657/622
630/630.1
630/630.1
630/630.1
507/619/525.1
507/619/525.1
507/619/525.1/1656
1660
1660
   16-6

-------
                                  Table  16-1




                                  (Continued)
EPA
Survey
Code
236
239
241
243
252
254
255
256
257
259
262
263
264
268
Pesticide Name
DEF [S,S,S-Tributyl
phosphorotrithioate ]
Simazine
Carbarn- S [Sodium
dimethyldithiocarbanate ]
Vapam [Sodium
methyldithiocarbamate ]
Tebuthiuron
Terbacil
Terbufos
Terbuthylaz ine
Terbutryn
Dazomet
Toxaphene
Merphos [Tributyl
phosphorotrithioate ]
Trifluralin
Ziram [Zinc
dime thyldithiocarbamate ]
GAS Somber
00078-48-8
00122-34-9
00128-04-1
00137-42-8
34014-18-1
05902-51-2
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
505/507/619/525. I/
1656
630/630.1
630/630.1
507/525.1
507/633/525.1/1656
1657/507/614.1/525.1
619/1656
507/619/525.1
630/630.1/1659
1656/505/508/608/
617/525.1
1657/507/525.1/622
1656/508/617/627/
525.1
630/630.1
*Monitor and report as total Trifluralin.
                                     16-7

-------
            A number of commenters stated that their plants have analytical
methods that differ from the methods listed in Table 161 to some degree.
Several of those commenters have submitted their methods as part of their
comments.  EPA has evaluated those methods and has determined that the
differences are within the range allowed by the Table 16-1 methods, providing
that the quality control criteria in the promulgated methods are met. Several
commenters also noted that their methods have been submitted to the permitting
authority for their plants and the methods have met the requirements and have
been accepted by the permitting authority. The concern expressed was that the
promulgation of these methods would require the discharger to resubmit the
methods for reevaluation,  at possibly considerable expense. Where the methods
were submitted with the comments or as supplemental information and comment,
EPA has evaluated those methods and has sent letters to the commenter with
EPA's evluation of that method. In  all cases, EPA believes that the
commenters' method is equivalent to the promulgated method. The commenter may
use that letter as demonstration to the permitting authority that the
commenter' s analytical method is equivalent to the promulgated method and
therefore may be used by the commenter for compliance monitoring.

Revisions to Analytical Methods--

            EPA listed the method numbers of the analytical methods required
for monitoring the pesticide active ingredients (PAIs) in Table 7 of the
proposed rule (57 FR 12601).  The methods referenced by number in Table 7 had
either been promulgated at 40 CFR Part 136 or copies were obtainable from the
EPA Sample Control Center or the National Technical Information Service (NTIS)
at the addresses given in the proposal (57 FR 12590), and a copy of the
obtainable methods was included in the docket for the proposed rule.

            EPA has revised and promulgated Table 7 of the proposed rule as
Table 7 in the final rule.  The revisions are the result of changes in method
numbers, corrections to method numbers, comments received, and revision and
development of additional methods by EPA.

            At the time of proposal, EPA was in the process of separating
Method 1618 into Methods 1656, 1657, and 1658 for the organo-chlorine
pesticides and PCBs, organo-phosphate pesticides, and phenoxy-acid herbicides,
respectively.  Table 7 of the proposed rule did not contain these individual
method numbers.   However,  the correct method numbers were listed in the
Development document for the proposed rule and the index of the methods
compendium titled "Methods for the Determination of Nonconventional Pesticides
in Municipal and Industrial Wastewater" (EPA 821/R-92-002, April 1992)
("Compendium"),  available from the EPA Sample Control Center and included in
the docket.  The active ingredients affected by the change from Method 1618 to
Method 1656 are propachlor, captafol, chloroneb, endrin, heptachlor,
methoxychlor, pentachloronitrobenzene, toxaphene, and trifluralin.  The active
ingredients affected by the change from Method 1618 to Method 1657 are
dichlorvos, mevinphos, stirofos, chlorpyrifos, diazinon, parathion methyl,
dioxathion, ethion, ethoprop, fenthion, malathion, methamidophos, naled,
fensulfothion, disulfoton, phosmet, azinphos methyl, bolstar, parathion,
                                     16-8

-------
phorate, DEF, terbufos, and merphos.  The active ingredients affected by the
change from Method 1618 to Method  1658 are 2,4-D and its salts and esters,
dichlorprop and its salts and  esters, MCPP and its salts and esters, and
dinoseb.

            Some of the method numbers listed in the Compendium for certain
PAIs were inadvertently omitted from Table 7 of the proposal.  The correct
method numbers are listed in Table 7 of the final rule.  The active
ingredients for which Method 1656 was added are triadimefon, propanil,
metribuzin,  alachlor, atrazine, bromacil and its salts and esters, butachlor,
chlorothalonil, DCPA, ethalfluralin, fenarimol, isopropalin, norflurazon,
benfluralin, propazine, simazine, terbacil, and terbuthylazine.   The active
ingredients for which the respective methods were added are: Method 515.1 for
DCPA and pentachlorophenol; Method 633.1 for pronamide; Method 1657 for
acephate; Method 515.2 for pentachlorophenol; and Methods 507 and 622 for
merphos.    EPA has dropped outdated industry methods that were not to be
included in Table 7 of the proposed rule and were not included in the methods
Compendium.   Industry Method  140A for gyphosate was dropped in favor of EPA
Method 547 and industry Method 131 for dazomet was dropped in favor of EPA
Method 1659.  Also EPA has dropped inapplicable methods for AIs for which they
were inadvertently listed in Table 7 of the proposed rule.  EPA dropped Method
1656 for DEF and merphos, for  which Method 1657 should have been listed and
for which it is now listed in  this final rule. EPA deleted the listing of
Method 508 for pyrethrin I and pyrethrin II because Method 508 does not cover
these compounds. EPA also dropped Method 1656 for bromoxynil in favor of
Method 1661, and for fenvalerate in favor of Method 1660.

            EPA has expanded the list of methods required for monitoring many
of the PAIs, and has included  the identification numbers of these methods in
Table 7.  In the proposal, EPA stated that the objective in allowing multiple
methods was to permit as much  flexibility as possible while controlling the
quality of the methods approved (57 FR 12590).  The additional methods
included in this final rule are EPA Methods 515.2 and 555 for determination of
the phenoxy-acid herbicides, Method 548.1 for determination of endothall, and
Method 553 for the determination of carbaryl, diuron, and linuron.  Method
515.2 was developed with pollution prevention objectives (to reduce solvent
use) in mind, and uses solid phase extraction (SPE) disks for extraction of
the herbicides from water.  Method 548.1 is an extensive revision of Method
548 and EPA recommends that users of Method 548 change to Method 548.1 because
of the simplicity and greater  reliability of Method 548.1.  Method 555 is a
new method for phenoxy-acid herbicides that uses high performance liquid
chromatography with a diode array detector.  Method 553 is a new method
employing SPE and liquid chromatography followed by particle-beam/mass
spectrometry.  These improved  and new methods are being included in this final
rule as additional methods that may be used and as allowable variants of the
methods proposed.   The active  ingredients affected by the addition of Method
515.2 are 2,4-D and its salts  and esters, 2,4-DB and its salts and esters,
dichlorprop and its salts and  esters, acifluorfen,  DCPA, dinoseb,  and
pentachlorophenol.   The active ingredients affected by the addition of Method
555 are 2,4-D and its salts and esters,  2,4-DB and its salts and esters, MCPA
                                     16-9

-------
and its salts and esters, MCPP and its salts and esters,   dichlorprop and its
salts and esters, acifluorfen, dinoseb, and pentachlorophenol.

            EPA listed Method 525.1 as an allowable method for many PAIs in
Table 7 of the proposed rule, and as the only method for Pronamide.  Method
525.1 was included in the set of methods obtainable from NTIS and included in
the docket.  However, many of the PAIs for which Method 525.1 was listed in
Table 7 of the proposal are not listed within Method 525.1 itself.  The reason
that these PAIs were not listed within Method 525.1 was that EPA's
Environmental Monitoring Systems Laboratory in Cincinnati, Ohio (EMSL-Ci) had
not revised Method 525.1 to include the PAIs,  although EMSL-Ci had produced
performance data demonstrating analysis of these PAIs using Method 525.1.  EPA
has included Method 525.1 in the revised Compendium and has printed the
performance data supplied by EMSL-Ci at the end of the Method because Method
525.1 is the only gas chromatography/mass spectrometry (GC/MS) method
available for many of the PAIs, because EPA wants to allow continued use of
Method 525.1 for the PAIs for which it was proposed, and because Method 525.1
was the only method proposed for measurement of pronamide.  Method 525.1 was
also added for the determination of ethoprop,  pentachlorophenol and toxaphene.


            EPA has also approved Method 507 for pronamide, as indicated in
Table 7 of the final rule, because the only major difference between Methods
525.1, which was proposed and is approved for pronamide,  and Method 507, which
was not proposed, is that Method 525.1 uses a mass spectrometer detector
whereas Method 507 uses a nitrogen-phosphorus detector (NPD).  EPA has also
approved Method 507 for cyanazine, based on data submitted by industry.  These
data show that cyanazine, a triazine herbicide closely related to the other
triazine herbicides listed in Method 507, can be analyzed using GC/NPD.
Method 515 was changed to Method 615 for MCPA and its salts and esters as a
result of a typographical error.  Fenvalerate, pyrethrin I, and pyrethrin II
were added to Method 1660 based on new test data.

Corrections and Additions to Methods Compendium--

            EPA has revised the Compendium that was included in the docket and
discussed in the proposed rule .  Typographical errors were corrected and a
technical correction was made to EPA Method 1660 reducing by a factor of 10
the Method Detection Limits (MDLs),  estimated MDLs, minimum levels, and
concentrations for certain quality control acceptance criteria, for the
pyrethrin/pyrethroid active ingredients covered by Method 1660.  The factor of
10 technical correction was the result of improper calculations in the
original version of Method 1660.  This final rule is not affected by the
corrections because the effluent limits for the pyrethrin/pyrethroid active
ingredients covered by this rule are above the higher minimum levels and MDLs
published in the original version of the Compendium.

            To provide a single set of documents for the methods required for
monitoring the regulated PAIs that are not promulgated at 40 CFR Part 136, EPA
has expanded the Compendium to include the proposed Method 525.1, newly
                                    16-10

-------
developed Methods 515.2, 553 and 555, the revised Method and 548.1, and the
other methods that EPA listed as obtainable from NTIS in the proposed rule (57
FR 12590) that are applicable to the regulated PAIs.  The revised  (two volume)
Compendium is also available from the U.S. EPA Office of Water.  EPA has
retained Method 642 in the Compendium because the decision not to  regulate
biphenyl came too late to remove Method 642 from the Compendium.   Compliance
monitoring of the priority pollutants, as in the proposal, is required to be
conducted using methods contained in 40 CFR 136.

            EPA is today promulgating all of these methods so they will be
available for compliance monitoring of PAIs in effluent from the manufacture
of the 120 regulated PAIs; for many PAIs, more than one analytical method is
being promulgated.  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.

            The analytical methods promulgated today are listed in Table 16-1.
This list  references method numbers contained in the documents  identified
below.  Both of the documents containing the methods are available in the
docket for this rulemaking.  The documents may also be obtained as follows:

Document Title and Number                          Source

"Methods for the Determination of Nonconventional  EPA Sample Control Center
Pesticides in Municipal and Industrial             300 N. Lee Street
Wastewater" Volume I EPA-821-R-93-010-A            Alexandria, VA  22314
Revision 1

"Methods for the Determination Nonconventional     EPA Sample Control Center
Pesticides in Municipal and Industrial             300 N. Lee Street
Wastewater" Volume II EPA-821-R-93-010-B           Alexandria, VA  22314
            These documents include methods for the 120 PAIs regulated today
as well as other PAIs.  A number of PAIs which are not manufactured in the
United States are incorporated into products that are formulated in the United
States.   The Agency is continuing its evaluation of these methods,  and
developing new methods, for potential use in monitoring discharges from PFPR
plants.   EPA intends to propose effluent guidelines for the PFPR industry in
January, 1994.

            EPA is approving these analytical methods so that all pesticide
methods for water and Wastewater developed by EPA to date will be available
for use by industry and by laboratories that test for these pesticides, and in
anticipation of EPA's future rulemaking for Pesticides Formulators and
Packagers.   However,  the fact that EPA is approving the use of a published
method for measuring a specific PAI does not mean that EPA definitely will
regulate (or not regulate) that PAI in a future rulemaking.
                                    16-11

-------
            The promulgated 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 final effluent
limitations guidelines and standards. The methods for monitoring the PAIs
included in the final rule are listed in Table 7 of the final rule.  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 promulgating multiple methods is
to permit as much flexibility as possible while controlling the quality of the
methods approved.

Method Flexibility--

            EPA will continue to allow flexibility in the selection of methods
and flexibility within methods, as stated in the proposed rule (57 FR 12590),
and within the methods themselves, consistent with the flexibility allowed in
the 40 CFR Part 136, Appendix A methods (49 FR 43234).  To further support
this flexibility, EPA has produced a document titled "Guidance on Evaluation,
Resolution, and Documentation of Analytical Problems Associated with
Compliance Monitoring" (EPA 821-B-93-001, February 1993) (the "Monitoring
Guidance").  This document gives details of the flexibility allowed in
resolving analytical problems and the documentation required under the NPDES
regulations when a method is altered.  This document is also available from
the EPA Sample Control Center, 300 N. Lee Street, Alexandria, VA 22314.

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 is promulgating 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 the proposed
rule.

            Where possible, EPA tests existing methods to determine if an
active ingredient can be measured by these existing methods.  If these tests
are successful, EPA revises the method to incorporate the new analyte.  In
                                     16-12

-------
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
promulgated in this final 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.

16.2.4      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 begins;  if unsuccessful, EPA works closely
with its scientific consultants and the  laboratory to try other approaches.
                                     16-13

-------
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 reproducibility
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.

            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 sample 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
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 obtains 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.
                                     16-14

-------
16.3        INVESTIGATION OF OTHER ANALYTICAL TECHNIQUES

            In addition to methods developed for the final 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.
                                    16-15

-------

-------
                                  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 Section 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 Section 304(b)(4) of the Act.

BMP - Best management practices, as defined by Section 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 Section 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 Section
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.

Indirect Discharger - An industrial discharger that introduces wastewater into
a publicly-owned treatment works.
                                     17-1

-------
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  Quality Environmental 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 Section 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 Section 306 of the Act.

OCPSF - Organic chemicals, plastics, and synthetic fibers manufacturing point
source category. (40 CFR Part 414).

PAI - Pesticide Active Ingredient.

Point Source Category - A collection of industrial sources with similar
function or product, established by Section 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 Section 307(b) of the Act.

PSNS - Pretreatment standards for new sources of indirect discharges under
Section 307(b) and (c) of the Act.
                                     17-2

-------
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

-------

-------
                                  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 Wvandotte Corp. v. Costle. 614 F. 2d 21 (1st Cir. 1980).

4.          BASF Wvandotte Cort>. 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.

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.
                                     18-1

-------
                                 REFEREENCES

                                  (Continued)

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"),
            Toksikolgjgu 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
            Environments",  Environmental Letters. 3(3):171-201, 1972.

23.         Fest, C. , and K. J. Schmidt, The Chemistry of Organophosphorus
            Pesticides. Springer-Verlag, New York,  1973.

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.

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
            Manufacturing Wastewaters.   EPA Contract No. 68-03-3371, December
            1990.
                                     18-2

-------
                                 REFEREENCES

                                  (Continued)

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.,  Hvdrolvtic 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.

34.         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.

                                     18-3

-------
                                 REFEREENCES

                                  (Continued)

37.         Marchenko,  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 Technoloev.
            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 "Khiaiya 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.

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.


                                     18-4

-------
                                 REFEREENCES

                                  (Continued)

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,
            February 1990.

53.         "Standard Methods for the Examination of Water and Wastewater",
            15th Edition, American Public Healfh 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
            Foundation, Denver, CO, 1989.

55.         Tchobanoglous, George, and Edward D. Schoeder, Water Quality.
            Addison-Wesley Publishing Company, Reading, MA, 1985.

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.

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
            OrEanic 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.
                                     18-5

-------
                                 REFEREENCES

                                  (Continued)

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,
            No.  131,  July 9,  1988.

68.         United States Environmental Protection Agency, "Effluent
            Guidelines and Standards  for the Pesticide  Chemicals Category -
            Regulatory Program",  Federal Register.  Volume 55,  No. 209, October
            29,  1990.

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
            Enforcement System (FATES)  Database.  National Library of Medicine.

71.         United States Environmental Protection Agency, "Guidelines
            Establishing Test Procedures for the Analysis of Pollutants Under
            the  Clean Water Act;  Final Rule and Interim Final Rule and
            Proposed Rule", 40 CFR Part 136, Federal Register. FRL 2636-6,
            Volume 49, No. 209, October 26, 1984.

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.

                                     18-6

-------
                                 REFEREENCES

                                  (Continued)

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,
            Plastics,  and Synthetic Fibers Category Effluent Limitations
            Guidelines,  Pretreatment Standards,  and New Source Performance
            Standards -  Extension of Comment Period, Correction Notice, and
            Notice of Availability",  40 CFR Parts 414 and 416,  Federal
            Register.  FRL-2911-4, Volume 50, No. 198, October 11, 1985.

76.         United States Environmental Protection Agency, "Organic Chemicals,
            Plastics,  and Synthetic Fibers Category Effluent Limitations
            Guidelines and Standards, and New Source Performance Standards -
            Amendments to 40 CFR Parts 414 and 416", 40 CFR Parts 414 and 416,
            Federal Register. FRL 3230-5, Volume 52, No. 214, November 5,
            1987.

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
            Regulations", 40 CFR Part 414, Federal Register.  FRL 3577-9,
            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
            3726-6, Volume 55, No. 126, June 29, 1990.

79.         United States Environmental Protection Agency, "Organic Chemicals,
            Plastics,  and Synthetic Fibers Category Effluent Limitations
            Guidelines,  Pretreatment Standards,  and New Source Performance
            Standards -  Proposed Rule", 40 CFR Part 414, Federal Register. FRL
            3809-4, Volume 55, No. 202, October 18, 1990.

80.         United States Environmental Protection Agency, "Pesticide
            Chemicals  Category Effluent Limitations Guidelines,  Pretreatment
            Standards, and New Source Performance Standards - Proposed
            Regulation",  40 CFR Part 455, Federal Register. WH-FRL-2220-1,
            Volume 47, No. 230, November 30, 1982.

81.         United States Environmental Protection Agency, "Pesticide
            Chemicals  Category Effluent Limitations Guidelines,  Pretreatment

                                     18-7

-------
                                 REFEREENCES

                                  (Continued)

            Standards,  and New Source Performance Standards - Final
            Regulation", 40 CFR Part 455, Federal Register. OW-FRL-2877-6,
            Volume 50,  No. 193, October 4, 1985.

82.         United States Environmental Protection Agency,  "Pesticide
            Chemicals Category Effluent Limitations Guidelines,  Pretreatment
            Standards,  and New Source Performance Standards - Final Rule -
            Withdrawal", 40 CFR Part 455, Federal Register. OW-FRL-3128-1,
            Volume 51,  No. 240, December 15, 1986.

83.         United States Environmental Protection Agency,  "Pesticide
            Chemicals Manufacturing Point Source Category,  Part 455 Subchapter
            N - Effluent Limitations and Guidelines - Interim Final
            Rulemaking", Federal Register. FRL 637-5, Volume 41, No. 211,
            November 1, 1976.

84.         United States Environmental Protection Agency,  "Pesticide
            Chemicals Manufacturing Point Source Category Part 455,  Subchapter
            N - Effluent Guidelines and Standards - Final Rule", Federal
            Register. FRL 887-6, Volume 43,  No. 80, April 25, 1978.

85.         United States Environmental Protection Agency,  "Pesticide
            Chemicals"Manufacturing Point Source Category,  Part 455 -
            Amendments to Final Rule",  Federal Register.  FRL 973-7,  Volume  43,
            No. 190,  September 29, 1978.

86.         United States Environmental Protection Agency,  Pesticide Fact
            Handbook. Noyes Data Corporation,  Park Ridge, NJ, 1988.

87..         United States Environmental Protection Agency,  Pesticide
            Manufacturing Facility Census for 1986. June  1988.

88.         United States Environmental Protection Agency,  Process Design
            Manual for the Stripping of Organics. EPA-600/2-84-139.

89.         United States Environmental Protection Agency,  Proposed Effluent
            Guidelines - Rulemaking for the  Pesticide Chemicals  Category.
            Office of Water and Waste Management, Washington DC, Winter 1983.

90.         United States Environmental Protection Agency,  Toxic Release
            Inventory System (TRIS) Database.

91.         Viesman,  Warren,  Jr., and Mark J.  Hammer, Water Supply and
            Pollution Control. Harper and Row Publishers, New York,  1985.

92.         Weber, W. J., Jr., Phvsicochemical Processes..  John Wiley and
            Sons, New York, 1972.
                                     18-8

-------
                                 REFEREENCES

                                  (Continued)

93.         Weigman, Diana L.,  editor, Pesticides in the Next Decade:  The
            Challenges Ahead -  ProceedinES of the Third National Research
            Conference on Pesticides. November 8-9.  1990. Virginia Water
            Resources Research Center, Virginia Polytechnic Institute and
            State University, Blacksburg, VA,  1990.

94.         Worthing, C. R.,  editor, The Pesticide Manual. The Lavenham Press
            Limited, Lavenham,  Suffolk, Great Britian,  1987.
                                     18-9

-------