£EPA
           United States
           Environmental Protection
           Agency
           Office Of Water
           (WH-552)
EPA 821 R-92-005
April 1992
Development Document
For Best Available Technology,
Pretreatment Technology,
And New Source Performance
Technology For The
Pesticide Chemical Industry

Proposed
                                  Printed on Recycled Paper

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                 PROPOSED

      TECHNICAL DEVELOPMENT DOCUMENT

                  FOR THE

           PESTICIDE CHEMICALS

          MANUFACTURING CATEGORY

     EFFLUENT LIMITATIONS GUIDELINES,

        PRETREATMENT STANDARDS,  AND

     NEW SOURCE PERFORMANCE STANDARDS
             William K.  Reilly
               Administrator

            LaJuana  S. Wilcher
 Assistant Administrator, Office of Water

            Thomas P. O'Farrell
Director, Engineering and Analysis  Division

              Marvin B.  Rubin
           Chief, Energy Branch

            Thomas E. Fielding
              Project Officer
              March  31,  1992
     Engineering and Analysis Division
     Office  of  Science  and Technology
   U.S.  Environmental Protection Agency
          Washington, D.C.  20460

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                              TABLE OF CONTENTS

                                                                          Page


SECTION 1 - INTRODUCTION

1.0    LEGAL AUTHORITY	1-1

1.1.    BACKGROUND   	1-1
       1.1.1      Clean Water Act	1-1
       1.1.2      Section 304(m)  Requirements and Litigation  	   1-6
       1.1.3      Pollution Prevention Act	1-7
       1.1.4      Prior Regulation and Litigation for the Pesticide
                  Chemicals Category  	   1-7

1.2    SCOPE OF TODAY'S PROPOSED RULE   	1-10

SECTION 2   SUMMARY

2.0    OVERVIEW OF THE INDUSTRY   	2-1

2.1    SUMMARY OF THE PROPOSED REGULATIONS  	   2-3
       2.1.1      Applicability of the Proposed Regulations 	   2-3
       2.1.2      BPT	2-3
       2.1.3      BCT	2-4
       2.1.4      BAT	2-6
       2.1.5      NSPS	2-9
       2.1.6      PSES	2-19
       2.1.7      PSNS	2-26

SECTION 3   INDUSTRY DESCRIPTION

3.0    INTRODUCTION   	3-1

3.1    DATA COLLECTION METHODS	3-1
       3.1.1      Pesticide Product Registration Process  	   3-2
       3.1.2      Selection of PAIs for Study	3-3
       3.1.3      Development of the "Pesticide Manufacturing
                  Facility Census of 1986"  	   3-5
       3.1.4      EPA's 1988-1991 Sampling of Selected
                  Pesticide Manufacturers 	  3-29
       3.1.5      Indus try-Supplied Data	3-33
       3.1.6      EPA Bench-Scale Treatability Studies  	  3-34
       3.1.7      Data transferred from the OCPSF Rulemaking	3-38

3.2    OVERVIEW OF THE INDUSTRY   	3-41
       3.2.1      Geographical Location of Manufacturing Facilities .  .  .  3-41
       3.2.2      SIC Code Distribution	3-43
       3.2.3      Age of Facilities	3-45

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                         TABLE OF CONTENTS (Continued)
        3.2.4     Market  Types	3-45
        3.2.5     Type  of Facilities	3-48

3.3     PESTICIDE PRODUCTION   	 3-49
        3.3.1     Types of Pesticides	3-49
        3.3.2     1986  Pesticide Active  Ingredient Production  	 3-50
        3.3.3     Distribution  of  PAI  Production by Facility     	3-51
        3.3.4     Distribution  of  PAI  Production During the Year   .... 3-62

3.4     PESTICIDE MANUFACTURING PROCESSES  	 3-63
        3.4.1     Batch vs.  Continuous Processes   	 3-64
        3.4.2     General Process  Reactions  	 3-65
        3.4.3     Intermediate/By-product Manufacture  	 3-77

3.5     CHANGES IN THE INDUSTRY	3-79

SECTION 4  -  INDUSTRY  SUBCATEGORIZATION

4.0     INTRODUCTION   	4-1

4.1     BACKGROUND   	4-2
        4.1.1     November 1, 1976, Interim  Final BPT Guidelines   ....  4-3
        4.1.2     April 25,  1978,  Promulgated BPT Guidelines   	  4-4
        4.1.3     November 30,  1982, Proposed BAT, BCT, NSPS, PSES,
                  PSNS  Guidelines	4-5
        4.1.4     June  13,  1984, Notice  of Availability (NOA)	4-6
        4.1.5     October 4, 1985, Promulgated BAT, NSPS, PSES, and
                  PSNS  Guidelines	4-6

4.2     CURRENT SUBCATEGORIZATION BASIS  	  4-7
        4.2.1     Product Type  and Raw Materials	4-7
        4.2.2     Manufacturing Process  and  Process Changes 	  4-7
        4.2.3     Nature  of Waste  Generated  	  4-9
        4.2.4     Dominant Product 	 4-10
        4.2.5     Plant Size	4-10
        4.2.6     Plant Age	4-10
        4.2.7     Plant Location	4-11
        4.2.8     Non-Water  Quality Characteristics 	 4-12
        4.2.9     Treatment  Costs  and  Energy Requirements 	 4-13

4.3     PROPOSED SUBCATEGORIES    	 4-13
        4.3.1     Organic  Pesticide Chemicals Manufacturing 	 4-14
        4.3.2     Metallo-Organic  Pesticide  Chemicals Manufacturing .  .   .4-15
                                      11

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                        TABLE OF CONTENTS (Continued)


                                                                          Page

SECTION 5   WATER USE AND WASTEWATER CHARACTERIZATION

5.0    INTRODUCTION   	5-1

5.1    WATER USE AND SOURCES OF WASTEWATER	5-1
       5.1.1      PAI Process Wastewater	5-4
       5.1.2      Other Pesticide Wastewater Sources  	   5-6
       5.1.3      Other Facility Wastewater  Co-Treated with
                  Pesticide Wastewater  	   5-8

5.2    WASTEWATER VOLUME BY DISCHARGE MODE	5-12
       5.2.1      Definitions	5-12
       5.2.2      Discharge Status of Pesticide Manufacturing Facilities  5-13
       5.2.3      Flow Rates by Discharge Status	5-13

5.3    WATER REUSE AND RECYCLE	5-15

5.4    RAW WASTEWATER DATA COLLECTION   	5-20
       5.4.1      Industry Supplied Self-Monitoring Data  	  5-20
       5.4.2      EPA Pesticide Manufacturers Sampling Program  	  5-22

5.5    WASTEWATER CHARACTERIZATION  	  5-24
       5.5.1      Conventional Pollutants 	  5-25
       5.5.2      Priority Pollutants   	  5-32
       5.5.3      Pesticide Active Ingredient Pollutants  	  5-40
       5.5.4      Nonconventional Pollutants  	  5-41

5.6    WASTEWATER POLLUTANT DISCHARGES  	  5-43

SECTION 6   POLLUTANT PARAMETERS SELECTED FOR REGULATION

6.0    INTRODUCTION   	6-1

6.1    CONVENTIONAL POLLUTANT PARAMETERS  	   6-1

6.2    PRIORITY POLLUTANT   	6-3

6.3    NONCONVENTIONAL POLLUTANTS   	   6-9

SECTION 7 -  TECHNOLOGY SELECTION AND LIMITS  DEVELOPMENT

7.0    INTRODUCTION   	7-1

7.1    TREATMENT PERFORMANCE DATABASES  	   7-2
                                      ill

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                         TABLE OF CONTENTS (Continued)
        7.1.1     Analytical Data Submitted with the Pesticide
                  Manufacturing Facility Census for 1986 and
                  Associated Data	7-3
        7.1.2     Treatability Test Data	7-5
        7.1.3     Existing Treatment Performance Databases  	   7-9

7.2     WASTEWATER TREATMENT  IN  THE  PESTICIDE  CHEMICALS MANUFACTURING
        INDUSTRY   	7-10
        7.2.1     Carbon Adsorption	7-13
        7.2.2     Hydrolysis	7-16
        7.2.3     Chemical Oxidation/Ultraviolet Decomposition  	  7-19
        7.2.4     Resin Adsorption  	  7-21
        7.2.5     Solvent Extraction  	  7-23
        7.2.6     Distillation	7-24
        7.2.7     Membrane Filtration 	  7-25
        7.2.8     Biological Treatment  	  7-29
        7.2.9     Evaporation	7-31
        7.2.10     Chemical Precipitation/Filtration 	  7-32
        7.2.11     Chemical Reduction  	  7-34
        7.2.12     Coagulation/Flocculation  	  7-35
        7.2.13     Incineration  	  7-36
        7.2.14     Stripping  	  7-37
        7.2.15     Pre- or Post-Treatment	7-39
        7.2.16     Disposal of Solid Residue from Treatment  	  7-41

7.3     TREATMENT  PERFORMANCE DISCUSSION   	  7-43
        7.3.1     Carbon Adsorption 	  7-44
        7.3.2     Hydrolysis	7-48
        7.3.3     Chemical Oxidation/Ultraviolet Decomposition  	  7-50
        7.3.4     Resin Adsorption  	  7-51
        7.3.5     Solvent Extraction  	  7-52
        7.3.6     Distillation	7-54
        7.3.7     Biological Treatment  	  7-55
        7.3.8     Oxidation/Reduction and Physical Separation 	  7-56
        7.3.9     Incineration	7-57

7.4     EFFLUENT LIMITATIONS  DEVELOPMENT FOR PAIs    	  7-60
        7.4.1     Statistical Analysis of Long-Term Self-Monitoring Data  7-60
        7.4.2     Calculation of Effluent Limitations Guidelines
                  Under BAT	7-67
        7.4.3     Calculation of Effluent Limitations Guidelines
                  Under NSPS	7-93
        7.4.4     Analysis of POTW Pass-Through for PAIs	7-98
        7.4.5     Calculation of Effluent Limitations Guidelines
                  Under PSES and PSNS	7-100
                                      IV

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                        TABLE OF CONTENTS  (Continued)
7.5    EFFLUENT LIMITATIONS DEVELOPMENT FOR PRIORITY POLLUTANTS   .  .  .
       7.5.1      Calculation of Effluent  Limitations  Guidelines
                  Under BAT	7-103
                  7.5.1.1     Volatile and Semi-Volatile Organic
                              Pollutants	7-104
                  7.5.1.2     Brominated Organic Pollutants 	   7-112
                  7.5.1.3     Lead	7-114
                  7.5.1.4     Cyanide 	   7-116
       7.5.2      Calculation of Effluent  Limitations
                  Guidelines Under NSPS	7-117
       7.5.3      Calculation of Effluent  Limitations
                  Guidelines Under PSES	7-117
       7.5.4      Calculation of Effluent  Limitations
                  Guidelines Under PSNS	7-120

7.6    EFFLUENT LIMITATIONS DEVELOPMENT FOR CONVENTIONAL POLLUTANTS
       AND COD	7-121

SECTION 8   ENGINEERING COSTS

8.0    INTRODUCTION   	8-1

8.1    ENGINEERING COSTING  	   8-1
       8.1.1      Cost Methodologies	8-1
       8.1.2      Cost Procedures	8-2

8.2    COST MODELING	8-6
       8.2.1      Model Evaluation  	   8-6
       8.2.2      CAPDET	8-15
       8.2.3      Pesticide Industry Cost  Model 	  8-28

8.3    TREATMENT TECHNOLOGIES         	  8-32
       8.3.1      Activated Carbon  	  8-37
       8.3.2      Biological Treatment  	  8-39
       8.3.3      Chemical Oxidation  	  8-45
       8.3.4      Off-Site Incineration 	  8-46
       8.3.5      Distillation	8-50
       8.3.6      Equalization	8-52
       8.3.7      Filtration	8-52
       8.3.8      Hydrolysis	8-54
       8.3.9      Hydroxide Precipitation 	  8-57
       8.3.10     Resin Adsorption  	  8-58
       8.3.11     Steam Stripping 	  8-59
       8.3.12     Monitoring for Compliance 	  8-68

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                         TABLE OF CONTENTS (Continued)


                                                                          Page

SECTION  9  -  BEST  PRACTICABLE  CONTROL TECHNOLOGY  (BPT)

9.0     INTRODUCTION   	9-1

9.1     BPT APPLICABILITY	9-1

SECTION  10    BEST AVAILABLE TECHNOLOGY  ECONOMICALLY ACHIEVABLE  (BAT)

10.0    INTRODUCTION   	10-1

10.1    SUMMARY OF BAT EFFLUENT LIMITATIONS GUIDELINES   	10-2

10.2    IMPLEMENTATION OF THE BAT EFFLUENT LIMITATIONS GUIDELINES  .... 10-3
        10.2.1    National Pollutant Discharge Elimination System
                   (NPDES) Permit  Limitations   	 10-3
        10.2.2    NPDES Monitoring Requirements  	 10-5

10.3    BAT EFFLUENT LIMITATIONS GUIDELINES  	 10-6

SECTION  11    NEW  SOURCE PERFORMANCE  STANDARDS  (NSPS)

11.0    INTRODUCTION   	11-1

11.1    SUMMARY OF NSPS EFFLUENT LIMITATIONS GUIDELINE   	11-1

11.2    IMPLEMENTATION OF THE NSPS EFFLUENT LIMITATIONS GUIDELINES    .  .  . 11-2
        11.2.1    National Pollutant Discharge Elimination System
                  (NPDES) Permit  Limitations   	 11-2
        11.2.2    Monitoring  Requirements  	 11-3

11.3    NEW SOURCE PERFORMANCE STANDARDS (NSPS)   	 11-3

SECTION  12    PRETREATMENT STANDARDS  FOR EXISTING SOURCES  (PSES) AND
PRETREATMENT  STANDARDS FOR NEW SOURCES  (PSNS)

12.0    INTRODUCTION   	12-1

12.1    SUMMARY OF PSES AND PSNS   	12-3

12.2    PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES  (PSES/PSNS)   . 12-4

SECTION 13 -  BEST CONVENTIONAL POLLUTANT  CONTROL TECHNOLOGY  (BCT)

13.0    INTRODUCTION   	13-1
                                      VI

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                        TABLE OF CONTENTS  (Continued)


                                                                          Page

13.1   JULY 9, 1986 BCT METHODOLOGY   	13-2

13.2   BCT TECHNOLOGY OPTIONS   	13-4

13.3   BCT COST TEST ANALYSIS         	13-6
       13.3.1     The POTW Cost Test	    13-6
       13.3.2     Application to the Organic Pesticide Chemicals
                  Manufacturing Subcategory 	    .    13-7

13.4   CONCLUSIONS	13-9

SECTION 14   METALLO-ORGANIC PESTICIDE CHEMICALS MANUFACTURING
             SUBCATEGORY	14-1

SECTION 15   NON-WATER QUALITY ENVIRONMENTAL IMPACTS

15.0        INTRODUCTION  	15-1

15.1        AIR POLLUTION	15-1

15.2        SOLID  WASTE	15-5

15.3        ENERGY REQUIREMENTS  	  15-6

SECTION 16   ANALYTICAL METHODS

16.0   REGULATORY BACKGROUND AND REQUIREMENTS   	  16-1

16.1   CLEAN WATER ACT  (CWA)	16-1
       16.1.2     Safe Drinking Water Act (SDWA)  	  16-3

16.2   PROPOSED METHODS   	  16-9
       16.2.1     Methods  for PAI Pollutants  	  16-9
       16.2.2     Methods  for Metals  	   16-11
       16.2.3     Development of Methods  	   16-11
       16.2.4     Procedures for Development and
                  Modification of Methods 	   16-13
       16.2.5     Method Writing and Modification 	   16-15

16.3   INVESTIGATION OF OTHER ANALYTICAL TECHNIQUES   	   16-16

SECTION 17   GLOSSARY

SECTION 18   REFERENCES
                                      VI1

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                                 LIST  OF TABLES


                                                                          Page

2-1     PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT	2-5

2-2     BCT EFFLUENT LIMITATIONS FOR THE ORGANIC PESTICIDE CHEMICALS
        MANUFACTURING SUBCATEGORY  	  2-7

2-3     BAT AND PSES EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDE ACTIVE
        INGREDIENTS (PAIS)   	 2-10

2-4     BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
        DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL
        TREATMENT    	2-15

2-5     BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
        DIRECT DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE
        BIOLOGICAL TREATMENT   	 2-17

2-6     NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD    . 2-20

2-7     NSPS AND PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES
        ACTIVE INGREDIENTS (PAIS)  	 2-21

2-8     EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS PRETREATMENT
        STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)   	 2-27

3-1     LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)  	  3-7

3-2     TREATMENT UNIT OPERATIONS SAMPLED  	 3-31

3-3     COMPARISON OF THE GEOGRAPHIC DISTRIBUTION OF THE OCPSF vs.
        PESTICIDE INDUSTRY BY REGION   	 3-44

3-4     DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES BY DECADE OF
        OPERATION	3-46

3-5     PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS REPORTED TO
        BE MANUFACTURED IN 1986	3-52

3-6     NUMBER OF PESTICIDE ACTIVE INGREDIENTS PRODUCED IN 1986 BY
        NUMBER OF MANUFACTURING FACILITIES   	 3-60

3-7     NUMBER OF MANUFACTURING FACILITIES BY NUMBER OF PESTICIDE
        ACTIVE INGREDIENTS PRODUCED 	 3-60

3-8     DISTRIBUTION OF FACILITIES BY QUANTITY OF PAI PRODUCTION   .... 3-61
                                     viii

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                          LIST OF TABLES (Continued)
                                                                          Paee
5-1    PESTICIDE ACTIVE INGREDIENT PROCESS WASTEWATERS GENERATED IN
       1986 BY EFFLUENT TYPE	5-7

5-2    WASTEWATER GENERATED FROM OTHER PESTICIDES WASTEWATER SOURCES  .  .   5-9

5-3    OTHER FACILITY WASTEWATER GENERATED FROM SOURCES OTHER THAN
       PESTICIDE PRODUCTION AND CO-TREATED WITH PESTICIDE WASTEWATER  .  .  5-11

5-4    TOTAL PROCESS WASTEWATER FLOW BY TYPE OF DISCHARGE   	5-14

5-5    PESTICIDE PROCESS WASTEWATER FLOW FOR THE ORGANIC PESTICIDE
       SUBCATEGORY  (SUBCATEGORY A) AND THE METALLO-ORGAN1C PESTICIDE
       SUBCATEGORY  (SUBCATEGORY B)  	  5-16

5-6    TYPES OF WASTEWATER RECYCLE OPERATIONS REPORTED  	  5-17

5-7    PRIORITY POLLUTANT DATA-FACILITY SELF MONITORING   	  5-35

5-8    PRIORITY POLLUTANT DATA   EPA SAMPLING ORGANIC PESTICIDE
       CHEMICALS MANUFACTURING  	  5-38

6-1    PRIORITY POLLUTANTS SELECTED FOR REGULATION  	   6-5

7-1    TREATMENT TECHNOLOGIES USED BY THE PESTICIDE CHEMICALS
       MANUFACTURING INDUSTRY AS REPORTED IN THE 1986 FACILITY CENSUS   .  7-12

7-2    PAI  STRUCTURAL GROUPS	7-69

7-3    PAIs AND PAI STRUCTURAL GROUPS WITH PAI LIMIT DEVELOPMENT
       METHODOLOGIES  	  7-80

8-1    CAPDET LARGE FACILITY UNIT PROCESSES   	  8-22

8-2    CAPDET SMALL FACILITY UNIT PROCESSES   	  8-25

8-3    WASTE INFLUENT CHARACTERISTICS   	  8-27

8-4    UNIT COST DATA   	8-29

8-5    PROGRAM CONTROL/OUTPUT SELECTION     	  8-31

8-6    PESTICIDES OPTION  1   TOTAL COSTS  BY PLANT   	 8-34

8-7    DESIGN PARAMETERS  FOR THE BIOLOGICAL TREATMENT  COST MODULE   .  . . 8-42
                                       ix

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                          LIST OF TABLES  (Continued)
                                                                          Page

8-8     PRIORITY POLLUTANTS DIVIDED INTO GROUPS ACCORDING TO HENRY'S
        LAW CONSTANT VALUES	8-63

8-9     STEAM STRIPPING DESIGN PARAMETERS FOR HENRY'S LAW CONSTANT
        PARAMETERS   	8-64

9-1     EXISTING BPT EFFLUENT LIMITATIONS FOR THE PESTICIDE CHEMICALS
        POINT SOURCE CATEGORY (40 CFR PART 455)	9-2

9-2     ORGANIC PESTICIDE CHEMICALS EXCLUDED FROM THE 1978 BPT
        SUBCATEGORY A GUIDELINES   	  9-3

9-3     PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT	9-5

10-1    BAT EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDE ACTIVE
        INGREDIENTS (PAIS)   	 10-7

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

10-3    BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR
        DIRECT DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE
        BIOLOGICAL TREATMENT   	  10-14

11-1    NSPS EFFLUENT LIMITATIONS FOR CONVENTIONAL POLLUTANTS AND COD  .  . 11-5

11-2    PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES ACTIVE
        INGREDIENTS (PAIS)   	 11-6

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

11-4    NSPS FOR PRIORITY POLLUTANTS FOR PLANTS THAT DO NOT HAVE
        END-OF-PIPE BIOLOGICAL TREATMENT   	  11-13

12-1    PSES FOR ORGANIC PESTICIDE ACTIVE INGREDIENTS (PAIS)   	 12-5

12-2    PSES FOR PRIORITY POLLUTANTS   	12-10

12-3    PSNS FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)  	  12-12

12-4    PSNS EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS  	  12-17

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                          LIST OF TABLES (Continued)
                                                                          Page

13-1   POTW COST TEST RESULTS FOR THE ORGANIC PESTICIDE CHEMICALS
       MANUFACTURING SUBCATEGORY  	  13-10

16-1   TEST METHODS FOR PESTICIDE ACTIVE  INGREDIENTS  	 16-4
                                      XI

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                                LIST OF FIGURES


                                                                          Page

3-1     FLOW CHART FOR DETERMINING INCLUSION OF PAI IN PESTICIDE
        MANUFACTURING FACILITY CENSUS FOR 1986   	  3-6

3-2     DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES BY EPA
        REGION   	3-42

3-3     1986 PESTICIDE MARKET COMPOSITION  	 3-47

3-4     REACTION MECHANISMS FOR s-TRIAZINES AND ATRAZINE AND AMETRYN   .   . 3-66

3-5     REACTION MECHANISMS FOR CARBOFURAN AND NABAM   	 3-68

3-6     REACTION MECHANISMS FOR PROPANIL AND ALACHLOR  	 3-71

3-7     REACTION MECHANISMS FOR ISOPROPALIN  	 3-72

3-8     REACTION MECHANISMS FOR 2,4-D  	 3-74

3-9     REACTION MECHANISMS FOR PARATHION AND PHORATE  	 3-76

3-10    REACTION MECHANISM FOR GLYPHOSATE  	 3-78

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

5-2     INDUSTRY SELF-MONITORING BOD LEVELS IN FINAL EFFLUENT DISCHARGE   . 5-30

5-3     INDUSTRY SELF-MONITORING TSS LEVELS IN FINAL DISCHARGE   	 5-31

5-4     INDUSTRY SELF-MONITORING pH LEVELS IN FINAL DISCHARGE 	 5-33

5-5     INDUSTRY SELF-MONITORING COD LEVELS IN FINAL DISCHARGE   	 5-44

8-1     FLOWCHART USED TO DETERMINE TREATMENT COSTS FOR PAIS  	8-3

8-2     FLOWCHART USED TO DETERMINE TREATMENT COSTS FOR PRIORITY
        POLLUTANTS   	8-4
                                      xii

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                                  SECTION 1




                                 INTRODUCTION









1.0         LEGAL AUTHORITY









            This regulation is being proposed under the authorities of




Sections 301, 304, 306, 307, and 501 of the  Clean Water Act (the Federal Water




Pollution Control Act Amendments of 1972,  33 U.S.C. 1251 et seq.,  as amended




by the Clean Water Act of 1977, Pub. L. 95-217,  and the Water Quality Act of




1987, Pub. L. 100-4), also referred to as  "the Act."









1.1.        BACKGROUND









1.1.1       Clean Water Act









            The Federal Water Pollution Control Act Amendments of 1972




established a comprehensive program to "restore and maintain the chemical,




physical, and biological integrity of the  Nation's waters," (Section 101(a)).




To implement the Act, EPA is to issue effluent limitations guidelines,




pretreatment standards and new source performance standards for industrial




dischargers.
                                      1-1

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            These guidelines and standards are summarized briefly below:









            1.     Best Practicable Control Technology Currently Available




                  (BPT)  (Section 304(b)(l) of the Act).









            BPT effluent limitations guidelines are generally based on the




average of the best existing performance by plants of various sizes, ages, and




unit processes within the category or subcategory for control of pollutants.









            In establishing BPT effluent limitations guidelines, EPA considers




the total cost of achieving effluent reductions in relation to the effluent




reduction benefits, the age of equipment and facilities involved, the




processes employed, process changes required, engineering aspects of the




control technologies, non-water quality environmental impacts (including




energy requirements) and other factors as the EPA Administrator deems




appropriate (Section 304(b)(l)(B) of the Act).  The Agency considers the




category or subcategory-wide cost of applying the technology in relation to




the effluent reduction benefits.  Where existing performance is uniformly




inadequate, BPT may be transferred from a different subcategory or category.









            2.     Best Available Technology Economically Achievable (BAT^




                  (Sections 304(b)(2)(B) and 307(a)(2) of the Act).









            In general, BAT effluent limitations represent the best existing




economically achievable performance of plants in the industrial subcategory or
                                      1-2

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category.  The Act establishes BAT as the principal national means of




controlling the direct discharge of priority pollutants and nonconventional




pollutants to navigable waters.  The factors considered in assessing BAT




include the age of equipment and facilities involved,  the process employed,




potential process changes, and non-water quality environmental Impacts




(including energy requirements, (Section 304(b)(2)(B)).  The Agency retains




considerable discretion In assigning the weight to be  accorded these factors.




As with BPT, where existing performance Is uniformly inadequate,  BAT may be




transferred from a different subcategory or category.   BAT may Include process




changes or internal controls,  even when these technologies are not common




industry practice.









            3.    Best Conventional Pollutant Control  Technology (BCT)




                  (Section 304(a)(4) of the Act).









            The 1977 Amendments added Section 301(b)(2)(E) to the Act




establishing BCT for discharges of conventional pollutants from existing




industrial point sources.  Section 304(a)(4) designated the following as




conventional pollutants:  Biochemical oxygen demanding pollutants (BOD), total




suspended solids (TSS), fecal coliform, pH, and any additional pollutants




defined by the Administrator as conventional.  The Administrator designated




oil and grease as an additional conventional pollutant on July 30, 1979  (44  FR




44501).
                                      1-3

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             BCT is  not an additional  limitation, but  replaces BAT for the




 control  of conventional pollutants.   In addition to other  factors specified in




 Section  304(b)(4)(B),  the Act  requires  that  BCT limitations be established in




 light  of a two  part "cost-reasonableness"  test.   fAmerican Paper Institute v.




 EPA, 660 F.2d 954  (4th Cir.  1981)].   EPA's current methodology for the general




 development of  BCT  limitations was  issued  in 1986  (51 FR 24974; July 9, 1986).









             4.    New  Source Performance Standards (NSPS)  (Section 306 of the




                  Act).









             NSPS are based on  the best  available demonstrated treatment




 technology.   New plants  have the opportunity to install the best and most




 efficient  production processes and wastewater treatment technologies.  As a




 result,  NSPS  should represent  the most  stringent numerical values attainable




 through  the application of the best available control technology for all




 pollutants  (i.e., conventional, nonconventional, and  priority pollutants).  In




 establishing  NSPS,  EPA is  directed to take into consideration the cost of




 achieving  the effluent reduction and  any non-water quality environmental




 impacts  and energy  requirements.









            5.    Pretreatment Standards for Existing Sources (PSES) (Section




                  307(b) of  the Act).









            PSES are designed  to prevent the discharge of pollutants that pass




through,  interfere with, or  are otherwise  incompatible with the operation of
                                      1-4

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publicly owned treatment works (POTWs).   The  Act requires pretreatment




standards for pollutants that pass through POTWs or interfere with POTWs'




treatment processes or sludge disposal methods.  The legislative history of




the 1977 Act indicates that pretreatment standards are to be technology-based




and analogous to the BAT effluent limitations guidelines for removal of toxic




pollutants.  For the purpose of determining whether to promulgate national




category-wide pretreatment standards, EPA generally determines that there  is




pass-through of a pollutant and thus a need for categorical standards if the




nation-wide average percent of a pollutant removed by well-operated POTWs




achieving secondary treatment is less than the percent removed by the BAT




model treatment system.









            The General Pretreatment Regulations, which set forth the




framework for the implementation of categorical pretreatment standards, are




found at 40 CFR Part 403.  (Those regulations contain a definition of pass-




through that addresses localized rather than national instances of pass-




through and does not use the percent removal comparison test described above.




See 52 FR 1586, January 14, 1987.)









            6.    Pretreatment Standards for New Sources (PSNS) (Section




                  307(b) of the Act).









            Like PSES, PSNS are designed to prevent the discharges of




pollutants that pass through, interfere with, or are otherwise incompatible




with the operation of POTWs.  PSNS are to be issued at the same time as NSPS.
                                      1-5

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New indirect dischargers, like the new direct dischargers, have the




opportunity to incorporate  into their plants the best available demonstrated




technologies.  The Agency considers the same factors in promulgating PSNS as




it considers in promulgating NSPS.









1.1.2       Section 304Cm)  Requirements and Litigation









            Section 304(m)  of the Clean Water Act  (33 U.S.C. 1314(m)),  added




by the Water Quality Act of 1987, requires EPA to  establish schedules for (i)




reviewing and revising existing effluent limitations guidelines and standards




("effluent guidelines"), and (ii) promulgating new effluent guidelines.   On




January 2, 1990, EPA published an Effluent Guidelines Plan (55 FR 80),  in




which schedules were established for developing new and revised effluent




guidelines for several industry categories.  One of the industries for which




the Agency established a schedule was the Pesticide Chemicals ^category.









            Natural Resources Defense Council, Inc. (NRDC) and Public Citizen,




Inc., challenged the Effluent Guidelines Plan in a suit filed in U.S. District




Court for the District of Columbia (NRDC et al. v. Reillv. Civ. No. 89-2980).




The plaintiffs charged that EPA's plan did not meet the requirements of




Section 304(m).  A Consent  Decree in this litigation was entered by the Court




on January 31, 1992.  The Decree requires, among other things, that EPA




propose effluent guidelines for the manufacturing  subcategories of the




Pesticide Chemicals category by March, 1992, and take final action by July,




1993.
                                      1-6

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1.1.3       Pollution Prevention Act









            In the Pollution Prevention Act of 1990 (42 U.S.C.  13101 et seq.,




Pub.L. 101-508, November 5,  1990),  Congress declared pollution prevention the




national policy of the United States.   The Act declares that pollution should




be prevented or reduced whenever feasible; pollution that cannot be prevented




should be recycled or reused in an environmentally safe manner wherever




feasible; pollution that cannot be recycled should be treated;  and disposal or




release into the environment should be chosen only as a last resort.









1.1.4       Prior Regulation and Litigation for the Pesticide Chemicals




            Category









            EPA promulgated BPT for the Pesticides Chemicals Manufacturing




Category on April 25, 1978 (43 FR 17776; 40 CFR Part 455), and September




29, 1978 (43 FR 44846; 40 CFR Part 455, Subpart A).  The BPT effluent




limitations guidelines established limitations for chemical oxygen-demand




(COD), BODj,  TSS,  and  pH for wastewaters  discharged by the  organic pesticide




active ingredient (PAI) manufacturing subcategory  (Subcategory A), except that




discharges of  these pollutants resulting  from the manufacture of  25 organic




PAIs and classes of PAIs were specifically excluded from the limitations.  In




addition, BPT  set a limitation for this subcategory on total pesticide




discharge which was applicable to the manufacture  of 49 specifically  listed




organic PAIs.  BPT limitations requiring  zero discharge of process wastewater
                                      1-7

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pollutants were set for metallo-organic PAIs containing arsenic, mercury,




cadmium, or copper.









            Several industry members challenged the BPT regulation on




April 26, 1978 and the U.S. Court of Appeals remanded them on two minor issues




[BASF Wyandotte Corp. v. Costie. 596 F.2d 637  (1st Cir. 1979), cert, denied.




Eli Lilly v. Costle. 444 U.S. 1096  (1980)].  The Agency subsequently addressed




the two  issues on remand and the Court upheld  the regulations in their




entirety [BASF Wyandotte Corp. v. Costle. 614  F.2d 21 (1st Cir. 1980)].









            On November 30, 1982, EPA proposed additional regulations to




control  the discharge of wastewater pollutants from pesticide chemical




operations to navigable waters and to POTWs  (47 FR 53994).  The proposed




regulations included effluent limitations guidelines based upon BPT, BAT, BCT,




NSPS, PSES, and PSNS.  The proposed effluent limitations guidelines and




standards covered the organic pesticide chemicals manufacturing segment, the




metallo-organic chemicals manufacturing segment and  the formulating/packaging




segment  of the pesticide chemical industry.  In addition, the Agency proposed




guidelines for test procedures to analyze the  nonconventional pesticide




pollutants covered by these regulations  on February 10, 1983 (48 FR 8250).









            Based on the new information collected by EPA in response to the




comments on the November 30, 1982 proposal, on June 13, 1984, EPA published a




Notice of Availability (NOA) of new information (49 FR 24492).  In this NOA,




the Agency indicated it was considering changing its approach to developing
                                      1-8

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regulations for this industry.  EPA requested comments on the data.   EPA




published a second NOA of new information on January 24,  1985,  which primarily




made available for public-review technical and economic data which had




previously been claimed confidential by industry.









            EPA issued a final rule on October 4,  1985, that limited the




discharge of pollutants into navigable waters and into POTWs (50 FR 40672).




The regulation included effluent limitations guidelines and standards for the




BAT, NSPS, PSES,  and PSNS levels of control for new and existing facilities




that were engaged in the manufacture and/or formulation and packaging of




pesticides.  The regulation also established analytical methods for 61 PAIs




for which the Agency had not previously promulgated approved test procedures.









            Several parties filed petitions in the Court of Appeals




challenging various aspects of the pesticide regulation fChemical Specialties




Manufacturers Association,  et al..  v. EPA (86-8024)].  After a review of the




database supporting the regulation the Agency found flaws in the basis for




these effluent limitations guidelines and standards.   Subsequently, the




Agency and the parties filed a joint motion for a voluntary remand of the




regulation in the Eleventh Circuit Court of Appeals.   The Court dismissed the




case on July 25,  1986, in response to the Joint Motion.   Upon consideration




of the parties' motion to modify the dismissal, on August 29, 1986, the Court




modified its order to clarify the terms of the dismissal.  The Eleventh




Circuit Court of Appeals ordered that:  (1) the effluent limitation guidelines




and standards for the pesticide chemicals industry be remanded to EPA for
                                      1-9

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reconsideration and  further  rulemaking;  and  (2)  EPA publish a FEDERAL REGISTER

notice removing the  remanded pesticide regulation  from  the Code of Federal

Regulations.



            EPA formally withdrew  the regulations  from  the Code of Federal

Regulations on December 15,  1986  (51 FR  44911).  Although no errors were found

in the analytical methods promulgated October 4, 1985,  these methods were also

withdrawn to allow for further  testing and possible revision.  The BPT

limitations that were published on April 25, 1978  and September 29, 1978 were

not affected by the  withdrawal  notice and remain in effect.  Those existing

regulations are not  proposed to be changed in today's notice and EPA does not

request and will not evaluate public comments on them.



1.2         SCOPE OF TODAY'S PROPOSED RULE



            The regulation proposed today covers two manufacturing

subcategories of the pesticide  chemicals industry:
                  Subcategory A:  Manufacturers of organic pesticide
                  chemicals; and

                  Subcategory B:  Manufacturers of metallo-organic pesticide
                  chemicals.
            EPA will address the Pesticide Chemicals Formulating and Packaging

subcategory at a later date.
                                     1-10

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            In today's notice,  EPA is proposing to expand water pollution




control requirements for the organic pesticide chemicals manufacturing




subcategory by establishing effluent limitations guidelines and standards for




BAT, NSPS, PSES, and PSNS for new and existing facilities that are engaged in




the manufacture of organic pesticide chemicals.  In addition,  BCT for




conventional pollutants is proposed to be set equal to BPT for the organic




pesticide chemicals manufacturing subcategory.









            For the metallo-organic pesticide chemicals manufacturing




subcategory, current BPT limitations require no discharge of process




wastewater pollutants.  EPA is today proposing  to reserve BCT, BAT, NSPS,




PSES, and PSNS effluent limitations for this subcategory.









            The proposed effluent limitations guidelines and standards are




intended to cover discharges generated during the manufacture of PAIs from




chemical reactions.  (For one PAI, the effluent guidelines  apply only to




discharges of wastewater generated during the purification of that PAI to a




higher quality PAI product.)  These guidelines do not apply to the production




of pesticide products through the physical mixing, blending, or dilution of




PAIs without an intended chemical reaction (except where dilution is a




necessary step following chemical reaction to stabilize the product), nor do




these regulations apply to packaging or repackaging of pesticide products.




These two types of operations are part of the Pesticide Chemicals Formulating




and Packaging Subcategory which will be covered under a separate rulemaking at




a later date.  These regulations also do not apply to the manufacturer of
                                     1-11

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chemicals ("intermediate") which are not pesticides but which subsequently are




converted by further chemical reactions to pesticide active ingredients.   The




"intermediates" are covered by the Organic Chemicals, Plastics, and Synthetic




Fibers (OCPSF) effluent guidelines (40 CFR Parts 414 and 416).
                                      1-12

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                                   SECTION 2




                                    SUMMARY









2.0         OVERVIEW OF THE INDUSTRY









            According to 1986 data collected by EPA during the development of




this rule, the pesticide chemicals manufacturing industry includes 90




facilities whose production activities would be covered under the proposed




pesticide chemicals manufacturing regulation.  Over half of the pesticide




manufacturing facilities also conduct pesticide formulating and/or packaging




(PFP) activities.  In addition, more than half of the pesticide manufacturing




facilities generate wastewater discharges which are currently regulated under




the Organic Chemicals, Plastics, and Synthetic Fibers (OCPSF) Point Source




Category (see 40 CFR Part 414).









            There are approximately 128 pesticide active ingredients (PAIs)




and classes of PAIs representing 186 individual active ingredients (Pyrethrin




I and Pyrethrin II are counted as one PAI because they are not separated in




the commerical product) manufactured by 225 separate pesticide production




processes.  Of the reported 225 manufacturing processes used to produce




pesticides in 1986, 178 were batch processes.  A "typical" facility




manufactures one active ingredient and is the only facility in the country




producing that PAI.  "Typical" production is between 1,000,000 and 10,000,000




pounds of total PAI for the year.
                                      2-1

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             The  technical study included all  90  facilities.   Of  the  90




 facilities,  67 are  dischargers:  32 facilities are  direct  dischargers, and 36




 are  indirect dischargers  (one facility is both a direct and  indirect




 discharger).  The remaining 23 facilities do  not discharge pesticide




 manufacturing process  wastewater:  15  facilities  dispose of their wastewater by




 either  on-site or off-site deepwell injection or incineration, and 8




 facilities  generate ho process wastewater because  of recycle/reuse operations




 or because  they  do  not use water.









             As a result of the wide variety of raw materials and processes




 used and  of products manufactured  in  the pesticide chemicals manufacturing




 industry, a wide variety  of pollutants are found in the wastewaters  of this




 industry.   This  includes  conventional pollutants (pH,  BOD, and TSS) , a variety




 of toxic  priority pollutants,  and  a large number of nonconventional  pollutants




 (i.e.,  COD  and the  PAIs) .   The PAIs are organic  and metallo-organic  compounds




 produced  by the  industry  for sale.









             Pesticide  manufacturing plants use a broad range of  in-plant and




 end-of-pipe  controls and  treatment techniques to control  and treat the wide




variety of  pollutants.  The treatment technologies used include  physical




chemical  treatment  technologies  to remove PAIs,  followed  by  steam stripping to




remove volatile  priority  pollutants,  followed by biological  treatment to




remove non-volatile  priority pollutants and other  organic pollutants.  The




major physical-chemical treatment  technologies in  use  for PAI removal are
                                      2-2

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activated carbon, chemical oxidation, and hydrolysis.   More detail is provided




in Section 7.









2.1         SUMMARY OF THE PROPOSED REGULATIONS









2.1.1       Applicability of the Proposed Regulations









            The proposed pesticide chemicals manufacturing regulations would




apply to process wastewater discharges from existing and new pesticide




chemicals manufacturing facilities.  These regulations do not apply to




wastewaters from pesticide femulators and packagers,  which will be addressed




in a separate rulemaking.









2.1.2       BPT









            EPA promulgated BPT effluent limitations guidelines in 1978 (40 FR




17776; 43 FR 44846; 40 CFR Part 455) applicable to pesticide chemicals




manufacturing processes resulting from the manufacturing of:  (1)  All organic




PAIs (with some exceptions; see below), and (2)  'all metallo-organic PAIs




containing arsenic, mercury, cadmium, or copper.  For plants manufacturing




organic PAIs, the regulations limited COD, BOD, TSS, and pH.  The organic PAI




regulation also limited total pesticides in wastewaters resulting from the




manufacturing of 49 specific organics PAIs.  For metallo-organic PAIs, the BPT




limitations require that there be no discharge of process wastewater




pollutants.
                                      2-3

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             The  BPT limitations  for  organic  pesticide  chemical manufacturing



excluded  from regulation 25  specific PAIs  and classes  of  PAIs.   In addition,



organo-tin pesticides were not covered by  BPT.   EPA proposes  to  expand the



coverage  of  BPT  limitations  (for BOD5, COD, TSS, and pH) to include



manufacture  of 15  of the previously  excluded organic PAIs  and organo-tin PAIs.



Information  demonstrates that all manufacturers of these  PAIs are already



subject to permit  limitations that are at  least as stringent  as  the BPT



limitations.   Table 2-1  presents these 15  organic PAIs and organo-tin PAIs.







             The  existing BPT limitations  (i.e.,  those  promulgated in 1978) are



not proposed to  be changed.  Additionally, no change is proposed to the



existing  BPT effluent limitations guidelines for metallo-organic PAIs.







2.1.3        BCT







             The  Agency proposes  in this regulation to  set  BCT equal to BPT for



conventional  pollutants  under the organic  pesticide chemicals manufacturing



subcategory.   The  Agency proposes to reserve BCT for the metallo-organic
                                                 «


pesticide chemicals  manufacturing subcategory.







            The  technology basis for BPT under  the organic pesticide chemicals



manufacturing subcategory includes flow equalization and biological treatment



followed by clarification to remove  BOD, COD, and TSS.  Options  for further



removal of TSS and/or BOD, initially considered for evaluation as BCT



candidate technologies,  included multimedia  filtration, carbon adsorption,
                                      2-4

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                 Table 2-1




PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT
PAI Code
• • . . .
025
058
060
067
138
142
157
192
211
211.05
223
224
226
239
256
257
PAI
Cyanaz ine
Ametryn
Atrazine
Biphenyl
Glyphosate
Hexazinone
Methoprene
Organo-tin Pesticides
Phenylphenol
Sodium Phenylphenate
Prometon
Prometryn
Propazine
Simazine
Terbuthylaz ine
Terbutryn
                     2-5

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membrane  filtration,  incineration,  evaporation,  additional biological




oxidation (above  the  level  required to meet BPT), and clarification through




the use of settling ponds.   However,  only multimedia filtration was deemed a




feasible  option for BCT.  Multimedia filtration  was then  evaluated by the BCT




cost  test.   This  BCT  technology, however, failed the BCT  cost  test and is




therefore not being proposed as  BCT for  the organic pesticide  chemicals




manufacturing subcategory.   Since no other technologies were identified that




would be  expected to  enhance conventional pollutant removal above that




provided  by BPT technologies,  the Agency is proposing to  set BCT equal to BPT




limitations for conventional pollutants.  Table  2-2 presents the BCT organic




pesticide chemicals manufacturing subcategory effluent limitations.









2.1.4       BAT









             EPA based the proposed  BAT limitations for PAIs under the organic




pesticide chemicals manufacturing subcategory on the use  of the following




treatment technologies:  hydrolysis,  activated carbon, chemical oxidation,




resin adsorption,  solvent extraction, distillation, and/or incineration.









             Limitations for  PAIs were derived on a mass basis, using long-term




data where  available.  Where long-term data were  not available, limitations




were developed  based  on performance  data from either industry  or EPA




treatability studies.  In these cases, in lieu of BAT performance data from




full scale  operating  systems,  treatability studies were used to determine the




PAI concentration  achievable through  a specific  treatment technology.  These
                                      2-6

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                                  Table  2-2

                       BCT EFFLUENT LIMITATIONS FOR THE
             ORGANIC  PESTICIDE  CHEMICALS  MANUFACTURING  SUBCATEGORY
Effluent
Character is tic
BODj
TSS
pH
Maximum for
Any Oneway*
7.4
6.1
**
Average of Daily Values for
30 Consecutive Days Shall
Not Exceed*
1.6
1.8
**
 *Metric units:  kilogram/1,000 kg of PAI produced;  English units:  pound/
  1,000 Ibs of PAI produced; Established on the basis of pesticide production.

**Within the range of 6.0 to 9.0.
                                      2-7

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 concentration data were then applied to  the  total  flow of  PAI  contaminated




 streams  and the reported PAI production  data to  calculate  a mass based




 limitation.   In cases  where treatability studies did not contain sufficient




 information to determine process  variability,  daily and monthly variability




 were based on the  performance of  operating BAT treatment systems.  For some




 PAIs for which there were no treatability data,  limitations were developed




 based  on the treatment performance  achieved  for  chemically and structurally




 similar  PAIs.   This "technology transfer" was  supplemented by  treatability




 studies.









             BAT effluent limitations  for 28  priority pollutants are proposed.




 For 27 of the  28 priority pollutants  limitations are based on  the use of model




 control  technologies identified in  the OCPSF rulemaking.   Both the OCPSF end-




 of-pipe  biological  treatment subcategory and the non-end-of-pipe biological




 treatment subcategory  limitations are being  transferred for the priority




 pollutants  regulated under BAT  in the organic  pesticide chemicals




 manufacturing  subcategory.









             Derivation of the proposed BAT limitations  is  detailed in




 Section  7 of this document.   "Daily Maximum" and "Monthly  Average" production-




based limitations have  been calculated for each  regulated  PAI  pollutant.




 "Maximum  for any one day"  and "Maximum for Monthly Average'1 concentration




limitations have been  transferred from the OCPSF rulemaking for 23 of the 28




regulated priority pollutant.   The proposed  BAT  effluent limitations for




organic PAIs and classes  of PAIs and priority pollutants under the organic
                                      2-8

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pesticide chemicals manufacturing subcategory are listed in Tables 2-3,  2-4,




and 2-5.









            The Agency proposes to reserve BAT for the metallo-organic




pesticide chemicals manufacturing subcategory.









           'Once a pollutant is regulated, it will also be limited in the




National Pollutant Discharge Elimination System (NPDES) permit issued to




direct dischargers.  The limitations for pesticide chemicals manufacturing




plants include all priority pollutants regulated and those PAIs manufactured




at each plant.









2.1.5       NSPS









            EPA proposes new source performance standards (NSPS) for the




organic pesticide chemicals manufacturing subcategory on the basis of the best




available demonstrated technologies and a 28% achievable flow reduction for




certain PAIs.  NSPS are proposed for conventional pollutants (BOD, TSS,  and




pH) and COD on the basis of BPT model treatment technologies and a 28%




achievable flow reduction.  NSPS regulation of priority pollutants are based




on BAT model treatment technologies from the OCPSF rulemaking; because the




limitations for priority pollutants are concentration-based, the permit writer




would apply the 28% flow reduction when calculating NPDES permit effluent




limitations.   The proposed NSPS limitations for conventional pollutants and
                                      2-9

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 concentration data were  then applied to  the  total  flow of PAI contaminated




 streams  and  the  reported PAI production  data to  calculate a mass based




 limitation.   In  cases where  treatability studies did not contain sufficient




 information  to determine process variability,  daily and monthly variability




 were based on the  performance of operating BAT treatment systems.  For some




 PAIs for which there were no treatability data,  limitations were developed




 based  on the treatment performance  achieved  for  chemically and structurally




 similar  PAIs.  This "technology transfer" was  supplemented by treatability




 studies.









             BAT  effluent limitations  for 28  priority pollutants are proposed.




 For 27 of the 28 priority pollutants  limitations are based on the use of model




 control  technologies identified in  the OCPSF rulemaking.  Both the OCPSF end-




 of-pipe  biological treatment subcategory and the non-end-of-pipe biological




 treatment subcategory limitations are being  transferred for the priority




 pollutants regulated under BAT in the organic  pesticide chemicals




 manufacturing subcategory.









             Derivation of the proposed BAT limitations is detailed in




 Section  7 of this  document.   "Daily Maximum" and "Monthly Average" production-




based limitations have been  calculated for each regulated PAI pollutant.




 "Maximum for  any one day"  and "Maximum for Monthly Average" concentration




 limitations have been transferred from the OCPSF rulemaking for 23 of the 28




regulated priority pollutant.  The proposed  BAT effluent limitations for




organic PAIs and classes  of  PAIs and priority  pollutants under the organic
                                      2-8

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pesticide chemicals manufacturing subcategory are listed in Tables 2-3,  2-4,




and 2-5.








            The Agency proposes to reserve BAT for the metallo-organic




pesticide chemicals manufacturing subcategory.








           "Once a pollutant is regulated, it will also be limited in the




National Pollutant Discharge Elimination System (NPDES) permit issued to




direct dischargers.   The limitations for pesticide chemicals manufacturing




plants include all priority pollutants regulated and those PAIs  manufactured




at each plant.








2.1.5       NSPS








            EPA proposes new source performance standards (NSPS) for the




organic pesticide chemicals manufacturing subcategory on the basis of the best




available demonstrated technologies and a 28% achievable flow reduction for




certain PAIs.  NSPS are proposed for conventional pollutants (BOD, TSS,  and




pH) and COD on the basis of BPT model treatment technologies and a 28%




achievable flow reduction.  NSPS regulation of priority pollutants are based




on BAT model treatment technologies from the OCPSF rulemaking; because the




limitations for priority pollutants are concentration-based, the permit writer




would apply the 28% flow reduction when calculating NPDES permit effluent




limitations.   The proposed NSPS limitations for conventional pollutants and
                                      2-9

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                   Table 2-3
BAT AND PSES EFFLUENT LIMITATIONS FOR ORGANIC
      PESTICIDE ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient C*AI)
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 403 [Potassium N-
hydr oxyme thy 1 - N -
methyldithiocarbamate ]
BAT/PSES effluent limitations
Dally Maximum Shall Hot Exceed li./l.OOO Ib. SAT
production
1.19 x 10-4
Monthly
Average Shall
not Exceed
U>./1,000 Ib.
FAX production
3.40 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.32 x 10-2
8.82 x 10-4
7.23 x 10-*
2.10 x 10-3
2.56 x 10-3
2.74 x 10-2
3.22 x W*
1.91 x 10-1
8.79 x lO'3
2.68 x 10"4
3.12 x 10"*
9.14 x 10-4
1.02 x 10-3
1.41 x lO'2
1.09 x 10-4
5.14 x 10-2
No discharge of process wastewater pollutants
1.69 x 10-2
8.72 x 10-3
No discharge of process wastewater pollutants
1.24 x 10-'
3.95 x lO'3
3.95 x lO'3
5.74 x 10-3
4.18 x 10-2
1.27 x 10-3
1.27 x 10-3
1.87 x 10-3
                     2-10

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 Table 2-3




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Busan 853 [Potassium
dimethyldithiocarbamatej
Butachlor
Captafol
Carbarn S3 [Sodium
dimethyldithiocarbamate ]
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos'
Cyanazine
Dazomet3
DCPA
DEF
Diazinon1
Dichlorprop , salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
BAT/PSES effluent limitations
Daily Maximum Shall trot Exceed ib./l.OOO lit. PAI
production
5.74 x 10-3
3.53 x ID'3
Monthly
Average Shall
not Exceed
H>./1,000 Ib.
FAX production
1.87 x 10-3
1.09 x 10-3
No discharge of process wastewater pollutants
5.74 x 10-3
1.60 x 10-3
1.18 x W*
8.16 x 10-2
1.51 x lO'3
3.27 x W-4
1.63 x 10-3
5.74 x lO'3
7.79 x 10-2
1.15 x lO'2
2.82 x 10-3
1.87 x lO"3
7.30 x 10-*
2.80 x 10-5
3.31 x 10-2
4.57 x 10-"
9.96 x 10-3
8.11 x 10-4
1.87 x lO'3
2.64 x ID'2
5.58 x 10-3
1.12 x 10-3
No discharge of process wastewater pollutants
9.60 x 10-s
4.73
'3.40 x 10-2
7.33 x 10-3
3.15 x 10-2
2.95 x 10-3
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x lO'2
    2-11

-------
 Table 2-3




(Continued)
Organic Pesticide Active
Ingredient (PA!)
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Me thami dopho s
Methomyl1
Methoxychlor
Metribuzln
BAT/PSES effluent limitations
Daily Maximum Shall Sot Exceed It, /I, 000 Ib. FAX
product! on
Monttily
Average Shall
not Exceed
U>./1,ODO Ib.
PAI production
No discharge of process wastewater pollutants
2.20 x 10-2
3.22 x 10^
7.37 x HH
1.02 x 10-'
1.48 x 10-2
1.83 x 10-2
5.40 x 10-3
5.10 x 10-3
1.09 x 10-*
2.99 x 10-4
3.61 x 10-2
7.64 x 10-3
9.45 x 10-3
2.08 x 10-3
No discharge of process wastewater pollutants
8.80 x 10-3
7.06 x 10-3
5.74 x lO'3
2.69 x 10-3
2.35 x W^
2.90 x 10-3
2.49 x 10-3
1.87 x ID'3
1.94 x 10-3
9.55 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x lO'2
1.46 x 10-2
3.82 x lO'3
3.23 x 10-3
1.36 x lO'2
5.58 x lO'3
7.53 x 10-3
1.76 x lO'3
1.31 x 10-3
7.04 x lO'3
   2-12

-------
 Table 2-3




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Mevinphos
Nab am3
Nabonate3
Naled
Norflurazon
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendime thai in
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
BAT/PSES effluent limitations
Daily Maximum Shall Hot Exceed It. /1. 000 Ib. PAI
production
1.44 x 10-4
5.74 x 10-3
5.74 x lO'3
Monthly
Average Shall
not Exceed
Ib./ 1,000 It.
FAX production
5.10 x 10-3
1.87 x 10-3
1.87 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.72 x 10-2
7.72 x 10-4
7.72 x W*
5.75 x 10-*
3.21 x 10-3
2.32 x 10-*
2.51 x 10-*
7.42 x lO'3
3.43 x W-*
3.43 x W^
1.90 x 10-4
1.06 x 10-3
6.06 x 10-5
7.53 x 10-*
No discharge of process wastewater pollutants
2.10 x lO'3
2.10 x 10-3
2.00 x 10-*
5.34 x lO'3
1.06 x 10-3
2.10 x 10-3
9.14 x 10-*
9.14 x 10-*
6.90 x 10-5
1.66 x 10-3
4.84 x 10-*
9.14 x 10-*
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.10 x lO'3
9.14 x 10^
    2-13

-------
                                   Table 2-3

                                  (Continued)
Organic Pesticide Active
Ingredient (PAI)
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [ Sodium
methyldithiocarbamate ]
Ziram3 [Zinc
dimethyldithiocarbamate ]
BAT/PSES effluent limitations
Dally Maximum Shall. Hok Ercoad li./l.OOO Ib. PAI
• • "'.'••' PJ*OwlofcApn ••..;' ''' '• ',.,;.'
. :•• ' • • ' •.
4.10 x 10-3
2.88 x 10-4
9.78 x lO'2
1.51 x 10-'
4.09 x W-*
2.10 x 10-3
2.10 x lO'3
1.02 x 10-2
6.52 x 10-2
3.22 x 10*
5.74 x ID'3
5.74 x 10-3
Monthly
•.-Average Shall. '••
•'• not Eroead
lb./l,000 Ib,
• )PAI production
1.35 x 10-3
8.96 x lO'5
3.40 x 10-2
5.12 x 10-2
1.06 x 10^
9.14 x KH
9.14 x 10^
3.71 x 10-3
3.41 x 10-2
1.09 x 10-4
1.87 x lO'3
1.87 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
 wastewaters.

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

3  Monitor and report as total dithiocarbamates,  as Ziram.

4  Monitor and report as total tin.

5  Applies to purification by recrystalization portion of the process.
                                     2-14

-------
                                  Table 2-4

          BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS
FOR DIRECT DISCHARGE POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
2 - Chlorophenol
1 , 2 -Dichlorobenzene
1 , 4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
2 ,4-Dichlorophenol
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chi or ome thane
Bromome thane
Tr ib r omome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT/NSPS effluent limitations1
Maximum for
Any One Day
(pg/L)
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
25
59
89
211
59
26
Maximum for Monthly
Average
(M5/L)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
16
22
40
68
22
15
                                     2-15

-------
                                    Table 2-4

                                   (Continued)
 Priority Pollutant
                                            BAT/NSPS effluent  limitations1
                                             Maximum for
                                             Any One Day
                                               C«5/U
              Maximum for Monthly
                   Average
                    Cftg/L)
 Tetrachloroethylene

 Total  Cyanide

 Total  Lead2
 56

640

690
 22

220

320
'All units are micrograms  per liter.

2Metals limitations apply  only to noncomplexed metal-bearing waste streams.
Discharges  of lead from complexed metal-bearing process wastewater are not
subject to  these limitations.
                                      2-16

-------
                                Table 2-5

  BAT  EFFLUENT  LIMITATIONS AND  NSPS  FOR  PRIORITY  POLLUTANTS  FOR DIRECT
DISCHARGE POINT SOURCES THAT DO NOT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
1 , 2 - Dichlorobenzene
1 , 4 -Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Ch 1 o r ome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
BAT/NSPS effluent limitations1
Msnri mum for
Any One Day
Oig/L)
134
380
380
574
59
46
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Ma-rimum for Monthly
Average
(pg/L)
57
142
142
180
22
21
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
                                   2-17

-------
                                   Table 2-5

                                  (Continued)
Priority Pollutant
Total Cyanide
Total Lead2
BAT/NSPS effluent limitations1
Maximum for
Any One Day
<«5/D
640
690
Maximum for Monthly
Average
(MB/D
220
320
'All  units  are micrograms per liter.

Petals  limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead from  complexed metal-bearing process wastewater are not
subject to these limitations.
                                     2-18

-------
COD are given in Table 2-6; for PAIs in Table 2-7;  and for priority pollutants




in Tables 2-4 and 2-5.









            The Agency proposes to reserve NSPS for the metallo-organic




pesticide chemicals manufacturing subcategory.
2.1.6       PSES









            Pretreatment standards for existing sources which apply to




indirect dischargers are generally analogous to BAT limitations which apply to




direct dischargers.  The Agency is proposing PSES for the same PAIs regulated




under BAT and for 26 priority pollutants of the 28 regulated under BAT (which




the Agency has determined pass through POTWs).   The proposed standards would




apply to all existing indirect discharging organic pesticide chemicals




manufacturing plants.









            EPA determines which pollutants to regulate in PSES on the basis




of whether or not they pass through, cause an upset, or otherwise interfere




with operation of a POTW (including interference with sludge practices).  A




detailed discussion of the pass-through analysis conducted for priority




pollutants is presented in Section VI of the OCPSF Development Document.  PAI




pass-through analysis is presented in Section 7.
                                     2-19

-------
                                   Table  2-6

         NSPS  EFFLUENT LIMITATIONS  FOR CONVENTIONAL POLLUTANTS AND  COD
Effluent
Characteristic
COD
BOD5
TSS
PH
Maximum for Any
1 Day
9.36
5.33
4.39
*
Average of Daily Values
Consecutive Days Shall Not
for 30
Exceed**
6.48
1.15
1.30
*
'These  standards  incorporate a 28  percent flow reduction achievable by new
sources.

*Within the range 6.0 to 9.0.

**Metric units:  Kilogram/1,000 kg of PAI produced; English units:
Pound/1,000 Ib of PAI produced; established on the basis of pesticide
production.
                                     2-20

-------
                    Table  2-7
       NSPS AND PSNS EFFLUENT LIMITATIONS
FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen1
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 403
Bus an 853
Butachlor
Captafol
NSPS/PSNS Effluent Limitations
Dally MaziouB Shall Hot Exceed Ib./l.OOO
U>. PAI production
8.54 x 10-5
Monthly Average
Shall Hot Exceed
lb./l,000 li. PAI
production
2.45 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.67 x 10-2
6.35 x 10-*
5.21 x 10-"
1.51 x ID'3
1.85 x 10-3
1.97 x 10-2
2.32 x 10*
1.37 x 10-'
0
1.22 x 10-2
6.33 x lO'3
1.93 x 10-4
2.25 x 10-4
6.58 x 10-4
7.32 x 10-*
1.02 x 10-2
7.82 x 10-5
3.70 x lO'2
0
6.27 x 10-3
No discharge of process wastewater pollutants
3.89 x 10-2
2.84 x 10-3
2.84 x 10-3
4.14 x lO'3
4.14 x 10-3
2.54 x 10-3
3.01 x 10-2
9.14 x 10-*
9.11 x 10-4
1.35 x 10-3
1.35 x 10-3
7.87 x 10-4
No discharge of process wastewater pollutants
                      2-21

-------
 Table 2-7




(Continued)
Organic Pesticide Active
Ingredient
Carbarn S3
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cy anaz ine
Dazomet
DCPA
DBF [S,S,S-Tributyl
phosphorotrithioate ]
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin'-2
Ethion
NSPS/PSNS Effluent Limitations
Daily Maximum Shall Hot Exceed li./ 1,000
Ib. FAX production
4.14 x 10-3
1.07 x 10-3
1.18 x 10-4
5.87 x 10-2
1.09 x ID'3
2.35 x 10^
1.18 x 10-3
4.14 x 10-3
5.61 x 10-2
1.15 x 10-2
2.05 x 10-3
Monthly Average
Shall Hot Exceed
Ih./l.OOO Ib. PAI
production
1.35 x 10-3
4.76 x W^
2.80 x lO'5
2.39 x 10-2
3.29 x 10"4
7.17 x 10-5
5.84 x W^
1.35 x lO'3
1.90 x lO'2
5.58 x 10-3
8.13 x 10*
No discharge of process wastewater pollutants
6.88 x ID*5
3.41
1.51 x 10-'
5.28 x 10-3
2.27 x 10-2
2.13 x 10-5
1.03
5.76 x lO-2
2.72 x 10-3
1.01 x 10-2
No discharge of process wastewater pollutants
1.77 x 10-2
2.32 x 10-*
5.31 x 10^
5.25 x 10-3
7.85 x 10-3
2.15 x 10-"
   2-22

-------
 Table 2-7




(Continued)
Organic Pesticide Active
Ingredient
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate , salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Me thoxy chl o r
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norflurazon
NSPS/PSNS Effluent Limitations
Daily Maximum Shall Not Exceed lb./ 1,000
li, PAI production
7.31 x lO'2
1.06 x 10-2
1.32 x 10-2
3.91 x 10-3
Monthly Average
Shall Hot Exceed
lb./l,000 It. PAI
production
2.60 x 10-2
5.50 x 10-3
6.79 x 10-3
1.50 x ID'3
No discharge of process wastewater pollutants
5.42 x 10-3
5.07 x 10-3
4.14 x 10-3
1.94 x 10-3
1.69 x 10"
1.73 x 10-3
1.82 x 10-3
1.35 x 10-3
1.40 x 10-3
6.88 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.05 x 10-2
2.75 x 10-3
2.34 x 10-3
9.80 x 10-3
1.03 x 10*
4.14 x 10-3
4.14 x 10-3
5.58 x lO'3
5.42 x 10-3
1.27 x 10-3
9.25 x 10"
5.06 x 10-3
3.69 x 10-5
1.35 x lO'3
1.35 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
    2-23

-------
 Table 2-7




(Continued)
Organic Pesticide Active
Ingredient
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Pentachlorophenol , salts
and esters
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
S imaz ine
Stirofos
TCMTB
Tebuthiuron
Terbacil
NSPS/PSNS Effluent Limitations
Daily Hnriimm Shall Hot. Exceed Ib./l.OOO
Ib. PAI production
1.25 x lO'2
5.56 x W*
5.56 x 10-1
4.16 x 10^
8.81 x 1C'3
Monthly Average
Shall Hot Exceed
Ib./l.OOO Ib. PAI
production
5.36 x lO'3
2.45 x 1O4
2.45 x 10-4
1.38 x 10-4
2.79 x 10-3
No discharge of process wastewater pollutants
1.68 x 10-4
1.81 x 10"4
4.39 x 10-5
5.43 x 10-5
No discharge of process wastewater pollutants
1.51 x 10-3
1.51 x 10"3
1.28 x 10-4
3.84 x lO'3
7.63 x W-4
1.51 x 10-3
6.58 x 1O4
6.58 x 10-4
4.34 x lO'5
1.19 x 10-3
3.48 x W^
6.58 x 10"1
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.51 x 10-3
2.95 x ID'3
2.07 x W*
7.04 x 10-2
1.09 x 10-'
6.58 x 10*
9.72 x W*
6.45 x 10-5
2.45 x lO'2
3.69 x 10-2
   2-24

-------
                                  Table 2-7

                                  (Continued)
Organic Pesticide Active
Ingredient
Terbufos
Terbuthylaz ine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [Sodium
methyldithiocarbaraate]
Ziram3 [Zinc
dimethyldithiocarbamate ]
NSPS/PSNS Effluent Limitations
Daily Maximum Shall Hot Exceed Lb./ 1,000
11). FAX production
2.95 x 10-*
1.51 x 10-3
1.51 x 1C'3
7.35 x lO'3
4.69 x lO'2
2.32 x 1C"4
3.86 x 10-3
4.14 x 10-3
Monthly Average
Shall Hot Exceed
U>./1,000 Ib. PAI
production
7.62 x 10-5
6.58 x 10"
6.58 x 10"
2.67 x ID'3
2.46 x 10-2
7.82 x 10-5
1.39 x 10-3
1.35 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
 wastewaters.

2Monitor and report as total toluidine PAIs, as Trifluralin.

3Monitor and report as total dithiocarbamates,  as Ziram.

4Monitor and report as total tin.

5Applies to purification by recrystallization portion of the process.
                                     2-25

-------
             Indirect dischargers  generate  wastewater with  the  same pollutant




 characteristics  as  the direct dischargers;  therefore,  the  same technologies




 that were  discussed for BAT are appropriate for  application  of PSES.   For




 priority pollutants,  the Agency established PSES for all indirect dischargers




 on the  same  technology basis as PSES  in the OCPSF Development  Document.  PSES




 for PAIs and priority pollutants  in the organic  pesticide  chemicals




 manufacturing subcategory are shown in Tables  2-3 and  2-8, respectively.









             The  Agency proposes to  reserve PSES  for the metallo-organic




 pesticide  chemical  manufacturing  subcategory.









 2.1.7        PSNS









             PSNS which apply to new facilities are generally analogous to PSES




 which apply  to existing facilities.   The Agency  is proposing PSNS for  PAIs




 under the  organic pesticide chemicals manufacturing subcategory on the same




 technology basis as  PSES with a 28% achievable flow reduction  for certain




 PAIs.   For priority  pollutants, the Agency established PSNS  for all  indirect




 dischargers  on the  same technology  basis as PSNS in the OCPSF  Development




 Document.  PSNS  for  PAIs and priority pollutants in the organic pesticide




 chemicals  manufacturing subcategory are shown  in Tables 2-7  and 2-8,




 respectively.









            The  Agency proposes to  reserve PSNS  for the metallo-organic




pesticide  chemicals manufacturing subcategory.
                                      2-26

-------
                           Table 2-8

          EFFLUENT  LIMITATIONS  FOR  PRIORITY POLLUTANTS
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
1 , 2 -Dichlorobenzene
1,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-Trans-Dichloroethylene
1, 2-DIchloropropane
1, 3-Dichloropropene
2 , 4 - D ime thy Ipheno 1
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
T r ib r omome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
PSES/PSNS Effluent Limitations
Maximum for Any One Day
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Maximum for Monthly
Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
                              2-27

-------
                                   Table  2-8

                                  (Continued)
Priority Pollutant
Total Cyanide
Total Lead2
PSES/PSNS Effluent Limitations
Maximum for Any One Day
640
690
Maximum for Monthly
Average
220
320
'All units are micrograms per liter.

2Metals limitations apply only to noncomplexed metal-bearing waste streams.
 Discharges of lead and zinc from complexed metal-bearing process wastewater
 are not subject to these limitations.
                                     2-28

-------
                                   SECTION  3

                             INDUSTRY DESCRIPTION



3.0         INTRODUCTION



            This section discusses characteristics of the Pesticide Chemicals

Manufacturing Industry and presents the following topics:
            •     Methods of data collection used by EPA;
            •     Overview of the industry;
            •     Pesticide production;
            •     Pesticide manufacturing processes; and
            •     Changes in the industry.
3.1         DATA COLLECTION METHODS



            EPA has gathered and evaluated technical data from various sources

in the course of developing the effluent limitations guidelines and standards

for the Pesticide Chemicals Manufacturing Industry.  These data sources

include:
                  Responses to EPA's Questionnaire entitled "Pesticide
                  Manufacturing Facility Census for 1986" (the "Facility
                  Census");

                  EPA's 1988-1990 sampling of selected pesticide
                  manufacturers;

                  Industry self-monitoring data;

                  Industry treatability studies;
                                      3-1

-------
            •     EPA treatability studies;




            •     Previous EPA Office of Water studies of Pesticides Industry;




            •     Literature data;




            •     Toxic Release Inventory  (TRI) database;




            •     Data transferred from the OCPSF Rulemaking;




            •     Office of Pesticide Programs (OPP) database; and




            •     Other EPA studies of Pesticides Industry.









EPA used data from these sources  to profile the industry with respect to:




production; manufacturing processes; geographical distribution; and wastewater




generation, treatment, and disposal.  EPA  then characterized the wastewater




generated by pesticide manufacturing operations through an evaluation of water




use, type of discharge or disposal, and the occurrence of conventional,  non-




conventional, and priority pollutants.









3.1.1       PesticideProduct Registration Process









            A pesticide, as defined by the Federal Insecticide, Fungicide,  and




Rodenticide Act  (FIFRA), includes "any substance or mixture of substances




intended for preventing, destroying, repelling, or mitigating any pest,  and




any substance or mixture of substances intended for use as a plant regulator,




defoliant, or desiccant."  Under  FIFRA all pesticides must be registered with




EPA prior to shipment, delivery,  or sale in the United States.  A pesticide




product is a formulated product;  that is,  it is a mixture of an "active
                                      3-2

-------
ingredient" (the PAI) and "inert" diluents.   Each formulation has a distinct




registration.









            As part of its activities in regulating pesticides,  EPA requires




all producers of pesticides (technical grade and formulated product) to report




annually the amount of pesticides produced by that facility each year.   The




database containing these reports provides comprehensive data concerning the




PAIs produced in the United States and,  therefore, is an excellent single




source of information on which PAIs are potentially manufactured in the United




States.  This source is treated by EPA as Confidential Business  Information




because it contains production information.   Other sources, such as the




"Directory of Chemical Producers" published by SRI International, list




chemicals and the producer of each chemical, including chemicals typically




used as pesticides.  This source does not include any production information




and is publicly available.









            Although the data sources discussed above were very useful, the




most focused,  comprehensive source of information on which facilities




manufactured PAIs was the administrative record for the remanded 1985




pesticide chemicals effluent limitations guidelines and standards.









3.1.2       Selection of PAIs for Study









            For the Pesticide Chemicals Manufacturing Category,  there are 270




PAIs or classes of PAIs that EPA considered for regulation.  The initial basis
                                      3-3

-------
for this list was the 284 PAIs and classes of PAIs presented in Appendix 2 of

the October 4. 1985 regulation (50 FR 40672).  These 284 PAIs were originally

selected in 1977 on the basis of significant production and/or commercial use.

EPA then expanded this list to 835 PAIs by adding the following group of PAIs:
                  All salts and esters of listed organic acids (such as
                  2,4-D);

                  All metallo-organic PAIs  (consisting of an organic portion
                  bonded to arsenic, cadmium, copper, or mercury);

                  All organo-tin PAIs;

                  All PAIs that appeared to be structurally similar to other
                  listed PAIs  (such as organo-phosphorus pesticides);  and

                  Any other PAIs with an analytical method previously
                  demonstrated to be applicable to wastewater.
            EPA excluded from this list of 835 PAIs those PAIs already subject

to regulation under other effluent guidelines   specifically, those regulated

by OCPSF  (40 CFR Part 414), Inorganic Chemicals Manufacturing (40 CFR part

415), and Pharmaceuticals (40 CFR Part 439).  Information provided to EPA

under FIFRA indicated that 335 of those 835 PAIs were produced in 1984-1985,

and the other 500 were not produced for domestic use in either 1984 or 1985.

An additional 15 (of the 835) were added to the 335 PAIs because those 15 PAIs

had been manufactured prior to 1984 and might still be manufactured for

export.  The list of 350 PAIs and derivatives, such as salts and esters, was

then consolidated by putting salts and esters of a PAI into a PAI class, to

arrive at a total of 270 PAIs and classes of PAIs.  Because the consolidated
                                      3-4

-------
classes include all elements of the class, such as all salts and esters of




2,4-D (i.e., not just those in use in 1986), the 270 PAIs and classes of PAIs




actually include 606 of the 835 specific PAIs.  Figure 3-1 presents a flow




chart of the methodology for determining which PAIs were included in the




Pesticide Manufacturing Facility Census of 1986.  Table 3-1 lists the PAIs and




classes of PAIs considered for regulation.









3.1.3       Development of the "Pesticide Manufacturing Facility Census of




            1986"









            A major source of information and data used in developing effluent




limitations guidelines and standards is industry responses to questionnaires




distributed by EPA under the authority of Section 308 of the Clean Water Act.




These questionnaires typically request information concerning production




processes and pollutant generation, treatment, and disposal, as well as




wastewater treatment system performance data.  Questionnaires also request




financial and economic data for use in assessing economic impacts and the




economic achievability of technology options.









            EPA used its experience with previous questionnaires, including




the questionnaires distributed to the pesticides industry for the remanded




regulation, to develop a draft questionnaire for this study.  EPA sent the




draft questionnaire to pesticide industry trade associations, pesticide




manufacturers and pesticide formulator/packagers who had expressed interest,




and to environmental groups for review and comment.  Based on the comments
                                      3-5

-------
                                      Figure  3-1

                FLOW  CHART  FOR  DETERMINING INCLUSION OF PAI
           IN  PESTICIDE  MANUFACTURING FACILITY  CENSUS  FOR 1986
  284 PAIs
addressed in
  1985 Rule
                All salts or esters of PAIs addressed in 1985 Rule
                      (such as salts and esters of 2,4-D)
                       All specific examples of metallo-organic PAIs
              ( organic portion bonded to arsenic, cadmium, copper, or mercury)
                 All organo-tin PAIs
                PAIs with structural similarity to PAIs included in 1985 Rule
                       (such as organo-phosphorus compounds)
                 PAIs known to have an analytical method promulgated or ready
                     to promulgate under §304(h) of the Clean Water Act
  835 PAIs
  Identified
 as Potential
Candidates for
  Regulation
 WasPAl
Believed to
   Be In
Production?
                              606 PAIs condensed into
                              272 PAIs or classes of PAI
                                  Included in DCP
                             Was the
                           PAI a salt, aster,
                          or metallo-organic
                            of one of the
                               PAIs
                                         3-6

-------
                                                             Table 3-1




                                            LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

10S01
51501
42002
82901
29001
12601
12602
17901
109901
44901
55004
55001
84001
102401
82601
**
82001
**
PAI
Coda
1
2
3
4
5
6
6
7
8
9
10
11
12
13
14
14
15
15
Chemical Hane
1 , 1-Bis ( chlorophenyl) -2 , 2 , 2-tr ichloroethanol [Dicof ol]
l,2-Dihydro-3,6-pyridazinedione [Maleic Hydrazide]
1,2-Ethylene dibromide [EDB]
1,3,5-Triethythexahydro-s-Triazine (Vancide TB]
1 , 3-Di chloropropene
Fhenarsazine Oxide
10 , 10 ' -Oxybisphenoxarsine
[l-(3-Ch.loroallyl)-3,5,7-triaza-l-azoniaadamantane chloride]
[Dowicil 75]
l-(4-Chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l-yl)
-2-butanone (Triadimefon)
2,2' -Methylenebis (3,4, 6-trichlorophenol ) [Bexachlorophene ]
2,2' -Methy lenebis ( 4 , 6-di chlorophenol ) [Tetr achlorophene ]
2,2'-Methylenebis(4-chlorophenol) tDichlorophene]
2,2-Dichlorovinyl dimethyl phosphate [Dichlorvos]
2,3,5-TrimethylphenyJjnethylcarbajnate [Landrin-2]
2,3,6-Irichlorophenylacetic acid [Fenac]
2,3,6-Trichlorophenylacetic acid, salts and esters
2,4,5-Trichlorophenoxyacetic acid [2,4,5-T]
2,4,5-Trichlorophenoxyacetic acid, salts and esters
eta *
00115-32-2
00123-33-1
00106-93-4
07779-27-3
00542-75-6
00058-36-6
04095-45-8
04080-31-3
43121-43-3
00070-30-4
01940-43-8
00097-23-4
00062-73-7
02686-99-9
00085-34-7
**
00093-76-5
**
Structural Group
DDT
Heterocyclic
EDB
s-Triazine
Alkyl halide
Organoarsenic
Organoarsenic
Anmonium
1,2,4-Pentacylcictriazine
Bis tri chlorophenol
Aryl halide
Axyl halide
Phosphate
Carbamate
Trichlorophenylacetic acid
Trichlorophenylacetic acid
Phenoxy acid
Phenoxy acid
Pesticida Type
Insecticide
Herbicide, growth regulator
Fumigant
Fungicide
Nematocide
Fungicide
Fungicide
Disinfectant
Fungicide
Disinfectant
Disinfectant
Disinfectant
Insecticide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
u>

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
LO
03

30001
**
30801
**
80811
36001
31301
8707
15801
39001
84101
100101
19101
30501
**
PAI
Coda
16
16
17
17
18
19
20
21
22
23
2k
25
26
27
27
Chemical Hame
2,4-Dichlorophenoxyacetic acid [2,4-D]
2,4-Dichlorophenoxyacetic acid, salts and esters
2,4-Dichlorophenoxybutyric acid [2,4-DB]
2,4-Dichlorophenoxybutyric acid, salts and esters
2, 4-Dichloro-6-(0-chloroanilino) -s-Triazine [Anilazine]
2,4-Dinitro-6-octylphenylcrotonate, 2,6-Dinitro-
4-octylphenylcrotonate, and Nitrooctylphenols [Dinocap]
(The octyl's are a mixture of 1-Methylheptyl, 1-Ethylhexyl,
and 1-Propylpentyl)
2, 6-Dichloro-4-nitroaniline [Dichloran]
2-Bromo-4-hydroxyacetophenone [Bus an 90]
2-Carbomethoxy-l-methylvinyl dimethyl phosphate, and related
compounds [Mevinphos]
2-Chloroallyl diethyldithiocarbamate [Sulfallate]
2-Chloro-l-(2,4-dichlorophenyl)vinyl diethyl phosphate
[Chlorfenvinphos]
2-Chloro-4-(l-cyano-l-methylethyl)amino)-6-ethylamino) -s-Triazine
[Cyanazine]
2-Chloro-N-isopropylacetanilide [Propachlor]
2-Methyl-4-chlorophenoxyacetic acid [MCPA]
2-Methyl-A-chlorophenoxyacetic acid, salts and esters
CAS #
00094-75-7
**
00094-82-6
**
00101-05-3
39300-45-3
00099-30-9
02491-38-5
07786-34-7
00095-06-7
00470-90-6
21725-46-2
01918-16-7
00094-74-6
**
Structural Group
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
s-Triazine
Phenylcrotonate
Haloaryl
Miscellaneous
Phosphate
Dithiocarbamate
Phosphate
s-Triazine
Acetanilide
Chlorophenoxy acid
Chlorophenoxy acid
Pesticide Type
Herbicide
Herbicide
Herbicide
Herbicide

Insecticide
Fungicide
Slimicide
Insecticide
Herbicide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide

-------
                                                       Table 3-1  (Continued)
                                            LIST OF PESTICIDE ACTIVE  INGREDIENTS  (PAIS)

99901
67703
31401
**
31501
**
60101
80815
21201
**
35603
99001
67707
102401
101701
100501
28201
107801
Btt
Coda
28
29
30
30
31
31
32
33
3ino)-s-Triazine
2-(m-Chlorophenoxy)propionic acid fCloprop]
Z- (m-Chlorophenoxy Jpropionic acid, salts and esters
2-(Thiocyanomethylthio)benzothiazole [TCMTB)
2-((Hydroxymethyl)amino) ethanol [HAE]
2-((p-Chlorophenyl)phenylacetyl)-l,3-indandione [Chlorophacinone]
3,4,5-trimethylphanyl tnathylcarbamate [Landrin-1)
3,5-Dichloro-N-(l,l-ditnethyl-2-propynyl)benzamide [Pronamide]
3,5-Dimethyl-4-(methylthio)phenyl dimethylcarbaraate (Methiocarb]
3' ,4' -Dichloropropionanilide [Propanil]
3-Iodo-2-propynyl butylcarbamate [Polyphase antitnildaw)
CAS #
26530-20-1
00083-26-1
00120-36-5
**
00093-65-2
**
00148-79-8
22936-75-0
00101-10-0
**
21564-17-0
34375-28-5
03691-35-8
02655-15-4
23950-58-5
02032-65-7
00709-98-8
55406-53-6
Structural Group
Heterocyclic
Indandione
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
Chlorophenoxy acid
Heterocyclic
Triazine
Fhenoxyacetic acid
Phenoxyacetic acid
Heterocyclic
Alcohol
Indandione
Carbaraate
Chlorobenz amide
Carbamate
Chloropropionani lide

P«atiolde Type
Fungicide
Rodenticide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Herbicide
Herbicide
Herbicide
Fungicide
Bacteriostat
Rodenticide
Insecticide
Herbicide
Insecticide, Molluscide
Herbicide
Fungicide
OJ
VO

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



                                            LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIS)

86001
**
37507
101101
19401
**
19201
**
44401
84701
55501
59804
103301
114401
**
90501
FAX
Code
43

44
45
46
46
47
47
48
49
50
51
52
53
53
54
Chemical Hame
3-(a-Acetonylfurfuryl)-4-hydroxycoumarin [Coumafuryl]
3-(a-Acetonylfur£uryl)-4-hydroxycoumarin, salts and esters
4,6-Dinitro-o-cresol [DNOC]
4-Amino-6-
-------
                                                       Table 3-1 (Continued)



                                            LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

98301
69105
**
80801
106201
80803
105201
99101
8901
9501
10101
104301
17002
12301
12302
35301
PAI
Coda
55
56
57
58
59
60
61
62
63
64
65
66
67
68
68
69
Cheaical Hana
Aldicarb (2-Methyl-2-(n>ethylthio)propionaldehyde
O- (me thy Icarbamoyl )oxime )
[ALkyl* dimethyl benzyl Anmonium chloride
* (50Z C14, 401 C12, 101 C16)]
Allethrin (all isomars and allethrin coil)
Ametryn (2-(Ethylan>ino)-4-(isopropylamino)-6-(methylthio)-
s-Triazine
Amitraz (N'-2.4-Dimethylphenyl)-H-( ( (2,4-diraethylphenyl)
imino)methyl)-N-methyln>ethanimidainide)
Atrazine (2-Chloro-4-(ethylamino) -6- (isopropylamino) -s-Triazine)
Bendiocarb (2,2-Dimethyl-l, 3-benzodioxol-4-yl methylcarbamate
Benomyl (Methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate)
Benzene Hexachloride
Benzyl benzoate
Beta-Thiocyanoethyl esters of mixed fatty acids containing from
10-18 carbons [Lethane 384)
Bifenox [Methyl-5-(2,4-dichlorophenoxy)-2-nitrobenzoateJ
Biphenyl
Bromacil (5-Bromo-3-sec-Butyl-6-raathyluracil]
Bromacil, lithium salt
Brotaoxynil [3, 5-Dibromo-4-hydroxybenzonitrile)
CAS #
00116-06-3
68424-85-1
**
00834-12-8
33089-61-1
01912-24-9
22781-23-3
17804-35-2
00608-73-1
00120-51-4
00112-56-1
42576-02-3
00092-52-4
00314-40-9
53404-19-6
01689-84-5
Structural Group
Carbamate
Ammonium
Cyclopropanecarboxylic acid
s-Triazine

s-Triazine
Carbamate
Carbamate
Arylhalide
Aryl
Thiocyanate
Nitrobenzoate
Aryl
Uracil
Uracil
Benzonitrile
Pesticide Type
Insecticide
Antimicrobial
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Fungicide - vegetables
Disinfectant
Repellant
Insecticide
Herbicide
Fungicide
Herbicide
Herbicide
Herbicide
co
I

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




                                            LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

35302
112301
101*01
12501
**
81701
81301
56801
90601
90602
29901
**
58201
27301
81501
81901
25501
FAX
Coda
69
70
71
72
72
73
74
75
76
77
78
78
79
80
81
82
83
Cb««loal Haoa
Bromoxynil octanoate
Butachlor (N-(Butoxymethyl)-2-chloro-2' , 6' -diethylacetanilide]
'-Bromo-'-nitrostyrane [Giv-gard]
Cacodylic acid [Dlmethylarsenic acid]
Cacodylic acid, salts and esters
Captafol [eis-N-< (1,1,2, 2-Tetrachloroethyl)thio)-4-cyclohexene-
1,2-dicarboximide]
Captan [H-Trichloromethylthio-4-cyclohexene-l,2-carboxiniidel
Carbaryl [ 1-Naphthylmethylcarbamate]
Carbofuran [2,3-Dihydro-2,2-dimethyl-7-benzofuranyl
methy Ic arbamate ]
CarbosuLf an [ 2 , 2-Dihydro-2 , 2-dimethyl-7-benzof ur anyl ( dibutylamino )
thio )methy Icarbamate ]
Chloramben [3-Amino-2, 5-dichlorobenzoic acid]
Chloramben, salts and esters
Chlordahe [Octachloro-4 , 7-methanotetrahydroindane]
Chloroneb [l,4-Dichloro-2, 5-dimethoxybenzene]
Chloropicrin [Trichloronitromethane]
Chlorothalonil [2,4 , 5, 6-Tetrachloro-l , 3-dicyanobenzene ]
Chloroxuron [3-(4-(4-Cb.lorophenoxy)phenyl)-l,l-dimethylurea]
CAS *
01689-99-2
23184-66-9
07166-19-0
00075-60-5
**
02425-06-1
00133-06-2
00063-25-2
01563-66-2
55285-14-8
00133-90-4
**
00057-74-9
02675-77-6
00076-06-2
01897-45-6
01982-47-4
Structural Group
Benzonitrile
Acetanilide
Mi Ecellaneous
Organoarsenic
Organoarsenic
Phthalimide
Fhthalimide
Carbamate
Carbamate
Carbamate
Haloaryl
Baloaryl
Multiring halide
Arylchloride
Alkyl halide
Fhthalonitrile
Urea
F«sticide Type
Herbicide
Herbicide
Slimicide
Herbicide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide
Insecticide
Herbicide
Herbicide
Insecticide
Fungicide
Fumigant
Fungicide
Herbicide
CO

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


                                             LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIS)

83701
59102
59101
14504
24002
39105
109301
43401
28901
*«
27501
57601
104801
14502
11301
FAX
Cod*
84
85
86
87
88
89
90
91
92
92
93
94
95
96
97
Chemical Bane
Chloro-l-(2,4,5-trichlorophanyl)vinyl dimethylphosphate [Stirofos]
Chlorpyrifos methyl tO,0-Dimethyl 0-(3,5,6-trichloro-2-pyridyl)
phosphor othioate]
Chlorpyrifos [0,0-Diethyl 0-(3,5,6-trichloro-2-pyridyl)
[phosphorothioatej
Coordination product of Manganses 16Z, Zinc 21, and
Ethylenebisdithiocarbamate 622 [MancozebJ
Copper 8-hydroxyquinoLine
Copper ethylenediaminetetraacetate
Cyano(3-phonoxyphenyl)methyl 4-ehloro-a-(l-inethylethyl)
benzeneacetate (9CA) [Fenvalerate]
Cyclohaximide [3- (2- (3 , 5-0imethyl-2-oxocyclohexyl)-2-hydroxyethyl)
glutarimide]
Dalapon (2,2-dichloropropionic acid)
Dalapon, salts and esters
Decachloro-bis(2,4-cyclopentadiene-l-yl) [DienochlorJ
Demeton [0,O-Diethyl 0-(and S-)(2-ethylthio)ethyl)
phosphorothioate]
Desmedipham [Ethyl m-hydroxycarbanilate carbanilate]
DiAnnonium salt of ethylenebisdithiocarbamate
Dibromo-3-chloropropane [DBCP]
CAS #
00961-11-5
05598-13-0
02921-88-2
08018-01-7
10380-28-6
14951-91-8
51630-58-1
00066-81-9
00075-99-0
**
02227-17-0
08065-48-3
13684-56-5
03566-10-7
00096-12-8
Structural Group
Phosphate
Phosphorothioate
Phosphorothioate
Dithiocarbamate
Organocopper
Organo-copper
Benzeneacetic acid ester
Cyclic ketona
AUcylhalide
Alkylhalide
Arylchloride
Phosphor odithioate
Carbamate
Dithiocarbamate
EDB
PAatioide Type
Insecticide
Insecticide
Insecticide
Fungicide
Fungicide
Slimicide
Insecticide
Growth regulator
Herbicide
Herbicide
Miticide
Insecticide
Herbicide
Fungicide
Hematocide
CO

I-1
Ul

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

29801
**
29601
103401
32101
66501
57801
106201
69122
35001
53501
35201
58601
78701
57901
FAX
Ccxfo
98
98
99
100
101
102
103
104
105
106
107
108
109
110
111
' ' Chemical Bane
Dicamba [3,6-Dichloro-o-anisic acid]
Dicamba, salts and esters
Dichlone [2, 3-Dichloro-l, 4-naphthoquinone]
Diethyl 4,4'-o-phenylenebis(3-thioallophanate) [Thiophanata ethyl]
Di ethyl diphenyl dlchloroethane and related compounds [Per thane]
Diethyl dithiobis(thionoformate) [EXDJ
Diethyl 0-{2-isoprppryl-6-methyl-4-pyrimidinyl) phosphorothioate
[Diazinon]
Dif lubenzuron [H-{ ( (4-Chlorophenyl)amino)carbonyl)-
2 , 6-di f luor obenzami de ]
Diisobutylphenoxyethoxyethyl dimethl benzyl Ammonium chloride
[Benzethonium chloride]
Dimethoate [0,0-Dimethyl
[S- ( (methylcarbamoyl)methyl)phosphorothioate]
Dimethyl 0-p-nitrophenyl phosphorothioate [Parathion methyl]
Dimethyl phosphate ester of 3-hydroxy-N,N-dimethyl-cis-crotonate
[Dicrotophos]
Dimethyl phosphate ester of a-methylbenzyl 3-hydroxy-cis-crotonate
[Crotoxyphos]
Dimethyl 2,3,5,6-tetrachloroterephthalate [DCPA]
Dimethyul (2,2,2-trichloro-l-hydroxyethyl) phosphonate
[Trichlorofon]
CAS #
01918-00-9
**
00117-80-6
23564-06-9
00072-56-0
00502-55-6
00333-41-5
35367-38-5
00121-54-0
00060-51-5
00298-00-0
00141-66-2
07700-17-6
01861-32-1
00052-68-6
Structural Group
Aryl halide
Aryl halide
Aryl halide
Carbamate
DDT
Dithiocarbamate
Phosphorothioate
Benzamide
R4N
Phosphorodithioate
Phosphorothioate
Phosphate
Phosphate
Terephthalic acid ester
Phosphonate
Pastioide Typa
Herbicide
Herbicide
Fungicide
Fungicide
Insecticide
Herbicide
Insecticide
Insecticide
Disinfectant
Insecticide
Insecticide
Insecticide, Miticide
Insecticide
Herbicide
Insecticide

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


                                            LIST OF  PESTICIDE ACTIVE INGREDIENTS (PAIS)

37505
37801
67701
36601
38501
47201
63301
35505
44303
44301
79401
38901
** •
41601
113101
58401
41101
PAI
Code
112
113
114
115
116
117
118
119
120
121
122
123
123
124
125
126
127
Chemical Dane
Dinoseb [2-sec-Butyl-4,6-dinitrophenol]
Dioxathion [2,3-p-Dioxanedithiol S,S-bis(0,0-diethyl
[phosphorodithioate) ]
Diphacinone [2-(Diphenylacetyl)-l,3-indandione]
Diphenamid [N,N-Dimethyl-2,2-diphenylacetamide]
Diphenylamine
Dipropyl isocinchomeronate [MGK 326)
Disodium cyanodithioimidocarbonate [Nabonate]
Dluron (3-(3,4-Dichlorophenyl)-l, 1-dimethylurea]
Dodecylguanidine hydrochloride [Metasol DGH]
Dodine [Dodecylquanidine acetate]
Endosulfan [Hexachlorohexahydromethano-2,4, 3-benzodioxathiepin-
3-oxide]
Endothall [7-Oxabicyclo(2,2, l)heptane-2, 3-dicarboxylic acid]
Endothall, salts and esters
Endrin [Hexachloroepoxyoctahydro-endo , endo-diraethanonaphthalene ]
Ethalfluralin [N-Ethyl-N-(2-methyl-2-propenyl)-2,6-dinitro-
4- ( tr i fluoromethy 1 )benzeneamine ]
Ethion [0,0,0' ,0'-Tetraethyl S,S'-methylene bisphosphorodithioate]
Ethoprop [0-Ethyl S,S-dipropyl phosphorodithioate]
CAS t
00088-85-7
00078-34-2
00082-66-6
00957-51-7
00122-39-4
00113-48-4
00138-93-2
00330-54-1
13590-97-1
02439-10-3
00115-29-7
00145-73-3
**
00072-20-8
55283-68-6
00563-12-2
13194-48-4
Structural Group
Phenol
Phosphorodithioate
Indandione
Ac et amide
Arylamine
Aryl/aLkyl ester
Isocyanate
Urea
Ammonium
Ammonium
Multiring halide
Bicyclic
Bicyclic
Tricyclic
Toluidine
Phosphorodithioate
Phosphorodithioate
Pesticide Type
Herbicide
Insecticide
Rodenticide
Herbicide
Insecticide
Repellant
Slimicide
Herbicide
Fungicide
Fungicide
Insecticde
Herbicide
Herbicide
Insecticide
Herbicide
Insecticide
Insecticide
OJ

M
Ul

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


                                            LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

100601
28801
41405
59901
206600
53301
34801
35503
75002
81601
103601
**
103602
44801
115601
107201
PAI
Coda
128
129
130
131
132
133
134
135
136
137
138
138
139
140
141
142
Chemical Bane
Ethyl 3-methyl-4-(methylthio)phenyL l-(methylethyl)
phosphor amidate [Fenamiphos]
Ethyl 4,4'-dichlorob8nzilate [Chlorobenzilate]
Ethyl dlisobutylthiocarbamate [Butylate]
Famphur {0,O-Dimethyl 0-(p-(dimethylsul£amoyl)phenyl)
phosphorothioate]
Fenar imol [ a- ( 2-Chloropheny 1 ) - a- ( 4- chloropheny 1 )
-5-pyrimidinemethanol]
Fenthion [0.0-Diniethyl 0-(4-methylthio)-m-toluyl)phosphorothioate]
Ferbam [Ferric dimethyldithiocarbamate]
Fluometuron (1, l-Dimethyl-3-(a, a, a-trifluoro-m-tolyl)uraa]
Fluoroacetamide
Folpet [N-( (Trichloromethyl)thio)phthalimide)
GLyphosate [N- (Phosphonomethyl)glycine]
Glyphosate, salts and esters
Glyphosine [N,N-bis(Fhosphonomethyl)glycine]
Heptachlor [Beptachlorotetrahydro-4 , 7-methanoindene]
Hexadecyl cyclopropanecarboxylate [Cycloprate]
Hexazinone [ 3-Cyclohexyl-6-( dimethylami.no )- 1-methyl-
1.3,5-triazine-2,4-(lH,3H)-dione]
CAS t
22224-92-6
00510-15-6
02008-41-5
00052-85-7
60168-88-9
00055-38-9
14484-64-1
02164-17-2
00640-19-7
00133-07-3
01071-83-6
**
02439-99-8
00076-44-8
54460-46-7
51235-04-2
Structural Group
Fhosphoroamidate
Aryl halide
Carbamate
Fhosphorothioate
Pyrimidine
Fhosphorothioate
Dithiocarbamate
Urea
Amide
Fhthalimide
Phosphor amidate
Phosphor amidate
Phosphor amidate
Tricyclic
C-H-0
s-Triazine
Pactiolde Typ«
Nematocide
Miticide
Herbicide
Insecticide
Fungicide
Insecticide
Fungicide
Herbicide
Rodenticide
Fungicide
Herbicide
Herbicide
Herbicide
Insecticide

Herbicide
10
I

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



                                            LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIS)

109401
100201
47601
97401
9001
35506
39504
57701
14505
34802
114001
**
101201
100301
90301
PAI
Cod*
143
144
145
146
147
148
149
150
151
152
153
153
154
155
156
Chemical State
Isofenphos t 1-Methylethyl 2-((ethoxy((l-methylethyl)amino)
phosphinothioyl)oxy)benzoate]
Isopropalln [2 , 6-Dinitro-H, N-dipropy Icumidine ]
Isopropyl N-phenyl carbamate [Propham]
Karbutllate [tert-Butylcarbamic acid ester of 3-(m-hydroxyphenyl)-
1, 1-dimethylurea]
Lindens [gamma isomer of Benzene hexachloride, 99Z pure]
Linuron [3-(3,4-Dichlorophenyl)-l-methoxy-l-methylurea]
Malachite green [Ammonium(4-(p-(dimethylamino)-alpha-
phenylbenzylidine ) -2 , 5-cyclohexadien- 1-ylidene ) -dimethyl
chloride]
Malathion [0,0-Dimethyl dithiophosphate of diethyl
[mere apt o sue c inate ]
Maneb [Manganese salt of ethylenebisdithiocarbamate]
Manganous dimethyldithiocarbamate
Mefluidide [N-(2,4-dimethyl-5-« (trifluoromethyl)sulfonyl)
amino)phenylacetamide]
Mefluidide, salts and esters
Methamidophos [0, S-Dimethyl phosphor amidothioate]
Methidathion [0,0-Dimethyl phosphorodithioate, S-ester of
4-(mercaptomethyl)-2-methoxy-delta 2-l,3,4-thiadiazolin-5-one]
Methomyl [S-Msthyl N-< (methylcarbamoyl)oxy)thioacetimidatej
CAS t
25311-71-1
33820-53-0
00122-42-9
04849-32-5
00058-89-9
00330-55-2
00569-64-2
00121-75-5
12427-38-2
15339-36-3
53780-34-0
**
10265-92-6
00950-37-8
16752-77-5
Structural Group
Phosphoroamidothioate
Toluidine
Carbamate
Carbamate ester
Arylhalide
Urea
R4N
Phosphorodithioate
Dithiocarbamate
Dithiocarbamate
Acetamide
Acetamide
Phosphoroamidothioate
Phosphorodithion
Carbamate
Pecticide Type
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Herbicide
Fungicide, Bactariostat
Insecticide
Fungicide
Fungicide
Defoliant
Defoliant
Insecticide
Insecticide, Miticida
Insecticide
CO
I

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


                                            LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIS)

105401
34001
69134
53201
**
69129
68102
54101
108801
44201
14601
35502
35501
103001
80301
PAX
Coda
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
Chemical Kane
Methoprene [Isopropyl(E,E)-ll-methoxy-3,7, 11-trimethyl-
2,4-dodecadienoate]
Methoxychlor [2,2-bis(p-methoxyphenyl)-l, 1, 1-trichloroethane]
Mathylbenzethonium chloride
Methylbromide
Methylarsonic acid, salts and esters
MathyldodecyLbenzyl trinethyl Ammonium chloride 80Z and
methyldodecylxylylene bis(trimethylanmoniumchloride) 20Z
(HYAMINE 2389]
Methylene bisthiocyanate [Nalco 0-2303]
Methyl-2,3-quinoxalinedithiol cyclic S,S-dithiocarbamate
[Quinmethionate]
Metolachlor [2-Chloro-N-(2-ethyl-6-methylphenyl)-N-
(2-methoxy-l-a)ethylethyl)acetamide]
Mexacarbate [4-(Dimethylamino)-3,5-xylyl methylcarbamate]
Mixture of 83. 9Z Ethylenebis(dithiocarbamato) zinc and 16. 1Z
EthyLenebisdithiocarbamate, bimolecular and trimolecular cyclic
anhydrosulfides and disulfides [Metiram]
Monuron TCA = Monuron trichloroacetate
Monuron [3-(4-Chlorophenyl)-l, 1-dimethylurea]
N,N-Diethyl-2-(l-naphathalenyloxy)propionamide [Napropamide]
H.N-Diethyl-meta-toluaniide and other isotners [Deet]
CAS t
40596-69-8
00072-43-5
15716-02-6
00074-83-9
**
01399-80-0
06317-18-6
02439-01-2
51218-45-2
00315-18-4
09006-42-2
00140-41-0
00150-68-5
15299-99-7
00134-62-3
Structural Group
Estar
DDT
R4H
Alkyl halide
Organoarsenic
R4H
Thiocyanate
Heterocycle
Acetanilide
Carbamate
Dithiocarbamate
Urea
Urea
Amide
Toluamide
F«sticide Type
Regulator
Insecticide
Disinfectant
Fumigant
Herbicide
Disinfectant
Slimicide
Fungicide, Miticide
Herbicide
Insecticide
Fungicide
Herbicide
Herbicide
Herbicide
Repellant
t-1
03

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)


CO
1
t-1
kO

14503
34401
35801
105801
30701
30702
**
57001
84301
79501
79101
36501
32701
32501
105901
59201
PAJ
Code
172
173
174
175
176
176
176
177
178
179
180
181
182
183
184
185
: Chemical Hone
Nab am (Disodium salt of ethyleneblsdithiocarbamate]
Naled [l,2-Dibromo-2,2-dichloroethyl dimethyl phosphate]
Norea [3-Hexahydro-4,7-methanoindan-5-yl-l, 1-dimethylurea]
Nor f lur azon [ 4 -Chloro-5- (methy lamino ) -2- ( a , a , a-tr if luoro-ro-toly 1 ) -
3 ( 2H ) -pyr idazinone ]
N- 1-Naphthylphthalimide
Naptalam (N-1-Naphthylphthalamic acid)
Naptalam, salts and esters
N-2-Ethylhexyl bicycloheptene dicarboximide [MGK 264]
N-Butyl-N-ethyl-a , a , a-trif luoro-2 , 6-dinitro-p-toluidine
[Benfluralin]
0,0,0,0-Tetraethyl dithiopyrophosphate [Sulfotepp]
0,0,0,0-Tetrapropyl dithiopyrophosphate [Aspon]
0, 0-Diethyl 0- ( 3-chloro-4 -methy l-2-oxo-2H- 1-benzopyran- 7-yl
[Coumaphos]
0, 0-Diethyl 0-(p- (methy IsulfinyDphenyDphosphorothioate
[Fensulfothion]
0 , 0-Di ethyl S- ( 2- ( ethy Ithio ) ethyl ) phosphorodi thioate [ Disulf oton ]
0,0-Dimethyl 0-(4-nitro-m-tolyl)phosphorothioate [Fenitrothion]
0,0-Dimethyl S-(phthalimidomethyl)phosphorodithioate [Phosraet]
CAS #
00142-59-6
00300-76-5
18530-56-8
27314-13-2
05333-99-3
00132-66-1
**
00136-45-8
01861-40-1
03689-24-5
03244-90-4
00056-72-4
00115-90-2
00298-04-4
00122-14-5
00732-11-6
Structural Group
Dithiocarbamate
Phosphate
Urea
Heterocyclic
Fhthalamide
Fhthalamide
Fhthalamide
Bicyclic
Toluidine
Dithiopyrophosphate
Dithiopyrophosphate
Phosphorothioate
Fhosphorothioate
Fhosphorodi thioate
Fhosphorothioate
Fhosphorodi thioate
Ea«tioide Type
Fungicide
Insecticide
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Repellant
Herbicide
Insecticide
Insecticide, Miticide
Insecticide
Insecticide
Insecticide
Insecticide
Insecticide

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




                                           LIST OF PESTICIDE ACTIVE INGREDIENTS  (PAIS)

S8001
58702
**
**
**
**
**
59401
104201
103801
111601
111501
219900
41801
41701
FAX
Coda
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
: .. ' - .:•..• CbealctJ. Haoe
0,0-Dimethyl S-((4-oxo-l,2,3-benzotriazin-3(4H)-yl)methyl)
phosphorodithioate [Azlnphos Methyl]
0,0-Dimethyl S-( (ethylsulfiny 1) ethyl )phosphorothioate
[Oxyd erne ton methyl]
Organo-arsenic pesticides (not otherwise listed)
Organo-cadmium pesticides
Organo-copper pesticides
Organo-mercury pesticides
Organo-tin pesticides
ortho Dichlorobenzene1
Oryzalin [3,5-Dinitro-H4,H4-dipropylsulfanilanjide]
Oxamyl [Methyl N' ,N'-dimethyl-H-( (methylcarbamoyl)oxy)-
1-thiooxamidate]
Oxyfluorfen [2-Chloro-l-(3-ethoxy-4-nitrophenoxy)-
4- ( trif luoromethy 1 )benzene ]
0-Ethyl. 0-( 4- (methylthlo)phenyl) S-propyl phosphorodithioate
[Sulprofos]
0-Ethyl 0-(4-(methylthio)phenyl) S-propyl phosphorothioate {9CA}
[Sulprofos Oxon]
0-Ethyl 0-(p-nitrophenyl)phenylphosphonothioate [Santox]
0-Ethyl S-phenyl ethylphosphonodithioate [Fonofos]
CAS #
00086-50-0
00301-12-2
**
**
**
**
**
00095-50-1
19044-88-3
23135-22-0
42874-03-3
35400-43-2
38527-90-1
02104-64-5
00944-22-9
Structural Group
Fhosphorodithioate
Phosphorodithioate
Organoarsenic

Organocopper
Organ omercury
Tin alkyl
Aryl halide
Sulfanylimide
Carbamate
Miscellaneous
Fhosphorodithioate
Phosphorothioate
Fhosphonothioate
Fhosphonodithioate
Pmfciaide lypa
Insecticide
Insecticide
Coccidiostat

Fungicide
Disinfectant
Fungicide
Insecticide
Herbicide
Insecticide
Herbicide
Insecticide
Insecticide
Insecticide, Miticide
Insecticide
CO

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




                                            LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

47802
61501
57501
108501
56502
63001
**
108001
109701
98701
64501
64103
57201
97701
18201
5101
PAI
Coda
201
202
203
204
205
206
206
207
208
209
210
211
212
213
214
215
Chemical Bane
o-Isoproxyphenyl methylcaxbamate [Propoxur]
para Dichlorobenzene1
Parathion [0,0-Diethyl 0-(p-nitrophenyl)phosphorothioate]
Fandimethalln
[N-(l-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine]
Pentachloronitrobenzene
Pentachlorophenol
Pentachlorophenol, salts and esters
Perfluidone (1, 1. l-Trifluoro-N-(2-methyl-4-(phenylsulfonyl)phenyl>
methanesulfonamide]
Pennethrin [ C3-Phenoxyphenyl)methyl 3-(2,2-dichlorethenyl)-
2 , 2-dimethy Icy c lopropanecarboxy late ]
Phenmadipham [Methyl m-hydroxycarbanilate m-methyl carbanilate)
Phenothiazine
Phony Iphenol
Phorate [O,0-Diethyl S-( (ethylthio)methyDphosphorodithioate]
Fhos alone [0,0-Diethyl S-( (6-chloro-2-oxobenzoxazolin-3-yl)cnethyl)
phos phoro th i oat e }
Phosphamidon [2-Chloro-H,N-diethyl-3-hydroxycrotonamide aster of
dimethylphosphate]
Picloram [4-Amino-3,5,6-trichloropicolinic acid)
CAS f
00114-26-1
00106-46-7
00056-38-2
40487-42-1
00082-68-8
00087-86-5
**
37924-13-3
52645-53-1
13684-63-4
00092-84-2
00090-43-7
00298-02-2
02310-17-0
13171-21-6
01918-02-1
Structural Group
Carbamate
Aryl halide
Phosphorothioate
Benzeneamine
Aryl chloride
Phenol
Phenol
Sulfonamide
Cyclopropanecarboxilic acid
Carbamate
Beterocyclic
Phenol
Phosphorodithioate
Fhosphorodithioate
Phosphorothioate
Pyridine
Pesticide Type
Insecticide
Mothballs
Insecticide
Herbicide
Herbicide
Preservative
Preservative
Herbicide
Insecticide
Herbicide
Insecticide
Bacteriostat
Insecticide
Insecticide, Miticide
Insecticide
Herbicide
N)

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




                                            LIST  OF  PESTICIDE ACTIVE  INGREDIENTS  (PAIS)
:••
**
67501
69183
34803
102901
39002
101301
111401
80804
80805
97601
80808
77702
119301
69004
69001
PAX
Code
215
216
217
218
219
220
221
222
223
224
22S
226
227
228
229
230
< • ' y" " ' ChaaioaJ. Horn s" • '
Picloram, salts and esters
Piperonyl butoxide [(Butylcarbityl)(6-propylpiperonyl)ether)
Poly (oxyethyLene(dimethylimino)ethylene (dime thylimino)ethylene
dichloride (FEED (Busan 77))
Potassium dimethyldithiocarbamate [Busan 85)
Potassium H-hydroxymethyl-N-methyldithiocarbamate [Busan 40]
KN Methyl [Potassium H-methyldithiocarbamate]
Potassium N-( alpha- (nitroethyDbenzyl)ethylenediamine
[Metasol J26]
Profenofos [0-(4-Bromo-2-chlorophenyl) 0-ethyl S-propyl
[phosphosothioate]
Prometon [2,4-bis(Isopropylamino)-6-methoxy-s-Triazine]
Prometryn [2 , 4-bis ( Isopropy lamino ) -6- (methylthio ) -s-Triazine]
Propargite [2-(p-tert-Butylphenoxy)cyclohexyl-2-propynyl sulfite]
Propazine [ 2-Chloro-4 , 6- ( isopropy lamino ) -s-Triazihe )
Propionic. acid
Propyl (3-dimethy lamino )propyl carbamate hydrochloride
[Propamocarb and Fropamocarb HC1]
Pyrethrin coils
Pyrethrin I
CAS #
**
00051-03-6
31512-74-0
00128-03-0
51026-28-9
00137-41-7
53404-62-9
41198-08-7
01610-18-0
07287-19-6
02312-35-8
00139-40-2
00079-09-4
25606-41-1

00121-21-1
Structural Group
Pyridine
Ester
R4H
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Miscellaneous
Fhosphorothioate
s-Triazine
s-Triazine
Sulfite
s-Triazine
Alkyl acid
Carbamate

Cyclopropanecarboxylic acid
Pesticide Typo
Herbicide
Synergist
Fungicide
Fungicide
Fungicide
Fungicide
Fungicide, Slimicide

Herbicide
Herbicide
Insecticide, Miticide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide
to

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

OJ
NO
OJ

69002
69006
97801
58301
71003
74801
35509
82501
**
80807
103901
34804
75003
39003
57101
41301
41401
PAX
Code
231
232
233
234
235
236
237
238
238
239
240
241
242
243
244
245
246
Chemical Hume
Pyrethrin II
Pyrethrum (synthetic pyrethrin)
Resmethrin [ (5-Phenylmethyl)-3-£uranyl)methyl 2,2-dimethyl-3-
( 2 -methyl- 1 -pr openy 1 ) cy c lopropan e c arboxy late ]
Ronnal [O,O-Dimethyl 0-(2,4,5-trichlorophenyl)phosphorothioate]
Rotenone
S,S,S-Tributyl phosphorotrithioate [DEF1
Siduron [l-(2-Methylcyclohexyl)-3-phenylurea]
Silvex [2-(2,4, 5-Trichlorophenoxypropionic acid)}
Silvex, salts and esters
Simazine (2-Chloro-4, 6-bis(ethylamino)-s-Triazine]
Sodium bentazon (3-Isopropyl-lB-2, 1,3-benzothiadiazin-
4(3H)-one-2,2-dioxide]
Sodium dimethyldithiocarbanate [Carbam-S]
Sodium monofluoroacetate
Sodium methyldithiocarbamate [Vapam]
Sulfoxide [l,2-Methylenedioxy-4-(2-(octylsulfidynyl)
ptopyl) benzene]
S-Ethyl cyclohexylethylthiocarbamate [Cycloate]
S-Ethyl dipropylthiocarbamate [EPTC]
CAS *
00121-29-9
08003-34-7
10453-86-8
00299-84-3
00083-79-4
00078-48-8
01982-49-6
00093-72-1
**
00122-34-9
25057-89-0
00128-04-1
00062-74-8
00137-42-8
00120-62-7
01134-23-2
00759-94-4
Structural Group
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Phosphorothioate
Bio extract
Phosphorotrithioate
Urea
Phenoxy acid
Phenoxy acid
s-Triazine
Heterocylic n,s
Dithiocarbamate
Acetate salt
Dithiocarbamate
Heterocyclic
Carbaroate
Carbamate
Pesticide Typo
Insecticide
Insecticide
Insecticide
Insecticide
Insecticide
Defoliant
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Rodenticide
Fungicide
Insecticide
Herbicide
Herbicide

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)
u>
N>
M

**
67501
69183
34803
102901
39002
101301
111401
80804
8C80S
97601
80808
77702
119301
69004
69001
PAI
Cod*
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
:;;: *: ':-....••••••'•••••• CbeaioaJ. Hone
Picloram, salts and asters
Piperonyl butoxide [(Butylcarbityl)(6-propylpiperonyl)ether]
Poly ( oxy ethy Lane ( dimethy limino ) athy lane ( dimethy limino ) a thy lane
dichloride [FEED (Bus an 77)]
Potassium dimethyldithiocarbamate (Bus an 85]
Potassium N-hydrojcymethyl-N-methyldithiocarbamate [Bus an 40]
KN Methyl [Potassium N-mathyldithiocarbamate]
Potassium H-( alpha- (nitroethyl)benzyl)ethylenediamine
[Metasol J26]
Profenofos [0-(4-Bromo-2-chlorophenyD 0-ethyl S-propyl
tphosphosothioate]
Prometon [2 , 4-bis ( Isopropylamino ) -6-methoxy-s-Triazine]
Prometryn [2,4-bis(Isopropylamino)-6-(methylthio)-s-Triazine]
Propargite [2-(p-tert-Butylphanoxy)cyclohexyl-2-propynyl sulfite]
Propazine [2-Chloro-4 , 6- ( isopropylamino ) -s-Triazihe]
Fropionic acid
Propyl (3-dimethylaniino)propyl carbaoate hydrochloride
[Propamocarb and Fropamocarb HC1]
Pyrethrin coils
Pyrethrin I
CAS #
**
00051-03-6
31512-74-0
00128-03-0
51026-28-9
00137-41-7
53404-62-9
41198-08-7
01610-18-0
07287-19-6
02312-35-8
00139-40-2
00079-09-4
25606-41-1

00121-21-1
Structural Group
Pyridina
Ester
R4N
Dithiocarbamate
Dithiocarbamata
Dithiocarbamate
Miscellaneous
Phosphorothioate
s-Triazine
s-Triazine
Sulfite
s-Triazine
Aliyl acid
Carbamate

Cyclopropanecarboxylic acid
P«8tiaide Tjpe
Herbicide
Synergist
Fungicide
Fungicide
Fungicide
Fungicide
Fungicide, Slimicide

Herbicide
Herbicide
Insecticide, Miticide
Herbicide
Fungicide
Fungicide
Insecticide
Insecticide

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

69002
69006
97801
58301
71003
74801
35509
82501
**
80807
103901
34804
75003
39003
57101
41301
41401
PAI
Code
231
232
233
234
235
236
237
238
238
239
240
241
242
243
244
245
246
Chemical Hone
Pyrethrin II
Pyrethrum (synthetic pyrethrin)
Resmethrin E (5-Phenylmethyl)-3-furanyl)methyl 2,2-diniethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate)
Ronnel [0,0-Dimethyl 0-(2,4,5-trichlorophenyl)phosphorothioate]
Rotenone
S,S,S-Tributyl phosphorotrithioate [DBF]
Siduron [l-(2-Methylcyclohexyl)-3-phenylureal
Silvex [2-(2,4,5-Trichlorophenoxypropionic acid)]
Silvex, salts and esters
Simazine [2-Chloro-4 ,6-bis(ethylamino)-s-TriazineJ
Sodium bentazon J3-Isopropyl-lH-2, 1,3-benzothiadiazin-
4(3H)-one-2,2-dioxide]
Sodium dimethyldithiocarbanate [Carbam-S]
Sodium monofluoroac state
Sodium methyldithiocarbamate [Vapam]
Sulfoxide (l,2-Mathylenedioxy-4-(2-(octylsulfidynyl)
propyl) benzene]
S-Ethyl cyclohexylethylthiocarbamate [Cycloate]
S-Ethyl dipropylthiocarbamate [EPTC]
CAS f
00121-29-9
08003-34-7
10453-86-8
00299-84-3
00083-79-4
00078-48-8
01982-49-6
00093-72-1
**
00122-34-9
25057-89-0
00128-04-1
00062-74-8
00137-42-8
00120-62-7
01134-23-2
00759-94-4
Structural Group
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Phosphorothioate
Bio extract
Phosphorotrithioate
Urea
Phenoxy acid
Phenoxy acid
s-Triazine
Heterocylic n,s
Dithiocarbamate
Acetate salt
Dithiocarbamate
Heterocyclic
Carbamate
Carbamate
Pectlclde Type
Insecticide
Insecticide
Insecticide
Insecticide
Insecticide
Defoliant
Herbicide
Herbicide
Herbicide
Herbicide
Herbicide
Fungicide
Rodenticide
Fungicide
Insecticide
Herbicide
Herbicide

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




LIST OF PESTICIDE ACTIVE INGREDIENTS (PAIS)

to
^
£»

41402
41403
41404
35604
9801
105501
59001
12701
105001
80814
80813
63004
**
35602
102001
PAX
Coda
247
248
249
250
251
252
253
254
255
256
257
258
258
259
260
Chemical Dante
S-Ethyl hexahydro-lH-azepine-1-carbothioate [Molinate]
S-Propyl butylethylthiocaxbamate [Pebulate]
S-Propyl dipropylthiocarbamate [Vernolate]
S- (2-Hydroxypropyl) thiomethanasulf onata [HPTMS J
S-(0,0-Diisopropyl) phosphorodithioate ester of
N- ( 2-mer captoathy 1 ) benzenesulf onamide [ BensuLide }
Tebuthluron [N-(5-(l,l-Dimethylethyl)-l,3,4-thiadiazol-2-yl)-
S , H ' -dimethylur ea]
temephos [0,0,0' ,O'-Tetramathy 1-0,0' -thiodi-p-
phenylenephosphorothioabe]
Terbacil [3-tert-Butyl-5-chloro-6-methyluracil]
Terbufos [S-( ( (1, l-Dimethylethyl)thio)methyl) 0,0-diethyl
phosphorodithioate]
Terbuthylazine [2-(tert-Butylamino)-4-chloro-6-(ethylamino)-
s-Triazlne]
Terbutryn [2-(tert-Butylamino)-4-(ethylainino)-6-(inethylthio)-
s-Triazinel
Tetrachlorophenol
Tetrachlorophenol salts and esters
Tetrahydro-3 , 5-dimethyl-2H-l, 3 , 5-thladiazine-2-thione [Dazomet]
Thiophanate methyl [Dimethyl 4 , 4 ' -o-phanylenebis
( 3-thioallophanate ) ]
CAS #
02212-67-1
01114-71-2
01929-77-7
29803-57-4
00741-58-2
34014-18-1
03383-96-8
05902-51-2
13071-79-9
05915-41-3
00886-50-0
25167-83-3
**
00533-74-4
23564-05-8
Structural Group
Carbamate
Carbamate
Carbamate
Thiosulphonate
Phosphorodithioate
Heterocyclic
Phosphorothioate
Uracil
Fhosphorodithioato
s-Triazine
s-Triazine
Phenol
Phenol
Heterocyclic
Carbamate
P«»tioide type
Herbicide
Herbicide
Herbicide
Fungicide
Herbicide
Herbicide
Insecticide
Herbicide
Insecticide
Herbicide
Herbicide
Preservative
Preservative
Fungicide
Insecticide

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




                                               LIST OF  PESTICIDE ACTIVE INGREDIENTS  (PAIS)
u>
K)
en

79801
80501
74901
36101
86002
**
51705
14506
34805
78802
69005
69003
18301
PAJ
Code
261
262
263
264
265
265
266
267
268
269
270
271
272
Chemical lane
Thiraia [Tetramethylthiuram disulfide)
Toxaphene [technical chlorinated camphena (67-69Z chlorine)]
Tributyl phosphorotrithioate [Merphos]
Trif luralin [ a , a , a-Trif luoro-2, 6-dinitro-N , N-dipropyl-p-toluidine]
Warfarin [3-(a-Acetonylbenzyl)-4-hydroxycoumarin]
Warfarin salts and esters
Zinc 2-mercaptobenzothiazolate [Zinc MET)
Zineb [Zinc ethylenebisdithiocarbamate]
Ziram [Zinc dimethyldithiocarbamate]
S-(2,3,3-Trichloroallyl)diisopropylthiocarbamate
(3-Phenoxyphenyl)methyl d-cis and trans* 2,2-dimethyl-3-
(2-me thy IpropenyDcyclopropanecarboxy late
*(Max. d-cis 25Z; Min. trans 75Z) [Phenothrin]
(4-Cyclohexene-l,2-dicarboxiraido)methyl 2,2-dimethyl-3-
( 2-methylpropenyl ) eye lopropanecarboxy late [ Tetr amethr in ]
Isopropyl H-(3-chlorophenyl) carbamate [Chloropropham]
CAS t
00137-26-8
08001-35-2
00150-50-5
01582-09-8
00081-81-2
**
00155-04-4
12122-67-7
00137-30-4
02303-17-5
26002-80-2
07696-12-0
00101-21-3
Structural Group
Dithiocarbamate
Multiring halide
Fhosphorotrithioate
Toluidine
Hy dr oxy c oumar in
Hydroxycoumarin
Organozinc
Dithiocarbamate
Dithiocarbamate
s-Esterthiocarbamate
Cyclopropanecarboxylic acid
Cyclopropanecarboxylic acid
Carbaraate
Pesticide Type
Fungicide
Insecticide
Defoliant
Herbicide
Rodenticide
Rodenticide
Fungicide
Fungicide
Fungicide
Herbicide
Insecticide
Insecticide
Herbicide plant growth
regulator
Deleted because the chemical is covered by OCPSF Effluent Limitations Guidelines and Standards

-------
from those reviewers,  EPA determined that the draft questionnaire needed




extensive revision to better define and focus the questions and the pesticide




formulator/packager segment of the industry was significantly different from




the manufacturing segment and should be covered by a separate study.









            As required by the Paperwork Reduction Act, 44 U.S.C. 3501 et




seq., EPA submitted the revised questionnaire to the Office of Management and




Budget for review, and published a notice in the Federal Register that the




questionnaire was available for review and comment.  EPA also distributed the




revised questionnaire to the same industry trade associations, pesticide




industry facilities, and environmental groups that had provided comments on




the previous draft and to any others who requested a copy of the draft




questionnaire.









            Based on additional comments received, EPA made changes to the




questionnaire to reduce the extent of production process information requested




and clarify certain other questions.  EPA had included the request for




detailed production process information in part to have sufficient data to




adequately and rapidly respond to potential requests for variances from




effluent limitations and standards based on "fundamentally different factors."




However, the Water Quality Act of 1987 amended Section 301(n) of the Act,




superseding NPDES regulations at 40 CFR 122.21 regarding application for a




"fundamentally different factors" variance.  Based on that amendment, EPA




determined that detailed production process information should not be




requested of all questionnaire recipients.  OMB cleared the technical portion
                                     3-26

-------
of the questionnaire (the Introduction and Part A) for distribution on April




8, 1988, but denied clearance to the economic portion (Part B).   The economic




portion was subsequently revised, resubmitted and cleared.   (See "Economic




Impact Analysis of Effluent Limitations and Standards for the Pesticide




Manufacturers" for information concerning the development of the economic




portion of the questionnaire.)









3.1.3.a     Distribution of the Pesticide Manufacturing Facility Census for




            1986









            EPA's database for the remanded regulation identified 247




facilities that at one time had produced or manufactured pesticides.  Other




sources cited above (see Section 3.1.1) identified only facilities that were




already part of the list of 247 facilities.  Therefore, EPA believes that the




list covers all manufacturing facilities that were operating in 1986.









            Under the authority of Section 308 of the Act,  EPA distributed the




questionnaire entitled "Pesticide Manufacturing Facility Census for 1986"




(hereinafter, the "Facility Census") to all 247 facilities in EPA's database.




EPA received responses from all 247 facilities (a 100% response rate).   The




responses in many cases indicated that the facility did not manufacture PAIs




anymore and in some cases indicated that the facility was closed.  The




responses indicated that 90 facilities manufactured pesticides in 1986




compared to 120 facilities in 1985 (see Section 3.6 for a discussion on




changes in the industry).
                                     3-27

-------
            The questionnaire specifically requested information on: (1) the




PAI manufacturing processes used;  (2)  the quantity, treatment, and disposal of




wastewater generated during PAI manufacturing;  (3) the analytical monitoring




data available for PAI manufacturing wastewaters;  (4) the information on




treatability studies performed by  or for facilities; (5) the degree of co-




treatment (treatment of PAI manufacturing wastewater mixed with wastewater




from other industrial manufacturing operations  at  the facility); and (6) the




extent of wastewater recycling and/or  reuse at  the facility.  Information was




also obtained through follow-up telephone calls and written requests for




clarification of questionnaire responses.









            EPA also requested that pesticide manufacturing facilities submit




wastewater self-monitoring data.   Fifty-five facilities submitted some form of




self-monitoring data.  One facility submitted data only for conventional




pollutants, while 37 of the 55 facilities submitted conventional pollutant




data along with priority pollutant and/or nonconventional pollutant data




(including the PAIs).  Thirty-four of  the 55 facilities submitted priority




pollutant data, and 49 facilities  submitted data for PAIs.  However, much of




these data were not useful in characterizing pesticide process wastewaters.




In many cases, only one detection was  reported  for a specific pollutant, or




the sampling locations represented commingled wastewaters containing pollutant




discharges from other industrial processes, such as OCPSF production.  Often




the data represented sampling results  only at the end-of-pipe plant discharge.




As will be discussed in Section 5, self-monitoring data from only six




facilities were useful in characterizing priority pollutant discharges in raw
                                     3-28

-------
pesticide process wastewaters.  However, industry-supplied data from 27




facilities covering 55 PAIs were sufficient in establishing effluent




limitations.









            A summary of the information obtained from the "Facility Census"




is presented in this document and also reflects the additional data obtained




from follow-up telephone calls and written requests for clarification of the




information provided in responses to the questionnaire, as well as wastewater




concentration data submitted by facilities along with the Facility Census.









3.1.4       EPA's 1988-1991 Sampling of Selected Pesticide Manufacturers









            Between 1988 and 1991, EPA visited 32 of the 90 manufacturing




facilities.  During each visit, EPA gathered production process information




and information on waste and wastewater generation, treatment and disposal.




Based on these data and the responses to the Facility Census, EPA conducted




wastewater sampling at 20 of the 32 facilities in order to characterize




process discharges and treatment system performance.  In addition, EPA




collected wastewaters for treatability studies at seven of the 32 facilities.




Four of these seven were among the 20 facilities sampled in order to




characterize process discharges and treatment system performance.  That is,




EPA collected wastewater samples at 23 of the 32 facilities visited.  The




other nine facilities visited were not sampled:  two plants do not discharge




wastewater (they recycle/reuse their wastewater);  two plants had no wastewater




treatment; three plants had pesticide manufacturing process wastewater so
                                     3-29

-------
intimately commingled with wastewaters from other manufacturing processes that




sampling for characterization was not possible; one plant disposed of




wastewater by deep-well injection; and the ninth plant was not in production




during possible sampling times  (however, the ninth plant did provide long-term




self-monitoring data).









            During sampling activities, raw wastewaters from the manufacture




of 38 different PAIs were characterized.  Samples were also collected to




assist in the evaluation of the performance of 62 specific treatment unit




operations.  Table 3-2 presents a breakdown of the types of treatment units




sampled.  Through the treatability studies, EPA analyzed the efficacy of




activated carbon adsorption, membrane filtration, hydrolysis and alkaline




chlorination for control of 76  PAIs.  More detailed studies using actual




manufacturing process wastewater to develop additional treatment performance




data for activated carbon adsorption, hydrolysis, and alkaline chlorination




technologies were subsequently  conducted.  These more detailed studies




involved 13 specific PAIs included in today's proposed rule and are described




in more detail in Section 3.1.6.  Facilities were selected for sampling after




an evaluation of existing data  and responses to the Facility Census.  The




facilities were selected for sampling if the data indicated that the




wastewater treatment system was effective in removing PAIs, and the PAIs




manufactured appeared to be representative of one or more PAI structural




categories, such as organo-phosphate PAIs.  Wastewaters containing PAIs in 21




structural groups were analyzed during EPA sampling.
                                      3-30

-------
                                  Table  3-2




                       TREATMENT UNIT OPERATIONS  SAMPLED
Treatment Unit Operation
Biological Oxidation
Flocculation
Activated Carbon
Aeration
Multimedia Filtration
Chemical Oxidation
Pressure Filtration
Hydrolysis
Evaporation Pond
Steam Stripping
Dechlorination
Resin Adsorption
Metal Separation
Solvent Extraction
Air Stripping
UV Decomposition
Land Application
Coagulation
Mechanical Evaporation
Cyanide Destruction
Total Number of Units
29
8
19
1
5
14
8
11
2
11
4
2
1
13
5
2
1
2
1
1
Total Number of Units
Units Sampled
7
1
11
0
1
7
3
7
0
4
1
1
1
3
1
1
0
2
0
1
Note:  Plants operate more than one treatment unit.
                                     3-31

-------
            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
                                     3-32

-------
identified any information in the draft report that the facility considered




confidential business information.









3.1.5       Industry-Supplied Data









            All facilities which discharge wastewater directly to receiving




streams must have NPDES permits which establish effluent limitations and




monitoring requirements.   Some POTWs also require indirect dischargers to




monitor their effluent.  To make use of this self-monitoring data, the




Facility Census requested that each respondent provide all monitoring data




available for 1986 on raw waste loads, individual process stream measurements,




pollutant concentration profiles, or any other data on pollutants associated




with the manufacture of pesticide active ingredients.  EPA later requested




selected plants to provide additional monitoring data for 1987-1989.  Plants




selected to provide additional data were those with extensive self-monitoring




programs and wastewater treatment technologies that appeared to be exemplary.




EPA requested that all monitoring data be provided in the form of individual




data points rather than as monthly aggregates.









            Under authority of Section 308 of the Act, EPA also requested two




facilities to conduct more extensive sampling of their wastewater treatment




systems.  These two plants appeared to have exemplary PAI wastewater treatment




systems but the facilities had previously conducted no or only very limited




monitoring of their PAI wastewater.  The sampling programs conducted by these
                                     3-33

-------
two facilities at EPA's request provided needed long-term treatment system




performance data.









            Pesticide wastewater treatability studies performed by or for the




facility were also requested by EPA.  These additional data were also




considered in the development of effluent limitations guidelines.  Because




treatability data were lacking for some PAIs, individual PAIs, which were




expected to be treatable with a specific technology, were targeted for




treatability studies.  EPA collected samples of actual pesticide manufacturing




process wastewater at plants manufacturing those PAIs.  Following sample




collection, the samples were transferred to an EPA contractor for bench scale




testing.  The data were then used to develop limitations for these PAIs when




it was demonstrated that the technology was effective at PAI removal.









3.1.6       EPA Bench-Scale Treatability Studies









            EPA conducted a number of bench-scale studies to evaluate the




treatability of PAIs by various wastewater treatment technologies.   These




technologies included hydrolysis, membrane filtration, activated carbon




adsorption, chemical oxidation by alkaline chlorination and chemical oxidation




by ozone accompanied by irradiation with ultraviolet light.  Treatability




studies were conducted both on clean water to which PAIs were added




("synthetic wastewaters") and on actual pesticide process wastewaters.
                                     3-34

-------
            The hydrolysis,  membrane filtration,  and activated carbon isotherm




treatability studies used synthetic wastewaters.   General factors included in




the selection of specific PAIs for use in the synthetic wastewaters were the




availability of an analytical method for the specific PAI and the ready




availability of the PAI in a pure form from either government or commercial




sources.  Another factor in selecting the PAIs was the hydrolysis rate of each




PAI:  a too rapid hydrolysis rate could interfere in the chemical analysis of




the samples.









            The hydrolysis studies used PAIs selected in part based on the




existence of hydrolysis data gathered from a literature survey (for comparison




with EPA treatability study results),  and in part based on the lack of any




literature data, so as to fill in those data gaps.  All of the PAIs selected




were expected to hydrolyze under some conditions.









            In the hydrolysis treatability study,  a series of bench-scale




tests were conducted to determine the hydrolysis  rates of selected PAIs,




Thirty-eight PAIs were selected for testing and separated into four synthetic




test solutions.  The hydrolysis treatability study was conducted at three




different pH levels (2, 7, and 12) and at two different temperatures (20°C and




60°C).









            The activated carbon studies used PAIs selected from various




structural groups to determine which groups would be most amenable to




activated carbon technology.  Carbon adsorption isotherms were developed for
                                     3-35

-------
29 specific PAIs.  Some manufacturers of some PAIs in a few of the PAI




structural groups were known to use activated carbon technology to treat their




wastewaters; in these cases, the purpose of the carbon isotherm study was to




establish benchmarks for determining the potential efficacy of activated




carbon technology to other structural groups or to other PAIs in the same




structural group.  The results of the carbon isotherm tests were evaluated




using the Freundlich isotherm equation.









            The membrane filtration studies used PAIs selected to span the




molecular weight range of the 270 PAIs under consideration for regulation,




because the effectiveness of membrane filtration tends to vary according to




molecular weight.  In the membrane filtration treatability study, a series of




bench-scale tests were conducted to identify specific PAIs which could be




separated from water by various membrane materials.  Synthetic test solutions




containing 19 PAIs were tested on 7 different types of membranes.  The




membranes were manufactured from 3 types of materials (cellulose acetate,




thin-film composite, and Aramid) and were of various pore sizes, with nominal




molecular weight cut-offs ranging from 150 to 500.









            The treatability studies using actual pesticide manufacturing




process wastewater were conducted to supplement full-scale treatment system




performance data.  These studies helped to fill in gaps where little or no




treatability data were available for the PAI, and to help assess performance




of existing full-scale treatment systems where the performance of those




systems appeared to be inadequate compared to the performance of other
                                     3-36

-------
facilities treating the same or similar PAIs.  The PAIs selected for study




were the PAIs in production at the plants during the treatability study.









            EPA collected actual process wastewaters to determine adsorption




properties of specific PAIs using accelerated column tests.   Four PAIs were




evaluated as part of these tests which use bench scale results to estimate




full-scale carbon system performance, design and cost.  Two of the PAIs




studied in these tests were also evaluated as part of the carbon isotherm




s tudy.









            One series of chemical oxidation treatability studies was




conducted to determine the applicability of alkaline chlorination as a method




of treating pesticide manufacturing process wastewaters.  In these bench-scale




tests,  manufacturing wastewaters from six PAI processes were tested at




chlorine dosages equal to 50,100 and 125% of the chlorine demand for the




specific wastewater at pH 12 and ambient temperatures.  Contact times of 0.5,




1.5 and 4.0 hours were examined.









            Because alkaline chlorination of wastewater containing organic




matter may generate volatile organic toxic pollutants, which must subsequently




be controlled, EPA also conducted chemical oxidation treatability studies for




five of those same six PAIs using ozone rather than chlorine.  The preliminary




results of those studies indicate that ozone can achieve about the same degree




of PAI reduction as chlorine.  Chemical oxidation with ozone is usually more




expensive than chemical oxidation with chlorine.  However, ozone oxidation
                                     3-37

-------
does not produce volatile toxic pollutants.  When the cost of controlling



those volatile toxic pollutants is added to the cost of alkaline chlorination,



the total cost for chlorination may exceed the cost of ozone oxidation.







3.1.7       Data transferred from the OCPSF Rulemaking







            The Clean Water Act of 1977 stressed the control of toxic



pollutants, including 65 toxic pollutants and classes of pollutants.  From
                                                                   *


this list of 65, EPA has derived a subset of 126 individual "priority"



pollutants on which the Agency has focused (see, e.g., list of 126 priority



pollutants at 40 CFR Part 423, Appendix A).  EPA has determined that 28 of the



126 priority pollutants may be present in pesticides manufacturing



waste-waters, and EPA is proposing today to set direct discharge limitations



and pretreatment standards for these 28 priority pollutants.  For 23 of these



28 priority pollutants, EPA is relying on the OCPSF technical database to



propose limitations.  Limitations for one priority pollutant, cyanide, are



proposed based on long-term data collected from the pesticide industry.  The



other four priority pollutants being proposed for regulation today were not



regulated under OCPSF and there are no treatment performance data for these



four specific pollutants.  EPA developed proposed limitations for these four



priority pollutants by transferring limitations from other structurally



similar priority pollutants.  This is the same procedure that was used in



developing OCPSF limitations (40 CFR Part 414) when performance data was



lacking for certain priority pollutants.
                                     3-38

-------
            Limitations were developed under the OCPSF rulemaking for 23




priority pollutants that were also detected in pesticide manufacturers'




wastewaters during the EPA sampling and industry self-monitoring efforts.




Fifty-five of the 90 pesticide chemicals manufacturing facilities also




manufacture compounds regulated under the OCPSF category.  Based on these




factors, EPA is proposing that technical data from the OCPSF category and




effluent limitations for priority pollutants based on that data be transferred




to the pesticide chemicals manufacturing category as supporting data for the




proposed limitations for the priority pollutants in this regulation.









            EPA is relying on the OCPSF database to set BAT and NSPS




limitations for 23 priority pollutants.  The OCPSF limitations for volatile




priority pollutants were based on data from plants that exhibited efficient




volatile pollutant reduction using either in-plant steam stripping




technologies alone or in-plant steam stripping followed by biological




treatment.  OCPSF limitations were also based on activated carbon or in-plant




biological treatment for some semi-volatile organic priority pollutants.  The




OCPSF guideline established limitations for lead based on performance data




obtained from EPA's study of the metal finishing industry.









            EPA is also proposing to transfer PSES and PSNS and data




supporting those standards from the OCPSF category for the same 23 priority




pollutants.  EPA is relying on an analysis originally done to support the




OCPSF regulations to determine pass-through for these pollutants.  That




analysis demonstrates that 21 of the 23 priority pollutants do pass through a
                                     3-39

-------
POTW.  Therefore, EPA is proposing PSES and PSNS for 21 of those 23




pollutants.  EPA's pass-through analysis is discussed in more detail in




Section 7.









            Only technical data used to develop limitations are being




transferred from the OCPSF rulemaking for these 23 pollutants.  The economic




analysis evaluating whether attainment of these limitations is economically




achievable by pesticides manufacturers has been performed independently as




part of today's proposed rulemaking.









            EPA is also proposing BAT, NSPS, PSES, and PSNS limitations for




four brominated priority pollutants that are present in pesticides




manufacturers' wastewaters but which are not regulated under the OCPSF




guidelines.  The proposed limitations were developed based on steam stripping,




using the same procedure followed in developing the OCPSF regulations for




volatile pollutants where treatment performed data were unavailable.









            In the OCPSF regulation, EPA established effluent limitations for




28 priority pollutants based on steam stripping technology, but EPA had




performance data for only 15 of those 28 priority pollutants.  To develop




limitations for the 13 priority pollutants with no performance data, EPA




divided the 15 priority pollutants with data into 2 subgroups, a high




stripability subgroup and a medium stripability subgroup, based on Henry's Law




Constants  (a ratio of aqueous solubility, or tendency to stay in solution, to




vapor pressure, or tendency to volatize).  Based on each pollutant's Henry's
                                     3-40

-------
Law Constant, the 13 priority pollutants lacking performance data were




assigned to either the high or medium stripability subgroup, and the average




data for each subgroup was then transferred for limitations development.  (For




more details, see 52 FR 42540-41, November 5, 1987.)









            This same procedure was followed for each of the four brominated




volatile priority pollutants for which limitations are proposed today.









3.2         OVERVIEW OF THE INDUSTRY









            This subsection provides an overview of the Pesticide Chemicals




Manufacturing Industry by presenting general information on the geographical




locations, SIC code distribution, age, typical markets, and types of




facilities.









3.2.1       Geographical Location of Manufacturing Facilities









            In 1986, 90 manufacturing facilities,  located in 29 states,




reported producing 1 or more of 178 PAIs from the list of 270 PAIs and classes




of PAIs.  In addition, 8 other products were produced before and after 1986,




but not in 1986.  The majority of pesticide manufacturing facilities are




located in the eastern half of the United States,  with a large concentration




in the southeast corridor and Gulf Coast states.  Approximately 50% of all




pesticide production occurs in these areas.  The geographic distribution of




pesticide manufacturing facilities by EPA region is presented in Figure 3-2;
                                     3-41

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                                               Figure 3-2
U)
               35n
                0
                                 DISTRIBUTION OF  PESTICIDE MANUFACTURING
                                         FACILITIES BY EPA  REGION
                          Northeast      Southeast      Midwest
                                               Region
          West
                                   # Manufacturers
% PAI Manufacture
                                                                                      70%
                                                                                      0%

-------
EPA Regions I, II, and III are included in the "Northeast" region on the




figure, EPA Region IV is included in the "Southeast1' region, EPA Regions V,




VI, and VII are included in the "Midwest" region, and EPA Regions VIII, IX,




and X are included in the "West11 region.









            Table 3-3 presents the geographic distribution of OCPSF




manufacturing facilities by EPA Region as surveyed in 1983.  The distribution




of OCPSF manufacturing facilities is similar to the distribution of the




pesticide chemicals manufacturing industry.  Of the 90 pesticide chemicals




manufacturers, 55 also manufacture products covered under the OCPSF




guidelines.









3.2.2       SIC Code Distribution









            Standard Industrial Classification (SIC) codes, established by the




U.S. Department of Commerce, are classifications of commercial and industrial




establishments by type of activity in which they are engaged.  The primary




purpose of the SIC code is to classify the manufacturing industries for the




collection of economic data.  An operating establishment is assigned an




industry code on the basis of its primary activity, which is determined by its




principal product or group of products.  The primary product of a




manufacturing establishment is determined by the value of production.
                                     3-43

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                                   Table 3-3

                   COMPARISON OF THE GEOGRAPHIC DISTRIBUTION
                          OF THE OCPSF vs. PESTICIDE
                              INDUSTRY BY REGION
Region1
Northeast
Southeast
Midwest
West
TOTAL
No. of OGPSF
Manuf ac tur ing
Facilities
311
181
361
87
940
No. of
Pesticide
Manufacturing
Facilities
22
25
35
8
90
% of OCPSF
Manuf ac tur ing
Facilities
33.1
19.3
38.4
9.2
100
% of
Pesticides
Manuf ac tur ing
Facilities
24.4
27.8
38.9
8.9
100
'The  "Northeast" region includes EPA Regions I,  II,  and III;  the "Southeast"
region includes EPA Region IV;  the  "Midwest" region includes EPA Regions V,
VI, and VII; and the "West" region  includes EPA Regions VIII, IX, and X.
                                     3-44

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            This industry is included within, but not limited to, SIC Major Group




28, Chemical and Allied products.  More specifically,  facilities  manufacturing




PAls may be  engaged in one or more of the following SIC  groups: 2831; 2833; 2834;




2842; 2843;  2861; 2865; 2869;  2879; and 2899.









3.2.3       Age of Facilities









            The majority of facilities which currently manufacture  pesticide




active ingredients began manufacturing operations in the 1950s  and 1960s.   The




majority of pesticide manufacturing operations also began  about  this time and




pesticide operations start-ups continued into the  1970s.   The  oldest reported




pesticide operation began in 1909, while the most recent operation began in 1987.




Thirty-nine facilities  reported that pesticide operations began  at the same time




the facility operations began.  Table 3-4 presents the  distribution of pesticide




manufacturing facilities  by decade of when operations began at the facility, when




pesticide operations began at the facility,  and  when the most recent major




expansion of pesticide operations occurred.









3.2.4       Market Types









            Figure 3-3  presents the percent of PAI production by  market type from




information  reported  on the  1986  questionnaire  for   88  of the 90  pesticide




chemicals manufacturing facilities. Approximately 18% of 1986 pesticide active




ingredient production was delivered to industry,  commerce, or U.S.  government
                                     3-45

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                     Table  3-4
DISTRIBUTION OF PESTICIDE MANUFACTURING FACILITIES
              BY DECADE OF OPERATION
Decade
Prior to 1930s
1930s
1940s
1950s
1960s
1970s
1980s
No Response
TOTAL
No. of Facilities Reporting
Facility
Operations Began
15
6
9
16
20
12
8
4
90
Pesticides
Operations Began
1
7
6
16
22
22
12
4
90
Last Major Expansion of
Pesticides Operations
0
1
0
0
5
18
53
13
90
                       3-46

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                                Figure 3-3

                      1986 PESTICIDE MARKET COMPOSITION
                                U.S.  Home
                               and  Garden
                Other Markets
                     14%
        Exports
          14%
U.S.  Industry,  Commerce
    and Government
         18%
U.S.  Agriculture
      52%
                                  3-47

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markets.   Fifty-two  percent of  production was  reported to  be  used  in  the




agricultural end use market and 14% was exported.  The remaining PAI production




(-16%)  was  reported by  other market  types  including  OCPSF,  Pharmaceuticals,




formulating/packaging operations and home and garden use.









3.2.5       Type of Facilities









            Of the 90 pesticide manufacturing facilities,  55 generate wastewater




discharges which are currently regulated under  the OCPSF  Point Source Category.




Thirty-nine  of  these  facilities  co-treat  OCPSF  wastewater  with  pesticide




manufacturing wastewater.









            Over half of the 90 pesticide manufacturing facilities also conduct




pesticide formulating  and/or packaging  (PFP)  activities.  Nineteen  of these




facilities co-treat PFP wastewater with pesticide manufacturing wastewater.









            The  census  data  suggest  that  a   "typical"  facility  reported




manufacturing one active  ingredient in 1986,  was the only facility in the country




producing that  PAI,  produced between  1,000,000  and 10,000,000 pounds  total




pesticide active ingredient for the year, also manufactured OCPSF compounds,  and




conducted PFP operations.
                                     3-48

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3.3         PESTICIDE PRODUCTION



            A wide variety of pesticide active ingredients (PAIs) or classes of

PAIs are produced by the pesticide chemicals manufacturing industry.  A summary

of  the 270  pesticide active ingredients  considered  for  regulation,  their

production levels, and production distribution is presented below.



3.3.1       Types of Pesticides



            Pesticide active  ingredients (PAIs)  and classes  of  PAIs can  be

categorized into the following nine types of pesticides:



            •     Herbicides:  used for weed control;

            •     Insecticides:  used for control of insects;

            •     Rodenticides:  used for control of rodents;

            •     Fungicides:  used for control  of fungi;

            •     Nematocides: used for control of a particular class of worms,
                  which are often parasites  of animals and plants;

            •     Miticides:   used  for  control  of mites,   which  are  tiny
                  arachnids that  often  infest prepared food or act as parasites
                  on animals, plants,  or insects;

            •     Disinfectants:   used for control of bacteria and viruses;

            •     Defoliants:  used to remove leaves from growing plants;  and

            •     Synergists:  used  in  conjunction with other substances  to
                  enhance the effects of each.
                                     3-49

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Table 3-1 presents the 270 PAIs or classes  of  PAIs considered for regulation by




pesticide type.  One type of pesticide,  the rodenticides, were not manufactured




in 1986.









            The 270 PAIs or classes of PAIs may also be grouped into 67 groups,




based on their chemical structure (or arrangement of atoms in each molecule) as




shown in Table 3-1.  Pesticide active ingredients or classes of PAIs which have




the same structure have similarities in physical properties, such as molecular




weight  and  solubility.   These similarities may  result  in'similar  amounts and




types of pollutants  in  the wastewater  generated during the manufacture of the




pesticide.  Pesticide chemicals with similar structures may also be controlled




or removed from wastewater by similar wastewater treatment technologies.  These




topics  will be  discussed further  in Section  7 (Treatment Technologies  and




Performance Data).









3.3.2       1986  Pesticide Active Ingredient Production









            Based on responses to the Facility Census, the pesticide chemicals




manufacturing industry in  1986 manufactured 130 of the 270 PAIs and classes of




PAIs and 48 salts and esters of these active  ingredients  (for  a  total of 178




active  ingredients).   These PAIs were manufactured by 224 separate pesticide




production  processes.   In addition,  there were eight other PAIs  which were




manufactured either  before or after 1986,  but not during 1986.   A pesticide




production process  involves  the manufacture of one PAI or salt or ester at a




facility.   One  or more  individual  manufacturing  processes may  exist  at an
                                     3-50

-------
individual facility.   In addition, a facility may use  one set of unit operations




or one reactor to manufacture different PAI  products at different  times.   For




example,  a facility may manufacture two PAIs using the same equipment with one




PAI manufactured during the spring and the other manufactured during the fall.









            Total  1986  industry  production  reported  for  the  178  active




ingredients was approximately 1.2 billion pounds with 55% of this total accounted




for by herbicides.  Table  3-5 presents  the list of individual PAIs manufactured




in 1986 and the 8 PAIs manufactured before or after 1986.









3.3.3       Distribution of PAI Production by Facility









            Tables 3-6,  3-7, and 3-8 present different views of the distribution




of PAI production  by facility.    Table 3-6  presents   the  distribution of  PAIs




produced  by  number   of  manufacturing  facilities.    Table 3-7  presents  the




distribution of manufacturing facilities by  number of PAIs  produced.  Table 3-8




presents the distribution of facilities by quantity of production.  As shown in




Table 3-6, 144 of the  178 PAIs produced in 1986 were reported to be manufactured




by only one facility  in the United States.   As shown  in Table 3-7, 47 of the 90




manufacturing  facilities  reported producing only one active  ingredient.   The




remaining facilities  produced between 2 and 16 active  ingredients  each.  Each of




the 7 largest  pesticide active Ingredient manufacturing facilities produced more




than 45 million  pounds  of active ingredient  in  1986 and  together represented




almost half (47%) of all 1986 pesticide production for the 178 PAIs.
                                     3-51

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                    Table 3-5

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

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
AI Code
3.00
4.00
5.00
7.00
8.00
11.00
12.00
16.00
16.09
16.12
16.13
16.17
16.27
16.29
16.31
16.32
16.50
16.52
17.03
17.06
20.00
21.00
22.00
25.00
26.00
27.05
Common Name
EDB
Vancide TH
Dichloropropene
Dowicil 75
Triadimefon
Dichlorophene
Dichlorvos
2,4-D
2,4-D; 2-Butoxylethyl ester
2,4-D; Butyl ester
2,4-D; Diethano lamine salt
2,4-D; Dime thy lamine salt
2,4-D; Isooctyl (2-ethylhexyl) ester
2,4-D; Isoctyl (2-octyl) ester
2,4-D; Isopropylamine salt
2,4-D; Isopropyl ester
2,4-D; Trithano lamine salt
2,4-D; Trlisopropanolamine salt
2,4-DB; Dimethylamine salt
2,4-DB; 2-Ethylhexyl ester
Dichloran or DCNA
Bus an 90
Mevinphos
Cyanazlne or Bladex
Propachlor
MCPA; Dimethylamine salt
                       3-52

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

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

27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
AI Code
27.09
27.13
27.16
28.00
30.02
30.03
30.05
31.01
31.02
31.03
32.00
35.00
36.00
39.00
41.00
42.00
45.00
49.00
52.00
53.00
54.00
55.00
56.00
58.00
60.00
62.00
Common Name
MCPA; Isooctyl ester
MCPA; Sodium salt
MCPA; 2-Ethylhexyl ester
Octhilinone
2, 4 -DP; Dimethylamine salt
2,4-DP; Isooctyl ester
2,4-DP; 2-Ethylhexyl ester
MCPP; Diethanolamine salt
MCPP; Dimethylamine salt
MCPP; Isooctyl ester
Thiabendazole
TCMTB
HAE
Pronamide
Propanil
Polyphase antimildew or Guardsan 388
Metribuzin
Etridiazole
Acephate or Orthene
Acifluorfen
Alachlor
Aldicarb
Hyamine 3500
Ametryn
Atrazine
Benomyl
                       3-53

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

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

53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
AI Code
66.00
67.00
68.00
68.02
69.00
69.03
70.00
71.00
73.00
74.00
75.00
76.00
80.00
81.00
82.00
*84.00
86.00
88.00
*90.00
91.00
98.00
103.00
*107.00
110.00
112.00
Common Name
Bifenox
Biphenyl
Bromacil
Bromacil; Lithium salt
Bromoxynil
Bromoxynil; Octanoic acid ester
Butachlor
Giv-gard
Captafol
Captan
Sevin (Carbaryl)
Carbofuran
Chloroneb
Chloropicrin
Chlorothalonil
Stirofos
Chlorpyrifos
Bioquin
Fenvalerate
Cycloheximide
Dicamba
Diazinon
Methyl Parathion
DCPA
Dinoseb
                       3-54

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

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

78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
AI Code
113.00
115.00
117.00
118.00
*119.00
120.00
123.00
123.02
123.03
123.04
*124.00
125.00
126.00
127.00
129.00
130.00
132.00
133.00
135.00
138.00
138.01
140.00
142.00
144 . 00
*148.00
Common Name
Dioxathion
Diphenamid
MGK 326
Nabonate
Diuron
Metasol DGH
Endothall
Endothall; Salt
Endothall; Salt
Endothall; Salt
Endrin
Ethalfluralin
Ethion
Ethoprop
Chlorobenzilate or Acaraben
Butylate
Fenarimol
Fenthion or Baytex
Fluometuron
Glyphosate
Glyphosate; Isopropylamine salt
Heptachlor
Hexazinone
Isopropalin
Linuron
                       3-55

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              Table 3-5 (Continued)
PESTICIDE ACTIVE INGREDIENTS AND SALTS AND ESTERS
       REPORTED TO BE MANUFACTURED IN 1986

103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
AI Code
150.00
154.00
156.00
157.00
158.00
160.00
161.01
163.00
170.00
171.00
172.00
173.00
175.00
176.00
177.00
178.00
182.00
183.00
185.00
186.00
190.01
190.02
190.03
191.01
191.02
Common Name
Malathion
Me thami dopho s
Me thorny 1
Methoprene
Methoxychlor
Methylbromi.de or Bromomethane
Monosodium methyl arsenate
Nalco D-2303
Napropamide
Deet
Nab am
Naled
Norflurazon
N - 1 - Naph thy Iph thai imide
MGK 264
Benfluralin
Fensul f o th i on
DIsulfoton
Phosmet
Azinphos Methyl
Copper naphthenate
Copper octoate
Copper salt of fatty & resin acids
Phenyl mercuric dodecyl succinate
Phenyl mercuric acetate
                       3-56

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

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

128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
AI Code
191.03
191.05
192.01
192.02
192.03
192.04
192.05
192.06
192.07
192.08
196.00
197.00
200.00
203.00
204.00
*205.00
206.00
206.01
208.00
210.00
211.00
211.05
212.00
215.00
215.01
Common Name
Phenyl mercuric oxide
Chloromethoxy propyl mercuric acetate
Tributyltin neodecanoate
Tributyltin monopropylene glycol maleat
2- (Methyl- 2 -phenyolpropyl) distannoxane
Tricyclohexyl tin hydroxide
Tributyltin oxide
Triphenyl tin hydroxide
Tributyl tin fluoride
Tributyl tin benzoate
Oxyfluorfen
Bolstar (Sulprofos)
Fonofos
Parathion
Pendimethalin
PCNB
Pentachlorophenol (PGP)
Pentachlorophenol ; Sodium salt
Permethrin
Pheno th i az ine
Phenylphenol
Phenylphenol ; Sodium salt -
Phorate
Picloram
Picloram; Potassium salt
                       3-57

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              Table 3-5 (Continued)

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

153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
AI Code
215.03
216.00
218.00
219.00
220.00
221.00
223.00
224.00
226.00
227.00
230.00
232.00
236.00
239.00
241.00
243.00
245.00
246.00
247.00
249.00
250.00
251.00
252.00
253.00
254.00
Common Name
Picloram; Triisopropanolamine salt
Piperonyl butoxide
Bus an 85 Or Arylane
Bus an 40
KN Methyl
Metasol J26
Prometon or Caparol
Prometryn
Propazine or Milogard
Propanoic acid
Pyrethrin I
Pyrethrin II
DEF
S imaz ine
Carbarn- S or Sodam
Vapam
Cycloate or Ro-Neet
EPTC or Eptam
Molinate
Vernolate or Vernam
HPTMS
Bensulide or Betesan
Tebuthiuron
Temephos
Terbacil
                      3-58

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                             Table  3-5  (Continued)

               PESTICIDE ACTIVE  INGREDIENTS AND  SALTS AND  ESTERS
                      REPORTED TO BE MANUFACTURED  IN 1986
AI Code
178 255.00
179 256.00
180 257.00
181 259.00
182 *262.00
183 264.00
184 268.00
185 272.00
186 NA2
Common
Name
Terbufos or Counter
Terbuthylaz ine
Terbutryn
Dazomet
Toxaphene
Trifluralin or Treflan
Ziram
Chloropropham
Diphenyl antimony 2 -ethyl
hexoate
'This list also includes eight additional PAls manufactured between 1985 and 1990
(these PAIs are marked with an asterisk).

Voluntarily  submitted data for PAI not originally on  the list considered for
regulation.
                                     3-59

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                       Table 3-6

NUMBER OF PESTICIDE ACTIVE INGREDIENTS PRODUCED IN 1986
         BY NUMBER OF MANUFACTURING FACILITIES
AI Production At:
One Facility
Two Facilities
Three Facilities
Four Facilities
Five Facilities
Total
No. of PAIs
144
25
7
1
1
178
                       Table 3-7

    NUMBER OF MANUFACTURING FACILITIES BY NUMBER OF
         PESTICIDE ACTIVE INGREDIENTS PRODUCED
No . of PAIs Produced
One
Two
Three
Four
Five or More
Total
No. of Facilities
47
16
10
7
10
90
                          3-60

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                       Table  3-8




DISTRIBUTION OF FACILITIES BY QUANTITY OF PAI PRODUCTION
Number of Facilities
7
19
38
18
8
90
Range of PAI Production (Ibs)
>45,000,000
10,000,000-45,000,000
1,000,000-9,999,999
100,000-999,999
0-99,999
-1,150,108,000 (Ibs/yr)
                          3-61

-------
Approximately 42% of  the  facilities  produced between 1 million and 10 million




pounds of active ingredient in 1986.









3.3.4       Distribution of PAI Production During the Year









            The  bulk of  PAIs identified  in the  Facility  Census  are  either




herbicides or insecticides.  These PAIs are used during the growing season, or




in the case of preemergent PAIs, just before the growing season.  Therefore, PAI




production is expected to be seasonal.   PAIs  must als.o be formulated into final




end use products prior to  sale or use.  Therefore,  the manufacture of the PAIs




would be  expected  to precede the  time  of use.  Herbicide  production in 1986




increased rapidly through the fall and early  winter and peaked in March of that




year, just prior to the growing season.  However,  the 1986 production data for




other pesticide  types (e.g.,  disinfectants)  indicated that  production often




reflects individual  facility  manufacturing schedules rather than any seasonal




trends.









            Most of the facilities indicated that pesticide production operations




were managed on a campaign basis  and that  production  of  a specific PAI occurred




as a short-term production run from a few  days to a few  months.  For some other




PAIs, however, production often continued nearly year round.
                                     3-62

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3.4         PESTICIDE MANUFACTURING PROCESSES









            There are two stages in the production of pesticides:  the manufacture




of a  PAI,  followed  by  the formulation and  packaging of  the  PAI.   A  PAI is




manufactured by the chemical reaction of two  or more raw materials often in the




presence of solvents,  catalysts, and acidic or basic reagents. The raw materials




may include any of a  large number of organic and inorganic compounds.  Pesticide




active ingredients may also be used as raw  materials  in manufacturing derivative




PAIs typically through the formation of  various salts  and esters.  The proposed




pesticide chemicals manufacturing effluent guidelines and standards are intended




to control the  discharge  of  pollutants  in wastewater  generated  during  the




manufacture of PAIs from raw materials.   (For one PAI, the effluent guidelines




apply only to the discharge of wastewater generated during the purification of




that PAI to a higher quality PAI product.)  These regulations do  not apply to the




manufacturer of chemicals  ("intermediate") which  are  not  pesticides but which




subsequently  are  converted by  further  chemical  reactions  to  PAIs.    The




"intermediates" are covered by the OCPSF effluent guidelines (40 CFR Parts 414




and 416).









            The  formulation of pesticides  through the  mixing, blending,  or




dilution of one or more  PAIs, without an intended chemical reaction is distinct




from pesticide  manufacturing and will  be covered under  separate  guidelines.




Therefore,  formulation will not be discussed further  in this section.
                                     3-63

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            The manufacturing processes used by facilities  to produce pesticide




active ingredients  are highly  dependent upon the type of active ingredient(s)




being manufactured  at that facility.   The types of  processes  used (batch or




continuous), the process chemistry, and the intermediate/byproduct manufacture




are described in the next section.









3.4.1       Batch vs. Continuous Processes









            Batch processes are  those  in which raw materials and reagents are




added to  a reactor, a reaction  occurs,  and then product  is  removed from the




reactor.   The  composition of the reactor  changes  over  time,  but flow neither




enters nor leaves the reactor until the chemical reaction process is complete.




Of the 224 manufacturing processes used to produce  pesticides in 1986, 178 were




batch processes.  All salts and esters  produced in  1986 were manufactured using




batch processes.









            During  continuous  processes,  raw  materials  and  reagents  flow




continuously into the reactor and are converted  into product while they reside




in the reactor.   Product  also flows continuously out of the  reactor.  Continuous




processes may operate for days, weeks,  or months at a time.  Of the reported 224




manufacturing processes used to produce pesticides in 1986, 46 were continuous




processes.









            The survey data showed no relationship between the magnitude of daily




or annual production and the use of batch or continuous processes.  This result
                                     3-64

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was as expected because a number of variations exist, such as multistage batch




operations, and combinations of batch and continuous stages in a single process.









3.4.2       General Process Reactions









            The following paragraphs describe the generic reaction mechanisms for




several of the structural categories  of pesticide  active  ingredients.   The




mechanisms  described  are not  directly applicable  to  every pesticide  active




ingredient manufactured in each structural category.  They do  attempt to present




a general  mechanism for  the majority of pesticide  active ingredients produced




within each category.









            NITROGEN-CONTAINING PESTICIDES









            a.  s-Triazines









            s-Triazines are produced by reacting hydrogen cyanide and chlorine




to  form  cyanuric  chloride  followed by substitution  of one or  more  of  the




chlorines  with amines, mercaptans  or  alcohols  to  form  the desired product.




Atrazine is produced by the reaction of ethylamine and cyanuric chloride followed




by  the addition of isopropylamine.   Atrazine can  then be reacted with methyl




mercaptan  to  form ametryn.   The  general structure and reaction for  the s-




triazines  as well as the specific reactions for atrazine and ametryn are shown




in  Figure  3-4.
                                     3-65

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U)
                                                      Figure 3-4

                            REACTION MECHANISMS  FOR s-TRIAZINES AND ATRAZINE AND AMETRYN
                            HCN +  CI2
                                                                                a
                                                                            s-TRIAZINES
              a

C.H.NH.
                a

                                             (CH,hCHNH,
                                                              a
                                     ATRAZINE
                                                                            CH,SH

                                                                                       AMETRYN
    Marshall  Sittlg,  editor,  Pesticide  Manufacturing  and  Toxic Materials  Control  Encyclopedia.  Noyes  Data
    Corporation, Park Ridge, NJ , 1980; p.  51,  63.

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     b.      Carbamates




            The fundamental building block of carbamate pesticides is carbamic


acid, the monoamide of carbonic acid:
            0                                     O

            II                                     II
        HO- C-OH                              HO- C-NH2


        Carbonic acid                        Carbamic acid
Carbamates are made by the reaction of alkyl or aryl alcohols with isocyanate as


shown:
                                                 0

                                                 II
                      R-OH + R'-N=C=0  	> R-0- C-NHR'
            N-Methyl carbamates are produced when methyl isocyanate is used.  The


aryl N-methylcarbamates are easily formed when phenol and methyl isocyanate are


reacted.   The pesticide carbofuran can be synthesized by reacting 2,2-dimethyl-


2,3-dihydrobenzofuran with methyl isocyanate in the presence of triethylamine and


ether as shown  in  Figure  3-5.  (Nabam,  also shown in Figure 3-5,  is discussed


later in this section).   Other commercially feasible processes for  carbamates


involve the reaction of the alcohol with phosgene  followed by the appropriate


amine.
                                     3-67

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U)


-------
            Thiolcarbonic acid and diothiocarbonic acid are the sulfur analogs

of carbonic acid which can form thiolcarbamic acid and dithiocarbamic acid upon

the addition of an amide:
                        0                         S

                        II                        II
                   HS   C   OH               HS   C   OH


                Thiolcarbonic acid          Dithiocarbonic acid
                        0                         S

                        II                         II
                   HS   C   NH2               HS   C   NH2


             Thiolcarbamic acid             Dithiocarbamic acid
Dithiocarbamates are  produced by the  reaction of  an  alkyl amine  and carbon

disulfide with sodium hydroxide, as shown:
                                    NaOH       ||
                         RNH2 + CS2	> R-NH- C  -SR
In like manner, the ethylene-bisdithiocarbamates are produced by the reaction of

a diamine with carbon disulfide.  The reaction for Nabam using ethylenediamine

is shown in Figure 3-5.
                                     3-69

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     c.      Amides and Anilides




            Nitrogen containing pesticides that are not carbamic acid derivatives

can be made by reacting an amine with a carbonyl acid or carbonyl acid chloride.

At  this  stage  the  intermediate  can  then be  further reacted with  alcohols,

sulfonyl halides,  or other reagents  to  synthesize the desired product.   The

general reaction mechanism is shown below.  The specific reactions for propanil

and alachlor are shown in Figure  3-6.
                                                0

                                                II
                       RNH2 + R'-C-OH	> R'- C   NHR
            Other  mechanisms for  nitrogen-containing pesticides  include  the

reaction  of an  amine with  chloro-alkyls or  chloro-aryls,  where, by  simple

substitution, the desired pesticide can be formed.  The reaction for isopropalin

are shown in Figure 3-7.




     PHENOXYACETIC ACID HERBICIDES




     d.     2.4-D




            An alkyl substituted phenol or phenoxide is reacted with chlorine or

the alkyl substituted benzene or 2,4-dichlorophenol is reacted with carboxylic

acid and/or sodium hydroxide to produce 2,4-dichlorophenoxyacetate.  The product
                                     3-70

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u>
I
                                                      Figure 3-6

                                    REACTION MECHANISMS  FOR PROPANIL AND ALACHLOR
                                    +  CH3CH2COOH
                                                                        NHCC2H3
                                                         SOCI2
                                                                        a
                                                                       PROPANIL
                                                                     C,H
                                                                      2"5
                                                                                 H3COH2C
H5C2
                                                                         CHjOH

                                                                           NH3
                                                                                        ALACHLOR
    Marshall  Sittig,  editor,  Pesticide Manufacturing and  Toxic  Materials Control  Encyclopedia.  Noyes  Data
    Corporation,  Park Ridge,  NJ,  1980;  p.  32, 639.

-------
                                                    Figure 3-7


                                        REACTION MECHANISMS FOR ISOPROPALIN
                      Cl
-vj
KJ
                                                                                   N(C3H7)2
                                     +   (C3H7)2NH2
                      CH(CH3)2
                                                                                   CH(CH3)2


                                                                                 ISOPROPALIN
    Marshall  Sittig,  editor,  Pesticide  Manufacturing and  Toxic Materials  Control  Encyclopedia.  Noyes  Data

    Corporation, Park Ridge, NJ,  1980;  p.  460.

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can then be reacted with an alcohol to produce 2,4-D esters, an amine to produce

2,4-D amine salts,  or with sodium hydroxide  to produce 2,4-D sodium salts.  The

general reaction is shown in Figure 3-8.



            ORGANOPHOSPHORUS PESTICIDES



     e.      Phosphorothioates and Phosphorodithioates



            The fundamental  building  block of organophosphorus  pesticides  is

phosphoric acid having the chemical structure:
                                      0
                                      II
                                  RO- P - OR
The phosphorothioates  are derivatives of phosphorothioic acid, the sulfur analog

of phosphoric acid with the following structures:
                               0             S
                               II             II
                           RO- P - SR and  RO- P - OR
                               I               I
                              OR             OR
                                     3-73

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                                                     Figure  3-8



                                            REACTION MECHANISMS FOR 2,4-D
                                                                                      2,4-D ESTERS
                                                                              ROH
CO
i
              ONa
                      H
+     ClCH2COONa
                                    OCHzCOONa


                                          ,R
                                                                                 (RNH3)OH
2,4-D AMINE SALTS
                                                                             NaOH
                                                                                       2,4-D SODIUM SALTS
    Marshall  SIttig,  editor,  Pesticide  Manufacturing  and Toxic  Materials  Control Encyclopedia.  Noyes  Data

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

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The phosphorodithioates are further sulfur-substituted as follows:


                               S             0
                               II             II
                           RO- P - SR  and  RO- P - SR

                              OR            SR
To  synthesize  these organophosphorus  pesticides,  phosphorus  pentasulfide  is

reacted with an alcohol to form the phosphorothioic acid.  The acid can then be

chlorinated and further substituted with an alkyl or aryl group to produce the

desired product.  To form the phosphorodithioates,  the phosphorothioic acid is

reacted with formaldehyde or other appropriate reagents, and then further reacted

with  mercaptan to  form the  desired phosphorordithioate.   Example  chemical

reactions for parathion, a phosphorothioate, and phorate, a phosphorodithioate

are shown in Figure 3-9.



   f.        Phosphoroamidates



            Like the phosphorothioates, the phosphoroamidates are the nitrogen

analog of phosphoric acid having the chemical structure:
                                       S
                                       II
                                 R-0 -P - NHR

                                      OR
                                     3-75

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CO
                                                      Figure  3-9


                                     REACTION MECHANISMS FOR PARATHION AND PHORATE
        PS
         25
S
I
  — SH
                                        CI
                                                      S
                                                               ONa
                                                                     Acetone
                                                               NOj
                                                                                         PARATHION
          P2S3 + CH2H5OH
         S
         II
   (C2H5O)2P —SH
CH2=0
                                                                 S
                                                                 H
C2H5SH
                                            — SCH2SC2H5

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

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            Again,  the  reaction  involves  substitution of  the acid  with the




appropriate akyl groups to form the desired product.  The reaction for glyphosate




is shown in Figure 3-10.









3.4.3       Intermediate/By-product Manufacture









            In  the  1986  Pesticide  Manufacturing  Facility  Census,  the  EPA




specifically asked  for the  identification of pesticide  intermediates and the




amount of  intermediate  sold.   An intermediate,  as  defined  in  the  Pesticide




Manufacturing Facility Census for 1986,  is  any  "specific  precursor  compound




formed in the process of manufacturing an active ingredient."  For example, if




chemical A and chemical B are  reacted to form chemical C,  and then chemical C is




reacted further  to produce a PAI,  then chemical  C  is an  intermediate.   The




Facility Census  did not require facilities to  provide  detailed process chemistry




because industry  objected  to  providing sensitive  CBI, and  because the  Agency




determined that  its primary reason for requesting this information in preliminary




versions of the  Census questionnaire (for use  in  fundamentally different factors




variance determinations)  was no longer necessary.  Fifteen intermediates at 11




facilities were reported to be produced and sold in 1986.  These intermediates




are  associated  with 15 pesticide manufacturing  processes.   As  discussed in




Section  3.4,  the manufacturers  of  intermediates are  not  subject  to  this




regulation.
                                     3-77

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                                              Figure 3-10



                                    REACTION MECHANISM FOR GLYPHOSATE
                    o                                              o
                    II                                NaOH           II
                (HO)2PCH2C1  +  NH2CH2COOH              •    (HO)2PCH2NHCH2COOH
oo                                                  then HL,I
                                                                    GLYPHOSATE
Marshall  Slttig,  editor,  Pesticide  Manufacturing  and  Toxic  Materials  Control  Encyclopedia.  Noyes  Data

Corporation,  Park  Ridge, NJ,  1980; p. 441.

-------
            A by-product is  identified  as  a  stream from the reaction process,




other than intermediates or active ingredients, which  is sold.  For example, if




chemical A and chemical B are reacted to  form chemical C and chemical D, of which




chemical D.is the desired PAI, then chemical C is  a by-product  if sold.  Fifteen




by-products  at  17 facilities were reported  to be produced and sold in 1986.




These by-products are associated with 30 pesticide manufacturing processes.  The




manufacture of by-products are not subject to this regulation.









3.5         CHANGES IN THE INDUSTRY









            The  Facility  Census  of  1986  gives  a  snapshot of the  pesticide




chemicals manufacturing industry as it was in 1986.  However,  the industry had




and has undergone  changes  prior  to and since 1986.   The  nature  and  extent of




those changes are discussed below.









            Since  1986,  the Agency  is  aware  of  10  facility closings  and  1




facility opening. The 1986  Facility Census also identified  eight metallo-organic




pesticide manufacturers and 86 organic pesticide manufacturers (four facilities




manufacture both metallo-organic and organic pesticides) .  Since 1986,  the Agency




is aware of no metallo-organic and 10 organic pesticide manufacturers shutting




down facility operations.









            One hundred seventy-eight PAIs and salts and  esters  of  PAIs were




identified in the 1986 Facility Census as being manufactured that year from 224




production processes. The Agency believes that 16 production processes have been
                                     3-79

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closed since 1986 resulting in 14 organic chemical and 2 metallo-organic PAIs no




longer being produced; however,  these  PAIs  are  included  in this  regulation if




data were available to develop limitations.  In addition, several facilities have




decreased production of  PAIs due to economic factors or to  restricted use of




their pesticide products.









            The Agency has also  compared the list of PAIs  or classes of PAIs not




manufactured  in 1986 with the  OPP  database  of registered  pesticides  (FATES




Database) in order to identify if any of these PAIs  were now being manufactured.




Of  the 144  PAIs not manufactured  in  1986,  97 PAIs were reported as  being




formulated  and packaged  in 1986-1988  according to  the  FATES database.   The




remaining 47 PAIs were not reported in  FATES as being formulated or packaged.
                                      3-80

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                                   SECTION  4

                          INDUSTRY SUBCATEGORIZATION



4.0         INTRODUCTION



            Division of a point source category into groupings entitled

"subcategories" provides a mechanism for addressing variations between

products, raw materials, processes, and other parameters which result in

distinctly different effluent characteristics.  Regulation of a category by

subcategory provides that each subcategory has a uniform set of effluent

limitations which take into account technological achievability and economic

impacts unique to that subcategory.



            The factors considered in the subcategorization of the pesticide

point source category include:
                  Product type;
                  Raw materials;
                  Manufacturing process and process changes;
                  Nature of waste generated;
                  Dominant product;
                  Plant size;
                  Plant age;
                  Plant location;
                  Non-water quality characteristics;
                  Treatment costs and energy requirements.
                                      4-1

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            EPA evaluated these factors and determined that subcategorization

is necessary.  These evaluations are discussed in detail in the following

sections.  The pesticide chemicals point source category was divided into

three subcategories:
            A.    Organic pesticide chemicals manufacturing;
            B.    Metallo-organic pesticide chemicals manufacturing; and
            C.    Pesticide Chemicals Formulating and Packaging.
            Subcategory C, the pesticide chemicals formulating and packaging

industry, will be addressed separately at a later date.



4.1         BACKGROUND



            In the November 1, 1976, Federal Register. EPA promulgated interim

final BPT guidelines for the pesticide point source category establishing a

subcategorization approach which included five subcategories.   Comments

received on this notice were incorporated into the April 25, 1978 and

September 29, 1978 final rule which presented a revised subcategorization

approach including three subcategories.



            In the November 30, 1982, Federal Register. EPA proposed

additional guidelines (including BAT, BCT, NSPS, PSNS, and PSES) for the

pesticide point source category which established 13  subcategories.  A Notice

of Availability (NOA) appeared in the June 13, 1984,  Federal Register, which

presented on alternative subcategorization approach of three subcategories.
                                      4-2

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The October 4, 1985, Federal Register, which promulgated BAT, NSPS, PSNS,  and

PSES guidelines for the pesticide point source category incorporated the

alternative subcategorization approach of the June 13, 1984, Federal Register.

Subsequent to the October 4, 1985 promulgated rule, EPA voluntarily withdrew

the BAT, NSPS, PSNS, and PSES guidelines pursuant to litigation brought by the

industry.



            This section discusses the subcategorization methodologies for the

interim final and final BPT guidelines and the proposed and final BAT, NSPS,

PSNS,  and PSES guidelines which were later remanded and presents the concerns

and issues raised during the public comment periods for each.



4.1.1       November 1. 1976. Interim Final BPT Guidelines



            The interim final BPT effluent limitations guidelines promulgated

November 1, 1976 for the pesticide chemicals point source category established

five subcategories:



            •     The halogenated organic pesticides subcategory (Subpart A);

            •     The organo-phosphorous pesticides subcategory (Subpart B);

            •     The organo-nitrogen pesticides subcategory (Subpart C);

            •     The metallo-organic pesticides subcategory (Subpart D);  and

            •     The pesticide formulating and packaging subcategory
                  (Subpart E).
                                      4-3

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            The subcategories chosen reflected differences in the character,




volume, and treatability of wastewater streams due to manufacturing process




variables related to each grouping of chemicals.  EPA believed that the




differences in process wastewater characteristics were significant and




warranted the establishment of five separate subcategories.









4.1.2       April 25. 1978. Promulgated BPT Guidelines









            On promulgating the interim final regulations,  the Agency




recognized that certain ambiguities were present in its subcategorization




based on chemical structure.  Many pesticides contain more than one functional




group, such as halogens, phosphorous, sulfur, nitrogen, etc. and do not fit




the former subcategorization scheme.  Such compounds could not be readily




assigned to particular subcategories.  In order to resolve these ambiguities




and also in response to industry comments, the Agency re-examined its data to




determine if there were reasons to provide different effluent limitations on




the basis of chemical structure and other potential differences among plants.




Review of raw waste load characteristics revealed no consistent pattern




between or within chemical family groupings that would provide a basis for




subcategorization.  The Agency found that the quantities of pollutants in the




effluents of those plants with properly operated treatment technologies




installed were similar, regardless of the organic pesticide chemicals




manufactured.  The Agency, therefore, concluded that the wastewaters of all




organic pesticide chemicals can be treated or controlled to similarly




documented levels in the Agency's treatability database.  For the final BPT
                                      4-4

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regulation, the Agency consolidated the halogenated organic, organo-




phosphorous,  and organo-nitrogen pesticide subcategories into a single




subcategory,  designated as the organic pesticide chemicals manufacturing




subcategory.









            EPA retained distinct subcategories for the manufacture of




metallo-organic pesticide chemicals and formulating and packaging of pesticide




chemicals for the promulgated BPT effluent limitations guidelines.









4.1.3       November 30.  1982. Proposed BAT.  BCT.  NSPS. PSES. PSNS  Guidelines









            On November 30, 1982, EPA proposed additional regulations to




control the discharge of wastewater pollutants from pesticide chemicals




manufacturing and formulating/packaging operations to navigable waters and to




publicly owned treatment works (POTWs) (47 FR 53994).









            EPA proposed to subdivide the Organic Pesticide Chemicals




Manufacturing Subcategory (Subpart A) into 11 subcategories.  EPA proposed to




retain the Metallo-organic Pesticide Chemicals Manufacturing Subcategory and




the Pesticide Chemicals Formulating and Packaging Subcategory as the 12th and




13th subcategories.   EPA based this proposed new subcategorization scheme on




the nature of the priority pollutants and groups of priority pollutants which




had been detected or were likely to be present in pesticide wastewaters, and




the treatment technologies to remove those priority pollutants from industry




wastewater prior to discharge.
                                      4-5

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4.1.4       June 13. 1984. Notice of Availability (NOA)



            Commenters criticized the proposed subcategorization scheme on the

grounds that (1) the priority pollutant   PAI combination were often

inaccurate, (2) subcategorization by treatment technology assumed a technology

would be used when an alternative technology could be used, and (3) the

subcategorization scheme projected was overly complex and possibly unworkable.

Commenters recommended that EPA not change the subcategorization used for BPT.

The Agency in general agreed with these comments, and i-n the June 13, 1984

Notice of Availability (NOA) stated that it was considering reducing the

number of subcategories back to three:
                  Organic pesticide chemicals manufacturing;
                  Metallo-organic pesticide chemicals manufacturing; and
                  Pesticide chemicals formulating and packaging.
The NOA announced the availability of new information collected in response to

comments received on the November 30, 1982 proposal. -EPA then requested

comments on the new data and the new subcategorization.



4.1.5       October 4. 1985. Promulgated BAT. NSPS. PSES. and PSNS Guidelines



            Commenters supported the revised subcategorization scheme

presented in the June 1984 NOA.  Therefore, on October 4, 1985, the Agency

promulgated effluent limitations guidelines for BAT, NSPS, PSES, and PSNS

based on the three subcategories identified in the June  1984 Notice of New
                                      4-6

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Information.  The primary factors for subcategorizing plants in the industry

were dominant product type, manufacturing processes, and raw materials used.

As discussed in Section 1.2, the October, 1985 guidelines were voluntarily

withdrawn by EPA in 1986.



4.2         CURRENT SUBCATEGORIZATION BASIS



            In the current study, the Agency has developed new data and has

evaluated these data to determine the appropriate subcategorization.  Based on

this evaluation, the Agency believes the pesticides chemicals industry should

be subdivided into the same three subcategories established by BPT.  These

are:



            Subcategory A     Organic Pesticide Chemicals Manufacturing

            Subcategory B     Metallo-organic Pesticide Chemicals
                              Manufac tur ing

            Subcategory C     Pesticide Chemicals Formulating and Packaging



            The following paragraphs discuss EPA's consideration of the

factors listed previously (see Section 4.0) in determining appropriate

subcategories for the Pesticides Chemicals Category.  The primary bases for

subcategorizing plants in this industry were found to be product type and raw

materials used.
                                      4-7

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4.2.1       Product Type and Raw Materials









            Metals or metallic compounds are generally not used as raw




materials in the manufacture of organic pesticide chemicals, but such




substances are used as raw materials for metallo-organic pesticide chemicals




manufacturing.  For this reason, wastewaters from metallo-organic pesticide




chemicals manufacturing have a much higher concentration of metals and




metallo-organic compounds than wastewater from organic pesticide chemicals




manufacturing.  The types of treatment technologies effective for treating




wastewater from metallo-organic wastewaters are different from those




technologies used to treat organic pesticide chemicals, due to the higher




concentrations of metals and metallo-organic compounds in wastewaters from




metallo-organic pesticide chemicals.  Therefore, product type and raw




materials are appropriate bases for subcategorization of this industry.









4.2.2       Manufacturing Process and Process Changes









            Facilities that manufacture pesticide active ingredients use a




variety of unit operations, including chemical synthesis, separation,




recovery, purification, and product finishing.  The specific active ingredient




product dictates not only the raw materials that will be used but also the




sequence of unit operations and the quantity and quality of wastewater that is




generated.  Some pesticide chemicals manufacturing facilities have introduced




process changes which affect wastewater characteristics and quality.  In the




period from 1977 to 1986, a number of facilities eliminated the use of
                                      4-8

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priority pollutants as solvents.  Other facilities implemented solvent




extraction to recover raw materials, intermediates, or products from




wastewater streams for reuse within the process, and recycle of process




waters,  in order to minimize the discharge of pollutants from the




manufacturing process.  Given the wide range of process chemistry and unit




operations used in the manufacture of different pesticide active ingredients,




subcategorization based on the manufacturing process and process changes would




result in too many subcategories,  thus are not appropriate for the purpose of




delineating subcategories.









4.2.3       Nature of Waste Generated









            Based on an analysis of the data available to EPA,  there are no




consistent differences in the amount and identity of pollutants (except for




the active ingredient itself) in waste loads from different organic pesticide




chemicals manufacturing facilities.  However, manufacturers of metallo-organic




pesticide chemicals tend to generate smaller volumes of wastewater with higher




metal concentrations compared to manufacturers of organic pesticide chemicals




(see Section 5).  Therefore, the nature of the waste generated from pesticide




manufacturing operations is also a good basis for subcategorization that




differentiates between organic PAIs and metallo-organic PAIs.  This factor is




directly related to the product type and raw materials used, and therefore is




consistent with subcategorization based on product type and raw materials.
                                      4-9

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4.2.4       Dominant Product









            In the pesticide chemicals manufacturing category, there are a




large number of products produced.  The category also includes a large variety




of manufacturing processes and wastewater characteristics.  Subcategorization




based on dominant product manufactured would result in a large number of




subcategories and is therefore not appropriate for subcategorization for the




pesticide chemicals manufacturing industry.









4.2.5       Plant Size









            Plant size and production capacity do not impact characteristics




of wastewater produced during the manufacture of pesticide chemicals based on




data available to EPA.  The size of the plant will not affect the




effectiveness of treatment technologies (i.e., the pollutant concentration




levels in the effluent that can be achieved with treatment technologies),




although it can affect the cost of treatment facilities and the cost of




treatment per unit of production.  Overall, EPA does not believe that plant




size is an appropriate method of subcategorization for the pesticide chemicals




manufacturing industry.









4.2.6       Plant Age









            The age of a plant or a production process can sometimes have a




direct bearing on the volume of wastewater generated, how the wastewater is
                                     4-10

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segregated, and the ability of the plant to implement new treatment




technologies.  Compared to new plants, older facilities tend to have a greater




volume of wastewater and higher pollutant loadings,  even though pollutant




concentrations may be lower due to water contributions from noncontact




sources.  However, plants that began manufacturing one set of products may be




manufacturing entirely different products now.   Also, older facilities that




have continued to manufacture the same product have often improved or modified




the process and treatment technologies over time.   Therefore,




subcategorization on the basis of plant age is not appropriate.









4.2.7       Plant Location









            As discussed in Section 3, the majority of pesticide chemicals




manufacturing facilities are located in the eastern half of the United States,




with a concentration in the southeast corridor and Gulf Coast states.  Based




on analyses of existing data, plant location has little effect on wastewater




quality, although it may affect the cost of treatment and disposal of process




wastes.









            Facilities located in urban areas have higher land costs for




treatment facilities.  Distance from the plant to an off-site disposal




location may also increase costs of off-site disposal of solid or liquid




waste.  Climatic conditions may affect the performance of some treatment




technologies and necessitate special provisions (e.g., heating of biological




oxidation units in colder climates or cooling requirements in warmer
                                     4-11

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climates).  However, for pesticide chemicals manufacturing there are no




consistent differences in wastewater treatment performance or cost due to




location.  Therefore, geographical location is not an appropriate basis for




subcategorization.









4.2.8       Non-Water Quality Characteristics









            Non-water quality characteristics from the pesticide chemicals




manufacturing industry include environmental impacts due to solid waste




disposal, transportation of wastes to an off-site location for treatment or




disposal, and emissions to the air.  The impact from solid waste disposal is




dependent upon the treatment technology employed by a facility and the




quantity and quality of solid waste generated by that facility.  Contract




hauling wastewater from pesticide chemicals manufacturing creates a hazard




through the transportation of potentially hazardous materials.  However, both




of these impacts are a result of individual facility practices, rather than a




trend of different segments of the industry.









            Air emissions from the pesticide chemicals manufacturing industry




are somewhat related to the active ingredient product(s) manufactured and/or




the raw materials used.  However, most PAIs are very low in volatility




compared to the various solvents used in the manufacturing processes.  Since




the same solvents are used in manufacturing many different PAIs, therefore,




air pollution control problems and equipment utilized are not generally unique




to different segments of this industry.  For example, baghouses or wet
                                     4-12

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scrubbing devices remove particulates and vapors and toxic gases are




frequently incinerated.









            Based on these discussions, the Agency believes that




subcategorization on the basis of non-water quality characteristics is not




needed.









4.2.9       Treatment Costs and Energy Requirements









            The same treatment unit operation could be utilized for different




wastewater sources, such as steam stripping to remove volatile priority




pollutants and hydrolysis to remove organo-phosphorus pesticides.  However,




the cost of treatment and the energy required will vary depending on flow




rates, wastewater quality, and the amount and identity of pollutants in the




wastewater.  Moreover, alternative technologies could be selected by




dischargers.   Therefore, subcategorization based on treatment costs and energy




requirements is not appropriate.









4.3         PROPOSED SUBCATEGORIES









            Based on product type, raw materials, and the nature of waste




generated,  EPA has defined two subcategories for the pesticide chemicals




manufacturing industry.  The two subcategories are the same as the




manufacturing subcategories contained in the existing 40 CFR Part 455




regulations.
                                     4-13

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4.3.1       Organic Pesticide Chemicals Manufacturing









            This subcategory applies to discharges resulting from the




production of carbon-containing PAIs, excluding metallo-organic active




ingredients containing arsenic, cadmium, copper, or mercury.  Although organo-




tin pesticides fit the definition of a metallo-organic pesticide given in the




BPT regulation (see Section 455.32), organo-tin pesticides were not included




in the metallo-organic pesticide chemicals subcategory (see Section 455.31




(a)) during the 1978 rulemaking because wastewaters from their manufacture




have significantly different wastewater characteristics than wastewaters from




the manufacture of metallo-organic pesticides containing arsenic, cadmium,




copper, and mercury.  EPA does not believe it is appropriate to include the




organo-tin pesticides in the metallo-organic subcategory because their




pollutants are different, and the organo-tin production has larger volumes of




wastewater.  The amounts and types of pollutants from organo-tin pesticide




manufacture are closer to the amounts and types of pollutants from the




manufacture of the organic pesticide chemicals.  Therefore, EPA has determined




that organo-tin pesticides should be included in the organic pesticide




chemicals manufacturing subcategory.  EPA proposes to regulate the following




pollutants in this subcategory:  conventional pollutants, nonconventional




pollutants (including COD and the PAIs), and priority pollutants.
                                     4-14

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4.3.2       Metallo-Organic Pesticide Chemicals Manufacturing









            This subcategory applies to discharges resulting from the




manufacture of metallo-organic pesticide active ingredients that contain




mercury, cadmium, arsenic, or copper (see Section 455.30 and Section 455.31




(a)).  The three existing direct dischargers in this subcategory are currently




subject to BPT effluent limitations requiring zero discharge of process




wastewater pollutants.  Currently there are only five existing indirect




dischargers in this subcategory.
                                     4-15

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                                   SECTION 5




                   WATER USE AND WASTEWATER CHARACTERIZATION









5.0         INTRODUCTION









            In 1988, under the authority of Section 308 of the Clean Water




Act, the Environmental Protection Agency (EPA) distributed questionnaires




entitled, "Pesticide Manufacturing Facility Census for 1986," to 247




facilities that EPA had previously identified as possible pesticide active




ingredient manufacturers.  Responses to the questionnaire by these 247




facilities indicated that 90 facilities manufactured pesticides in 1986.  This




section presents information on water use at these 90 facilities.   This




section also presents information on process wastewater characteristics for




those pesticide chemicals manufacturing processes that were sampled by EPA and




for those pesticide chemicals manufacturing facilities that provided




self-monitoring data.









5.1         WATER USE AND SOURCES OF WASTEWATER









            As described in Section 3.5, pesticide active ingredient




manufacturing processes vary from facility to facility and from active




ingredient to active ingredient.  A simplified flow diagram for pesticide




active ingredient manufacture is presented in Figure 5-1, showing typical
                                      5-1

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                                                          Figure  5-1

                               EXAMPLE OF PESTICIDE ACTIVE INGREDIENT MANUFACTURING PROCESS
Raw Materials
     Solvent
Water
1 Other Reactan
l
i
Reaction — »> Intermediate —
Water Water
ts 1 1
l i
i i
* t
*
fe Reaction ^ Purification

1 1
1 1 1 I
i 1 i '
t ] t t
Wastewater Wastewater Wastewater
(e.g., Carrier/Reaction Media) ' (e.g., Water of Reaction) (e-9- Process
| Stream Wash)
T
r ^
Further processing
and/or sales.
May also be a
source of wastewater.
i ^

Water
1
I


l
l
i
t
Wastewater
(e.g., Product Wash)
Tvpes of Process Watt
Carrier/Reaction Media
Water of Formation
Product Wash
Process Stream Wash
Product
                                                                                         Equipment Wash
                                                                                         Pump Seal Wash
                                                                                         Pump Seal Water
                                                                                         Steam Jets/Vacuum Pumps
                                                                                         Scrubber Water

-------
streams which enter and leave the manufacturing process.  The manufacture of a




pesticide active ingredient requires several types of input streams.  These




include raw materials, solvents, other reactants,  and water.  Raw materials




are those organic and inorganic compounds that chemically react with one




another to form the pesticide active ingredient.  Solvents are organic or




inorganic compounds used as reaction or transport media, but which do not




participate in the chemical reaction.  Other reactants include acidic or basic




compounds used to facilitate, catalyze, or participate in the chemical




reaction (for example, an acidic reaction medium may be required to ensure the




desired pesticide product).   Water or steam may be added to the reaction




medium to act as a solvent or carrier, or water may be added during subsequent




separation or purification steps.









            Streams leaving the process include the active ingredient




products, by-products, intermediates which are sold or used in other




manufacturing processes, and liquid and solid wastes.  A by-product is a




compound formed during the reaction process other than the active ingredient




product which can be sold.  A common by-product in the pesticide manufacturing




industry is hydrochloric acid.  An intermediate is defined in the Facility




Census as "any specific precursor compound formed in the process of




manufacturing an active ingredient."  An intermediate is not a PAI itself but




instead is an organic chemical compound.   In some cases, part of the




intermediate is removed from the pesticide process for use in other




manufacturing processes or for sale.  Liquid and solid wastes include




hazardous and nonhazardous organic and inorganic wastes as well as wastewater.
                                      5-3

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In addition, some chemical compounds may leave the manufacturing process in

the form of air emissions.



            Three sources of wastewater were reported at pesticide

manufacturing facilities in 1986.  These include:
                  PAI process wastewater   water leaving the manufacturing
                  process.

                  Other pesticide wastewater   pesticide-containing wastewater
                  generated from sources not directly associated with the
                  manufacturing process, such as employee shower water or
                  contaminated storm water.

                  Other facility wastewater   wastewater from other
                  manufacturing operations, such as organic chemicals
                  production, or other facility sources, such as sanitary
                  wastewater, which is typically commingled and treated with
                  pesticide-containing wastewater. Other types of liquid
                  wastes  leaving the pesticide manufacturing process include
                  spent solvents, spent acids, and spent caustics.  These
                  wastes  can become process wastewaters when combined with
                  other sources of process wastewaters that are treated and/or
                  discharged.
These sources are described in more detail below.



5.1.1       PAI Process Wastewater



            Process wastewater is defined by EPA regulations at 40 CFR 122.2

as "any water which, during manufacturing or processing, comes into direct

contact with or results from the production or use of any raw material,

intermediate product, finished product, by-product or waste product."
                                      5-4

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            Specifically,  PAI process wastewaters associated directly with the

production process are:
                  Water of reaction:  water which is formed during the
                  chemical reaction, such as from the reaction of an acid with
                  an alcohol (see Section 3.5.2).

                  Process solvent:  water used to transport or support the
                  chemicals involved in the reaction process;  this water is
                  usually removed from the process through a separation stage,
                  such as centrifugation, decantation,  drying, or stripping.

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

                  Product washes:   water added to the reaction medium in order
                  to purify an intermediate product or active  ingredient by
                  washing away the impurities; this water is subsequently
                  removed through a separations stage;  or water which is used
                  to wash the crude product after it has been removed from the
                  reaction medium.

                  Spent Acid/Caustic:  Acid and basic reagents are used to
                  facilitate, catalyze, or participate in the  reaction
                  process.  Spent acid and caustic streams, which may be
                  primarily water, are discharged from the process during the
                  separation steps which follow the reaction step.
            Most of the above sources are present in manufacturing almost all

PAIs.  Other sources of process wastewater associated with pesticide

operations include:
                  Steam jets or vacuum pumps:  water which contacts the
                  reaction mixture, or solvents or water stripped from the
                  reaction mixture, through the operation of a venturi or
                  vacuum pump.

                  Air pollution control scrubber blowdown:  water or acidic or
                  basic compounds used in air emission control scrubbers to
                                      5-5

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                  control fumes from reaction vessels, storage tanks, and
                  other process equipment.

                  Equipment washes:  water used to clean process equipment
                  during unit shutdowns.

                  Pump seal water:  water used to cool packing and lubricate
                  pumps which may contact pesticide-containing water through
                  leakage and may therefore become pesticide-containing
                  wastewater.

                  General/Uncategorized process wastewater:  a combination of
                  sources or cases where total flow is greater than the sum of
                  individual identified parts.
These water uses could result in the water becoming contaminated with

pesticide active ingredient or other compounds used in the manufacturing

process.  These sources may be intermittent or absent entirely.  The water use

reported for each source is presented in Table 5-1.  As shown in the table,

about 34% of the water use is for product wash.



5.1.2       Other Pesticide Wastewater Sources



            In addition to process wastewater, other types of wastewater may
                                               »
be generated during pesticide production from non-process sources which can

also contain pesticide pollutants and other pollutants.  These include:
                  Showers used by pesticide production employees.   Many
                  facilities provide shower facilities for employees coming
                  off shift so that any PAIs that the employee may
                  inadvertently have contacted can be washed away before the
                  employee leaves the facility.  [Note:  Safety showers, which
                  are used to deluge an employee, clothing and all, in the
                  event of an accident, are always located near production
                  equipment.  Accidents are very infrequent and these showers
                  are therefore seldom used.  When used, any water generated
                                      5-6

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                                   Table  5-1

                PESTICIDE  ACTIVE  INGREDIENT PROCESS WASTEWATERS
                      GENERATED IN 1986 BY EFFLUENT TYPE
Effluent Type
Product Wash
Scrubber Slowdown
Process Stream Wash
Process Solvent
Spent Acid
General Process/
Unidentified Wastewater1
Contaminated Stormwater2
Steam Jet/Vacuum Pump
Equipment Wash
Spent Solvent
Spent Caustic
TOTAL
Waste Volume
(gal/yr)
487,669,000
207,232,000
201,058,000
196,042,000
178,212,000
58,894,000
43,810,000
28,255,000
22,492,000
15,001,000
6,890,000
1,445,554,000
Percent
33.7
14.3
13.9
13.6
12.3
4.1
3.0
2.0
1.6
1.0
0.5
100.0
# Facilities
40
33
35
29
7
17
4
7
18
15
4

'General process wastewater  also  includes water of reaction and pump seal
water.
Contaminated  stormwater  reported as  a  source of process wastewater is
presented here.  See Table 5-2 for contaminated stormwater reported as another
pesticide wastewater source.
                                      5-7

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                  is process wastewater and is included as a source of process
                  wastewater in Section 5.1.1.  Because of the infrequent use,
                  the amount of water is minuscule compared to other sources
                  of process wastewater.];

                  Laundries used to wash clothing from pesticide production
                  employees.  Many facilities provide on-site laundry
                  facilities to wash employee uniforms to remove any PAIs that
                  may inadvertently be on the uniform after the work shift.

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

                  Contaminated stormwater.  Accidents, leaks, spills,  shipping
                  losses, and fugitive emissions can all lead to PAIs and
                  other pollutants coming into contact with stormwater.  This
                  contaminated stormwater is process wastewater and should be
                  treated before discharge.
Not all plants have all of these sources, and none monitor the flows (except

for stormwater).  The number of plants reporting these sources is presented in

Table 5-2, along with the average estimated flows reported.  As shown in Table

5-2, the flows from employee showers, laundries, and safety equipment cleaning

are all very small compared to stormwater, which itself is a relatively small

portion of total industry wastewater generation (see Table 5-1).



5.1.3       Other Facility Wastewater Co-Treated with Pesticide Wastewater



            Often, a facility which manufactures pesticides also manufactures

other products.  Wastewaters generated from other operations may be co-treated
                                      5-8

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                                   Table  5-2

        WASTEWATER GENERATED  FROM OTHER  PESTICIDES WASTEWATER  SOURCES
Source
Showers
Laundry
Safety Equipment
Contaminated Stormwater1
# Facilities
(out of 90)
67
21
47
47
Average Wastewater
Generated (gal/day)
3,070
1,210
3,480
177,000
'Contaminated  stormwater reported as another source of pesticide wastewater is
presented here.  See Table 5-1 for contaminated stormwater reported as a
source of process wastewater.
                                     5-9

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with wastewater associated with pesticide manufacture.  Facilities reported

co-treating wastewater from the following production operations:
                  Pesticide Formulating/Packaging  (PFP) of "in-scope" and
                  "out-of-scope" PAIs  ("out of scope" PAIs are those PAIs not
                  included in the list of 270 PAIs and classes of PAIs
                  considered for regulation);

                  Organic Chemicals, Plastics, Synthetic Fibers (OCPSF);

                  Inorganic Chemicals;

                  Pharmaceuticals;

                  Other Manufacturing:  including production of out-of-scope
                  PAIs or wastewater from manufacturing operations not  listed
                  above; and

                  Other Wastewater:  including sources such as sanitary
                  wastewater.
Table 5-3 presents  the number of  facilities co-treating wastewater from these

operations along with the  average percent of total flow co-treated for each

wastewater source.   On the average, when pesticide manufacturing wastewater is

co-treated with other wastewaters,  the pesticide manufacturing wastewater

constitutes  38% of  the total wastewater being treated.  OCPSF operations

contributed  the largest percent of  wastewater co-treated with pesticide

wastewater at  39 manufacturing facilities.  Typically, 50% of the total
                                      5-10

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                                   Table 5-3

     OTHER FACILITY WASTEWATER GENERATED FROM SOURCES  OTHER THAN PESTICIDE
              PRODUCTION AND CO-TREATED WITH PESTICIDE WASTEWATER
Source
Pesticide Formulating/
Packaging
Organic Chemicals, Plastics,
and Synthetic Fibers
Inorganic Chemicals
Pharmaceuticals
Other Manufacturing
Wastewater
Other Wastewater2
#
Facilities1
19
39
14
9
17
27
Average % of Total
Flow Co-Treated
4
50
23
28
28
34
'A  facility  is  double  counted if it  co-treated more  than one  source  of water
with pesticide manufacturing wastewater.

20ther  wastewater  includes,  for example,  sanitary water.
                                     5-11

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wastewater volume from treatment systems that co-treat pesticide manufacturing




water with OCPSF water is due to OCPSF processes.  On the other hand, only 4%




of the total wastewater volume from treatment systems that co-treat pesticide




manufacturing water with PFP water is due to PFP processes.  Other facility




wastewater, such as sanitary wastewater, is commingled with pesticide




wastewater at 27 manufacturing facilities.









5.2         WASTEWATER VOLUME BY DISCHARGE MODE









5.2.1       Definitions









            Direct discharge refers to the discharge of a pollutant or




pollutants directly to waters of the United States (not to a publicly owned




treatment works).  Facilities that directly discharge wastewaters do so under




the National Pollutant Discharge Elimination System (NPDES) permit program.









            Indirect discharge refers to the discharge of pollutants




indirectly to waters of the United States, through publicly owned treatment




works (POTWs).









            No discharge refers to facilities that do not discharge their




wastewaters to waters of the United States, as a result of either reuse of




process water back into the product, no water use, recycle off-site or within




the plant in other manufacturing processes, or disposal off-site or on-site
                                     5-12

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that does not result in a discharge to waters of the United States (e.g., by




incineration, evaporation, or deep-well injection).









5.2.2       Discharge Status of Pesticide Manufacturing Facilities









            Thirty-two of the 90 manufacturing facilities are direct




dischargers, while 36 are indirect dischargers.   One facility discharges




wastewater both directly and indirectly; therefore, there are 67 dischargers.




Of the remaining 23 facilities,  15 facilities dispose of their wastewater by




on- or off-site deep well injection,  incineration,  or evaporation and 8




facilities generated no process wastewater by recycle/reuse or no water use.









5.2.3       Flow Rates by Discharge Status









            The total amount of process wastewater discharged from pesticide




manufacturing processes to waters of the United States was approximately 1.30




billion gallons in 1986, compared to 1.45 billion gallons generated.




Eighty-two percent of all process wastewater generated was discharged directly




to a receiving stream while 8% was discharged indirectly.  Most of the




remaining wastewater was disposed of by deep well injection (DWI).   Table 5-4




presents the volumes of pesticide process wastewater discharged or disposed in




1986.
                                     5-13

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                                   Table 5-4
              TOTAL PROCESS WASTEWATER FLOW BY TYPE OF DISCHARGE
                              (Gallons per Year)
Discharge
Status
Direct
Indirect
No Discharge1
TOTAL
Number of
Facilities
32
36
23
9 12
Percent of
Facilities
36
40
26
102
Total
Flow (gal)
1,179,246,000
117,938,000
148,370,000
1,445,554,000
111
  No  discharge"  facilities dispose of their wastewater through deep well
injection (DWI), incineration  (on or off-site), or evaporation.

2The  number  of facilities is greater than 90 and the percent is greater than
100 due to one  facility  that discharges both directly and  indirectly.
                                      5-14

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            Table 5-5 summarizes process wastewater flows by discharge status




for organic pesticide chemicals manufacturing (Subcategory A) and metallo-




organic pesticide chemicals manufacturing (Subcategory B).   Over 99% of the




wastewater generated and the wastewater discharged in the pesticide




manufacturing industry is due to manufacturing of organic pesticide




(Subcategory A) products.









5.3         WATER REUSE AND RECYCLE









            Recycling or reuse of process wastewater during pesticide




production in 1986 was reported by 25 of the 90 manufacturing facilities.




Because of the diversity within the industry, it is difficult to summarize the




types of recycle operations which are currently available.   Table 5-6,




therefore, presents general descriptions of current recycling operations.









            One group of PAIs in Subcategory A was examined in more detail.




This group manufactures PAIs by reaction of phenoxy acids to form either salts




or esters.  The manufacture of phenoxy esters generates "water of formation",




due to the chemistry of the esterification reaction, while the manufacture of




phenoxy salts does not generate any process waste streams but requires water




to be added to the reactor since the salts are sold in solution.  Therefore,




use of the water of reaction from the formation of the ester as make-up water




for salt formation could eliminate a source of pollution.
                                     5-15

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                                   Table  5-5

                   PESTICIDE PROCESS  WASTEWATER FLOW FOR THE
              ORGANIC PESTICIDE SUBCATEGORY (SUBCATEGORY A) AND
          THE METALLO-ORGANIC PESTICIDE  SUBCATEGORY (SUBCATEGORY B)
Discharge Status
Direct
Indirect
No Discharge1
TOTAL
Total Subcategory A
Flow (gal)
1,179,246,000
117,317,000
146,318,000
1,442,881,000
Total Subcategory B
Flow (gal)
0
621,000
2,052,000
2,673,000
'"No  discharge"  facilities dispose of their wastewater 'through deep well
injection (DWI), incineration (on or off-site), or evaporation.
                                      5-16

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                                   Table  5-6

               TYPES  OF WASTEWATER RECYCLE OPERATIONS  REPORTED

Recovery of process input or product
Reused in pesticide manufacturing process
Reused in formulating/packaging process
Reused in equipment washwater
Reused as cooling water or scrubber water
Reused contaminated stormwater in manufacturing
process
TOTAL
# Facilities
14
8
2
2
2
1
29i
'The number  of  facilities  exceeds  25  due  to multiple  recycle  operations  at
some facilities.
                                     5-17

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            Reuse of reaction waters from the esterification processes as feed

water for phenoxy salt neutralization and formulation serves the dual purpose

of eliminating a contaminated wastewater discharge and recovering the phenoxy

acid active ingredient.



            The ability of a facility to reuse waters as feed to the

neutralization reaction depends on:


            1)    The ratio of production between the esterification and
                  neutralization process; and

            2)    The quality of the water recovered from the esterification
                  process.


The production ratio is important because approximately 0.5 pounds of water

are normally added to make each pound of product during the manufacture and

formulation of phenoxy salts, while approximately 0.08 pounds of reaction

water are generated from the esterification of 1 pound of product.  Given

these ratios, a facility will achieve a perfect water balance if 1 pound of

phenoxy salts are produced for every 6.25 pounds of phenoxy ester produced.

Therefore, if the quantity of phenoxy salts produced at a facility is more

than 16% of the quantity of phenoxy esters produced, there will be

insufficient esterification water generated to meet phenoxy salt formulation

requirements, and fresh make-up water or reactor vessel washwater must also be

used as formulation feedwater.  Conversely, if phenoxy salt production is less

than 16% of phenoxy ester production, the facility will generate more

esterification reaction water than may be used in salt formulations, and water

will have to be disposed.
                                     5-18

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            In 1986, of the facilities which manufactured both phenoxy salts




and esters, phenoxy salt production was always much higher than 16% of phenoxy




ester manufacture, indicating that these facilities should have been able to




reuse all esterification water that year.  However, three additional factors




affect the amounts of esterification water a facility may reuse.  First,




purity requirements for waters used in the manufacturing of phenoxy salts have




an effect on the amount of esterification reaction water which may be reused




in this way.  Secondly, while the amount of water generated by the




esterification reaction may be determined stoichiometrically,  the water




requirements for phenoxy salt neutralization and formulation will vary based




on the specific product registrations being produced.  Finally, phenoxy salts




and esters are often manufactured in short production runs throughout the




year, depending on immediate consumer demand, and a facility may not be able




to store these waters until they can be reused.









            In general, reaction water from the esterification of a given




phenoxy acid active ingredient may only be used in the manufacture of salts of




the same active ingredient.  The importance of this requirement varies




depending on the application and labeling of the phenoxy salt product, and too




high a contamination level may affect the final product registration.  It is




also important that the water used in phenoxy salt formation have a low




alcohol content, because alcoho-1 can cause cloudiness within the phenoxy salt:




formulation product.  An effective alcohol/water separation stage at the




esterification process is critical to the yield of a high quality water that




may be reused in phenoxy salt manufacturing.
                                     5-19

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            All but one of the U.S. facilities which convert phenoxy acids to




salts and esters reuse the waters generated by the esterification reaction as




make-up water for salt formation.  When production schedules do not allow




immediate use of esterification process wastewater for salt formation, the




esterification process wastewater is typically stored until needed.  When




demand for the phenoxy acid ester exceeds the demand for the phenoxy acid salt




so much that there is not enough storage capacity for the wastewater, the




excess wastewater is disposed of.  All plants that recycle the esterification




process wastewater have had this wastewater incinerated when necessary,




although typically this has occurred only once in several years.









5.4         RAW WASTEWATER DATA COLLECTION









            Section 3.1 of this document introduced the many wastewater data




collection efforts undertaken for development of these regulations.  Studies




that produced data on raw wastewater characteristics include industry-supplied




self-monitoring data submitted as a follow-up to the Facility Census and data




obtained from EPA sampling at pesticide manufacturing facilities.  Results of




these data gathering efforts are described in more detail below.









5.4.1       Industry Supplied Self-Monitoring Data









            As part of the Facility Census, EPA requested that pesticide




manufacturing facilities submit any available wastewater monitoring data and




requested that these data be submitted as individual data points (as opposed
                                     5-20

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to monthly averages, for example).  In response, facilities submitted




monitoring data for conventional and priority pollutants, as well as for PAIs




and other non-conventional pollutants, such as COD.  However, these monitoring




data usually represented pollutant concentrations in end-of-pipe wastewater




streams.  Therefore, EPA made additional requests for data from sampling




locations that would characterize pesticide process wastewater discharges




prior to commingling with wastewaters from other industrial sources.  Many




facilities were able to provide these types of monitoring data for raw




pesticide process wastewaters and also for sampling locations that allowed EPA




to evaluate certain treatment technologies.









            The PAI analyses were often quite detailed and were provided for




raw and treated process wastewaters.  Monitoring data submitted for 55 PAIs




from 27 facilities were of sufficient quality to develop BAT/PSES guidelines




based on plant performance.









            Priority pollutant data submitted by facilities were not quite as




useful.  In most cases, these priority pollutant data were collected at




sampling locations representing commingled wastewaters.  For this reason, it




was difficult to attribute many of these pollutants to the pesticide




processes.  In some cases, however, facilities had analyzed raw pesticide




process wastewaters for priority pollutants.  These data usually matched well




with the facility's indication in the Facility Census that the pollutant was




known or believed present in their pesticide process wastewaters.  Although




quantitative priority pollutant data were supplied by 43 facilities for a
                                     5-21

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total of 49 priority pollutants, only 11 facilities reported these




concentration data for raw pesticide process wastewaters.









            The conventional and nonconventional (other than the PAIs)




pollutant data were also submitted for both in-plant and end-of-pipe sampling




locations.  At sampling points following commingling of other industry-related




wastewaters, however, it was not possible to attribute these pollutants solely




to the pesticide processes.  These data were useful in evaluating the overall




performance of the end-of-pipe BPT treatment systems.









5.4.2       EPA Pesticide Manufacturers Sampling Program









            As described above in Section 5.4.1, the wastewater self-




monitoring data submitted as a follow-up to the Facility Census were the




result of sampling and analyses conducted by individual plants and their




laboratories.  To expand and augment these wastewater characterization data,




EPA conducted sampling episodes at 20 pesticide manufacturing facilities




between 1988 and 1990.  Through this sampling effort, EPA verified the




presence of many of the priority pollutants that were indicated as known or




believed present according to responses to the Facility Census.  In addition,




EPA verified the presence of certain priority pollutants that may not have




been reported by the facilities, but were expected to be present based on




EPA's process analysis.
                                     5-22

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            The sampling episodes also allowed EPA to test analytical methods




for the PAIs.  Results of the PAI analyses obtained by EPA contract




laboratories were compared with results obtained by the facilities'




laboratories when the facilities chose to split samples with EPA.  EPA also




requested and reviewed information on the analytical methods typically used by




the facilities to quantify the concentration of PAIs in their wastewaters.









            Facilities were selected for sampling based on self-monitoring




data which indicated that the wastewater treatment system was effective in




removing PAIs, and the PAIs manufactured at the facility appeared to be




representative of one or more PAI structural groups.  During the sampling




episodes,  raw wastewaters from the manufacture of 38 different PAIs were




characterized.  In addition,  EPA sampled at various locations throughout the




treatment systems at these facilities to evaluate pollutant removal




performance.









            The EPA sampling episodes were usually three days in duration.




Samples were collected to represent a "snapshot characterization" of the




wastewater stream at each sampling point.  Automatic sampling devices were




used where possible to collect the daily composite samples.  If an automatic




sampler could not be used, discrete equal volume grab samples, or aliquots,




were manually collected at equal time intervals and added to the compositing




container (a specially clean 10-liter glass jar).  At the end of each daily




sampling period,  each composite sample was poured into specially cleaned




individual fraction containers for shipment to the EPA contract laboratories.
                                     5-23

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These fractions included analyses for: Group I  (BOD5,  TSS,  total fluoride,  and




pH);  Group II (TOG, COD, ammonia nitrogen, and  nitrate and nitrite nitrogen);




extractable (semi-volatile) organics; metals; and the pesticide active




ingredient(s).  The fractions for volatile organics, cyanide, and oil and




grease analyses were not poured from the composite containers, but manually




collected as  individual grab samples during each daily sampling period.









            After  the individual sample fraction containers were filled each




day,  they were preserved according to EPA protocol.  In addition, the samples




were maintained at 4°C  (using ice) during storage and shipment, with the




exception of  the metals fraction which does not need to be kept iced.  The




purpose of this procedure was to minimize any potential degradation reactions,




including biological activity, that could occur in the samples prior to




analysis.  It was  not necessary to follow this  procedure for the metals




fraction since these analyses are not specific  to the compounds containing the




metal analyte but  rather are reported as total  metals contained in the sample




(such as total copper,  total mercury, etc.).









5.5         WASTEWATER  CHARACTERIZATION









            The pesticide chemicals manufacturing industry generates process




wastewaters containing  a variety of pollutants.  Most of this process




wastewater receives some treatment, either in-plant at the process unit prior




to commingling with other facility wastewaters  or in the end-of-pipe




wastewater treatment system.  This section presents the Agency's database on
                                     5-24

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the pollutant characterization of pesticide wastewaters generated by pesticide

chemicals manufacturing facilities.   This database was compiled from the two

data gathering efforts previously described in Section 5.4.  Wastewater

characterization data were used by EPA to evaluate which pollutants are

present in industry wastewaters at significant levels that merit regulation

and to determine which technologies are applicable for treatment of

wastewaters containing these pollutants.   Wastewater characterization is

discussed separately below for conventional pollutants, priority pollutants,

PAIs,  and other non-conventional pollutants.  Treatment technologies are

discussed later in Section 7.



5.5.1       Conventional Pollutants



            Conventional pollutants include:
            •     Biochemical Oxygen Demand (BOD5) ;
            •     Total Suspended Solids (TSS);
                  pH;
            •     Oil and Grease (O&G);  and
            •     Fecal Coliform.
            The most widely used measure of general organic pollution in

Wastewater is five-day biochemical oxygen demand (BOD5) .   BOD5 is the quantity

of oxygen used in the aerobic stabilization of wastewater streams.  This

analytical determination involves the measurement of dissolved oxygen used by

microorganisms to biodegrade organic matter and varies with the amount of

biodegradable matter that can be assimilated by biological organisms under
                                     5-25

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aerobic conditions.  The nature of specific chemicals discharged into




wastewater affects the BOD5 due to the differences in susceptibility of




different molecular structures to microbiological degradation.  Compounds with




lower susceptibility to decomposition by microorganisms or that are more toxic




to microorganisms tend to  exhibit lower BOD5 values,  even though the total




amount of organic pollutant may be much higher than compounds exhibiting




substantially higher BOD5 values.   Therefore,  while BOD5 is a useful gross




measure of organic pollutant,  it does not give a useful measure of specific




pollutants, particularly priority pollutants and PAIs.









            Total solids in wastewater is defined as the residue remaining




upon evaporation at just above the boiling point.  Total suspended solids




(TSS) is the portion of the total solids that can be filtered out of solution




using a 1 micron filter.   Raw wastewater TSS content is a function of the




active ingredients manufactured and their processes, as well as the manner in




which fine solids may be removed during a processing step.  It can also be a




function of a number of other external factors, including storm water runoff,




runoff from material storage areas, and landfill leachates that may be




diverted to the wastewater treatment system.  Solids are frequently washed




into the plant sewer and removed at the wastewater treatment plant.  The total




solids are composed of matter which is settleable, in suspension, or in




solution and can be organic, inorganic, or a mixture of both.  Settleable




portions of the suspended  solids are usually removed in a primary clarifier.




Finer materials are carried through the system, and in the case of an




activated sludge system, become enmeshed with the biomass where they are then
                                     5-26

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removed with the sludge during secondary clarification.  Some manufacturing




plants may show an increase in TSS in the effluent from the treatment plant.




This characteristic is usually associated with biological systems and




indicates an inefficiency of secondary clarification in removal of secondary




solids.  Treatment systems that include polishing ponds or lagoons may also




exhibit this characteristic due to algae growth.









            pH is a unitless measurement which represents the acidity or




alkalinity of a wastewater stream (or any aqueous solution),  based on the




dissociation of the acid or base in the solution into hydrogen (H+)  or




hydroxide (OH") ions, respectively.









            Raw wastewater pH can be a function of the nature of the processes




contributing to the waste stream.  This parameter can vary widely from plant




to plant and can also show extreme variations in a single plant's raw




wastewater,  depending on such factors as waste concentration and the portion




of the process cycle discharging at the time of measurement.   Fluctuations in




pH are readily reduced by equalization followed by a neutralization system, if




necessary.  Control of pH is important regardless of the final disposition of




the wastewater stream (e.g., indirect discharge to a POTW or direct discharge)




to maintain favorable conditions for various treatment system unit operations,




as well as receiving streams.









            Raw wastewater oil and grease (O&G) is an important parameter in




some wastewaters as it can interfere with the smooth operation of wastewater
                                     5-27

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treatment plants and, if not removed prior to discharge, it can interfere with




the biological life in receiving streams and/or create films along surface




waters.  However, oil and grease monitoring involves use of a solvent to




extract oil and grease from the sample.  This solvent usually also extracts




organic materials other than petroleum oil, such as priority pollutants and




the PAIs.   None of the pesticide plants sampled or visited have any petroleum




oil problems in wastewater; the oil and grease measurements reflect only gross




levels of organics and are poor measures of priority pollutants and PAIs




(because there are much more accurate pollutant-specific methods for these




parameters).  Therefore, oil and grease is not an important parameter in




pesticide wastewaters.









            The drinking water standard for microbial contamination is based




on coliform bacteria.  The presence of coliform bacteria in wastewater, a




microorganism that resides in the human intestinal tract, indicates that the




wastewater has been contaminated with feces from humans or other warm-blooded




animals.   The promulgated BPT limitations do not include a limit for coliform




bacteria,  because very few pesticide manufacturing plants directly discharge




sanitary wastewater, and because coliform bacteria is not expected to be




present in the PAI contaminated wastewater streams generated by pesticide




manufacturing facilities.  EPA did not pursue any further data collection




efforts characterizing fecal coliform in pesticide manufacturing plants for




this regulation.
                                     5-28

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            Self-monitoring data submitted by pesticide manufacturers included




substantial amounts of conventional pollutant analytical results.  The data




indicate that conventional pollutant levels are widely scattered for in-plant




process streams.  Analytical data developed through EPA's sampling program




show the same results.  Industry data characterizing final effluent streams




show that, on average, plant wastewater treatment systems are removing




conventional pollutants to consistently low levels.  For almost all (>99%)




BODj  and TSS  results  reported  for  end-of-pipe  discharge,  the  results were




below the industry-average concentration-based daily maximum BPT limit for the




respective pollutant.  The average concentration-based BPT limit was




calculated based on the concentration-based BPT limits for each plant in EPA's




database.  The individual plant concentration-based BPT limits were back




calculated from the mass-based BPT limit by factoring in each plant's flow




rate and production rate.  For pH, most (>88%) of the results reported for




end-of-pipe discharge were within the BPT limits of between 6 to 9.




Analytical data developed through EPA's sampling program show the same results




for the conventional pollutants.









            The industry-submitted BOD5  data characterizing end-of-pipe




discharge are summarized in Figure 5-2.   The table displays the number of BOD5




results reported in ranges of 100 mg/L,  and compares the results with the




industry average daily maximum BPT limit of 582 mg/L.  The table shows that




the BODj levels  in end-of-pipe  discharges are  typically under 100 mg/L.  The




industry-submitted TSS data characterizing end-of-pipe discharge are




summarized in Figure 5-3, along with the industry average daily maximum BPT
                                     5-29

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en
I
CO
O
               3000n
                                               Figure 5-2


                        INDUSTRY SELF-MONITORING BOD LEVELS IN FINAL EFFLUENT DISCHARGE
                                                                        Average BP " Limit

                                                                            582mg/L
                       0-100
100-200   200-300   300-400   400-500   500-600
           BOD Concentration (mg/L)
>600

-------
Ul

U)
              5000-f
           -8  1000
                  0
                                             Figure 5-3

                       INDUSTRY SELF-MONITORING TSS  LEVELS  IN FINAL EFFLUENT  DISCHARGE
                       493$
                                                                        Average BPT Limit
                                                                           480mg/L
                       0-100
100-200     200-300    300-400    400-500
        TSS Concentration (mg/L)
>500

-------
limit of 480 mg/L.  Similar to BOD5,  the table shows  that the .TSS  levels  in




end-of-pipe discharges are typically under 100 mg/L.  The industry-submitted




pH data characterizing end-of-pipe discharge are summarized  in Figure 5-4,




along with the BPT limit range of between 6 and 9.  The figure shows that the




majority of the results were within the BPT range.









5.5.2       Priority Pollutants









            Data characterizing the pesticide manufacturing process wastewater




with respect to priority pollutants have been gathered by EPA qualitatively




from industry responses to the Facility Census and quantitatively from




industry supplied self-monitoring data and EPA sampling and  analysis episodes.




In addition, the EPA Toxic Release Inventory System (TRIS) was used to confirm




the presence of priority pollutants in pesticide manufacturing wastewaters at




some facilities.  Due to the aggregated nature of the reporting in TRIS,




however, it was not useful for quantifying priority pollutant discharges in




pesticide wastewaters.  Many of the plants with priority pollutant emissions




exceeding the TRIS reporting thresholds manufacture pesticide and non-




pesticide chemicals.  For this reason, these priority pollutant emissions




could not be attributed solely to the pesticide processes.









            In- the Facility Census, respondents were asked to identify all




priority pollutants that were known or believed to be present in wastewaters




from each pesticide manufacturing process or indicate if those priority




pollutants were known to be absent.  They were also asked to indicate the
                                     5-32

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en
I
Co
             3000-r
                 0
                                              Figure  5-4


                        INDUSTRY SELF-MONITORING pH LEVELS IN FINAL EFFLUENT DISCHARGE
BP" Limit Range

     6-9
          « 1500-
                     0-2   2-4    4-6   6-7    7-8    8-9   9-10  10-11 11-12  12-13  13-14
                                                  pH Ranges

-------
source of the priority pollutant  (i.e., raw material, reaction by-product,




solvent, catalyst, or contaminant).  Priority pollutants were reported by 47




pesticide manufacturing facilities in their responses to the Facility Census.




A total of 60 unique priority pollutants were known or believed present in




wastewaters associated with the production of 83 PAIs at these 47 facilities.




Twenty-two facilities reported that no priority pollutants would be expected




in their pesticide manufacturing process wastewaters, and the other 21




facilities did not know whether priority pollutants would be present.









            In addition to reporting priority pollutants in the Facility




Census, some facilities also submitted priority pollutant data obtained during




self-monitoring sampling.  As discussed earlier in this section, most of these




data were not generally useful since they represented end-of-pipe sampling




locations at facilities that also manufacture non-pesticide chemicals.




However, six facilities submitted priority pollutant concentrations for raw




process wastewaters where multiple detections were reported.  Table 5-7




summarizes the priority pollutant data submitted by these organic pesticide




chemical (Subcategory A) manufacturing facilities (no Subcategory B facilities




submitted priority pollutant data for raw process wastewaters).  Table 5-7




shows the minimum and maximum concentrations reported for each priority




pollutant as well as the total number of samples analyzed for each pollutant




and the number of these samples with detectable concentrations.  These data




are aggregated for all facilities, so the maximum and minimum concentrations




may represent samples collected at different facilities.  Table 5-7 also shows




whether or not at least one of the facilities submitting data for each
                                     5-34

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                                                       Table 5-7

                                    PRIORITY POLLUTANT DATA-FACILITY SELF MONITORING

Pollutant
Tetrachlorome thane
Hexachloroe thane
2,4, 6-Trichlorophenol
Chloroform
2-Chlorophenol
2 ,4-Dichlorophenol
2 ,4-Dimethylphenol
Methylene Chloride
Chlorome thane
Phenol
Toluene
Cyanide

Number of
Samples
Analyzed
21
2
10
32
12
6
5
30
8
5
6
235

Number of
Reported
Detections
11
2
10
28
12
6
2
24
4
4
6
235
Reported Concentrations (/jg/L)
Minimum
0.5
260
590
0.5
7
13,350
2,300
0.5
3
100
2,200
180
Maximum
3,100
1,300
15,700
110,000
24,320
108,000
2,600
7,400,000
50
690
400,000
7,625,000

Known or
Believed
Present
Known
-
Known
Known
Believed
Known
-
Known
Known

Known
Known
Ul
LJ

-------
priority pollutant had indicated in the Facility Census that the pollutant was




known or believed present in their process wastewaters.  Nine of the 12




priority pollutants shown in the table were reported as known or believed




present in pesticide process wastewaters.









            To verify the presence of priority pollutants reported as known or




believed present by facilities and to augment the limited priority pollutant




data submitted by facilities, EPA conducted sampling episodes at 20 pesticide




manufacturing facilities.  As discussed in Section 5.4, in each episode




samples were collected for three days at locations throughout the wastewater




generation, treatment, and discharge path.  A report that there was detection




of a priority pollutant in at least two daily samples at the same location




would indicate high probability that the priority pollutant was in fact




present.  Reported detection of a priority pollutant in only one sample would




cast doubt on the presence of that pollutant.









            Where priority pollutants were reported detected in only one




sample at any sample site, EPA used the following procedure to evaluate the




report.  First, EPA examined samples collected at other sites during the




episode for reported detections for that same pollutant in pesticide




manufacturing process wastewaters.  Second, EPA examined the details of the




production process to determine if the pollutant was a raw material, by-




product, or a likely contaminant of any raw materials or solvents used in the




process.  Finally, EPA contacted knowledgeable plant personnel to determine if




the pollutant was a known or likely contaminant, and to determine if the plant
                                     5-36

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had also detected the pollutant during sampling; particularly if the pollutant




was detected during sampling conducted the same day EPA sampled and if the




sample was analyzed by the plant using the same or a similar analytical method




as EPA.









            EPA sampling at the 20 facilities reported detection of 70




priority pollutants in pesticide manufacturing wastewaters.   However,  in many




cases, the priority pollutants were detected in only one sample at one sample




site,  and the presence of the pollutants could not be confirmed after checking




all the sources described above.  EPA's conclusion in these  cases,  where




detections could not be confirmed, is that the reported results are incorrect




and the pollutant is not in fact present.   In addition, some of the pollutants




that were detected at the same sample point on multiple days were present in




only trace amounts and often very close to the analytical detection limit.









            Table 5-8 presents priority pollutant characterization data for




raw process wastewaters based on EPA sampling at organic pesticide chemicals




(Subcategory A) manufacturing facilities.   The table shows the minimum and




maximum concentrations detected for each priority pollutant  that was confirmed




present during the sampling episodes.  These data are aggregated to include




all sampling episodes, and, therefore, the minimum and maximum concentrations




may have been reported for wastewater samples collected at different




facilities.  Table 5-8 also shows whether or not at least one of the




facilities where each priority pollutant was confirmed present either knew or
                                     5-37

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                Table 5-8
 Priority Pollutant Data   EPA Sampling
Organic Pesticide Chemicals Manufacturing
Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2 - Dichloroe thane
1,1, 1-Trichloroe thane
Hexachloroe thane
Chloroform
2 - Chlorophenol
1 , 2 - Dichlorobenzene
1 , 4-Dichlorobenzene
1 , 1-Dichloroethene
Trans- 1, 2-Dichloroethene
2 , 4-Dichlorophenol
Ethylbenzene
Methylene Chloride
Ch 1 o r ome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Nitrobenzene
Phenol
Tetrachloroethene
Toluene
Trichloroethene
Cyanide
Lead
Concentration
(/4J/L)
Minimum
16
892
38
1,007
30
34
12
40
70
84
133
16
11,890
71
14
55
93
22
21
27
32
25
51
27
19
50
930
Maximum
31,000
44,260
113
3,255,900
60
5,346
20,110
8,264
14,202
554
261
18
360,940
9,550
11,261,100
111
42,679
29,370
39,434
1,197
44
97,794
402,655
331,649
38
2,740,000
1,600
Known or Believed Present
Believed
Known
	
Known
	
	
Known
Believed
	
	
	
	
Believed
Known
Known
	
Known
Known
Known
	
	
Believed
Believed
Known
	
Known
	
                  5-38

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believed that the priority pollutant was present in their wastewaters.  Of the




27 priority pollutants shown in the table, 15 (- 55%) were reported as either




known or believed present according to Facility Census responses from the




sampled facilities.









            EPA also collected samples at three metallo-organic pesticide




manufacturing (Subcategory B) facilities.  During two of the sampling




episodes, however, only one sample of raw process wastewater could be




collected at each facility.  In all three episodes,  the specific metal used in




the production of the metallo-organic pesticide (e.g., copper in organo-copper




pesticides) was detected in the raw wastewaters.  The detected concentrations




were also much greater than the concentrations expected in wastewaters due to




equipment corrosion.  Some organic priority pollutants were also reported, and




some of these were expected to be present due to solvent or raw material use




in the pesticide process.  However, as mentioned earlier,  in two sampling




episodes only one sample each was collected,  and, therefore, there is some




doubt as to whether other priority pollutants that were reported are actually




present.









            The priority pollutant characterization data presented in this




section for organic and metallo-organic pesticide process wastewaters were




used by EPA to evaluate which priority pollutants should be regulated.  The




decision to regulate was not based solely on whether a priority pollutant was




verified present during sampling; EPA evaluated a number of other factors as




well, such as whether the pollutant was present in more than trace amounts.
                                     5-39

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However, most of the priority pollutants shown in Table 5-8 are being




regulated as will be discussed in Section 6.









5.5.3       Pesticide Active Ingredient Pollutants









            Raw wastewater data for PAIs are available from both industry




self-monitoring and EPA sampling.  The industry self-monitoring data were not




quite as useful for quantifying PAI concentrations in raw wastewaters because




the sampling locations often represented commingled or partially treated




wastewaters.  Unlike priority pollutants, PAIs detected in commingled




wastewaters could be attributed to the pesticide processes since other




industrial production at the facility would not generate wastewaters




containing PAIs.  The facility self-monitoring data did confirm that when




wastewaters are generated during the production of a specific PAI, that PAI is




usually present in those wastewaters.  Fifteen facilities submitted PAI data




for raw and partially treated wastewaters associated with 29 unique PAIs




manufactured in 1986.  A total of 5,153 samples were analyzed by the 15




facilities, and PAIs were reported in concentrations above the detection




limits for 4,756 of these samples, or about 92% of the samples.  In many




cases, the PAI was reported above the detection limit in every sample that was




analyzed.









            EPA sampling also confirmed the presence of PAIs in raw process




wastewaters.  As discussed earlier, EPA sampled at 20 pesticide manufacturing




facilities, and these sampling episodes were used to characterize pesticide
                                     5-40

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wastewaters from 38 different PAI processes, as well as to evaluate analytical




methods for the PAIs.  Detections were reported for 34 of the 38 PAIs in




samples of the raw process wastewaters; that is, about 90% of the PAI




processes sampled generated wastewaters containing the PAI at concentrations




above the analytical detection limit.  Specific results obtained during EPA




sampling of raw process wastewaters are not presented in this document due to




confidentiality concerns   in many cases, presenting results for specific PAIs




would identify where EPA conducted the sampling episodes.









5.5.4       Nonconventional Pollutants









            Nonconventional pollutants include chemical oxygen demand (COD),




total organic carbon (TOG),  as well as other organic pollutants not previously




mentioned.  COD is a measure of organic material in a wastewater that can be




oxidized as determined by subjecting the waste to a powerful chemical




oxidizing agent (such as potassium dichromate) in an acidic medium.




Therefore, the COD test can show the presence of organic materials that are




not readily susceptible to attack by biological microorganisms.  As a result




of this difference, COD values are almost invariably higher than BOD3 values




for the same sample.  The COD test cannot be substituted directly for the BOD5




test because the COD/BOD3  ratio  is  a  factor  that  is  extremely variable and  is




dependent on the specific chemical constituents in the wastewater.   However,  a




COD/BODj ratio  for  the wastewater  from a  single manufacturing facility with a




constant product mix or from a single manufacturing process may be




established.  This ratio is applicable only to the wastewater from which it
                                     5-41

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was derived and cannot be utilized to estimate the BOD3 of another  facility's




wastewater.  It is often established by facility personnel to monitor process




and treatment plant performance with a minimum of analytical delay.  As




production rate and product mix changes, however, the COD/BOD5  ratio  must be




reevaluated for the new conditions.  Even if there are no changes in




production, the ratio should be reconfirmed periodically.









            TOG measurement is another means of determining the pollution




potential of wastewater.  This measurement shows the presence of organic




matter in wastewater and is especially applicable to small concentrations.




Certain organic compounds may be resistent to oxidation and the measured TOG




value will be less than the actual amount.  The promulgated BPT limitations do




not include a limit for TOG.  TOG is a parameter which is controlled under the




BOD5 and COD regulations.   In addition,  the  most  highly toxic TOG constituents




will be organic PAIs and priority pollutants, which will be individually




regulated.









            EPA's sampling data collection efforts included analyses for non-




priority organic and metal pollutants.  The metals found most frequently in




pesticide manufacturing plant wastewater include sodium, iron,  barium,




calcium, manganese, potassium, iodine, and strontium.  Other inorganic, non-




priority pollutants frequently detected include phosphorus, silicon,  and




sulfur.  Non-priority organic pollutants detected in more than 10 percent of




the samples collected include 2-propanone, 2-butanone, 1,4-dioxane, and




xylenes.  However, many of the compounds discussed above were detected in
                                     5-42

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commingled wastewaters and cannot be attributed to the PAI processes.  Also,




in many cases,  these compounds were detected in trace amounts or are currently




being controlled by treatment technologies in place at the facilities where




they were detected.









            The only non-conventional pollutant currently regulated under BPT




(aside from the PAIs) is COD.  Self-monitoring data submitted by pesticide




manufacturers included substantial amounts of COD analytical results.  Similar




to the data submitted for the conventional pollutants, the industry data




indicate widely-scattered COD levels in in-plant process streams,  but




consistently low COD levels in end-of-pipe discharge are summarized in Figure




5-5.  The figure shows that the majority (>90%) of the COD results for end-of-




pipe discharge streams were below the industry average daily maximum BPT limit




of 1,025 mg/L (the calculation of industry average concentration-based BPT




limits is discussed in Section 5.5.1).









5.6         WASTEWATER POLLUTANT DISCHARGES









            The concentration data discussed above were used by the Agency to




estimate pollutant loadings discharged by pesticide chemicals manufacturing




facilities.  In estimating these wastewater pollutant discharges,  EPA




accounted for in-plant and end-of-pipe treatment currently in-place at each




facility.  The Agency's estimates for annual discharges of conventional




pollutants, priority pollutants, and nonconventional pollutants (including the




PAIs) are discussed below.  The performance of the treatment technologis in-
                                     5-43

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ui

I
          1000
                         INDUSTRY SELF-MONITORING
                                              figure 5-5
                  COD LEVELS IN FINAL EFFLUENT
                                                                    DISCHARGE
                                                                   Average BPT Limit
                                                                       1025 mg/L
                0-200
200-400     400-600          OO
        COD Concentration (mg/L)
                                                                            >1(X»

-------
place at pesticide manufacturing facilities are discussed later in Section 7.




The costs to upgrade current facility treatment systems to comply with the




proposed regulations are discussed in Section 8.









            EPA estimates that approximately 2.7 million pounds per year of




the conventional pollutants BOD5  and  TSS  and 7.2 million pounds per year  of




the nonconventional pollutant COD are discharged directly by organic pesticide




chemical manufacturing facilities.   Because the BOD5  and TSS  discharged by




this industry are compatible with POTWs,  these parameters are not currently




monitored by any of the five indirect dischargers that manufacture metallo-




organic pesticides.  Therefore, EPA cannot estimate the quantity of BOD5  or




TSS discharged to POTWs by these facilities; these facilities also do not




monitor for COD.  There are no facilities that discharge process wastewater




resulting from the manufacture of organo-arsenic,  organo-copper,  or organo-




mercury PAIs directly to receiving streams.









            The pesticide chemicals industry manufactures large volumes of




PAIs, and the use of contact process water, as well as the collection of




spills, leaks, and rainwater results in significant discharges of organic PAIs




and priority pollutants from this industry.  EPA estimates that approximately




200,00 pounds of PAI's and 17,000 pounds of priority pollutants per year are




discharged directly to surface waters by Subcategory A plants after currently




available treatment.  In addition,  it is estimated that 5.8 million pounds per




year of volatile organic priority pollutants are present in PAI wastewaters




with considerable potential for volatilization  to the atmosphere.
                                     5-45

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            Indirect dischargers in the pesticide manufacturing industry, like




the direct dischargers, use as raw materials, and produce as products or




byproducts many nonconventional pollutants (including PAIs) and priority




pollutants.  As in the case of direct dischargers, they may be expected to




discharge many of these pollutants to POTWs at significant mass or




concentration levels,  or both.  EPA estimates that indirect dischargers of




organic pesticides annually discharge approximately 110,000 pounds of PAIs and




29,000 pounds of priority pollutants to POTWs.
                                      5-46

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                                   SECTION  6




                 POLLUTANT PARAMETERS SELECTED FOR REGULATION









6.0         INTRODUCTION









            As discussed in Section 5, EPA evaluated all available wastewater




characterization data to determine the presence or absence of conventional,




non-conventional (including the PAIs), and priority pollutants in pesticide




process wastewaters.  Using this information, EPA selected specific pollutants




to be proposed for regulation.  This section presents the criteria used in the




selection process and identifies those pollutants to be regulated under BPT,




BAT, PSES, NSPS,  and PSNS for the organic pesticides chemicals manufacturing




subcategory (Subcategory A).   No new limitations and standards are being




proposed for the metallo-organic pesticide chemicals manufacturing subcategory




(Subcategory B),  and, therefore, Subcategory B is not discussed in this




section.  Section 14 presents the Agency's decision making for Subcategory B.









6.1         CONVENTIONAL POLLUTANT PARAMETERS









            Conventional pollutants include BOD5,  TSS,  fecal  coliform,  pH,  and




oil and grease.  These pollutants are general indicators of water quality




rather than specific compounds.  Current BPT for the organic pesticide




chemicals manufacturing subcategory regulates the pH and the quantity of BOD5




and TSS discharged in process wastewaters;  except for the wastewater
                                      6-1

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discharges from 25 specifically excluded organic PAIs and classes of PAIs.

These 25 specific PAIs and classes of PAIs were specifically excluded due to a

lack of treatment data available  in 1978.  Since then, the Agency has

collected data on 15 organic PAIs within the group of 25 PAIs and classes of

PAIs, and BPT will be amended to  include these PAIs.  These 15 PAIs are

presented below.
                  Ametryn                 Terbuthylazine
                  Prometon                Glyphosate
                  Prometryn               Phenylphenpl
                  Terbutryn               Hexazinone
                  Cyanazine               Sodium Phenlyphenate
                  Atrazine                Biphenyl
                  Propazine               Methoprene
                  Simazine
EPA has also developed analytical methods and collected effluent data to

support BPT coverage of organo-tin pesticides.



            Although EPA is amending the applicability of BPT to cover

previously excluded PAIs and classes of PAIs, no additional conventional

pollutants are being selected for regulation.  Limitations are not being

established for oil and grease and fecal coliform.  Oil and grease

measurements in this industry are not related to petroleum oil.  The

analytical method includes in the oil and grease measurement organic compounds

such as the priority pollutants and the PAIs, which are being regulated

separately under this proposed rulemaking.  Also, fecal coliform is not

expected to be present at significant concentrations in pesticide process
                                      6-2

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wastewaters.  For these reasons, oil and grease and fecal coliform are not




being selected for regulation.









6.2         PRIORITY POLLUTANT









            There are currently no regulations covering the discharge of




priority pollutants in wastewaters generated during organic pesticide




chemicals manufacturing, with the exception of those priority pollutants




regulated as PAIs under 40 CFR 455.20(b).  Priority pollutants are indirectly




covered under 40 CFR 455.32 for the metallo-organic pesticides subcategory




since current BPT requires no discharge of process wastewater pollutants from




facilities in this subcategory.









            As discussed in Section 5,  EPA sampling verified the known or




believed presence of priority pollutants in many pesticide process




wastewaters, and also verified the presence of certain priority pollutants




that could be present due to the process chemistry.  However, some priority




pollutants reported as known or believed present by facilities were not




confirmed during EPA sampling.  In some cases, this was because EPA did not




sample at the facility reporting the priority pollutant, and in other cases,




the PAI process associated with the reported priority pollutant was not in




operation during EPA sampling at that facility.









            Three priority pollutants which were not confirmed during EPA or




industry sampling, and therefore not shown on Table 5-10 or 5-11, are
                                      6-3

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bromomethane, 1,2-dichloropropane, and 1,3-dichloropropene.  However, the




Agency believes these priority pollutants are present in pesticide process




wastewaters.  Bromomethane was reported as known to be present in wastewater




at two facilities due to use as a raw material in these PAI processes and




believed to be present at one other facility as a contaminant.  One facility




reported that 1,2-dichloropropane was known present in wastewaters as a waste




product of the PAI process, and a separate facility believed this pollutant to




be present as a contaminant.  The third priority pollutant, 1,3-




dichloropropene, is manufactured as a PAI and was also reported by one




facility as believed to be present as a contaminant.  Because these three




priority pollutants are known or believed present in wastewaters at multiple




facilities, the Agency is selecting them for regulation.  Limits have also




been developed for these pollutants under the OCPSF rulemaking, and, as will




be discussed in Section 7, limits are being transferred to cover these three




pollutants as well as the other priority pollutants discussed earlier in




Section 5.









            Not all of the priority pollutants shown in Table 5-11 are being




selected for regulation by the Agency.  Some of those priority pollutants were




detected in only trace amounts, will indirectly be controlled by the proposed




PAI limitations, or were detected in only one or a very small number of




wastewaters.  After evaluating all of these factors, the Agency selected for




regulation 26 organic priority pollutants, lead, and total cyanide.  The 28




priority pollutants selected for regulation are presented in Table 6-1.  The
                                      6-4

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                 Table 6-1




Priority Pollutants Selected for Regulation
Pollutant Number
004
006
007
010
Oil
023
024
025
027
029
030
031
032
033
034
038
044
045
046
047
048
051
055
065
085
Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1,2-Dichloroethane
1,1, 1-Trichloroethane
Chloroform
2-Chlorophenol
1 , 2-Dichlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethene
Trans- 1, 2-Dichloroethene
2 ,4-Dichlorophenol
1 , 2 - Dichloropropane
1 , 2-Dichloropropene
2 , 4-Dimethylphenol
E thy Ib enz ene
Methylene Chloride
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethene
                    6-5

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Table 6-1




(Continued)
Pollutant Number
086
121
122
Pollutant
Toluene
Cyanide
Lead
    6-6

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development of limitations for these priority pollutants is discussed in
Section 7.
            EPA is not selecting 95 priority pollutants for regulation,  and
the reason for excluding or not regulating each of these pollutants is
discussed below.
            •     The pollutant has not been detected in the effluent with the
                  use of analytical methods promulgated pursuant to Section
                  304(h) of the Act or other state-of-the-art methods.
 Acrylonitrile
 1,1,2-Trichloroethane
 2-Chloroethyl vinyl ether
 3,3'-Dichlorobenzidine
 2,6-Dinitrotoluene
 4,6-Dinitro-o-cresol
 Bis (2-Chloroisopropyl) ether
 Bis (2-Chloroethoxy) methane
 N-Nitrosodimethylaniine
 N-Nitrosodiphenylamine
 Pentachlorophenol
 Butyl benzyl phthalate
 Acenaphthalene
 Benzo (A) pyrene
 Benzo (GHI) perylene
 Dimethyl phthalate
 Dibenzo (A,H) anthracene
 Ideno (1,2,3-CD) pyrene
 Aldrin
 Dieldrin
Chlordane
4, 4 '-DDT
4, 4 '-DDE
4,4'-DDD
ct-Endosulfan
/3-Endosulfan
Endosulfan sulfate
a-BHC
7-BHC
5-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
2,3,7, 8-Tetrachlorodibenzo-p-dioxin
                                      6-7

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                 The pollutant is present only in trace  amounts  and is
                 neither causing nor likely to cause  toxic  effects.   In
                 addition,  the pollutant is present in amounts too  small  to
                 be effectively reduced by technologies  known to the
                 Administrator.
2-Chloronaphthalene
1,3-Dichlorobenzene
2,4-Dinitrotoluene
1,2-Diphenylhydrazine
Bis (2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
1,1-Dichloroethane
                 The pollutant is detectable in the  effluent  from  only  a
                 small number of sources and the pollutant  is uniquely
                 related to only those sources.
Acenapthene
Acrolein
Benzidene
1,2,4-Trichlorobenzene
Hexachlo rob enz ene
1,1,2,2-Tetrachloroethane
Chloroethane
Bis (2-Chloroethyl) ether
Parachlorometacresol
Fluoranthene
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
Isophorone
Nitrobenzene
2-Nitrophenol
2,4-Dinitrophenol
Di-n-octyl Phthalate
Benzo (A) anthracene
Benzo fluoranthene
Benzo (B) fluoranthene
Chrysene
Anthracene
Fluorene
Phenanthrene
Pyrene
Vinyl chloride
                                    6-8

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                  The pollutant will be effectively controlled by the
                  technologies which are the basis for controlling certain
                  pesticide active ingredients in the proposed effluent
                  limitations guidelines and standards.
                               Hexachloroethane

                          N-Nitrosodi-n-propylamine

                               Endrin aldehyde

                              Heptachlor epoxide

                           1,1,2-Trichloroethylene

                            2,4,6-Trichlorophenol
                  EPA is not regulating the following priority pollutants due
                  to lack of treatability data.   These priority pollutants
                  were not detected during sampling but would be expected in
                  wastewaters from the manufacture of certain pesticides.
                  However, those pesticides were not in production when
                  sampling activities were scheduled by EPA.
                             Hexachlorobutadiene

                          Hexachlorocyclopentadiene

                                4-Nitrophenol
                  EPA is also not regulating Asbestos because there is no
                  promulgated Section 304(h) analytical method for that
                  pollutant in water.
6.3         NONCONVENTIONAL POLLUTANTS



            Nonconventional pollutants selected for regulation by the Agency

include certain PAIs and one other non-conventional pollutant,  COD.   Current

BPT regulations limit the discharge of COD from both organic and metallo-

organic pesticide manufacturing subcategories.   The BPT numerical limitations
                                      6-9

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for COD discharged by the organic pesticides manufacturers are not being




amended although EPA is proposing to extend the applicability of BPT to cover




COD resulting from the manufacture of 15 previously excluded organic PAIs and




classes of PAIs and the organo-tin pesticides.









            Under Subcategory A, 170 individual PAIs were manufactured in




1986; and 8 PAIs were manufactured from 1985-1989, but were not manufactured




in 1986.  Therefore, a total of 178 individual PAIs are being considered for




potential regulation.  Of these, 122 individual PAIs are being selected by the




Agency for regulation under either BAT, NSPS, PSES, or PSNS.   EPA is not




proposing regulations for 56 individual PAIs.  Of the 56 PAIs, all production




ceased for 12 PAIs before the Agency could gather data.  Analytical methods




are unavailable for 14 other PAIs, so the Agency could not gather data.  All




wastewaters for 14 other PAIs are currently disposed of in deep wells subject




to regulation under EPA's Underground Injection Control (UIC) program.  EPA




decided to develop data and regulations for PAIs with actual discharges to




surface waters.  For the remaining 16 PAIs, insufficient data exist on their




treatability.  Either the plants do not monitor for the PAI or the available




data are inadequate to demonstrate that the technology in use is the best




available technology.  In addition, the available bench scale treatability




data are inadequate and there are no structurally similar PAIs with data which




could be transferred.  Available toxicity data indicates that these 16 PAIs




are less toxic than most of the 122 PAIs for which PAI effluent limitations




are proposed.
                                     6-10

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                                   SECTION  7




                 TECHNOLOGY  SELECTION AND  LIMITS DEVELOPMENT









7.0         INTRODUCTION









            This section identifies and describes the wastewater control and




treatment technologies currently used or available  for the reduction and




removal of conventional pollutants, PAIs,  and priority pollutants discharged




in pesticide chemicals manufacturing process wastewater and presents a summary




of treatment performance achievable by technology based on industry




submissions and treatability tests on these control and treatment




technologies.  This section also discusses the development of effluent




limitations guidelines and standards for PAIs and priority pollutants in




Subcategory A of the pesticide chemicals manufacturing industry.









            Section 7.1 presents a summary of treatment performance databases




available to the Agency on wastewater control.  The Agency has compiled three




databases; one from industry-submitted data,  one from wastewater sampling




conducted by EPA, and a third from treatability studies conducted on




wastewaters or synthetic wastewaters containing PAIs.









            Section 7.2 presents a description of in-plant versus end-of-pipe




treatment and an overview of the current and proposed treatment technologies




used in the pesticide chemicals manufacturing industry for treatment of




conventional pollutants, PAIs, and priority pollutants.  This section also
                                      7-1

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discusses the disposal of  solid residues that are generated from wastewater




control and  treatment technologies.









             Section  7.3 presents  treatment performance data for technologies




considered to be  BAT and Section  7.4 presents the methodology used to develop




the  limitations and  standards  for the pesticide chemicals manufacturing




industry.  Section 7.4 also presents those cases where limitations requiring




no discharge of process wastewater pollutants have been proposed and discusses




options available for compliance  with proposed zero discharge standards.




Effluent limitations guidelines and standards development for Subcategory B




PAIs are discussed in Section  14.









7.1          TREATMENT PERFORMANCE DATABASES









             The sources of treatment performance data available for the




pesticide chemicals  manufacturing industry include:  analytical data on PAI




treatment submitted  with the Pesticide Manufacturing Facility Census for 1986




or collected during  EPA short-term sampling and treatability sampling efforts




between 1988 and  1991, EPA sponsored bench-scale treatability tests on




selected PAIs, and existing treatment performance databases.  The treatment




performance  database for conventional pollutant parameters and COD is from the




previous regulation  of BPT under  the pesticide chemicals manufacturing




subcategory.   The treatment performance database for priority pollutants is




from the previous regulation of the OCPSF point source category.  Sections




7.1.1 to 7.1.3 discuss these databases in more detail.
                                      7-2

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7.1.1       Analytical Data Submitted with the Pesticide Manufacturing




            Facility Census for 1986 and Associated Data









            The U.S. EPA Engineering and Analysis Division (formerly the




Industrial Technology Division) of the Office of Water issued the Pesticide




Manufacturing Facility Census for 1986.  As described in Section 3.1.3, this




questionnaire requested engineering and economic data regarding pesticide




manufacturing processes, wastewater generation,  treatment,  and handling




procedures from each plant that received the questionnaire.   In addition, this




questionnaire requested submittal of all wastewater monitoring data collected




in 1986, in the form of individual data points.   The intent of this request




was to obtain a full year of daily monitoring data from each respondent.  The




questionnaire further requested that the data identify the sample points as




shown earlier in the questionnaire process and treatment diagrams,




specifically from wastewater streams leaving manufacturing processes and




entering and exiting treatment systems.









            Additional data were obtained from some of the survey respondents




following the initial review of their 1986 data, and in many cases the




additional data included more recent information than 1986 monitoring data.




Data were also obtained from a previous (mid to late 1970's) EPA survey of




wastewater discharged by pesticide chemical manufacturers.   This earlier




survey was similar to the 1986 survey because it was also conducted under the




authority of Section 308 of the Clean Water Act and requested the same type of




information.
                                      7-3

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            EPA sampled pesticide manufacturing process wastewater at various




locations throughout the wastewater generation, treatment, and discharge path




at 20 facilities to screen the wastewater for the presence of PAIs and




priority pollutants and to evaluate control technology performance.  Included




for consideration with the data submitted with the EPA surveys were selected




data obtained from these EPA short-term sampling efforts conducted at




pesticide manufacturing facilities between 1988 and 1990.









            Of the 90 pesticide manufacturing plants that responded to the




1986 survey, 51 plants submitted long-term wastewater monitoring data.  When




the data submitted by a plant were found to be insufficient or to require




further explanation, a formal request for additional information was made to




the plant by EPA.  In addition to the data submitted in response to the 1986




survey, the Agency reviewed and considered long-term data from six plants from




the earlier EPA survey (containing data from the mid- to late 1970s).  The




data from this earlier survey do not differ significantly from the data of the




1986 survey in terms of format.  Short-term sampling data collected during




site visits by EPA to pesticide manufacturing plants between 1988 and 1990




were also reviewed and considered by the Agency.









            The industry-submitted long-term data, data from the earlier EPA




survey, and the short-term EPA sampling data were entered into an Agency




treatment performance database.  The long-term data submitted by industry




contained mostly PAI data.  The Agency evaluated these data extensively in the




course of developing limitations as discussed in Section 7.4.
                                      7-4

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7.1.2       Treatability Test Data









            In preparation of this proposed rulemaking effort for the




pesticide chemicals manufacturing industry, EPA undertook numerous bench-scale




treatability studies using both synthetic pesticide wastewaters, as well as,




where practical, actual process wastewaters.  These treatability studies




investigated activated carbon adsorption, hydrolysis,  membrane filtration,  and




chemical oxidation (using alkaline chlorination and using ozonation enhanced




with ultraviolet (UV) light).









            Activated Carbon Adsorption









            Activated carbon adsorption isotherm tests were performed on 29




selected PAIs chosen from the list of 270 PAIs considered for regulation




grouped according to their production volume.  The carbon isotherm studies




used PAIs selected from various structural groups to determine which groups




would be most adaptable to activated carbon technology.  Some manufacturers of




some PAIs in a few of those groups were known to use activated carbon




technology to treat the wastewaters and treatability data from those




manufacturers were available;  in this case, the purpose of the carbon isotherm




studies was to establish benchmarks for determining the potential efficacy of




activated carbon technology to other structural groups.  Results were obtained




for all 29 PAIs.  Twenty-five of the 29 PAIs tested exhibited some adsorption




capacity.
                                      7-5

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            Next, Accelerated Column Tests (ACTs) were conducted to generate




treatability data for the removal of atrazine, vapam, chlorothalonil, and




diazinon by the use of activated carbon.  This technique was used to develop




effluent concentration breakthrough curves for atrazine, diazinon, and




chlorothalonil.  For vapam, no calculations were made as the high feed




concentration resulted in immediate breakthrough.  The atrazine and diazinon




wastewater were obtained from plants that operate full-scale carbon treatment




systems.  The ACT data from both tests were comparable to the full-scale




system data with respect to carbon usage and carbon loading.  Results of these




studies were used in estimating full-scale carbon systems designs and cost.









            Hydrolysis









            Hydrolysis was evaluated as a wastewater treatment technology




through a series of bench-scale tests to determine the hydrolysis rates of




selected PAIs in reagent grade water (i.e., not actual wastewater).  General




factors in EPA's selection of specific PAIs for use in the synthetic




wastewaters were the availability of an analytical method for the specific PAI




and the ready availability of the PAI in a pure form from either government or




commercial sources.









            The hydrolysis studies were conducted in some cases to confirm the




results of literature hydrolysis data for certain PAIs, and in other cases




were conducted because of the lack of any literature data to fill in those




gaps.  All of the PAIs selected were expected to hydrolyze under some
                                      7-6

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conditions.  Thirty-nine PAIs from six structural groups were tested at three




different pHs (2, 7, and 12) and two different temperatures (20°C and 60°C).




The test results indicated that the hydrolysis rates of the PAIs varied from




almost immediate to virtually no reaction in the 24-hour test time for the




various PAIs and conditions tested.  One phosphorodithioate PAI was tested in




a field study at pH 12 and 60°C.  The half life ranged from 0.72 hours (at an




initial PAI concentration of 5 mg/1) to 1.94 hours (at an initial PAI




concentration of 57 mg/1).









            Membrane Filtration









            Membrane filtration was evaluated as a method of pesticide




removal.  The membrane filtration studies used PAIs selected to span the




molecular weight range of the 270 PAIs and classes of PAIs under consideration




for regulation,  because the effectiveness of membrane filtration tends to vary




with molecular weight.  In the membrane filtration treatability studies,  EPA




conducted a series of bench-scale tests to identify specific PAIs which could




be separated from water by various membrane materials.  Synthetic test




solutions containing 19 PAIs were tested on 7 different types of membranes.




The membranes were manufactured from 3 types of materials (cellulose acetate,




thin-film composite, and Aramid) and were of various pore sizes, with nominal




molecular weight cut-offs ranging from 150 to 500.  The test results indicated




that reverse osmosis was an effective method of pesticide removal.  The best




results were obtained with the thin-film composite (TFC) membranes.  Removals
                                      7-7

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of 90% or greater were obtained throughout the test, with the majority of PAIs




being rejected at 99% or greater.









            Alkaline Chlorination









            Alkaline chlorination was evaluated as a method of PAI removal




using wastewater generated during the manufacture of 6 dithiocarbamate PAIs




(Metam, Namet, KN-Methyl, Nabonate, Dimet, and TCMTB).  The treatability




studies using actual pesticide manufacturing process wastewater were conducted




to supplement full-scale treatment system performance data, to fill in gaps in




performance data where no treatability data were available for the PAI, and to




help assess performance of existing full-scale treatment systems where the




performance of those systems appeared to be inadequate compared to performance




of other facilities treating the same or similar PAIs.  The PAIs selected for




study were the PAIs in production at the plants during the treatability study.




The bench-scale study was conducted at three chlorine dosages at three




different contact times.  The test results indicate alkaline chlorination was




an effective treatment for all PAIs but TCMTB.  The chlorine demand for TCMTB




was found to be greater than 100,000 mg/1 and therefore was not considered a




feasible treatment option.









            Because alkaline chlorination of wastewater containing organic




matter may generate volatile organic toxic pollutants, which must subsequently




be controlled, EPA also conducted chemical oxidation treatability studies for




five of those same six PAIs using ozone rather than chlorine.  The preliminary
                                      7-8

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results of those studies indicate that ozone can achieve about the same degree

of PAI reduction as chlorine.  Chemical oxidation with ozone is usually more

expensive than chemical oxidation with chlorine.  However,  ozone oxidation

does not produce volatile toxic pollutants.   When the cost of controlling

those volatile toxic pollutants is added to the cost of alkaline chlorination,

the total cost for chlorination may exceed the cost of ozone oxidation.



7.1.3       Existing Treatment Performance Databases



            The treatment performance databases used in the analysis of

treatment of conventional pollutants, COD, and priority pollutants include the

pesticide chemicals industry BPT database and the OCPSF database.   These

databases are not repeated here but can be found in the following documents:
                  DevelopmentDocument for Final Effluent Limitations
                  Guidelines for the Pesticide Chemicals Manufacturing Point
                  Source Category.   Found in the docket to this proposed
                  regulation and in the docket to the Tuesday,  April 25, 1978
                  FRN which presents the final BPT regulations  for the
                  pesticide chemical manufacturing point source category (also
                  available through the National Technical Information System
                  [NTIS]).

                  Development Document for Effluent Limitations Guidelines New
                  Source Performance Standards and Pretreatment Standards for
                  the Organic Chemicals and the Plastics and Synthetic Fibers
                  Point Source Category - Volume I and II.  EPA 440/1-87/009.
                                      7-9

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7.2         WASTEWATER TREATMENT IN THE PESTICIDE CHEMICALS MANUFACTURING




            INDUSTRY









            The major treatment technologies currently employed by plants in




the pesticide chemicals manufacturing industry to treat wastewaters on-site




are:  biological treatment, activated carbon adsorption, on-site incineration,




chemical oxidation/chlorination/dechlorination, hydrolysis, steam stripping,




resin adsorption, hydroxide precipitation, and solvent extraction.  The Agency




found that the pesticide chemicals manufacturing industry primarily selects




in-plant controls for the removal of highly concentrated pollutants from




process wastewaters.  [These in-plant controls are then often followed by




biological treatment usually after these streams are combined with other




facility wastewater].  In addition, facilities performing recycle/reuse of




treated wastewaters do so in many cases following various in-plant treatment




units.  End-of-pipe treatment systems employ physical, chemical, and




biological treatment and are designed to treat combined process and facility




wastewaters.  The typical treatment sequence is physical-chemical treatment to




remove PAIs, followed by steam stripping to remove volatile priority




pollutants,  followed by biological treatment to remove non-volatile priority




pollutants and other organic pollutants.









            Table 7-1 summarizes the in-plant and end-of-pipe controls for the




removal of pollutants from pesticide industry process wastewaters.  Table 7-1




also presents the number of plants that reported using each of the listed




technologies in the Facility Census for 1986.  It should be noted that many
                                     7-10

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plants use more than one type of treatment technology to effect significant

removals of pollutants.



            At least some treatment is currently being provided to over 99% of

the wastewaters discharged directly and to about 92% of the wastewaters

discharged to POTWs.   While many plants provide extensive treatment to remove

PAls, priority pollutants, and other pollutants, some plants provide no

treatment.  The majority of plants have some treatment but that treatment

often needs to be upgraded to improve its effectiveness and to remove

additional pollutants.  The following 14 technologies have been demonstrated

to provide treatment of PAIs and/or priority pollutants in the pesticide

chemicals manufacturing industry (these technologies are presented in no

particular order):
            •     Carbon Adsorption;
            •     Hydrolysis;
            •     Chemical Oxidation/Ultraviolet Decomposition;
            •     Resin Adsorption;
            •     Solvent Extraction;
            •     Distillation;
            •     Membrane Filtration;
            •     Biological Treatment;
            •     Evaporation;
            •     Chemical Precipitation/Filtration;
            •     Chemical Reduction;
            •     Coagulation/Flocculation;
            •     Incineration; and
            •     Steam Stripping.
A description of each of these technologies is presented below.
                                     7-11

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                 Table  7-1

    TREATMENT TECHNOLOGIES USED BY THE
PESTICIDE CHEMICALS MANUFACTURING INDUSTRY
 AS REPORTED  IN  THE  1986 FACILITY  CENSUS
Treatment Technology
Biological Treatment
Carbon Adsorption
Chemical Precipitation/Filtration
Chemical Oxidation
Coagulation/Flocculation
Distillation
Evaporation
Hydrolysis
Incineration
Resin Adsorption
Solvent Extraction
Steam Stripping
Ultraviolet Decomposition
Total Number
of Facilities
25
14
7
11
8
1
1
6
3
2
3
4
2
                   7-12

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7.2.1       Carbon Adsorption




            Adsorption is the primary mechanism for removal of organic

pollutants from wastewater by activated carbon.  Activated carbon has a very

large surface area per unit mass which is available for assimilation of

contaminants.   The main driving forces for adsorption of a solute on the

adsorbent is attraction of the solute (or adsorbate) to the adsorbent and/or a

hydrophobic (water-disliking) characteristic of the adsorbate.




            Biodegradation of contaminants from microbial growth on the carbon

can improve organics removal and reduce the carbon usage rate for certain

wastewaters, but adsorption is the primary mechanism for organics removal.

Some biologically degradable compounds are difficult to adsorb and prediction

of degradation rates is difficult, so biodegradation is not usually considered

in the design of activated carbon systems unless an extensive pilot-scale

study is conducted.




            The carbon adsorption capacity (the mass of the contaminant

adsorbed per mass of carbon) for specific organic contaminants is related to
                                    4
the characteristics of the compound,  the carbon characteristics,  the process

design,  and the process conditions.  In general, adsorption capacity is

inversely proportional to the adsorbate solubility.  Within a homologous

series of organic compounds, adsorption increases with increasing molecular

weight since solubility decreases with increasing molecular weight (e.g.,

Parathion is more strongly adsorbed than EPTC).  Thus nonpolar,  high molecular
                                     7-13

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weight organics with low solubility are adsorbed more readily than polar, low




molecular weight organics with high solubilities.  Competitive adsorption of




other compounds has a major effect on adsorption (i.e., the carbon may begin




preferentially adsorbing one compound over another compound and may even begin




desorbing the other compound).  Process conditions (such as pH and




temperature), process design factors (such as granular vs. powdered carbon,




contact time, and number of columns in series), and carbon characteristics




(such as particle size and pore volume) also effect adsorption capacity.









            When the adsorptive capacity of the carbon is exhausted, the spent




carbon is either disposed of or regenerated, the choice generally to be




determined by economics.  The carbon is regenerated by removing the adsorbed




organics from the carbon.  Three methods for carbon regeneration are steam




regeneration, thermal regeneration, and physicochemical regeneration.  Thermal




and steam regeneration volatilize the organics which are removed from the




carbon in the gas phase.  Afterburners are required to ensure destruction of




the organic vapors and a scrubber may be necessary to remove particulates.




Physicochemical regeneration removes the organics by a solvent, which can be a




water solution.  Thermal and steam regeneration are most commonly used for




carbon from wastewater treatment.









            Activated carbon is commonly utilized in the form of granular-




carbon columns that operate in either an upflow or downflow mode.  Powdered




carbon is used less frequently for wastewater treatment due to the difficulty




of regeneration and reactor system design considerations although it may be
                                      7-14

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used in conjunction with biotreatment systems.  Carbon adsorption is used as




both an in-plant and end-of-pipe treatment technology.  In-plant carbon




adsorption protects treatment downstream from high concentrations of toxic




pollutants that could adversely affect system performance.  For example,




carbon adsorption may remove pollutants which would be toxic to a downstream




biological treatment system.  In-plant carbon adsorption treatment also




enables removal of pollutants from low volume waste streams before they are




commingled with other facility wastewaters.  Commingling of untreated waste




streams contaminates much larger volumes of wastewater,  which could then be




more difficult and costly to treat.  On the other hand,  activated carbon may




also be applied as end-of-pipe treatment when certain pollutants contained in




commingled wastewaters are not effectively removed by previous treatment




steps.  For example, certain pollutants, although not toxic to a biological




treatment system, may not be effectively removed by the  biological system and




an end-of-pipe activated carbon system may be necessary  to treat the




pollutants effectively.  The biological system may remove other organics




which, if not removed, could reduce total adsorptive capacity of the activated




carbon system.









            In the pesticide manufacturing industry,  activated carbon




adsorption is or has been used to treat PAIs in the following structural




groups:  acetamides, aryl halides,  benzonitriles,  carbamates,  phenols,




phosphorodithioates, pyridines,  pyrethrines, s-triazines,  tricyclic,




toluidines, and ureas.  In addition,  EPA and industry treatability studies




have demonstrated sufficient treatability of pesticides  in the acetanilide,
                                     7-15

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terephthalic acid, and uracil structural groups using carbon to establish this




treatment as a basis for control of specific PAIs in these groups.  Carbon has




also been shown in treatability studies to be an effective polishing control




for thiocarbamate PAIs, although insufficient information is currently




available to determine the effluent quality achievable by full-scale treatment




systems for thiocarbamate PAIs.









            In the case of many of the PAIs which are or have been treated




using carbon, expediency has appeared to drive treatment system selection




rather than optimal  system design.  For example, wastewaters from the




manufacture of carbamate and phosphorothioate PAIs which can be readily




hydrolyzed at alkaline conditions have instead been treated using activated




carbon.  In those cases, carbon may have been chosen originally because of its




ability to remove other pollutants of concern from the wastewater, or because




of an incomplete assessment of treatment options.  Due to the cost of carbon




regeneration or replacement, the use of activated carbon to treat high volume




streams is often a more expensive option than other physical-chemical




treatment methods; therefore an evaluation of other treatment technologies may




result in a system which provides equal performance at a lower cost.









7.2.2       Hydrolysis









            Hydrolysis is a chemical reaction which occurs in water, alters




the target compound  by reaction with water, and is not catalyzed by light or
                                     7-16

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microorganisms.  Usually the hydroxyl  group  (OH") is introduced into the

reactant, displacing another group:



                0                        0
                 II                        II
            (RO)2-P-S-R  +  OH- ---> (R0)2 -P-OH  +  (SR)-



            Carbamate hydrolysis occurs by the  following  reaction:



                  0
                  I
                  C

            R,-N     0   Rj + H20	> RjOH +  R,-NH + C02
                I                                 I
               R,                               R,




The acid hydronium ion can also enter  into hydrolysis reactions.




            As the reactions above illustrate,  hydrolysis  is a destructive

technology in which the original molecule forms  two or more new molecules.   In


some cases, the reaction continues and other  products are  formed.




            The primary design parameter considered for hydrolysis  is  the

half-life, which is the time required  to react  50% of the  original  compound.

The half-life of a reaction is generally dependent on the  reaction  pH  and

temperature and the reactant molecule.  Hydrolysis reactions can be catalyzed

at low pH, high pH,  or both, depending on the reactant.  In general, an

increase in temperature will increase  the hydrolysis rate.  Improving  the

conditions for the hydrolysis reaction results  in a shorter half-life, and

therefore the size of the reaction vessel required is reduced.
                                     7-17

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            Hydrolysis is a treatment technology which should be strongly




considered for wastewaters which contain carbamate, phosphate,




phosphorothioate, phosphorodithioate, and phosphonothioate PAIs.  For




virtually all PAIs in these structural groups for which treatability testing




was performed, a half-life less than 30 minutes was achieved at high




temperature  (60°C) and high pH (pH 12).  Literature data shows that many of




the PAIs in  fact react even faster than EPA's study demonstrated.  Study




conditions were  such that the "zero" reaction time was in fact at least 15




minutes  (i.e., 15 minutes had elapsed between the time the initial sample was




taken and analyzed).  In some cases, the PAI had been completely destroyed




within that  15 minute period (i.e., the PAI was not detected in the sample).




In such  cases, the half-life was estimated to be at less than 30 minutes, and




a 30-minute  half-life was used in calculating reactor sizes and retention




times, hence cost, for treatment.  Literature data, however, confirms that for




PAIs such as malathion the half-life is less than one minute.









             For  many compounds high pH and ambient temperature were enough to




result in a  half-life less than an hour, especially for the carbamates.   Acid




hydrolysis was only effective for a small number of compounds tested.




However, for organophosphorus and carbamate pesticide hydrolysis, alkaline




hydrolysis is usually faster than acid hydrolysis.  The urea PAIs tested were




not hydrolyzed effectively, so long reaction times would be necessary to treat




most urea PAIs.
                                     7-18

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            Acid hydrolysis of dithiocarbamate PAIs can achieve short half-




lives; however, this reaction results in evolution of carbon disulfide gas;




therefore, hydrolysis is not considered to be feasible for dithiocarbamate




PAIs.  Hydrolysis has also been used to treat triazine PAIs,  but only at high




temperature with catalyst because this reaction proceeds very slowly in the




normal range of conditions used in wastewater treatment.









7.2.3       Chemical Oxidation/Ultraviolet Decomposition









            Chemical oxidation is a reaction process in which one or more




electrons are transferred from the oxidizing chemical (electron donor) to the




targeted pollutants (electron acceptor) causing their destruction.   Oxidants




typically used in industry include chlorine, hydrogen peroxide,  ozone, and




potassium permanganate.  Of these oxidants,  chlorine is most commonly used




under alkaline conditions to destroy such compounds as cyanide (metal




finishing, inorganic chemicals, and pesticides industry) and pesticides.









            Chemical oxidation has been demonstrated by the pesticide industry




to be effective at destroying alkyl halide,  DDT-type, phenoxy,




phosphorothioate, and dithocarbamate PAIs in manufacturing wastewaters.  In a




bench-scale alkaline chlorination treatability study by EPA,  chlorine dosages




equivalent to 50, 100 and 125% of the chlorine demand for specific




dithiocarbamate pesticides wastewaters were evaluated.  Treatment results




indicated alkaline chlorination could reduce the effluent PAI concentration




below the analytical detection limit; however, chlorine dosage requirements
                                     7-19

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and reaction times varied for each pesticide evaluated.  The major drawback to




alkaline chlorination of pesticide manufacturing wastewaters is the production




of chlorinated organic compounds which must subsequently be removed by an




additional treatment technology.  Compounds not present in the raw wastewater




but detected in at least two of the test reactors included chloroform,




bromodichloromethane, dibromochloromethane, and acetone.  Based on the past




performance of alkaline chlorination in the pesticide industry and on the




bench-scale treatment study, the effluent limitations for dithiocarbamates are




based on this technology but with the addition of a treatment technology




(steam stripping) to reduce chlorinated organics.









            A recent oxidation technology to emerge for the oxidation of




dithiocarbamate PAIs is ozone in combination with ultraviolet light.  This




technology, initially developed for the metal finishing industry to treat iron




complexed  cyanide, has recently been suggested by EPA as an alternative to




chlorine oxidation for treatment of pesticide manufacturing wastewaters.  The




ozone-UV light process focuses on the production of the highly oxidative




hydroxyl radicals from the absorption of UV light (254 run wavelength) by




ozone.  These hydroxyl radicals completely oxidize the PAI (e.g., to carbon




dioxide, nitrate, sulfate and water) avoiding the formation of halogenated




organic compounds such as those produced during alkaline chlorination.









            The oxidation of dithiocarbamate pesticides by ozone and UV light




has recently been demonstrated by EPA in a bench-scale treatability study.




The study, involving five different dithiocarmate PAIs spiked into deionized
                                      7-20

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water, investigated various initial pHs and UV light intensities.  Results




indicated the PAI concentration could be reduced to levels at or near the




analytical limit of detection within minutes at low UV light intensities and




at initial pHs between 7 and 9.  Optimum treatment conditions have not yet




been determined.









            The preliminary results of this study indicate that ozone can




achieve about the same degree of PAI reduction as chlorine.  Chemical




oxidation with ozone is usually more expensive than chemical oxidation with




chlorine.  However, ozone oxidation does not produce volatile toxic




pollutants.   When the cost of controlling those volatile toxic pollutants is




added to the cost of alkaline chlorination, the total cost for chlorination




may exceed the cost of ozone oxidation.









7.2.4       Resin Adsorption









            Resin adsorption is a separation technology that may be used to




extract and,  in some cases, recover dissolved organic solutes from wastewater.




Resins are typically microporous styrene-divinylbenzenes,  acrylic esters, or




phenol-formaldehydes.   Each type may be produced in a range of densities, void




volumes,  bulk densities,  surface areas, and pore sizes.   The formaldehyde




resins are granular,  and the others are in the form of beads.
                                     7-21

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            Resin adsorption involves two basic steps:
                  The liquid waste stream is brought into contact with the
                  resin, allowing the resin to adsorb the solutes from the
                  solution; and

                  The resin is regenerated by removing the adsorbed chemicals,
                  often accomplished by simply washing with the proper
                  solvent.
            Caustic, formaldehyde, or solvents such as methanol, isopropanol,

and acetone can accomplish regeneration of spent resin.  Pesticide facilities

have used solvents such as methanol.  Batch distillation of regenerant

solutions separate and return products to the process.



            Resin adsorption is applicable for all members of the phenol

family as well as amines, caprolactam, benzene, chlorobenzen.es,  and

chlorinated pesticides; however, the cost of this technology may be

prohibitive.  The adsorption capacity of resins depends on the type and

concentration of specific organics in the wastewater as well as the pH,

temperature, viscosity, polarity, surface tension, and background

concentrations of other organics and salts.  As with carbon adsorption, the

adsorptive capacity of resins increases as solubility decreases.



            Resin adsorption is similar in nature to activated carbon with the

main difference being that resins are chemically regenerated while carbon is

usually thermally regenerated.  A potential advantage of resins is that they

are more easily tailored for removal and recovery of specific pollutants.
                                     7-22

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However, resins generally have a lower adsorptive capacity than carbon, and




are not likely to be competitive with carbon for the treatment of high volume




waste streams containing moderate or high concentrations of mixed wastes with




no recovery value.  For this reason, resins have generally been restricted to




application where few other treatment options have proven useful.









7.2.5       Solvent Extraction









            Solvent extraction, also referred to as liquid-liquid extraction,




involves the separation of the constituents of a liquid solution by contact




with another immiscible liquid for which the impurities have a high affinity.




The separation is based on physical differences that affect differential




solubility between solvents and may be enhanced by adding reagents to cause a




definite chemical reaction.









            The end result of solvent extraction is to separate the original




solution into two streams--a treated stream and a recovered solute stream




(which may contain small amounts of water and solvent).   Solvent extraction




may thus be considered a recovery process because the solute chemicals are




generally recovered for reuse of further treatment and disposal.   The process




for extracting a solute from solution will typically include three basic




steps:









            •     Mixing of solvent with waste stream;




            •     Extraction and separation; and
                                     7-23

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                  Recovery of solvent from the treated stream, either by
                  distillation or steam stripping.
Solvent extraction generates a treated wastewater residual, which is

discharged, and an extract, which in some cases may be recycled and reused.

The use of solvent extraction as a unit process operation is common in the

pesticide chemicals industry.  Often, the process function and wastewater

treatment function of solvent extraction are integrated as water contaminants

are returned with the solvent to the process; in these cases, the facility

often does not consider the extraction to be a treatment process, although the

net result is to reduce total loading of pollutants discharged from the

process.  Solvent extraction is most effectively applied to segregated process

streams where the potential for collecting specific residuals for reuse is

greatest.



7.2.6       Distillation



            Distillation is the separation of the constituents in a wastewater

stream by partial vaporization of the mixture and separate recovery of vapor

and residue.  The main use of distillation in pesticide manufacturing

operations is in the separation of alcohols used in the manufacture of esters

of phenoxy-based PAIs from wastewaters.  The alcohols can then be reused in

future manufacturing, while the wastewater, once separated from alcohols and

solvents, can be reused in the manufacture of salts of phenoxy PAIs, or in

phenoxy product formulations.  In this process, the phenoxy ester product is

heated, driving off the alcohol and water.  The alcohol is then condensed.
                                     7-24

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            For non-phenoxy PAIs, distillation has been used to separate water




from pesticide process streams as a final purification stage.  Although the




purity of the distillate will be a function of the volatility of the PAI,  the




distilled wastewater will normally have no detectable concentration of the




PAI.









7.2.7       Membrane Filtration









            Membrane filtration is a term applied to a group of processes  that




can be used to separate suspended, colloidal, and dissolved solutes from a




process wastewater.  Membrane filtration processes utilize a pressure driven,




semipermeable membrane to achieve selective separations.   Much of the




selectivity is established by designations relative to pore size.   The pore




size of the membrane will be relatively large if precipitates or suspended




materials are to be removed, or very small for the removal of inorganic salts




or organic molecules.  During operation, the feed solution flows across the




surface of the membrane, clean water permeates the membrane, and the




contaminants and a portion of the feed remain.  The clean or treated water is




referred to as the permeate or product water stream, while the stream




containing the contaminants is called the concentrate, brine, or reject.









            In a typical industrial application,  the product water steam will




either be discharged, or more likely,  recycled back to the manufacturing




process.   The reject stream is normally disposed, but in those situations




where the reject does not contain any specifically objectionable materials,  it
                                     7-25

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too can potentially be recycled back to the process.  As an example, a reject




stream from a system treating a wastewater generated from many different




processes would likely have to be disposed.  However, if the membrane system




were used on a process where the wastestream contained only a specific PAI,




the reject stream could possible be recycled back to the process.  Depending




on the characteristics of the wastewater and the type of process used, 50-95%




of the feed stream will be recovered as product water.









            Types of membrane filtration systems available include




microfiltration, ultrafiltration (UF), and reverse osmosis (RO).   Microfilters




are generally capable of removing suspended and colloidal matter with




diameters  greater than 0.1 micron  (3.94 x 10~* inches).   The systems can be




operated at feed pressures of less  than 50 psig.  The feed stream does not




require extensive pretreatment, and the membrane is relatively resistant to




fouling and can be easily cleaned.  A microfiltration system would not be an




effective method of treatment unless the PAIs were insoluble or were attached




to other suspended material in the  wastewater.  Microfiltration has been used




in the pesticide industry in applications where an adsorbent material and/or




flocculent is added prior to the membrane system.  The PAIs are adsorbed or




become attached to the floe which forms and is ultimately separated by the




microfilter.  Microfilters are capable of recovering up to 95% of the feed




stream as product water.









            Ultrafiltration is similar to microfiltration, with the difference




being that a UF membrane has smaller pores.  The "tightest" UF membrane is
                                     7-26

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typically capable of rejecting molecules having diameters greater than 0.001




micron  (3.94 x 10"* inches) or nominal molecular weights greater than 2000.




The systems operate at feed pressures of 50-200 psig.  Some pretreatment may




be necessary to prevent membrane fouling.  UF systems would only be effective




in removing PAIs which are insoluble or attached to other suspended material




(most PAIs have molecular weights from 150 to 500 molecular weight units).




For most UF designs, the introduction of adsorbents or flocculants to the feed




stream  is not recommended since they may plug the membrane module.  UF systems




are also capable of recovery of up to 90-95% of the feed as product water.









            Reverse osmosis systems have the ability to reject dissolved




organic and inorganic molecules.  For organic (noncharged) molecules such as




PAIs, membrane rejection is a function of the membrane pore size.   Typically,




membranes with a pore size of 0.0001 to 0.001 microns are used to remove PAIs.




RO membranes have been shown to be capable of removing the majority of PAIs




with molecular weights greater than 200.   Unlike microfiltration and




ultrafiltration,  RO membranes are capable of rejecting inorganic ions.   The




mechanism for salt rejection is the electro-chemical interaction between the




membrane and the constituents in the wastewater.   Based on the strength of




their ionic charge (valence),  the ions are repelled from the charged surface




of the membrane and will not pass through the pores.   Although RO membranes




may be rated based on molecular weight cutoff,  they are normally rated on




their ability to reject sodium chloride.   Typical sodium chloride rejection




for an industrial type membrane would be  90-95  percent.
                                     7-27

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            RO systems used in industrial applications are designed to operate




a feed pressures of 250-600 psig.  RO membranes are very susceptible to




fouling and may require an extensive degree of pretreatment.  Oxidants which




may attack the membrane, particulates,  oil, grease, and other materials which




could cause a film or scale to form must be removed by pretreatment.  The RO




product water stream will usually be of very high quality and suitable for




discharge, or more importantly, reuse in the manufacturing process.  Standard




practice is to dispose of the reject stream.  Dissolved solids present in the




feed stream will be concentrated in the reject and will limit the




opportunities for recycle.  RO systems will be capable of recovering 50-90% of




the feed as product water.  The recovery that can be obtained as well as the




required feed pressure to operate the system will be a function of the




dissolved solids concentration in the feed.









            The membranes used in the filtration process are made from a




number of different materials.  Microfiltration membranes are commonly made




from woven polyester or ceramic materials.  UF and RO membranes are fabricated




from cellulose acetate, polysulfone, polyamide, or other polymeric materials.




The most common material  is cellulose acetate.  Although cellulose acetate




membranes are lower cost  and not as susceptible to fouling, removal of some




low molecular weight PAIs such as carbaryl, fluometuron, chloropropham, and




atrazine have been shown  to be only marginal.  In addition, mass balances




conducted for short-term  tests have shown a significant amount of the PAI




rejection may be due to adsorption to the membrane as opposed to rejection by




it.
                                     7-28

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            Bench- and pilot-scale studies have demonstrated excellent




rejection (>99%) of a wide range of PAIs using thin-film composite (TFC)




reverse osmosis membranes.  TFC membranes usually consist of three distinct




layers, a polyester support layer,  a porous interlayer (polysulfone),  and a




proprietary ultrathin barrier coating (often polyamide).   TFC membranes are




more expensive and in some cases, more susceptible to fouling than cellulose




acetate.  For relatively clean wastestreams (no suspended solids or oil and




grease), TFC membranes appear to represent an effective method of removing the




target PAIs and producing a high quality product water stream.   Bench- and/or




pilot-scale testing is, however, recommended for most potential applications




to ensure that the system will be properly designed to prevent or minimize




membrane fouling which will negatively impact the performance of the system.









7.2.8       Biological Treatment









            Biological treatment is a destruction technology in which toxic




organic pollutants in wastewaters are degraded by microorganisms.   These




microorganisms oxidize soluble organics and agglomerate colloidal and




particulate solids.  This technology generates a waste biosludge.









            Common forms of biological treatment include lagoons,  activated




sludge, and trickling filter systems.  In lagoon systems, wastewater is




biologically treated to reduce the degradable organics and also reduce




suspended solids by sedimentation.   The biological process taking place in the




lagoon can either be aerobic or anaerobic, depending on the design of the
                                     7-29

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lagoon.  The activated sludge process is used primarily for the removal of

organic material from wastewater.  It is characterized by a suspension of

aerobic and facultative microorganisms maintained in a relatively homogenous

state by mixing or by turbulence induced by aeration.  These microorganisms

oxidize soluble organics and agglomerate colloidal and particulate solids in

the presence of dissolved molecular oxygen.  The trickling filter system is an

attached-growth biological system based on trickling wastewater over the

surface of a biological growth on solid media (usually rock, wood, or

plastic).   Trickling filters are effective for the removal of suspended or

colloidal materials, but less effective for the removal of soluble organics.



            Biological treatment (including aerated lagoons, activated sludge,

and trickling filter systems) is most effective on those priority pollutants

which are effectively adsorbed onto the suspended solids in the system, where

biological activity occurs, and are readily biodegradable.  The mechanism of

pollutant removal may be one or more of the following:



            •     Biological degradation of the pollutant;

            •     Adsorption of the pollutant onto sludge with is separately
                  disposed; or

            •     Volatilization of the pollutant into the air (in the case of
                  aerated systems).



            In the  last two cases, the pollutant is simply transferred from

one medium to another, rather than actually being "removed."  Some pollutants

may require specially acclimated biomass and/or longer detention times to be
                                     7-30

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effectively removed by biological treatment.  In these cases, in-plant




biological treatment can be an effective and potentially less costly




alternative to carbon adsorption technology for control of these priority




pollutants and PAIs.









7.2.9       Evaporation









            Evaporation occurs when a solvent, usually water, vaporizes from a




solution or slurry, and completion of the evaporation process results in




drying. This technology can be used to vaporize off water,  thereby




concentrating the solute in the remaining solution, and is  related to




distillation,  sublimation,  and stripping, because they are  all processes based




on the common principles of vaporization.









            In spray evaporation, or drying, a wet slurry is converted to a




vapor, which is released,  and a dry, free flowing powder, which may be




recovered as product or disposed of as waste.   A spray evaporation/drying




treatment system normally consists of a drying chamber.   The waste slurry is




injected into the chamber through an atomizer which disperses the stream.  A




cyclone is created by injecting a high flow warm air stream countercurrent to




the atomized slurry.   In the spray drying chamber,  the solids settle out of




the air while the moisture is evaporated.









            The solids which settle out of the primary and  secondary chambers




of the spray evaporation system may be either pesticide product ready for
                                     7-31

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formulation and packaging, or a solid waste stream requiring disposal or




recycle.  The water vapors are extracted from the primary chamber, filtered to




further remove particulate in the secondary chamber, and then exhausted to the




atmosphere, generating no wastewater.  If the solvent is not water, it is




necessary to condense or scrub the vapors to prevent hazardous air emissions.









            This technology is appropriate for separation of non-volatile and




insoluble PAIs from manufacturing wastewaters or from process solvents.  It is




not appropriate for wastewater streams containing volatile organic priority




pollutants or cyanide, unless air pollution control devices are added to the




exhaust prior to venting to the atmosphere.









            One pesticide manufacturer currently uses spray evaporation for




the control of effluents from two pesticide active ingredients.  However,




sufficient data are not available to estimate the amount of PAI discharge




eliminated through the use of this technology.









7.2.10      Chemical Precipitation/Filtration









            Chemical precipitation is a separation technology in which the




addition of chemicals during treatment results in the formation of insoluble




solid precipitates from the organic or inorganic compounds in the wastewater.
                                     7-32

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Polishing filtration then separates the solids formed from the wastewater.

Chemical precipitation is generally carried out in four phases:



            1.    Addition of the chemical to the wastewater;

            2.    Rapid (flash) mixing to distribute the chemical
                  homogeneously into the wastewater;

            3.    Slow mixing to promote particle growth by various
                  flocculation mechanisms; and

            4.    Filtration to remove the flocculated solid particles.



Chemical precipitation is used frequently as a technology to remove metals

from industrial wastewaters.  Chemical reagents are added to the wastewater

during treatment leading to the formation of insoluble solid precipitates from

the organic or inorganic compounds in the wastewater.  The precipitated metals

may then be removed by physical means such as sedimentation,  filtration, or

centrifugation.



            Hydroxide precipitation is the conventional method of removing

metals from wastewater.  Reagents such as slaked lime (CA(OH)2) or  sodium

hydroxide are added to the wastewater to adjust the pH to the point where

metal hydroxides exhibit minimum solubilities and are precipitated.  Sodium

hydroxide is more expensive than lime, but generates a smaller volume of

hydroxide sludge.  Hydrogen sulfide, ferrous sulfide, or soluble sulfide

salts, such as sodium sulfide, are used to precipitate many heavy metal

sulfides.  Because most metal sulfides are even less soluble than metal

hydroxides at alkaline pH levels, greater metal removal can often be
                                     7-33

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accomplished through the use of sulfide rather than hydroxide as a chemical




precipitant.  However, sulfide treatment may be more difficult to use due in




part to the possibility of evolution of highly toxic hydrogen sulfide gas.




Carbonate precipitation is another method of removing metals from wastewater




by adding carbonate reagents such as calcium carbonate to the wastewater to




precipitate metal carbonates.









            Chemical precipitation is an effective technique for removing




metals from industrial wastewaters.  This technology operates at ambient




conditions and  is well suited to automatic control.  Hydroxide precipitation




removes metal ions such as antimony, arsenic, trivalent chromium, copper,




lead, mercury,  nickel, and zinc.  Sulfide precipitation can be used to remove




mercury, lead,  and silver while carbonate precipitation removes antimony and




lead from wastewater.









7.2.11      Chemical Reduction









            Reduction is a chemical reaction in which electrons are




transferred to  the chemical being reduced from the chemical initiating the




transfer (the reducing agent).  Sulfur dioxide, sodium bisulfite, sodium




metabisulfite,  and ferrous sulfate form strong reducing agents in aqueous




solution and are often used in industrial waste treatment facilities for the




reduction of hexavalent chromium to the trivalent form.
                                      7-34

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            In the pesticides industry, chemical reduction has been used to




treat wastewaters containing an alkyl halide PAI.   The PAI is reduced with the




addition of sodium bisulfite and ultraviolet light (i.e., sunlight).









7.2.12      Coagulation/Flocculation









            Coagulation and flocculation are commonly used in conjunction to




enhance settling of suspended particles ranging in size from those particles




large enough to settle readily to those small enough to remain suspended.




Coagulation is the chemical destabilization of the particles and flocculation




is the physical process that agglomerates particles (too small for




gravitational settling) so that they may be successfully removed in subsequent




settling processes such as sedimentation, clarification, or filtration.









            Coagulation is the process of destabilizing colloidal particles so




that particle agglomeration can occur during flocculation.  Chemical




coagulants are typically added to the wastewater in a rapid-mix tank to ensure




that they are dispersed in the wastewater stream as rapidly as possible.




Commonly used coagulants are those which are iron or aluminum-based (such as




alum), lime, and polymers.  For a given wastewater, optimum coagulation




conditions depend on various factors including pH,  temperature,  chemical




composition of the wastewater,  mixing conditions,  and most importantly, the




coagulant used.
                                     7-35

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            Flocculation is a separation technique where the wastewater is




agitated in order to cause very small suspended particles to collide and




agglomerate into larger, heavier particles or floes and settle out.  A common




type of flocculator used today is the paddle flocculator employed in a series




of flocculation chambers.  The paddle gently agitates the water causing the




collision of the floe particles with one another, and the chambers lead to




laminar flow conditions to prevent floe destruction while providing sufficient




mixing to achieve floe formation.









            Coagulation and flocculation are commonly used in the pesticide




manufacturing industry to remove metallo-organic PAIs and the metallic




byproducts of metallo-organic PAI manufacture from process wastewaters.









7.2.13      Incineration









            Incineration is a destruction technology which involves heating




wastes to high temperatures in order to destabilize chemical bonds and destroy




toxic organic pollutants.  Incineration is actually a combination of oxidation




and pyrolysis, both which involve chemical changes resulting from heat.




Oxidation involves reaction with oxygen, while pyrolysis refers to




rearrangement or breakdown of molecules at high temperatures in the absence of




oxygen.  A controlled incineration process oxidizes solid, liquid, or gaseous




combustible wastes to carbon dioxide, water, and ash.  Common types of




incinerators are rotary kiln, multiple hearth, liquid injection, fluidized




bed, and pyrolysis.  This technology typically generates ash and scrubber
                                     7-36

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water, although liquid injection incinerators typically generate only scrubber




water.









            In the pesticide chemicals industry, incinerators destroy wastes




containing compounds such as:  hydrocarbons,  chlorinated hydrocarbons,




sulfonated solvents, and pesticides.  Sulfur and nitrogen-containing compounds




will produce their corresponding oxides and should not be incinerated without




consideration of the effect on air quality.  Halogenated hydrocarbons may not




only affect the air quality but may also corrode the incinerator surfaces.









7.2.14      Stripping









            Steam stripping is a separation technology that removes relatively




volatile compounds from a wastewater by the passage of steam through the




wastewater.  The stripped volatiles are usually processed further by recovery




or incineration.   This technology generates air emissions from the stripping




treatment (which may be condensed to other liquid streams).









            Steam stripping is essentially a  fractional distillation of




volatile components from a wastewater stream.   The volatile component may be a




gas or an organic compound that is soluble in the wastewater stream. This




treatment technology also removes water immiscible compounds such as




chlorinated hydrocarbons.  Steam stripping employs super-heated steam to




remove volatile pollutants of varying solubility in wastewater.   Specifically,




the technology involves passing super-heated  steam through a preheated
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wastewater stream column packed with heat resistant packing material or metal




trays in counter-current fashion.  Removal of the volatile compounds of the




wastewater.stream occurs because  the organic volatiles tend to vaporize into




the steam until the compound's concentration in the vapor and liquid phases




(within the stripper) are  in equilibrium.









            The amount  of  volatiles that can be removed and the effluent




pollutant  concentration levels that can be attained by a steam stripper are a




function of the height  of  the stripping column, the amount of packing material




and/or the number of metal trays  in the column, and the steam pressure in the




column.  After the volatile pollutant  is extracted from the wastewater into




the superheated steam,  the steam  is condensed to form two layers of immiscible




liquids--the  aqueous and volatile layers.  The aqueous layer is recycled back




to the steam  stripper influent feed stream because it may still contain low




levels of volatile compounds.  The volatile layer is recycled to the process




or disposed of, depending  on the  specific plant's requirements.









            Steam strippers are designed to remove individual volatile




pollutants based on a ratio of their aqueous solubility (tendency to stay in




solution)  to  vapor pressure (tendency  to volatilize).  This ratio is known as




the Henry's Law Constant.   The column  height and diameter, amount of packing




or number  of  trays, the operating steam pressure, and the temperature of the




heated wastewater feed  of  a steam stripper are varied according to the




strippability (using Henry's Law  Constant) of the volatile pollutants to be




removed.  Volatile compounds with lower Henry's Law Constants require greater
                                      7-38

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column height, more trays or packing material, greater steam pressure and




temperature, more frequent cleaning, and generally more careful operation than




do volatiles with higher strippability.   (See the final OCPSF rule, 52 FR




42540, for a further description of steam stripping technology).









7.2.15      Pre- or Post-Treatment









            The pesticide chemicals manufacturing industry uses equalization,




neutralization, and/or filtration to pre- or post-treat process wastewaters.









            Equalization









            Equalization dampens flow and pollutant concentration variation of




wastewater prior to subsequent downstream treatment.  By reducing the




variability of the raw waste loading, equalization can significantly improve




the performance of downstream treatment processes that are more efficient if




operated at or near uniform hydraulic, organic,  and solids loading rates.




Increased treatment efficiency reduces effluent variability associated with




slug raw waste loadings.  Equalization is accomplished in a holding tank or a




pond.  The retention time of the tank or pond should be sufficiently long to




dilute the effects of any highly concentrated continuous flow or batch




discharges on treatment plant performance.
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            Neutralization



            Neutralization adjusts either an acidic or a basic waste stream to

a more neutral pH.  Neutralization of acidic or basic waste streams is used in

the following situations:



            •     To enhance precipitation of dissolved heavy metals;

            •     To prevent metal corrosion and damage to other construction
                  materials;

            •     As a preliminary treatment allowing effective operation of
                  the biological treatment process;

            •     To provide neutral pH water for recycle uses; and,

            •     To reduce detrimental effects on a facility's receiving
                  water.



Neutralization may be accomplished in either a collection tank, rapid mix

tank, or equalization tank by commingling acidic and alkaline wastes, or by

the addition of chemicals.  Alkaline wastewaters are typically neutralized by

adding sulfuric or hydrochloric acid, or compressed carbon dioxide.  Acidic

wastewaters may be neutralized with limestone or lime slurries, soda ash, or

caustic soda.  The selection of neutralizing agents depends upon cost,

availability, ease of use, reaction by-products, reaction rates, and

quantities of sludge formed.  The most commonly used chemicals are lime  (to

raise the pH) and sulfuric acid (to lower the pH).
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            Filtration



            Filtration is a separation technology designed to remove solids

from a wastewater stream by passage of most of the wastewater through a septum

or membrane that retains the solids on or within itself.  Filters can be

classified by the following factors:
                  The driving force (i.e., the manner by which the filtrate is
                  induced to flow, either by gravity or pressure);

                  The function (i.e.,  whether the filtrate or the filtered
                  material is the product of greater value);

                  The operating cycle (i.e., whether the filter process occurs
                  continuously or batchwise);

                  The nature of the solids (i.e., the size of the particles
                  being filtered out);  and

                  The filtration mechanism (i.e., whether the filtered solids
                  are stopped at the surface of the medium and pile up to form
                  a filter cake or are trapped within the pores or body of the
                  filter medium).
7.2.16      Disposal of Solid Residue from Treatment



            Many of the wastewater treatment processes discussed in previous

parts of this section generate solid residues (i.e., sludges).   Treatment

processes generating sludges include biological treatment,  chemical

precipitation, and coagulation/flocculation treatment.  Sludge is treated

prior to disposal to reduce its volume and to render it inoffensive (i.e.,

less odorous).  Sludge treatment alternatives include thickening,
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stabilization, conditioning, and dewatering.  Sludge disposal options include




combustion and disposal to land.









            Sludge Treatment Alternatives









            Sludge thickening is the first step in removing water from sludges




to reduce their volume.  It is generally accomplished by physical means,




including gravity settling, flotation, and centrifugation.  Stabilization




makes sludge  less odorous and putrescible, and reduces the pathogenic organism




content.  The technologies available for sludge stabilization include chlorine




oxidation, lime stabilization, heat treatment, anaerobic digestion, and




aerobic digestion.  Conditioning involves the biological, chemical, or




physical treatment of a sludge to enhance subsequent dewatering techniques.




The most common methods used to condition sludge are thermal and chemical




conditioning.  Dewatering is the removal of water from solids to achieve a




volume reduction greater than that achieved by thickening.  This process is




desirable for preparing sludge for disposal and for reducing the sludge volume




and mass to achieve lower transportation and disposal costs.  Some common




dewatering methods include filtration in a vacuum filter, filter press, or




belt filter,  centrifugation, thermal drying in beds, and drying in lagoons.









            Sludge Disposal Alternatives









            Combustion serves as a means for the ultimate disposal of organic




constituents  found in sludge.  Some common equipment and methods used to
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incinerate sludge include fluidized bed reactors, multiple hearth furnaces,




atomized spray combustion, flash drying incineration, and wet air oxidation.




Environmental impacts of combustion technology that should be considered




include discharges to the atmosphere (particles and other toxic or noxious




emissions),  to surface waters (scrubbing water),  and to land (ash).









            The disposal of sludge to land may include the application of the




sludge on land as a soil conditioner and as a source of fertilizer for plants.




This is typically used with sludges from biological treatment systems.  In




addition, sludge can be stockpiled in landfills or permanent lagoons.  In




selecting a land disposal site,  consideration must be given to guard against




pollution of groundwater or surface water supplies.









7.3         TREATMENT PERFORMANCE DISCUSSION









            EPA has collected and evaluated data available on potential BAT




treatment technologies for the pesticide chemicals manufacturing industry.




The following technologies are discussed in more  detail,  specifically in




reference to PAI treatment performance:   carbon adsorption,  hydrolysis,




chemical oxidation/ultraviolet decomposition,  resin adsorption,  solvent




extraction,  distillation,  biological treatment,  oxidation/reduction and




physical separation,  and incineration.
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7.3.1       Carbon Adsorption









            In the pesticide manufacturing industry, activated carbon




adsorption is or has been used to treat PAIs in the following structural




groups:  acetamides, benzonitriles, carbamates, phenols, phosphorodithioates,




pyridines, pyrethrins, s-triazines, tricyclic, toluidines, and ureas.  In




addition, EPA and industry treatability studies have demonstrated sufficient




treatability of pesticides in the acetanilide, terephthalic acid, and uracil




structural groups using carbon to establish this treatment as a basis for




control of specific PAIs in these groups.  Carbon has also been shown in




industry treatability  studies to be an effective polishing control for




thiocarbamate PAIs, although insufficient information currently exists.









            Based on long-term concentration data achieved using activated




carbon adsorption,  the EPA is currently proposing limitations based on




activated carbon adsorption technology for individual PAIs in the following




structural groups:  acetanilides, aryl halides, benzonitrils, bicyclics,




phenols, phosphorothioate compounds, pyrethrins, toluidines, and ureas.




Plants incorporating activated carbon adsorption into their PAI treatment




train  currently achieve an average of 99.97% removal of  the PAI loading from




their  discharge.  These systems currently account for the prevention of the




discharge of approximately 430,000 pounds of pesticide active ingredient per




year.
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            One method of evaluating the performance of a treatment  system  in




removing pesticide active ingredients is to compare the long-term mean




effluent concentration of the PAI in the treated effluent with the detection




limit for the PAI in the sample matrix.  For pesticide active ingredients




treated using activated carbon adsorption in treatment systems achieving BAT




performance levels, the long-term mean to detection limit (LTM/MDL)  ratio




varies from 3.19 to 7.35 (i.e., for these compounds, the average concentration




following treatment ranged from 3.19 to 7.35 times the minimum detection limit




for the compound in the effluent).  The use of this factor allows for the




comparison of different applications of activated carbon treatment.  For




example, a dedicated activated carbon treatment unit prior to dilution at the




process area may achieve excellent percent removals but still have an effluent




concentration orders of magnitude higher than the concentration following




mixing and dilution with non-pesticide contaminated streams.  However, the




minimum detection limit for the process discharge will reflect the ability to




treat and monitor treatment performance levels in the specific matrix, and




therefore indicates the bottom concentration limit at which efficient




treatment system operation can be maintained.









            Data were collected from plant supplied long-term monitoring data,




when activated carbon influent and effluent data were both available, and from




EPA sampling data.   Removal efficiency by group varies from 99.97% for aryl




halides, to 86.3% for pyrethrins.
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            In addition to the PAI being treated, a number of factors can




effect the efficiency of the carbon systems.  Both the efficiency and cost




effectiveness of activated carbon can be enhanced if the carbon treats




wastewater from a single process, and if PAI contaminated and non-PAI




contaminated process streams are further segregated.  This is because of the




types of competitive effects which will occur between adsorption of various




compounds in complex wastewater matrices.   In systems where a dedicated




activated carbon was the first stage used in removing the PAI from the




wastewater, an average of 99.2% removal was achieved across all PAIs.









            When carbon was used as a polishing  treatment following other PAI




removal treatment technologies, the average removal dropped to 84.5%, due to




the greatly reduced initial concentration of PAI.  Also, besides the




competitive effects involved in treating complex matrices with activated




carbon, when the effluent concentration approaches the minimum detection




limit, the calculated removal efficiencies  decrease due to the statistical




effects of analyses below the detection limit.   However, while the calculated




efficiency of removing pesticides from less contaminated streams drops, for




those PAIs using carbon as a polishing step very low effluent concentrations




were achieved in the carbon effluent, with  an average of 8.6 ppb PAI detected.




Therefore, the ratio of average concentration to minimum detection limit is




comparable to that of systems treating more concentrated process streams.









            Using an activated carbon system dedicated to removal of a




specific PAI from the undiluted process discharge will also improve
                                      7-46

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efficiency, as the pH and the rate of carbon bed changes can be optimized to




remove the targeted compound.  For example, for all PAIs being treated in a




process-specific carbon system, average removals of 97.4% were achieved, with




a median of 99.1% removal.  However, when PAI wastewaters were intermingled




prior to carbon adsorption, removal average efficiencies fell to 88.9%, with a




median of 90.0 percent.









            In the case of many of the PAIs which are or have been treated




using carbon, expediency has appeared to drive treatment system selection




rather than optimal system design.  For example, wastewaters from the




manufacture of phenoxy, carbamate, and phosphorothioate PAIs which can be




readily hydrolized at alkaline conditions have been treated using activated




carbon.   Industry-wide, 89.15% removal of phosphorothioates is achieved using




activated carbon in BAT systems;  however, for those phosphorothioates treated




in dedicated systems the removal efficiency through the use of activated




carbon improves to 99.07 percent.   Operating activated carbon treatment




systems have achieved removal efficiencies of 99.87   99.99% for carbamate




PAIs and 99.95% for phenoxy PAIs.   However,  for both of these groups, BAT data




has been collected based on other, less expensive treatment technologies.   In




those cases,  carbon may have been chosen originally because of its ability to




remove other pollutants of concern from the wastewater,  or because of an




incomplete assessment of treatment options.   Due to the cost of carbon




regeneration or replacement the use of activated carbon to treat high volume




streams  is often a more expensive  option than other physical-chemical
                                     7-47

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treatment methods.  Therefore an evaluation of other treatment technologies




may result in a system which provides equal performance at a lower cost.









            Through the use of activated carbon adsorption to comply with the




proposed BAT and  PSES guidelines for organic pesticides chemicals




manufacturers, the EPA estimates that an additional 165,000 pounds of active




ingredient will be eliminated from plant discharges annually.









7.3.2       Hydrolysis









            Hydrolysis has been identified as the most effective technology




for achieving high levels of destruction of pesticide active ingredients in




the carbamates and organophosphate structural groups.  This technology has




been demonstrated at a number of manufacturing facilities, and in both EPA and




industry-supplied treatability studies.









            Depending on the retention time, the temperature, and the pH, PAI




treatment systems based on hydrolysis can have excellent performance.  For




facilities currently including hydrolysis as a stage in their wastewater




treatment system, an average of 99.55% removal of the PAI is achieved through




treatment.  In reviewing current performances by industry in treating




pesticide wastewaters, the EPA has determined that PAI treatment systems




incorporating hydrolysis are responsible for removing approximately 93,700




pounds of pesticide from process discharges each year.  These systems proved




capable of reducing the amount of PAI in wastewater to the extent that the
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average long-term mean effluent concentration for facilities using hydrolysis




as a PAI treatment technology was 2.69 times the minimum detection limit for




the individual PAI.  At many of facilities, no PAI was detected at the




detection limit in more than half the sample results reported.









            The EPA reviewed published sources for information on hydrolysis,




and documented the half-lives and effluent concentrations demonstrated at




different temperatures and pHs.   In these studies, data with both experimental




conditions and half-lives reported were available for 96 of the PAIs covered




in this regulatory study.  Within those,  51 PAIs had demonstrated half-lives




of less than 1 day, 33 had half-lives of less than 1 hour,  and 14 had half-




lives of 10 minutes.   The EPA sponsored treatability studies at more uniformly




controlled conditions on those PAIs which were manufactured in 1986 for which




hydrolysis appeared to be a potential BAT technology, and hydrolysis did prove




highly effective in destroying the targeted PAIs in aqueous solutions.   For 30




of 36 PAIs tested in the phosphate, phosphorothioate, phosphonothioate,  and




carbamate structural groups, a half-lives of less than 1/2 hour was achieved




by treating the PAI at temperatures of 60°C and a pH of 12.  Confidential




industry data also supports the use of hydrolysis for the treatment of a




number of PAIs currently either discharged or deep-well injected untreated,




although this data has generally not contained sufficient detail for




determination of achievable concentration at full-scale systems.









            The EPA is proposing hydrolysis as a technology basis for a number




of PAIs which are not currently treated using this technology, but for which
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treatability studies have demonstrated excellent destruction of the PAI.  It




is estimated that the utilization of hydrolysis to treat these PAIs would




result in the removal of an additional 84,400 pounds of PAI from plant




discharges annually.









7.3.3       Chemical Oxidation/Ultraviolet Decomposition









            Chemical oxidation has been demonstrated by industry to be




effective at destroying alkyl halide, DDT-type, phenoxy, phosphorothioate, and




dithiocarbamate PAIs in manufacturing wastewaters.  For those facilities




currently incorporating chemical oxidation in their PAI treatment train, an




average of 99.42% destruction of PAI is achieved, preventing about 8,300




Ibs/year of PAI from being discharged.









            While PAIs in a number of these groups may be treated using other




technologies, the use of chemical oxidation is an excellent candidate for the




treatment of dithiocarbamate PAIs.  In treatability studies available,




dithiocarbamate PAIs do not appear to be uniformly treatable through the use




of activated carbon adsorption.  Meanwhile, while these compounds are readily




hydrolyzable at acidic conditions, a byproduct of the acidic hydrolysis




reaction is carbon disulfide gas, which could result in dangerous conditions




due to the highly flammable nature of CS2 gas.









            The EPA performed treatability studies on a number of actual




process wastewater samples containing dithiocarbamate PAIs using alkaline
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chlorination as a treatment technology.  All dithiocarbamates tested proved




amenable to destruction through alkaline chlorination.  However, during




sampling at a facility which utilized alkaline chlorination to treat




dithiocarbamate PAIs, the EPA did find that this treatment technology is




capable of generating chlorinated priority pollutants.  Therefore,  in




assessing the economic impacts of the use of alkaline chlorination to treat




dithiocarbamates, the EPA projected the use of steam stripping for the removal




of chlorinated organics.   At the same time, EPA is conducting treatability




studies on technologies which are not currently used in the pesticide




manufacturing industry using ozonation and ultraviolet light (UV) catalyzed




ozonation to initiate oxidation of dithiocarbamates in water.   The use of




ozonation would prevent the generation of halocarbons, and thus eliminate the




need for the use of additional priority pollution control technologies.   The




ozone and UV catalyzed ozone treatability studies conducted so far,  however




have not identified the best treatment conditions.









            The EPA estimates that the use of alkaline chlorination to destroy




dithiocarbamate pesticide active ingredients not currently being treated will




result in the elimination of 5,700 pounds of PAI from plant discharges




annually.









7.3.4       Resin Adsorption









            Resin adsorption is currently used to treat specific pesticide




active ingredients which have not proved amenable to other treatment
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technologies.  The technology is similar to activated carbon, in that the




resin removes the pollutant from the wastewater stream, rather than destroying




it, and therefore will become saturated with the PAI over time.  However,




regeneration of resin can be performed in place by washing the resin with a




solvent designed to dissolve and remove the PAI from the treatment unit.  To




ensure adequate performance, it is critical that the resin be regenerated on a




sufficient frequency.









            BAT treatment systems relying on resin adsorption achieve around




97% removal of the pesticide active ingredient from the water achieve very low




discharge concentrations ranging from 3 to 32 ppb PAI in the treated effluent.




BAT is being proposed based on resin adsorption for those PAIs for which




actual plant operating data on resin adsorption is available.  Because this




technology is very specific to both the PAI and the wastewater matrix being




treated (high levels of other contaminants can quickly foul resins and degrade




performance), EPA did not select resin adsorption as a BAT technology for




those PAIs where no plant performance data currently exists.









7.3.5       Solvent Extraction









            Solvent extraction is used by a number of facilities to remove




PAIs from high concentration process brines, either prior to additional




treatment or by itself.  As the use of solvent extraction on wastewaters prior




to discharge from the manufacturing unit is often considered a process stage




rather than a treatment stage, long-term data does not exist on the treatment
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performance of these systems.  During EPA sampling episodes, the influents and




effluents from many solvent extraction systems were sampled; an average PAI




removal of 86.1% was achieved.









            There were wide differences in performance,  as percent removals




ranged from 58% to 99.85%, while achievable concentrations ranged from less




than 9 ppb up to 50 ppm for individual units.  This variation has to do with




the mechanism of solvent extraction, the solvents used and PAIs removed,  as




well as the design factors (contacting method, decanting method,  etc.) for




each unit.  Solubility has the greatest impact on the system performance,  as




the minimum achievable concentration of PAI in the wastewater is  a function of




the solubility of the PAI in both the water and the solvent.  If the solvent




extraction system has sufficient contact time between the solvent and the




wastewater, a very consistent effluent concentration will be achieved, as the




system will reach an equilibrium between the PAI concentration in the




wastewater and solvent phases.  The EPA received data on one PAI  which




demonstrated that solvent extraction alone,  without other downstream treatment




technologies, could achieve BAT performance levels.   Because sufficient




contact time must be maintained to ensure optimal system performance, the EPA




has projected costs for additional equalization capacity for those facilities




expected to comply with BAT/PSES guidelines through the  use of existing




solvent extraction systems.









            EPA estimates that through the use of equalization to enhance




existing solvent extraction systems, approximately 100 pounds of  PAI discharge
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will be eliminated per year, and wide variations in effluent loadings would be




eliminated.









            As the effective use of solvent extraction as a treatment stage is




highly dependent on the configuration of the process and the type of PAI, the




EPA is not proposing solvent extraction as a technology basis for any PAIs not




currently being treated through extraction.  However, in a proper application




solvent extraction has the  potential for reducing the loading to other




treatment systems, as well  as  to achieve economic benefits through the




recovery of product and raw materials.









7.3.6       Distillation









            Distillation  is the separation of  the constituents in a wastewater




stream by partial vaporization of  the mixture  and separate recovery of vapor




and residue.   The main use  of  distillation in  pesticide manufacturing




operations  is  in the separation of alcohols used in the manufacture of esters




of phenoxy-based PAIs from  wastewaters.  The alcohols can then be reused in




future manufacturing, while the wastewater, once separated from alcohols and




solvents,  can  be reused in  the manufacture of  salts of phenoxy PAIs, or  in




phenoxy product formulations.  In  this process, the phenoxy ester product is




heated, driving off the alcohol and water, and the alcohol is then condensed




separately  from the water.  Currently operational systems have demonstrated




the ability to generate a water stream containing the phenoxy product which is




almost completely free of alcohol, and can therefore either alone or through
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blending meet the water specifications necessary for use in product




formulations.









            For non-phenoxy PAIs, distillation has been used to separate water




from pesticide process streams as a final purification stage.  Although the




purity of the distillate will be a function of the volatility of the PAI,  the




distilled wastewater will normally contain no detectable concentrations of the




PAI.  The remaining solution can then be recycled into the process, or




disposed as a hazardous waste.









            The EPA received no effluent monitoring data for use in evaluating




the performance of systems using distillation to eliminate the discharge of




pesticide wastewaters.  In systems where distillation and complete recycle is




practiced, no wastewater is discharged from the process,  and therefore no




monitoring is required.  For those facilities relying on distillation to




separate PAI from the wastewater so that the water may be discharged,




monitoring pesticide concentrations in the wastewater is not currently




required.









7.3.7       Biological Treatment









            In the case of one pesticide active ingredient,  biological




treatment has  been demonstrated to achieve PAI removal levels characteristic




of BAT performance.  This facility currently achieves removals of greater  than




98% PAI during biological oxidation,  discharging less than 0.5 pounds of PAI
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in wastewater per million pounds of PAI manufactured.  However, few PAIs




demonstrate this amount of biodegradability.  This level of success using




biological treatment in treating pesticide wastewaters required the proper




acclimatization of the biomass to the PAI being controlled, as well as




significant attention to design and maintenance of proper hydraulic loading




rates to the biological treatment system.









7.3.8       Oxidation/Reduction and Physical Separation









            For wastewaters contaminated with pesticides based on metal ions,




removal of the PAI can often be best achieved through the addition of




chemicals which enhance the ability of the PAI to be removed through physical




separation technologies such as settling or filtration.  In the case of




wastewaters containing tri-organotin compounds, this can be achieved through




reacting the organotin complex with an oxidizing agent, thereby creating a tin




molecule which will settle out as a solid.  In addition, the oxidizing agents




may react with other metals in the wastewater, thereby creating other




insoluble metal complexes which will scavenge unoxidized organotin compounds




during settling.  Removal of organotins can also be enhanced through the use




of cationic polymers in combination with the oxidation step.









            Industry treatability and operating data demonstrates that




oxidation/settling is an effective method for treating tri-organotin




compounds.  Removal efficiencies of up to 99.5% have been achieved on a long-




term basis using this technology.
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7.3.9       Incineration









            A number of pesticide manufacturing facilities currently utilize




on-site incineration as the primary method for disposing of all PAI




contaminated wastewaters.  Properly operated incineration systems can be




capable of achieving virtually 100% destruction of the PAI in wastewater




streams.  While the PAIs and other pollutants of concern are completely




destroyed, an effluent stream is generated from the scrubber on the




incinerator overheads.  At some facilities, the incinerators do not achieve




100% efficiency, and trace amounts of PAI remain in the scrubber discharge.




EPA estimates that approximately 4,000 pounds of PAI are destroyed annually




through on-site incineration of PAI manufacturing wastewater.









7.4         EFFLUENT LIMITATIONS DEVELOPMENT FOR PAIs









            This section discusses the development of effluent limitations




guidelines and standards for PAIs in Subcategory A of the pesticide chemicals




manufacturing industry.  This section also presents those cases where




limitations requiring no discharge of process wastewater pollutants have been




proposed and discusses options available for compliance with proposed zero




discharge standards.









            EPA identified two regulatory options for consideration to reduce




the discharge of PAIs by organic pesticide manufacturers.  Option 1 would base




BAT,  NSPS, PSES and PSNS limitations on the efficacy of hydrolysis, activated
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carbon, chemical oxidation, resin adsorption, biological treatment, solvent

extraction, and/or incineration to control the discharge of PAIs in

wastewater, as demonstrated by either industry monitoring data or by

treatability studies.  Option 2 would require zero discharge of pesticide

manufacturing wastewater pollutants by PAI manufacturers, based on the use of

on-site or off-site incineration and/or recycle and reuse.



            EPA is proposing BAT, NSPS, PSES, and PSNS limitations for

Subcategory A plants based upon Option 1.  As discussed'elsewhere in this

section, the identified BAT control technologies achieve a high level of

pesticide pollutant removal while avoiding cross-media transfer of pollutants.

A zero discharge requirement is also proposed for certain PAIs under Option 1

where zero discharge has been demonstrated to be achievable through water

reuse or the lack of water use.  The Agency proposes to reject the second

option, zero discharge of all pesticide manufacturing wastewater pollutants,

because of the cross-media implications of the transfer of pollutants as well

as the severe economic impacts that would result from implementing this

option.



            Sections 7.4.1 through 7.4.6 provide a detailed discussion of the

steps  followed in the determination of effluent limitations guidelines and

standards for PAIs.  These steps include:
             7.4.1        Statistical  analysis of long-term self-monitoring
                         data;
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            7.4.2       Calculation of effluent limitations guidelines under
                        BAT;

            7.4.3       Calculation of effluent limitations guidelines under
                        NSPS;

            7.4.4       Analysis of POTW pass-through for PAIs;  and

            7.4.5       Calculation of effluent limitations guidelines under
                        PSES and PSNS.
            Where long-term self-monitoring data are available, the

calculation for the daily production-based limitation was performed by:

(1) fitting daily PAI concentration data to a modified delta-lognormal

distribution, the same statistical procedure that was used in the OCPSF

rulemaking, (2) estimating the 99th percentile of PAI concentration from the

fitted distribution of daily concentration measurements,  (3) multiplying the

estimated 99th percentile of concentration by daily average flow, and

(4) dividing the result by daily average production to give the daily

production-based limitation.  The 4-day average production-based limitation

was calculated similarly except that, by definition for 4-day average

limitations, the 95th percentile of the distribution of 4-day average values

was substituted for the 99th percentile of daily concentration measurements.

The 4-day average is equivalent to the monthly average because EPA is

proposing weekly (four times per month) monitoring to demonstrate compliance.

These procedures are discussed in the following section.
                                     7-59

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7-4.1       Statistical Analysis of Long-Term Self-Monitoring Data



            This subsection describes the statistical approach that was

applied to the industry-submitted long-term pesticides pollutant data to

estimate long-term averages and variability factors.



            Many manufacturers who responded to the Facility Census submitted

data on concentrations of PAIs measured  in process wastewater.  To develop

concentration-based  limitations and variability factors, EPA modeled the

concentration data for each plant-PAI combination using a modification of the

delta-lognormal distribution.  This distribution was chosen because the data

for most PAI's consisted of a mixture of measured (i.e., detected) values and

nondetects.  The modified delta-lognormal assumes that all nondetects occur at

the detection limit  and that the measured concentrations follow a lognormal

distribution (i.e.,  the logarithms of the measured data are normally

distributed).  The modified delta-lognormal1 distribution is identical to a

lognormal  distribution if there are no nondetects in the data.



            The mean, variance, 99th percentile, daily variability factor, and

the four-day variability factor were estimated by fitting the concentration

data to the modified delta-lognormal distribution.  The estimated 99th

percentile of the distribution provides  the concentration-based daily maximum

limitation for each  plant-PAI combination.  The daily variability factor is a
      'This modification of the delta-lognormal distribution was used by EPA in
establishing  limitations  for the  Organic  Chemicals,  Plastics,  and  Synthetic
Fibers point  source  category.
                                      7-60

-------
statistical quantity that is defined as the ratio of the estimated 99th

percentile of a distribution divided by the expected value of the

distribution.  Similarly, the four-day variability factor is defined as the

estimated 95th percentile of the distribution of four-day means divided by the

expected value of the four-day mean.



            The modified delta-lognormal model is a mixture distribution in

which all the detected concentrations follow a standard lognormal distribution

(i.e., the logarithm of the concentration is normally distributed with mean n

and standard deviation a),  and all the nondetects are assumed to have a

concentration value equal to the detection limit.  The cumulative distribution

function, which gives the probability that an observed concentration (C) is

less than or equal to some specified level (c),  can be expressed as a function

of the following quantities:



            D     =     the detection limit,

            5     =     the probability of a nondetect,

            I(c-D)   =  an indicator function which equals 1 for c>D and 0
                        otherwise,

            H     =     the mean of the distribution of log transformed
                        concentrations,

            a     =     the standard deviation of the distribution of log
                        transformed concentrations,

            y     =     variable of integration.
                                     7-61

-------
The equation of  the  cumulative distribution function is as follows
            F(c)  = P(csc) = 6l(c-D)  + (i-d)
 1— flexpf-
2^H y  *A
                                                           2a2
             The  expected value E(C) of the concentration under  this


distribution function is given by
                                = 6ZH(l-*)exp||i+-^|,                        (2)
and the variance V(C)  is given by the following expression:
                                                                   02       (3)

        V(C) = (1-6) exp (2jn-a2) [exp  (o2)-(l-5)] + 6 (1-6) D[£>-2exp (|i + i-)].
                                                                    lO
The 99th  percentile of the distribution can be expressed  in  terms  of p,  a,  and


the inverse  normal cumulative distribution function  ($"') , as follows:
                                      7-62

-------
Finally, the daily variability factor VF(1) is defined as  the  99th  percentile




divided by the mean:
                                 VF(l) =
            To estimate daily variability factors for each plant-PAI dataset,




the following calculations were performed.  The estimate, /t, of the log mean




was calculated by taking the arithmetic average of the log transformed




detects.  The estimate, a, of the log standard deviation was calculated by




taking the sum of the squared differences between the log concentrations and




/t, divided by the number of detects minus one.  The estimated probability of a




nondetect, S, was calculated by dividing the number of nondetects by the




number of observations .  These quantities were then substituted into equations




(2) and (4) to give estimates E(C) and C,, of the mean concentration and the




99th percentile, respectively.  Finally, the resulting estimated mean and 99th




percentile were substituted into equation (5) to yield the daily variability




factor estimate,
            The daily variability factor multiplied by the long-term mean




yields the value used by EPA as the daily maximum limitation.  An analogous




measure of the maximum limitation for the average (or mean) of four daily




concentration measurements can also be defined and estimated from the data.




The definition of the four-day variability factor, VF(4) ,  is the 95th
                                     7-63

-------
percentile of the distribution  of  four-day means,  divided by  the  expected




value of four-day means.









            The value  of VF(4)  can be  estimated from the daily  concentration




data by exploiting  the statistical properties  of the four-day mean,  C4, and




approximating the distribution  of  C4 by the modified delta-lognormal model




(this approximation can be  shown to be close  to the  actual  distribution).   To




develop the estimate of VF(4),  first note that the logarithm  of C4 is normally




distributed with unknown mean and  standard deviation denoted  by fj,4 and OA,




respectively.  Also, E(C4) = E(C) because the  expected value  of a sum of




random variables divided by a constant is equal to the  sum of their




expectations  divided by that constant.  And V(C4) = V(C)/4 because the




variance  of a sum  of independent random variables divided  by  a  constant  is




equal  to  the  sum of their variances divided by the square  of  that constant.




Finally,  the  probability  that C4 is  a  nondetect  is 6",  since the mean of  four




independent concentrations  is a nondetect only if all four are  nondetects,  and




the probability  of this occurring  is equal to the product  of  the  component




probabilities,  or  8* if the  daily  nondetect probability is S.









            The  following equations therefore hold:
                           = E(C) =
                                      7-64

-------
          i
    V(C4) =-^(C)=(l-54)exp(2ji4+a42) (exp (042)
          4t




and






                      C95(4) ^ma
                                        2 -  -
            Equations  (6) and  (7)  can be  algebraically solved for cr4  in  terms



of the mean and variance of the daily concentrations,  the probability of a



nondetect, and the detection limit.   This expression is as follows:
                                                                           (9)

                            ~42         42      -
To derive an estimate, a4,  of the left-hand side of equation (9), each



quantity on the right-hand side was replaced by  its  estimate  computed from the



daily concentration data; i.e., E(C) was  replaced by E(C) ,  V(C)  by  'fr(C) ,  and S



by 5.  Next, the estimated cr4 together with S and E(C) were substituted into



(6), which was solved to yield an estimate jj,A of /*4.    Finally, /j,4 and <74 in (8)



were replaced by their estimates to yield an estimated value  of  the 95th



percentile of the distribution of the  four- day mean,  and this  estimate  was



divided by E(C) to give the estimated  variability factor
            Most plants provided a single  detection limit  for each PAI .



However, seven plant-PAI combinations reported multiple  detection limits.



Because the modified delta- lognormal distribution is based on a single
                                      7-65

-------
detection Limit, EPA had to select the detection limit to be used for the




statistical analyses in these cases.









            When multiple detection limits were reported for a plant-PAI




dataset, the detection limit associated with the greatest number of nondetects




was used to estimate limitations.  Daily limitations would not have changed




significantly if alternative detection limits had been selected.  This can be




seen by examining equation  (4), which shows that the daily limitation equals




the maximum of  two  terms:   detection limit D, and a second term independent of




D.  When this equation was  evaluated, the second term exceeded D for all




alternative detection limits,  showing that the daily limitation was




independent of  the  detection limit.









            The estimated four-day limitation value is affected, but only




minimally, by the choice of detection limit, as seen by equation (8), which




shows  that the  limitation is the maximum of two terms:  the detection limit D,




and a  second term that is itself a function of D.  To determine how the four-




day limitation  values vary  with changes in D, they were calculated for each




reported alternative detection limit.  The results showed that the four-day




limitation is highly insensitive to changes in the assumed detection limit.









            A change in detection limit affects the values of both the daily




and four-day variability factors, which are defined as the ratios of the




respective limitations to the mean concentration.  The numerator of the ratio




for the daily variability factor does not depend on D, but the denominator
                                      7-66

-------
 (see equation  (2)) is an increasing function of D.  This means that selection

 of a higher detection limit would have resulted in a lower estimated daily

 variability factor.



            Changes in detection limit have a lesser effect on estimated four-

 day variability factors than on daily variability factors, because both the

 numerator and  denominator of the four-day variability factor ratio increase

 when D increases.



 7.4.2       Calculation of Effluent Limitations Guidelines Under BAT



            The Agency based BAT limitations for organic PAIs on the

 performance of hydrolysis,  activated carbon, chemical oxidation,  biological

 treatment, solvent extraction,  resin adsorption, and/or incineration treatment

 systems.  Limitations development was based on:
                  Long-term data obtained on PAIs with BAT performance data;
                  and

                  The transfer of statistical data in combination with the
                  results of treatability studies for PAIs for which there are
                  no BAT performance data.
Where long-term data were available, production-based mass limitations were

calculated using daily average production (in pounds per day) and mass

discharge.  For the PAIs without BAT treatment performance data, BAT treatment

performance for PAIs having similar chemical structures were established and
                                     7-67

-------
then compared for applicability.  Effluent limitations were generated for the

PAIs for which there were no performance data by:
                  Setting achievable concentrations for each structural group
                  and technology performance based on treatability study
                  results;

                  Applying variability factors for each structural group and
                  for each technology; and

                  Determining mass discharge allowances based on long-term
                  average flow and annual production levels.
            EPA identified  69 PAI  structural groups.  These groups and the

PAIs in them are listed  in  Table 7-2.  The Agency is proposing numerical and

zero discharge limits  for 93 PAIs  and  salts and esters of PAIs in 33 of these

groups.  These PAIs and  groups are listed in Table 7-3.  Fifteen of these PAIs

and salts and esters are receiving zero discharge limitations because there

are plants manufacturing these pesticides who are currently achieving zero

discharge.  The zero discharge technologies in-place at the BAT facilities for

these PAIs include dry manufacturing processes, manufacturing processes which

do not discharge wastewater, recovery  and reuse of wastewater, on-site

incineration of wastewater, and distillation of wastewater for reuse.

Numerical limitations  are being proposed for the remaining 78 PAIs and salts

and esters.  Of these  78 PAI groups, 62 are associated with plants that have

full-scale treatment systems in place.



            The Agency based BAT limitations for these 62 PAIs on actual data

of PAI concentrations  in wastewaters treated by the full-scale BAT treatment
                                      7-68

-------
     Table  7-2




PAI STRUCTURAL GROUPS
Structural Group
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
Acetamide
Acetamide
Acetamide
Acetanilide
Acetanilide
Acetanilide
Acetanilide
Alcohol
Alkyl Acid
Alkyl Halide
Alkyl Halide
Alkyl Halide
Aryl
PAI #
14
15
15
16
16
17
27
30
31
34
46
47
238
115
136
242
26
54
70
165
36
227
81
92
160
67
PAI Name
2,3,6-T, S&E
2,4,5-T
2,4,5-T, S&E
2,4-D, S&E
2,4-D
2,4-DB, S&E
MCPA, S&E
Dichlorprop, S&E
MCPP, S&E
Chlorprop , S&E
CPA, S&E
MCPB, S&E
Silvex
Diphenamide
Fluor oacetamide
Sodium fluoroacetate
Propachlor
Alachlor
Butachlor
Metolachlor
HAE
Propionic acid
Chloropicrin
Dalapon
Methyl bromide
Biphenyl
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
No Discharge
Numerical
No Discharge
No Discharge
No Discharge
No Discharge
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved (PP Reg)
No Discharge
        7-69

-------
 Table 7-2




(Continued)
Structural Group
Aryl Amine
Aryl Halide
Aryl Halide
Aryl Halide
Aryl Halide
Aryl Halide
Aryl Halide
Benzeneamine
Benzoic Acid
Benzoic Acid
Benzonitrile
Benzonitrile
Bicyclic
Bicyclic
Bicyclic
Bicyclic
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
PAI #
116
20
80
98
110
129
205
204
53
78
69
69
123
123
177
262
13
38
40
42
48
55
61
62
75
76
PAI Name
Diphenylamine
Dichloran
Chloroneb
Dicamba
DCPA
Chlorobenzilate
PCNB
Pendimethalin
Acifluorfen
Chloramben
Bromoxynil
Bromoxynil octanoate
Endothall
Endothall, S&E
MGK 264
Toxaphene
Landrin 2
Landr in 1
Methiocarb
Polyphase
Aminocarb
Aldicarb
Bendiocarb
Benomyl
Carbaryl
Carbofuran
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved
Numerical
Reserved
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved
No Discharge
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
    7-70

-------
 Table 7-2




(Continued)
Structural Group
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate/Urea
Chlorobenz amide
Chlorophene
Chlorophene
Chlorophene
Chloropropionanilide
Chloropropionanilide
Coumarin
Coumarin
Cyclic Ketone
DDT
DDT
DDT
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
PAI #
77
95
100
145
156
166
170
195
260
272
146
39
9
10
11
41
82
43
265
91
1
101
158
23
87
102
PAI Name
Carbosulfan
Desmedipham
Thiophanate ethyl
Propham
Me thorny 1
Mexacarbate
Napropamide
Oxamyl
Thiophanate methyl
Chloropropham
Karbutilate
Pronamide
Hexachlorophene
Tetrachlorophene
Dichlorophene
Propanil
Chlorothalonil
Coumafuryl
Warfarin
Cycloheximide
Dicofol
Perthane
Methoxychlor
Sulfallate
Mancozeb
EXD
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
   7-71

-------
 Table 7-2




(Continued)
Structural Group
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
EDB
EDB
EDB
Ester
Ester
Ester
Ester
HCp
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
Heterocyclic
PAI #
134
151
152
167
172
218
219
220
241
243
261
267
268
3
5
97
64
117
157
216
93
28
32
35
49
175
FAI Name
Ferbam
Maneb
Manam
Metiram
Nab am
Bus an 85
Bus an 40
KN Methyl
Carbarn- S
Vapam (Metham Sodium)
Thiram
Zineb
Ziram
EDB
Dichloropropene
DBCP
Benzyl benzoate
MGK 326
Methoprene
Piperonyl butoxide
Dienochlor
Octhilinone
Thiabendazole
TCMTB
Etridiazole
Norflurazon
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Numerical
Reserved
No Discharge
    7-72

-------
 Table 7-2




(Continued)
Structural Group
Heterocyclic
Heterocyclic
Heterocyclic
Hydrazide
Iminamide
Indandione
Isocyanate
Lindane
Lindane
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
PAI #
210
240
259
2
59
114
118
63
147
21
29
37
71
90
96
153
164
196
201
209
214
221
225
228
235
244
PAI Name
Nemazine
Sodium bentazon
Dazomet
Maleic Hydrazide
Amitraz
Diphacinone
Nabonate
BHC
Lindane
Bus an 90
Pindone
Chlorophacinone
Giv-gard
Fenvalerate
Amobam
Mefluidide
Quinomethionate
Oxyfluorfen
Propoxur
Phenmedipham
Phosphamidon
Metasol J26
Propargite
Previcur N
Rotenone (Mexide)
Sulfoxide
Limit Type
Reserved
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
   7-73

-------
 Table 7-2




(Continued)
Structural Group
Miscellaneous
Miscellaneous
NR4
NR4
NR4
NR4
NR4
NR4
NR4
NR4
! NR4
Nitrobenzoate
Organoantimony
Organoarsenic
Organoarsenic
Organoarsenic
Organoarsenic
Organocadmium
Organocopper
Organocopper
Organocopper
Organomercury
Organotin
Organozinc
Phenol
PAI #
269
270
7
56
105
120
121
149
159
162
217
66
273
6
72
161
188
189
88
89
190
191
192
266
44
PAI Name
Triallate
Phenothrin
Dowicil 75
Hyamine 3500
Benzethonium chloride
Metasol DGH
Dodine
Malachite Green
Methyl benzethonium
chloride
Hyamine 2389
PBED (Bus an 77)
Bifenox
Or gano -Antimony
Thenarsazine Oxide
Cacodylic acid
Monosodium methyl
arsenate
Organo- Arsenic
Organo - Cadmium
Bioquin (Copper)
Copper EDTA
Organo -Copper
Organo -Mercury
Or gano -Tin
Zinc MBT
DNOC
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
    7-74

-------
 Table 7-2




(Continued)
Structural Group
Phenol
Phenol
Phenol
Phenol
Phenol
Phenylcrotonate
Phophorothioate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphonate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
PAI #
112
206
206
211
258
19
94
12
22
24
84
108
109
173
111
128
138
138
139
52
143
154
106
113
126
127
PAI Name
Dinoseb
PCP; sodium salt
PCP
Phenylphenol
Tetrachlorophenol
Dinocap
Demeton
Dichlorvos
Mevinphos
Chlorfenvinfos
Stirofos
Dicrotophos
Crotoxyphos
Naled
Trichlorofon
Fenamiphos
Glyphosate, S&E
Glyphosate
Glyphosine
Acephate
Isofenphos
Methamidophos
Dimethoate
Dioxathion
Ethion
Ethoprop
Limit Type
Numerical
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
No Discharge
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
No Discharge
Reserved
Reserved
No Discharge
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved
   7-75

-------
 Table 7-2




(Continued)
Structural Group
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
PAI #
150
155
183
185
185
185
186
197
199
200
212
213
251
255
85
86
103
107
131
133
179
180
181
182
FAI Name
Malathion
Methidathion
Disulfoton
Pho sine t , s ingl e
crystallized
Phosmet, double
crystallized
Phosmet
Azinphos Methyl
(Guthion)
Bolstar
Santox (EPN)
Fonofos
Phorate
Phosalone
Bensulide
Terbufos
Chlorpyrifos methyl
Chlorpyrifos
Diazinon
Parathion methyl
Famphur
Fenthion
Sulfotepp
Aspon
Coumaphos
Fensulfothion
Limit Type
Numerical
Reserved Not Mfg in 1986
Numerical
No Discharge
No Discharge
Reserved
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
    7-76

-------
 Table 7-2




(Continued)
Structural Group
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorotrithioate
Phosphorotrithioate
Phthalamide
Phthalimide
Phthalimide
Phthalimide
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyridine
Pyridine
Pyrimidine
Quinolin
PAI #
184
187
198
203
222
234
253
236
263
176
73
74
137
57
208
229
230
231
232
233
271
275
215
215
132
50
PAI Name
Fenitrothion
Oxydemeton methyl
Suprofos oxon
Parathion ethyl
Profenofos
Fenchlorphos (Ronnel)
Temephos
DBF
Merphos
Naptalam
Captafol
Cap tan
Folpet
Allethrin
Permethrin
Pyrethrin coils
Pyre thrum I
Pyre thrum II
Pyrethrins
Resmethrin
Tetramethrin
Pyrethrin I & II
Picloram
Picloram
Fenarimol
Ethoxyquin
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Numerical
Numerical
Reserved
No Discharge
Reserved
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
No Discharge
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved
Numerical
Reserved Not Mfg in 1986
   7-77

-------
 Table 7-2




(Continued)
Structural Group
Quinolin
Quinone
Sulf anil amide
Sulfonamide
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiocyanate
Thiocyanate
Thiosulphonate
Toluamide
Toluidine
Toluidine
Toluidine
Toluidine
Triazathione
Tricyclic
Tricyclic
Tricyclic
Tricyclic
Uracil
Uracil
PAI #
51
99
194
207
130
141
245
246
247
248
249
65
163
250
171
125
144
178
264
45
79
122
124
140
68
68
PAI Name
Quinolinol sulfate
Dichlone
Oryzalin
Perfluidone
Butylate
Cycloprate
Cycloate
EPTC
Molinate
Pebulate
Vernolate
Le thane 60
Nalco D-2303
HPTMS
Deet
Ethalfluralin
Isopropalin
Benfluralin
Trifluralin
Metribuzin
Chlordane
Endosulfan
Endrin
Heptachlor
Bromacil; lithium salt
Bromacil
Limit Type
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved Not Mfg in 1986
Reserved
Reserved
Reserved
Numerical
Numerical
Numerical
Numerical
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Numerical
No Discharge
Numerical
    7-78

-------
 Table 7-2




(Continued)
Structural Group
Uracil
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
Urea
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
PAI #
254
83
104
119
135
148
168
169
174
237
252
4
8
18
25
33
58
60
142
223
224
226
239
256
257
PAI Name
Terbacil
Chloroxuron
Diflubenzuron
Diuron
Fluometuron
Linuron
Monuron TCA
Monuron
Norea
Siduron
Tebuthiuron
Vancide TH
Triadimefon
Anilazine
Cyanazine
Belclene 310
Ametryn
Atrazine
Hexazinone
Prometon
Prometryn
Propazine
Simazine
Terbuthylaz ine
Terbutryn
Limit Type
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved
Numerical
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Reserved Not Mfg in 1986
Numerical
Reserved
Numerical
Reserved Not Mfg in 1986
Numerical
Reserved Not Mfg in 1986
Numerical
Numerical
Reserved
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
   7-79

-------
                               Table 7-3




PAIs AND PAI STRUCTURAL GROUPS WITH PAI LIMIT DEVELOPMENT METHODOLOGIES
Structural Group
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
2,4-D
Acetanilide
Acetanilide
Acetanilide
Aryl
Aryl Halide
Aryl Halide
Aryl Halide
Benzeneamine
Benzoic Acid
Benzonitrile
Benzonitrile
BIcyclic
Bicyclic
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Chlorobenz amide
Chloropropionanilide
PAI #
16
16
17
27
30
31
26
54
70
67
80
110
205
204
53
69
69
123
262
55
62
75
76
156
39
41
PAI Name
2,4-D
2,4-D, S&E
2,4-DB, S&E
MCPA, S&E
Dichlorprop, S&E
MCPP, S&E
Propachlor
Alachlor
Butachlor
Biphenyl
Chloroneb
DCPA
PCNB
Pendime thai in
Acifluorfen
Bromoxynil
Bromoxynil octanoate
Endothall, S&E
Toxapbene
Aldicarb
Benomyl
Carbaryl
Carbofuran
Me thomyl
Pronamide
Propanil
Limit Type
Numerical
No Discharge
No Discharge
No Discharge
No Discharge
No Discharge
Numerical
Numerical
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
CO
DIS/REC/ND
DIS/REC/ND
DIS/REC/ND
ND
DIS/REC/ND
AC
AC
AC
ND
CO
AC, BO
AC
IN
HD
AC
AC
ND
AC
HD
HD
HD
HD
HD
AC
BO
                                  7-80

-------
 Table 7-3




(Continued)
Structural Group
Chloropropionanilide
DDT
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Heterocyclic
Heterocyclic
Heterocyclic
Isocyanate
Miscellaneous
Organotin
Phenol
Phosphate
Phosphate
Phosphate
Phosphate
Phosphor oamidate
Phosphoroamidothioate
Phosphoroamidothioate
Phosphorodithioate
Phosphor odithioate
Phosphorodithioate
Phosphorodithioate
PAI #
82
158
172
218
219
220
241
243
35
175
259
118
90
192
112
12
22
84
173
138
52
154
113
126
150
183
PAI Name
Chlorothalonil
Methoxychlor
Nab am
Bus an 85
Bus an 40
KN Methyl
Garb am -S
Vapam (Metham Sodium)
TCMTB
Norflurazon
Dazomet
Nabonate
Fenvalerate
Organo-Tin
Dinoseb
Dichlorvos
Mevinphos
Stirofos
Naled
Glyphosate, S&E
Acephate
Methamidophos
Dioxathion
Ethion
Malathion
Disulfoton
Limit Type
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
No Discharge
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
BO
CO
CO
CO
CO
CO
CO
CO
HD
DIS/REC
CO
CO
HD, BO, SE
CO, CL
AC
HD
HD
HD
ND
ND
IN
HD, AC
HD, AC
AC
HD
HD, BO, AC
   7-81

-------
 Table 7-3




(Continued)
Structural Group
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphor otrithioate
Phosphorotrithioate
Phthalimide
Pyrethrin
Pyrethrin
Pyrimidine
Toluidine
Toluidine
Toluidine
Toluidine
Triazathione
Tricyclic
Tricyclic
Uracil
PAI #
185
185
186
197
212
255
86
103
107
133
182
203
236
263
73
208
230
132
125
144
178
264
45
124
140
68
PAI Name
Phosmet, double crystallized
Phosmet, single crystallized
Azinphos Methyl (Guthion)
Bolstar
Phorate
Terbufos
Chlorpyrifos
Diazinon
Parathion methyl
Fenthion
Fensulfothion
Parathion ethyl
DEF
Merphos
Captafol
Permethrin
Pyre thrum I
Fenarimol
Ethalfluralin
Isopropalin
Benfluralin
Trifluralin
Metribuzin
Endrin
Heptachlor
Bromacil
Limit Type
No Discharge
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
No Discharge
Numerical
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
ND
ND
HD, BO, AC
HD, BO, AC
IN
IN
CO
AC
HD, BO
HD, AC
HD, BO, AC
HD, BO
HD, BO, AC
HD, BO, AC
IN
AC, RA
IN
IN
AC
IN
AC
AC
HD, AC
RA
RA
AC
    7-82

-------
                                         Table 7-3

                                        (Continued)
Structural Group
Uracil
Uracil
Urea
Urea
Urea
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
s-Triazine
PAI #
68
254
119
148
252
8
25
58
60
223
224
226
239
256
257
PAI Name
Bromacil; lithium salt
Terbacil
Diuron
Linuron
Tebuthiuron
Triadimefon
Cyanazine
Ametryn
Atrazine
Prometon
Prometryn
Propazine
Simazine
Terbuthylazine
Terbutryn
Limit Type
No Discharge
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
Numerical
BAT
Technology
ND
AC
AC, BO
AC, BO
IN
HD, AC
HD, BO
AC
HD, BO
AC
AC
AC
AC
AC
AC
AC = Activated Carbon
BO = Biological Oxidation
CL = Clarification
CO = Chemical Oxidation
DIS = Distillation
HD = Hydrolysis
IN = Incineration
ND = No  Discharge
RA = Resin Adsorption
REC = Recycle
SE = Solvent Extraction
                                           7-83

-------
systems operated at BAT levels at these plants, when such full-scale data were




available.  In some cases, pilot-scale data for BAT treatment systems were




used when data from the full-scale systems were not available.  In other




cases, data were available for PAIs manufactured by plants that had full-scale




treatment systems in-place, but the treatment  systems were not achieving BAT




treatment levels in final effluent.  At some plants this was due to design




factors such as equalization  capacity, or due  to operational factors such as




reagent addition or carbon bed regeneration rate, which resulted in less than




optimum treatment system performance.  In these cases, E-PA based BAT limits on




treatability study data demonstrating the achievable optimum performance.  At




other plants,  the BAT  treatment was not applied to all the process wastewater




streams generated during the  manufacture of a  particular PAI.  In these cases,




EPA based BAT  limits on the full-scale treatment data extrapolated to cover




all process wastewater streams.









            BAT treatment system data were not available for 16 of the 78




PAIs.  For  15  of these PAIs,  short-term treatability study data were used in




combination with variability  factors transferred from plants operating full




scale  systems  with  the same BAT treatment technologies.  For the remaining PAI




group  (pyrethrins), the Agency  is proposing zero discharge limitations based




on off-site incineration.  Given the high toxicity of pyrethrins and the




relatively  low wastewater flow  rates generated during pyrethrin manufacture,




off-site  incineration  is  the  most economical treatment option.
                                      7-84

-------
            More specifically, for each of the 62 PAI groups mentioned above,




control technologies (including process controls and wastewater treatment




systems) are already in place in at least one plant which manufactures the




PAI.  For 47 of these PAIs, sufficient full-scale data are available,




including mass discharge rates and production rates, to develop BAT mass-based




limitations.  Daily maximum and four-day maximum average discharge limitations




were based on achievable effluent concentrations demonstrated by in-place and




currently-operating BAT treatment, i.e., the results of plant self-monitoring.




The achievable daily maximum and four-day maximum average concentrations were




then multiplied by average long-term flow rates to determine the long-term




mass discharge of PAI,  and then divided by long-term production rates to




generate discharge limitations based on the production of the specific PAI.




Flow and production data were obtained,  in order of preference,  from available




data either supplied with the self-monitoring data set,  from 1986 or 1977




Section 308 census data submissions,  or from EPA sampling data or site visit




reports.









            For six of the PAIs manufactured at plants with BAT-type




technology in-place, BAT limitations are based on structurally similar (and




analytically indistinguishable) PAIs manufactured at the plants.  For example,




one facility manufactures two similar phosphorotrithioates,  and has monitoring




data indicating effective treatment,  through hydrolysis, of one of these PAIs.




The second phosphorotrithioate cannot be analytically distinguished from the




first because it rapidly oxidizes to it.  The second PAI would either react




via hydrolysis at the same rate as the first or would oxidize to the first and
                                     7-85

-------
then hydrolyze.  The second PAI can achieve the same BAT limit as the first




PAI.   In the same way, two toluidine PAIs cannot be analyzed separately and




apart from a third toluidine PAI; therefore, the BAT limitations for these two




PAIs have been set equal to the BAT limitations for the third toluidine PAI.




The same methodology was used to develop BAT limitations for a benzonitrilile




PAI,  a dithiocarbamate PAI, and a phosphorothioate PAI.  These PAIs are not




analytically discernable from structurally similar PAIs, and therefore have




been regulated based upon the BAT limitations for their matching PAIs.









            For nine of the PAIs manufactured at plants with BAT-type




technology in-place, the technology is either being used to control only a




portion of the process wastewater or is not operating at BAT performance




levels.  In these cases, BAT limitations were based on the effluent quality




which could be achieved through extending and optimizing BAT technology to




control all process wastewaters.  For those PAIs manufactured at plants




employing BAT technology on only a portion of the process wastewater, the




achievable daily maximum and four-day maximum average concentrations were




multiplied by average long-term flow rates for the entire process wastewater




discharge, treated and untreated wastewater, to determine the long-term PAI




mass discharge.  For those PAIs manufactured at plants employing BAT




technology but not operating at BAT performance levels, BAT limitations were




based on discharge concentrations demonstrated to be achievable either by




plant data or by treatability studies, and on variability factors derived from




actual system performance.  Daily maximum and four-day maximum average
                                      7-86

-------
discharge limitations were then calculated by multiplying by the average  long-




term flow rates and then dividing by the long-term production rates.









            Numerical BAT limitations are being proposed for 15 PAIs, in  8




structural groups, based on treatability study data combined with data




transfer of actual system performance data.  As discussed earlier in this




section, treatability studies were conducted to characterize the efficacy with




which activated carbon, hydrolysis, and chemical oxidation could treat certain




PAIs.  When PAI concentration data were not available for wastewater streams




treated by full-scale BAT treatment systems, the Agency based BAT on the




transfer of limitations and estimated performance data for structurally




similar PAIs.  Variability factors for the treatment of these PAIs were based




on the performance of BAT treatment systems utilizing the same technology, and




when sufficient data were available,  on PAIs with similar structures.









            EPA is proposing BAT limitations for two uracil PAIs,  one




chlorobenzamide PAI,  one phosphorodithioate PAI,  and four s-triazine PAIs




based on short-term activated carbon adsorption treatability study data,




because there are no available full-scale operating data.  A treatability




study provided isotherm and continuous column data for the treatment of these




PAIs in activated carbon adsorption systems.  The treatability study data were




used to demonstrate that the PAIs are treatable to achievable BAT




concentrations; however, it was necessary to relate this information to actual




operating systems to generate achievable daily maximum and four-day average




maximum BAT concentrations,  as well as the mass-based effluent limitations.
                                     7-87

-------
In order to do this, EPA transferred arithmetic factors  (as described below)




and variability factors from other activated carbon adsorption systems




operating at low PAI effluent concentrations.









            The arithmetic factor deals with the practicality of analyzing for




the PAI at concentrations very close to the detection limit.  For all PAIs




treated using activated carbon adsorption, an arithmetic factor was developed




to reflect the amount that the mean effluent concentration was above the




detection limit used to analyze that matrix.  It was assumed that each




facility utilizes as low a detection limit as is practical to achieve




consistent long-term analyses for each PAI in each plant's wastewater matrix.




This factor is a ratio of the long-term mean effluent concentration (LTM) to




minimum detection limit (MDL), and ranged from 1.03 to 7.35 for the systems




considered, with an average ratio of 4.31.  This ratio was used in conjunction




with the minimum detection limit used by one of the PAI manufacturing plants




in their analysis of the PAI  in treated wastewater samples to calculate an




achievable long-term mean concentration.  In no cases did this calculation




procedure generate concentrations lower than those achieved in treatability




testing.









            The statistical variability factors applied  to limitations




development were those calculated for average BAT activated carbon systems.




BAT operating data for 6 full-scale activated carbon systems and one small




scale activated carbon system which rely on activated carbon to control




pesticides were used to develop daily maximum and four-day maximum average
                                      7-88

-------
variability factors.  The data sets used to develop these factors were not




necessarily generated from systems incorporating the two optimal design




parameters recommended above and, therefore, effluent concentrations were




higher than would be expected with these optimizations.  The average




variability factors calculated were 7.15 (daily) and 2.41 (four-day).




Achievable daily maximum and four-day average BAT effluent concentrations were




then calculated using the arithmetic and variability factors and the




treatability study concentrations.  These concentrations were converted to




mass normalized limitations using the long-term average process discharge flow




for each specific PAI,  and the average production for each specific PAI




manufacturing process which discharges water.









            In the case of the four s-triazine PAIs, industry did provide EPA




with long-term monitoring data characterizing treated effluent (though not




from activated carbon)  from the manufacture of two other s-triazine PAIs.  EPA




therefore used the average long-term monitoring data results as a target for




the performance levels achievable for s-triazines manufactured by other




facilities.  EPA treatability studies on plant wastewater demonstrated that




even greater s-triazine removal rates could be achieved through the use of




granular activated carbon (GAG) adsorption.  Additional treatability study




information supporting this conclusion was available from the s-triazine




manufacturers themselves.   The BAT limitations were therefore based on the




removal rates achievable through the use of granular activated carbon.




Variability, factors were transferred and mass-based BAT limitations were




calculated based on the methodology discussed above.
                                     7-89

-------
            EPA is proposing BAT  limitations for a phosphorodithioate PAI




based on short-term hydrolysis treatability study data, because there are no




available full-scale operating data.  This treatability study was conducted on




a "synthetic" wastewater  stream;  that is, deionized water spiked with the PAI.




Hydrolysis is used to  treat a variety of  other phosphorodithioate PAIs, with




treatment efficacy quantified through long-term self-monitoring data on these




PAIs.  Literature data demonstrates  that  hydrolysis for this PAI takes place




faster than hydrolysis of other phosphorodithioates;  therefore, EPA concluded




that wastewater from the  manufacture of this PAI can  be -treated to equal




effluent concentrations.









            Similar to the methodology used to evaluate carbon adsorption as




BAT technology, daily  and four-day variability factors  (4.88 and 1.92,




respectively) and the  LTM/MDL factor (3.40) were transferred from hydrolysis




effluent data for other phosphorodithioate PAIs to describe BAT hydrolysis




system performance in  treating this  PAI.  These factors were used in




conjunction with the minimum detection limit reported by one of the




manufacturing plants for  their PAI analysis to calculate BAT concentrations




for this PAI.  These concentrations  were  then converted to mass normalized




limitations using the  long-term average process discharge flow and average




production for this PAI at this plant,









            EPA is proposing BAT  limitations for a carbamate PAI based on




short-term hydrolysis  treatability study  data, because  there are no available




full-scale operating data. As with  the phosphorodithioate PAI discussed
                                      7-90

-------
above, this treatability study was conducted on a "synthetic" wastewater




stream; that is, deionized water spiked with the PAI.  Hydrolysis is used to




treat a variety of other carbamate PAIs, with treatment efficacy quantified




through additional EPA treatability studies on these PAIs.  In particular, one




plant that manufactures this PAI also manufactures two other carbamate PAIs,




and treats the process wastewater with hydrolysis.  It was observed that




hydrolysis of this carbamate PAI takes place faster than hydrolysis of other




carbamates;  therefore, EPA concluded that wastewater generated during the




manufacture of this PAI can be treated to equal effluent concentrations.









            The daily and four-day variability factors (3.57 and 1.59,




respectively) and the average LTM/MDL ratio (1.19) were developed based on the




treatment data for the hydrolysis of the two carbamate PAIs manufactured with




this PAI.  These factors were used in conjunction with the minimum detection




limit reported by a carbamate manufacturing plant for their PAI analysis  to




calculate BAT concentrations.  These concentrations were then converted to




mass normalized limitations using the long-term average process discharge flow




and average production for the PAI at this plant.









            EPA is proposing BAT limitations for three dithiocarbamates PAIs




and one isocyanate PAI based on short-term chemical oxidation treatability




study data,  because there are no available full-scale operating data.   The




dithiocarbamates were treated as one group because the analytical method for




dithiocarbamates does not distinguish among individual PAIs.   The isocyanate




PAI is included with the dithiocarbamates because it is manufactured and
                                     7-91

-------
treated using technologies common to dithiocarbamate PAIs; in addition, the




analytical method cannot distinguish between the isocyanate PAI and the




dithiocarbamate PAIs.









            Self-monitoring and chemical oxidation treatability study data




were available at one plant utilizing chemical oxidation to treat




dithiocarbamate PAIs.  The plant self-monitoring data was not directly used to




set BAT limitations because this plant was treating to meet specific




limitations, rather than treating to achieve maximum PAI removal.  The




facility did report occasional non-detects, and achieved non-detects during




EPA sampling.  EPA checked these results by conducting a chemical oxidation




treatability study on actual plant wastewater samples containing




dithiocarbamate PAIs.  Results of the treatability study demonstrated that




effluent concentrations at or below the method detection limit were achievable




for each of these PAIs through chemical oxidation.  Variability factors were




developed based on the performance of the operating chemical oxidation system




at this plant, and these factors were applied to the proposed achievable




concentration and used with flow and production data from the same facility to




develop mass based limitations.









            EPA is proposing BAT limitations for a heterocyclic PAI based on




short-term hydrolysis treatability study data, because there are no available




full-scale operating data.  The treatability study data indicates that




hydrolysis of this PAI occurs very rapidly.  While there are no data on the




hydrolysis of any PAIs with a similar heterocyclic structure to this PAI,
                                     7-92

-------
treatability data are available for a number of PAIs with hydrolysis systems




performing at BAT levels that have half-lives approximately equal to this PAI.




Therefore, variability factors and LTM/MDL ratios were averaged from the list




of all hydrolysis-treated PAIs.  The average LTM/MDL was 2.44, and the average




variability factors were 4.18 (daily maximum) and 1.74 (four-day maximum




average).  Using this method, achievable daily maximum and four-day maximum




average BAT effluent concentrations were calculated.  These concentrations




were then converted to mass normalized limitations using the long-term average




process discharge flow and average production for the heterocyclic PAI at this




plant.









            A synthetic pyrethrin manufacturing facility currently discharges




a low volume of highly concentrated pyrethrin process wastewater to a POTW




without treatment.   Due to the high concentration of pyrethrin in the plant's




discharge water, and the relatively high toxicity of this PAI, treatment prior




to disposal is required.   Because the flow rate of the waste stream is low,




off-site incineration,  rather than implementation of on-site treatment, has




been determined to be the treatment option with the least cost.









7.4.3       Calculation of Effluent Limitations Guidelines Under NSPS









            NSPS represents the most stringent numerical values attainable




through the application of the best available demonstrated treatment




technologies.   The reasonableness of costs to implement the best treatment




technologies for new plants is considered when setting NSPS limitations.   EPA
                                     7-93

-------
is proposing NSPS limitations for all the PAIs for which BAT limitations are




being proposed.  The pesticide chemicals industry is unique, however, in that




expansion or changes in the  industry are not  likely to occur through the




manufacture of currently-produced PAIs at new facilities.   Instead, it  is more




likely that only new PAIs would be manufactured  at new facilities.  Since the




nature of the treatability of new PAIs cannot be readily predicted, the Agency




does not believe it is possible to develop NSPS  guidelines  for  treatment of




new PAIs.









            The Agency considered four options for NSPS limitations.  Two




options  are the same as the  two BAT options discussed previously:  basing




limitations on the demonstrated efficacy of BAT  control technologies and




requiring zero discharge.  The other two options include basing limitations on




the treatment performance data available for  BAT technologies modified  to




reflect  the capability for wastewater  flow reduction at new facilities, and




basing limitations on BAT treatment, flow reduction, and application of




membrane filtration technology for further pollutant reduction.









            As part of EPA's evaluation  of options for NSPS/PSNS PAI




guidelines, the Agency  investigated  trends in reduction of  contaminated




wastewater  discharges by newer manufacturing  facilities.  To derive the




average  flow  reduction achieved,  the Agency compared the 1977 Census industry




responses with  the  1986  Census responses to determine which PAI processes in




operation  in  1986 were not  in operation  during or before 1977.   For
                                      7-94

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Subcategory A, EPA identified 36 processes at 29 plants which appear to have




started-up since 1977.









            EPA determined the total process wastewater flow to treatment for




each product, and then calculated the average flow to treatment per pound of




product for both older (pre-1977) and newer (post-1977) plants.   EPA did not




include flows identified as storm water because the amount of stormwater is




not related to production process or production rate.  (There will be higher




storm water flows in rainy areas of the country than in arid areas.)









            "Older" (pre-1977) processes manufactured 737 million pounds of




PAIs per year, and generated 1,141 million gallons of total process




wastewater, of which 801 million gallons were contact wastewater.   This




results in production normalized wastewater discharges of 1.55 gallons per




pound of PAI for total process wastewater.  The corresponding "newer" (post-




1977) processes manufacture 94 million pounds of PAIs per year,  and generate




104 million gallons of total process wastewater.  This results in production




normalized wastewater discharges of 1.11 gallons per pound of PAI for total




process wastewater.









            Between the "Older" and "Newer" plants,  there is a difference of




0.44 (1.55-1.11) gallons per pound in total wastewater discharged,




representing a 28% reduction in flow.
                                     7-95

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            This reduction reflects both the higher degree of source




segregation practiced in newer processes, as well as a trend toward processes




generating only scrubber or stripper overheads through the use of closed loop,




solvent recovery systems.  Newer facilities also incorporate a greater degree




of segregation between contact streams resulting from pre-PAI formation steps




and post-PAI formation steps in the processes.  It is clear that selective




treatment using PAI destruction/removal technologies of only contaminated




wastewater streams can also reduce the flow to and therefore the cost of PAI




treatment processes.  Source segregation reduces the amount of PAI-




contaminated wastewater requiring treatment by a PAI destruction/removal




technology.  As a result, the size and throughput as well as the corresponding




cost of the PAI treatment step are reduced in newer facilities.









            There are two factors which affect the projected flow reductions




achievable.  First, the pesticides produced at the post-1977 plants typically




are new PAIs instead of new production of PAIs already being manufactured.  As




a result, it is generally not possible to directly compare wastewater flow




rates  from "Old" and "New" plants manufacturing the same PAI.  "New" plants,




however, would have the capability to better segregate wastewater streams and




therefore minimize the flow rate of PAI-contaminated wastewater to PAI




treatment.  Therefore, EPA believes that flow reduction equal to or greater




than 28% is achievable (except as described below for two PAIs), since




industry has already demonstrated this reduction in the newer plants.  Second,




despite dividing the industry into pre- and post-1977 processes, some of the




flows  documented as pre-1977 values may in fact already reflect some flow
                                      7-96

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reduction due to process modifications which have reduced or further




segregated flow.  Because information concerning modifications is not readily




available, these changes are not included in this analysis, but it is possible




that additional data would document a higher overall flow reduction than 28%




from the pre-1977 plants.









            The Agency is proposing NSPS effluent limitations for




Subcategory A PAIs to be the BAT limitations modified by 28% flow reduction




(except as described below).  In other words, NSPS for each PAI with a




numerical BAT effluent limitation is equal to the BAT limit multiplied by




0.72.  The Agency decided not to equate the NSPS limitations with the BAT




limitations,  because EPA believes that flow reduction has been demonstrated




and is achievable.  In addition, because flow reduction may decrease the BAT




treatment costs, new plants will likely include flow reduction as an integral




part of the plant design.  The Agency decided not to require zero discharge of




process wastewater pollutants as the NSPS limitations because the costs and




associated economic impacts of this option are considered to be essentially




the same as those for BAT Option 2, since the costs of on-site or off-site




incineration (and associated transportation costs) and recycle/reuse would be




the same at new and existing plants.  The NSPS zero discharge option,  like BAT




Option 2,  therefore would be extremely expensive.  The Agency proposes to




reject this option because the economic impact of this option would be too




severe.  The  Agency decided not to base NSPS on the addition of membrane




filtration technology to BAT treatment plus flow reduction because the removal
                                     7-97

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levels that this technology can achieve have not been demonstrated at any




pesticide chemicals manufacturing plant.









            There are two PAIs (carbofuran and DEF) being proposed for




regulation  (with non-zero limitations) that are being produced at plants or




process lines constructed after 1977.  Data from these newer plants/processes




show that they have achieved  flow reductions of at least 28% compared to




similar production processes  employed at older plants.  Therefore, because




there  is no information  demonstrating that further flow" reductions are




possible, EPA is setting the  proposed NSPS limitations for these two PAIs




equal  to the proposed BAT limitations.  In addition, equivalent NSPS




limitations are being set for merphos and DEF, because they are analytically




indistinguishable PAIs.









            The Agency has  determined that limitations that are more stringent




then BAT limitations required for existing plants can be achieved both




technically and economically.  These limitations provide for reduction of




pollutants  discharged into  the environment beyond that which is achieved by




BAT.   In addition, enhanced cross-media pollution control would be realized,




due to the  reduction in  wastewater  flow prior to treatment.









7.4.4       Analysis of  POTW  Pass-Through for PAIs









            Indirect dischargers  in the pesticide manufacturing industry, like




the direct  dischargers,  use as raw  materials and produce as products or
                                      7-98

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byproducts, many nonconventional pollutants (including PAIs) and priority




pollutants.  As in the case of direct dischargers, they may be expected to




discharge many of these pollutants to POTWs at significant mass or




concentration levels, or both.  EPA estimates that indirect dischargers of




organic pesticides annually discharge approximately 110,000 pounds of PAIs and




29,000 pounds of priority pollutants to POTWs.









            EPA determines which pollutants to regulate in PSES on the basis




of whether or not they pass through, interfere with,  or are incompatible with




the operation of POTWs (including interference with sludge practices)   The




Agency evaluates pollutant pass through by comparing the pollutant percentage




removed by POTWs with the percentage removed by BAT technology applied by




direct dischargers.  A pollutant is deemed to pass through POTWs when the




average percentage removed nationwide by well-operated POTWs (those meeting




secondary treatment requirements) is less than the percentage removed by




directly discharging pesticides manufacturing facilities applying BAT for that




pollutant.









            There is very little empirical data on the PAI removals actually




achieved by POTWs.  Therefore, the Agency is relying on lab data to estimate




the PAI removal performance that would be achieved by biotreatment at well-




operated POTWs applying secondary treatment.  The results of this laboratory




study are reported in the Domestic Sewage Study (DSS) (Report to Congress on




the Discharge of Hazardous Waste to Publicly Owned Treatment Works, February




1986, EPA/530-SW-86-004).   The DSS provides laboratory data under ideal
                                     7-99

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conditions to estimate biotreatment removal efficiencies at POTWs for




different organic PAI structural groups.









            For each of these PAI structural groups, the DSS shows that BAT




removal efficiencies are considerably greater than the PAI removals achieved




by biotreatment under laboratory conditions (99% removal by BAT versus an




optimistic estimate of 50% or less removal by the POTW as reported in the




DSS).  Results of this analysis indicate that organic PAIs that could be




efficiently removed by pretreatment technologies would pass through the




treatment systems at POTWs.









            In addition to pass-through, many of the pollutants in pesticide




manufacturing wastewaters are present at concentrations which may inhibit




biodegradation in POTW operations.  In  some cases, discharges into POTWs have




caused severe upsets at POTWs resulting in documented pass-through of PAIs and




operational problems at the  POTWs (a more detailed analysis is presented in




the  public record   DCN 4002).









7.4.5       Calculation of Effluent Limitations Guidelines Under PSES and PSNS









            Based on the results of the pass-through analysis, EPA is




proposing PSES limitations for the same PAIs that are receiving BAT




limitations.  Since indirect discharging organic pesticide manufacturing




facilities generate wastewaters with similar pollutant characteristics as




direct discharging facilities, the same treatment technologies discussed
                                     7-100

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previously for BAT are considered applicable for PSES.  The Agency considered




the same two limitation development options as for BAT:  basing limitations on




the demonstrated efficacy of BAT control technologies and requiring zero




discharge.  EPA is proposing PSES limitations based on the first option;




setting PSES equal to BAT.  Under this option, PSES for organic PAIs would be




set equal to BAT guidelines based on the use of hydrolysis,  activated carbon,




chemical oxidation, resin adsorption, solvent extraction,  and/or incineration.




This option is economically achievable and greatly reduces pollutants




discharged into the environment, as pollutants not recycled or reused are




destroyed by treatment.  Option 2 is proposed to be rejected because of the




cross-media implications of the transfer of pollutants as  well as the severe




economic impacts that would result from implementing this  option.









            Pretreatment standards for new sources were based on the pass-




through analysis utilized in the development of the PSES limitations and on




the flow reduction methodology utilized in the development of NSPS




limitations.  The pass-through analysis demonstrated the need for pretreatment




standards equivalent to the standards set for direct discharging pesticide




manufacturing facilities.   The flow reduction methodology demonstrated the 28%




reduction in wastewater flow generated by "new" (post-1977)  pesticide




manufacturing facilities/processes.   Since new indirect discharging




facilities,  like new direct discharging facilities, have the opportunity to




incorporate the best available demonstrated technologies,  including process




changes, in-plant controls,  and end-of-pipe treatment technologies, the PSNS




limitations should be equivalent with NSPS limitations.  The same technologies
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discussed previously for BAT, NSPS, and PSES are available as the basis for




PSNS.   Proposed PSNS for Subcategory A are based on the proposed PSES




technologies, modified to reflect the flow reduction capable at certain new




facilities.  EPA also considered the zero discharge option, but it was




rejected due to the resulting severe economic impact.









7.5         EFFLUENT LIMITATIONS DEVELOPMENT FOR PRIORITY POLLUTANTS









            This section discusses the development of effluent limitations




guidelines and standards for priority pollutants in Subcategory A of the




pesticide chemicals manufacturing industry.  As discussed in Section 13, EPA




is proposing to reserve further regulations for Subcategory B priority




pollutants.









            EPA is proposing effluent limitations and pretreatment standards




for 28 priority pollutants.  For 23 of these 28 priority pollutants, EPA is




relying on the OCPSF database to set limits that are identical to the limits




set for these pollutants in the OCPSF guidelines.  For four other priority




pollutants which were not regulated under OCPSF and for which there are no




treatment performance data, EPA is using limitations set in the OCPSF




guidelines for other priority pollutants that are deemed to have similar




"strippabilities".  This is the same procedure used in the OCPSF rulemaking




for developing limitations when performance data was lacking for certain




priority pollutants.  Limitations for one priority pollutant, cyanide, are
                                     7-102

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proposed based on actual long-term full-scale data from the pesticide




industry.









            For 23 priority pollutants, the Agency proposes to transfer BAT




limitations form the OCPSF category.   As discussed earlier in Section 3, 55 of




the 90 pesticide chemicals manufacturing facilities also manufacture compounds




regulated under the OCPSF category.  Typically,  wastewaters from pesticide




manufacture are ultimately commingled with OCPSF wastewaters generated at the




site and treated in the same end-of-pipe (EOP) wastewater treatment systems.




Even though pesticide wastewaters may be pre-treated to remove PAIs, their




priority pollutants are removed in the same EOP treatment system that removes




priority pollutants from OCPSF wastewaters.









7.5.1       Calculation of Effluent Limitations Guidelines Under BAT









            In the OCPSF rulemaking,  EPA identified treatment technologies




that have been shown to be effective  and the best available for removing




priority pollutants from commingled OCPSF and pesticide manufacturing




wastewater streams.  EPA has determined that 23 priority pollutants (22




volatile and semi-volatile organic priority pollutants and lead) regulated in




the OCPSF guidelines also may be found in wastewater streams from pesticides




manufacturing.  EPA therefore is proposing that the BAT limitations for these




23 pollutants be directly transferred to the pesticide chemicals manufacturing




category as BAT effluent limitations  guidelines.  Four priority pollutants




(bromomethane, tribromomethane,  bromodichlormethane,  and
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dibromochloromethane), detected at significant concentrations in pesticide




manufacturing wastewaters, were not regulated for BAT under the OCPSF




category.  EPA is proposing to set BAT effluent limitations for those four




pollutants by transferring OCPSF limitations for compounds that have similar




strippabilities.  BAT limitations for cyanide are being proposed based on




treatment data from pesticide manufacturing facilities.









7.5.1.1     Volatile  and  Semi-Volatile Organic Pollutants









            In the OCPSF  rulemaking, EPA based its BAT limitations and costs




for volatile organic  priority pollutants on in-plant steam stripping alone for




plants without end-of-pipe biological treatment.  For the volatiles limited on




the end-of-pipe biological treatment subcategory, the combination of steam




stripping and end-of-pipe biological treatment were used for limitations and




costing.  The data used to derive these limits for the end-of-pipe biological




treatment subcategory were taken from plants which exhibited good volatile




pollutant reduction  across the entire wastewater treatment system.  To




establish limits  for the  non-end-of-pipe biological treatment subcategory, EPA




used  steam  stripping data for volatile organic pollutants collected from




plants  that either did not have end-of-pipe biological treatment or provided




data  on the separate performance of the in-plant steam stripping treatment




technology.









            Steam stripping  employs super-heated steam to remove volatile




pollutants  of varying solubility in wastewater.  Specifically,  the technology
                                     7-104

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involves passing super-heated steam through a preheated wastewater stream




column packed with heat resistant packing materials or metal trays in counter-




current fashion.  Stripping of the organic volatiles constituents of the




wastewater stream occurs because the organic volatiles tend to vaporize into




the steam until their concentrations in the vapor and liquid phases (within




the stripper) are in equilibrium.









            Steam strippers are designed to remove individual volatile




pollutants based on a ratio (Henry's Law Constant) of their aqueous solubility




(tendency to stay in solution) to vapor pressure (tendency to volatilize).




The column height, amount of packing or number of trays,  the operating steam




pressure and temperature of the heated feed (wastewater)  are varied according




to the strippability (using Henry's Law Constant) of the volatile pollutants




to be stripped.  Volatiles with lower Henry's Law Constants require greater




column height, more trays or packing material, greater steam pressure and




temperature,  more frequent cleaning and generally more careful operation than




do volatiles with higher strippability. (See the final OCPSF rule, 52 FR




42540, for a further description of steam stripping technology).









            The final OCPSF data consisted of performance results from 7 steam




strippers at 5 plants for 15 volatile organic pollutants.  The data were




edited to ensure only data representing BAT level design and operation were




used to develop limitations.
                                     7-105

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            The Agency also identified two other treatment technologies as the




technology basis for the removal of certain semi-volatile organic pollutants




under the OCPSF regulations.  These two technologies are activated carbon




adsorption and in-plant biological treatment.  EPA also relied on the ability




of end-of-pipe biological treatment to achieve some additional pollutant




removal beyond carbon adsorption and in-plant biological treatment.  See 52 FR




42543-44 for a discussion of these technologies and a description of the data




that EPA relied on for setting the OCPSF limitations on these semi-volatile




organic pollutants.  Two of the pollutants (phenol and 2,4-dimethylphenol) are




among the 22 OCPSF organic priority pollutants that also occur in pesticides




manufacturers wastewaters and for which EPA is proposing today to set




limitations that are transferred from the OCPSF rule.









            For some of the OCPSF volatile and semi-volatile pollutants




(including some of the ones for which limitations are also being proposed in




today's notice for pesticides manufacturers), the available effluent data




consisted of measurements so low that very few exceeded the analytical




threshold level (10 ppb, the minimum level for most pollutants   see




Section X, Comment 7 of the OCPSF final rule, 52 FR 42562, November 5, 1987).




Since variability factors could not be calculated directly for these




pollutants, in the OCPSF rule, EPA transferred variability factors from




related pollutants (see 52 FR 42541).  EPA determined that the data from these




plants provided an adequate basis to set limitations for the OCPSF industry.
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            EPA  finds  that  it  is  appropriate to transfer  the  limitations  for




volatile and semi-volatile  organic pollutants  in the OCPSF industry  to  this




rulemaking  to set  limitations  on  the same pollutants in the wastestreams  of




pesticides  manufacturers.   The technologies identified (steam stripping




technology, in-plant biological treatment, and activated  carbon adsorption,




combined in some cases with end-of-pipe biological treatment) are available at




pesticides  manufacturing plants (these technologies are all already  in use at




certain pesticides manufacturing  plants or combined OCPSF/pesticides




manufacturing plants).  In  addition, these technologies will be capable of




removing from pesticides manufacturers' wastewaters the amounts of volatile




and semi-volatile pollutants necessary to meet the transferred limitations.




Specifically, EPA finds that applying these technologies to pesticides




manufacturers wastewaters will result in treatability levels for volatile and




semi-volatile organic pollutants  that are similar to the treatability levels




of these same pollutants in OCPSF wastewaters.   EPA stated in the OCPSF rule




that although the degree to which a compound is stripped can depend to some




extent upon the wastewater matrix, the basis for the design and operation of




steam strippers is such that matrix differences were taken into account for




the compounds the Agency evaluated.   A sort of the strippability data




confirmed that process wastewater matrices in the OCPSF industry generally do




not preclude compliance with the concentration levels established in the OCPSF




rulemaking  (52 FR 42540-41).  The wastewater matrices in the pesticides




manufacturers industry are generally similar to those in the OCPSF industry,




and so they generally would not preclude compliance with the concentration




levels being proposed for volatile pollutants.
                                     7-107

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            As explained above, the proposed rule does not derive limits




independently for 23 priority pollutants but expressly relies on the OCPSF




rulemaking and accompanying record for setting these limits.  In the




litigation over the OCPSF rule, an issue arose over EPA's methodology for




setting these priority pollutant limits.  Specifically, the issue concerned




EPA's decision to establish one set of priority pollutant limits for direct




discharger plants that do not use end-of-pipe biological treatment and a




different set of limits for those direct dischargers that do.









            Some, but not all, OCPSF plants use end-of-pipe biological




treatment to meet their limitations on conventional pollutants.  These plants




rely on other technologies to reduce their priority (toxic) pollutants;




however, the biological treatment has the incidental effect of removing some




further amount of the priority pollutants.  The OCPSF rule, therefore,




accounts for this further removal of toxics by the end-of-pipe biotreatment




systems by establishing one set of priority pollutant limitations for those




facilities that do not use end-of-pipe biotreatment (the OCPSF "Subcategory J"




limitations) and a different, generally more stringent set of limitations for




those plants that do  (the OCPSF "Subcategory I" limitations).









            In the OCPSF litigation, NRDC claimed that EPA had not




sufficiently aired this methodology for comment.  Also, on the merits, NRDC




claimed that EPA's approach is improper because it allows facilities to meet




fewer and less stringent limits on the priority pollutants by choosing not to




use end-of-pipe biological treatment to treat their conventionals.  The court
                                     7-108

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remanded this issue to EPA for further notice-and-comment proceedings, and the




Agency is in the midst of a new rulemaking to resolve this issue for the OCPSF




rule.









            On remand, EPA reconsidered this methodology and issued a




re-proposal in December, 1991 that adopts the same approach that was




originally promulgated (56 FR 63897).  The re-proposal discusses NRDC's claims




and explains in detail why EPA still believes the original approach is




appropriate.  To summarize that discussion,  the Agency recognized that certain




OCPSF facilities,  such as chlorosolvent plants,  have BOD3  levels  that are too




low to allow for effective biological wastewater treatment and do not require




end-of-pipe biological treatment to meet their BPT limitations.   A biological




system cannot operate effectively without a sufficient mass of organic




biodegradable material to sustain the microorganisms that consume the




biodegradable waste.  EPA concluded that these plants should not have their




BAT effluent limitations based on the performance of in-plant controls and




end-of-pipe biological treatment.  Therefore, the OCPSF Subpart J effluent




limitations were based solely on the performance of in-plant controls such as




steam stripping.









            NRDC urged the EPA to establish a raw waste "floor" level below




which biological end-of-pipe treatment is not appropriate or to limit the




applicability of Subpart J to those categories of OCPSF production that tend




to have low raw waste levels.  This suggestion appeared logical in theory but




EPA concluded that it was not feasible in practice.  The Agency explained
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that, due to the wide variety and complexity of raw materials and processes




used and of products manufactured in the OCPSF industry, it would be nearly




impossible to analyze each plant's wastestream to determine a technically




defensible BOD5 floor,  or series of floors for different plants  with different




operating and wastewater characteristics, especially when the literature does




not provide a theoretical basis  for a BOD5 cutoff.









            EPA also determined  that the BOD5 floor suggested by NRDC was not




necessary.  Common  sense and economic considerations dictate that OCPSF plants




will not opt to forego  end-of-pipe biological treatment  in order to qualify




for  the Subpart J BAT limitations.  Moreover, the Agency found  that Subpart J




will not result in  significantly greater environmental  loadings than




Subpart I.









            In addition, EPA found that NRDC's suggestions could result  in




undesirable treatment decisions.  The Agency's OCPSF regulatory scheme gives




the  regulated  community some degree of management discretion in selecting




appropriate combinations of source controls  or pollution prevention techniques




as well as appropriate  in-plant  or end-of-pipe wastewater management and




treatment techniques.   The Agency is concerned that the  attempt to establish  a




BOD5 floor would result in plants making undesirable treatment decisions  that




the  Agency did not  intend; for  example, a plant that has already installed or




is considering installing  in-plant product and by-product recovery may feel




compelled to reduce the effectiveness of  in-plant control to ensure that




sufficient organic  matter  is available to be able to operate an end-of-pipe
                                     7-110

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biological treatment system, or to operate such a system in a cost-effective




fashion.









            The proposed rule for the pesticides chemicals manufacturers, by




using limitations for priority pollutants that are directly transferred from




the OCPSF rulemaking, follows the OCPSF approach of setting two sets of




limits, one for plants that use end-of-pipe biological treatment and one for




plants that do not.  As with the OCPSF industry, some pesticides manufacturers




fall into each category.  EPA is proposing this approach in order to be




consistent with what was promulgated (and now re-proposed)  for OCPSF.




Moreover, consistency with the OCPSF regulations is necessary in some cases to




avoid having two different sets of limits applicable to the same pollutant




being discharged by a single combined OCPSF/pesticides plant.   EPA expects




that any change it may adopt in this approach when the December, 1991 OCPSF




re-proposal is made final will also be reflected in the final pesticides




manufacturing rule.









            EPA notes that there are two priority pollutants (2-chlorophenol




and 2,4-dichlorophenol) for which limitations are proposed for plants that use




end-of-pipe biological treatment but for which limitations  are not proposed




for plants that do not use end-of-pipe biological treatment.  This reflects




the approach used in the OCPSF rulemaking.  In the OCPSF rule, limitations for




these two priority pollutants were not proposed for plants  without end-of-pipe




biological treatment.because of a lack of treatability data and because a
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transfer of limitations was not possible (see the OCPSF Development Document,




Section 7).









            In this proposal for pesticides chemicals manufacturers, even for




those plants that use end-of-pipe biological treatment, the costs of that




treatment were not counted as part of the costs of meeting BAT.  This is




because end-of-pipe biological treatment is already being applied by these




plants to meet their existing BPT limits.









            In considering NRDC's suggestions, EPA concluded in the December,




1991 OCPSF re-proposal that the OCPSF point source category was too complex




for the Agency to approach perfect plant-specific knowledge of the industry.




The Agency noted, however, that in a smaller, less complex industry it might




be possible to assess more completely the intricacies of each plant's or each




plant category's treatment system.  The pesticides manufacturing industry does




contain a fewer number of plants than the OCPSF industry, but the types of




products and processes are nevertheless varied and complex.  EPA therefore




finds that, as with the OCPSF rulemaking, plant-specific knowledge of




pesticides manufacturing plants is similarly infeasible and it is thus




appropriate to follow the OCPSF rulemaking approach in this proposed rule.









7.5.1.2     Brominated Organic Pollutants









            Four priority pollutants (bromomethane, tribromomethane,




bromodichlormethane, and dibromochloromethane), detected at significant
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concentrations in pesticide manufacturing wastewaters, were not regulated for




BAT under the OCPSF category.  EPA is proposing to set BAT effluent




limitations for those four pollutants by transferring OCPSF limitations for




compounds that have similar strippabilities.









            Of the four brominated organic compounds found in pesticide




manufacturing process wastewater, one, bromomethane,  was excluded from




consideration under OCPSF guidelines because it was determined to be uniquely




related to specific sources.  The other three, tribromomethane,




bromodichloromethane,  and dibromochlormethane, were excluded because they were




only detected in trace amounts and therefore not expected to result in toxic




effects.  However, all 4 of these priority pollutants may be expected in the




discharge from processes which manufacture brominated PAIs such as bromacil




and bromoxynil, and 1 or more were detected in 7 of 20 EPA sampling episodes




between 1988 and 1990.









            Based on comparisons of Henry's Law coefficients for these




compounds with other priority pollutants which were regulated under OCPSF,  it




appears that all may be removed by steam stripping.  Two, bromomethane and




bromodichloromethane,  would be identified as  "highly strippable" under the




criteria utilized during OCPSF compliance costing,  while the others,




dichlorobromomethane and tribromomethane, would be  identified as "medium




strippable."
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            BAT guidelines are being proposed based on a comparison with




compounds having Henry's Law coefficients above and below the brominated




compound.  These compounds, with their Henry's Law coefficients (as listed in




the OCPSF development document, in mg/1 in air/mg/1 in water), are as follows:
Brominated Compound
Bromomethane
Tribromomethane
Bromodichloromethane
Dibromochloromethane
8.21
0.023
0.10
0.041
Regulated Compound (high)
none
Naphthalene
Chloroform
1 , 2-Dichloroethane

0.019
0.14
0.046
Regulated Compound (low)
1 , 1-Dichloroethene
Hexachlorobenzene
Methylene Chloride
1,1, 2-Tetr achloroethane
7.92
0.028
0.096
0.032
EPA decided to base BAT concentration guidelines on the compounds closest to




the Henry's Law coefficients of the brominated compound which have the highest




limitations under OCPSF.  These concentrations are as follows:
Brominated Compound
Bromomethane
Tribromomethane
Bromodichloromethane
Dibromochloromethane
Regulated Compound
1, 1-Dichloroethene
Naphthalene
Methylene Chloride
1, 2-Dichloroethane
Dally Max
25 ppb
59 ppb
89 ppb
211 ppb
Four -day Max
16 ppb
22 ppb
40 ppb
68 ppb
 7.5.1.3
Lead
             The  OCPSF  rule  set  a  concentration-based limitation on lead, to be




applied  only to  the  flows discharged  from metals-bearing process wastewaters




(see  52  FR  42542).   Compliance  could  be monitored in-plant or, after




accounting  for dilution by  nonmetal-bearing process wastewater and non-process
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wastewaters, at the outfall.  The OCPSF rule stated that the permit writer




may, on a case-by-case basis, provide additional discharge allowances for




metals in non-OCPSF process or other wastewaters where they are present at




significant levels.  When BAT limits have not been established, these




allowances must be based upon the permit writer's best professional judgment




of BAT.









            The OCPSF concentration limits for lead were based on the use of




hydroxide precipitation technology, which is the standard metals technology




that forms the basis for virtually all of EPA's BAT metals limitations for




metal-bearing wastewaters.  Because very little OCPSF data on the




effectiveness of hydroxide precipitation technology were available,  EPA




decided to transfer data for this technology from the Metal Finishing




Industry.









            EPA finds that it is appropriate to transfer the limitations for




lead in the OCPSF industry to this rulemaking to set limitations on lead in




the wastestreams of pesticides manufacturers.  The technology identified,




hydroxide precipitation, is available at pesticides manufacturing plants.   In




addition, this technology will be capable of removing from pesticides




manufacturers wastewaters the amounts of lead necessary to meet the




transferred limitations.









            Specifically, EPA finds that applying this technology to




pesticides manufacturers wastewaters will result in a treatability level for
                                     7-115

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lead that is similar to the treatability level of lead in OCPSF wastewaters.




The concentrations of lead in pesticides manufacturers wastewaters are




generally in the range found at OCPSF plants.  As discussed in the OCPSF rule,




this transfer of technology and limitations from the Metal Finishing Industry




Category to the OCPSF rule, and now to the pesticides manufacturers rule, is




further supported by the principle of precipitation.  Given sufficient




retention time and the proper pH  (which is achieved by the addition of




hydroxide, frequently in the form of lime), and barring the binding up of




metals in strong organic complexes (which are not present in pesticides




manufacturers wastewaters), a metal exceeding its solubility level in water




can be removed to a particular level   that is, the effluent can be treated to




a level approaching its solubility level for each constituent metal.  This is




a physical/chemical phenomenon that is relatively independent of the type of




wastewater (barring the presence  of strong complexing agents) (see discussion




at 52 FR 42543).









7.5.1.4     Cyanide









            The proposed limitations for total cyanide are not transferred




from OCPSF but instead are based  on the median values of the effluent data




from treatment systems incorporating chemical oxidation and biological




treatment at two pesticide manufacturing facilities and five organic chemicals
                                     7-116

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manufacturing facilities, along with effluent data from one pesticides

manufacturing facility with biological treatment only.  The effluent data are:
Plant Type
A
A
A
B
B
B
B
B

Treatment
BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO
CO/BO

# Analyses (# > DL)
703 (703)
2 (1)
3 (1)
6 (6)
1 (0)
4 (4)
1 (0)
25 (23)
Median = 0.0854 mg/L
Daily VF = 7.4
Four-Day VF - 2 . 6
Effluent Long -Term
Average (mg/L)
0.7398
0.0750
0.0147
0.2960
0.0100
0.4576
0.0100
0.0959
Daily Limit =0.64 mg/L
Monthly Limit =0.22 mg/L
Footnotes:
A   Pesticide Manufacturing Plant         BO   Biological Oxidation
B   Organic Chemical Manufacturing Plant  CO   Chemical Oxidation
7.5.2
Calculation of Effluent Limitations Guidelines Under NSPS
            The Agency is proposing to set NSPS limitations equal to BAT for

priority pollutants discharged by Subcategory A pesticide manufacturing plants

because the limitations are concentration-based.  The capability of reduced

wastewater flow at new plants would be taken into account by the permit writer

to arrive at mass-based permit limits.
7.5.3
Calculation of Effluent Limitations Guidelines Under PSES
            To evaluate the need for PSES for the priority pollutants,  EPA

relied on an analysis originally done to support the OCPSF regulations.  (See
                                     7-117

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Section 6 of the OCPSF Technical Development Document.)  Prior to promulgation




of the OCPSF effluent guidelines, EPA conducted a study of well-operated POTWs




that use biological treatment (the "50-Plant Study").  The 50-Plant study




determined the extent to which priority pollutants are removed by POTWs.  The




principal means by which the Agency evaluated pollutant pass-through was to




compare the pollutant percentage removed by POTWs with the percentage removed




to comply with BAT limitations.









            Because some of the data collected for evaluating POTW removals




included influent levels of priority pollutants that were close to the




detection limit, the POTW data were edited to eliminate influent levels less




than 100 ppb and the corresponding effluent values,  except in cases where none




of the influent concentrations exceeded 100 ppb.  In the latter case, where




there were no influent data exceeding 100 ppb,  the data were edited to




eliminate influent values less than 20 ppb and the corresponding effluent




values.  These editing rules were used to allow for the possibility that low




POTW removals simply reflected the low influent levels.









            EPA then averaged the remaining influent data and also averaged




the remaining effluent data for the POTWs.  The percent removal achieved for




each priority pollutant was determined from these averaged influent and




effluent levels.  This percent removal was then compared to the percent




removal achieved by BAT treatment technology.  Based on this analysis, EPA




determined that 47 priority pollutants of the 63 priority pollutants regulated




under OCPSF passed-through POTWs.  Not all of these priority pollutants are
                                     7-118

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present in pesticides manufacturers wastewaters.  As noted, 23 of the priority




pollutants present in OCPSF wastewaters are also present in pesticides




manufacturers wastewaters.  The OCPSF pass-through analysis shows that 21 of




these 23 priority pollutants pass through; the only priority pollutants of




those 23 for which pass-through is not demonstrated are 2-chlorophenol and




2,4-dichlorophenol.









            Consistent with the OCPSF rulemaking,  EPA is setting the




pretreatment standards for existing sources for the priority pollutants equal




to the set of BAT limitations that applies to plants that do not have end-of-




pipe biological treatment.  In the OCPSF pass-through analysis for setting




pretreatment standards, POTW removals were compared to BAT-level removal at




plants that did not have end-of-pipe biological treatment.









            There are very little data to determine POTW removals for the four




brominated priority pollutants:  bromomethane, bromoform (tribromomethane),




dicromochloromethane, and bromodichloromethane.  However, these pollutants are




structurally very similar to chloromethane and chloroform (trichloromethane),




which were shown to pass through by the OCPSF analysis.  In addition, EPA




sampling at pesticide plants where the brominated priority pollutants are




found shows that extensive volatilization occurs in sewers rather than removal




via treatment, and the Agency would expect similar volatilization to occur




when the pollutants are discharged to a POTW.  This volatilization would not




occur with BAT treatment, which removes (and destroys or recycles) the




pollutants from the wastewater before volatilization can occur.  Therefore,
                                     7-119

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the Agency proposes to determine that pass-through does occur for these four




brominated priority pollutants.









            Based on the 50-plant study, the average percent removal of




cyanide by well-generated POTWs achieving secondary treatment is about 54%




whereas, based on full-scale data, the BAT technology removes more than 99




percent.  Therefore, pass through does occur for cyanide.









            Based upon the above considerations, EPA has concluded that PSES




regulations are warranted for  all of the pollutants regulated under BAT for




direct dischargers, except 2-chlorophenol and 2,4-dichlorophenol.









7.5.4       Calculation of Effluent Limitations Guidelines Under PSNS









            The Agency is proposing PSNS limitations for 26 of the 28 priority




pollutants addressed under NSPS.  As discussed under PSES, two priority




pollutants, 2-chlorophenol and 2,4-dichlorophenol, have not been shown to pass




through a POTW and therefore are not being proposed for regulation under PSNS.




EPA is proposing concentration-based PSNS limitations equal to the PSES




limitations.
                                     7-120

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7.6         EFFLUENT LIMITATIONS DEVELOPMENT FOR CONVENTIONAL POLLUTANTS AND




            COD









            BPT limitations set in 1978 for Subcategory A PAIs control the




discharge of COD, BOD5,  TSS,  and pH when their  presence  in wastewaters  results




from the manufacture of any PAIs,  except for 25 PAIs specifically exempted.




As discussed in Section 9, EPA is today proposing to amend the BPT




applicability provision for Subcategory A PAIs to include 15 of these 25




previously excluded PAIs, as well as the organotin pesticides.  As discussed




in Section 13, no BCT treatment technologies were identified that passed the




BCT cost test.  As a result, the Agency is proposing to set the BCT




limitations for Subcategory A PAIs equal to the BPT limitations.









            NSPS effluent limitations and standards would also be set equal to




BPT limitations but would reflect a reduction in wastewater flow of 28% in the




manner described above for PAIs.
                                     7-121

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                                   SECTION 8




                              ENGINEERING COSTS









8.0         INTRODUCTION









            This section discusses the costs for treatment technologies for




the pesticide chemicals manufacturing industry for compliance with the BAT,




NSPS, and PSES/PSNS effluent limitations guidelines.  This section also




describes the engineering costing methodology for specific treatment




technologies.









8.1         ENGINEERING COSTING









            This section describes the costing methodologies used to develop




treatment costs for the treatment technology options upon which the effluent




limitations guidelines are based.









8.1.1       Cost Methodologies









            First,  the processes of each plant were evaluated to determine raw




pollutant discharges.   Next, the pollutant discharge levels were compared with




the proposed effluent concentration levels for each of two options:  the




achievable concentration levels in effluent from the treatment technology




identified as the best demonstrated and available for Option 1, and no




discharge of process wastewater pollutants for Option 2.  Finally, the
                                      8-1

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specific treatment technology or treatment technology sequence upon which the




proposed effluent concentration levels are based was selected and sized for




each individual process.  The cost, both purchase price  (capital cost) and




annual operation and maintenance cost  (annual O&M cost), was then calculated




for the additional treatment.









8.1.2       Cost Procedures









            Figures 8-1 and  8-2 diagram the procedures,  followed in designing




additional treatment systems for individual pesticide manufacturing facilities




and calculating the costs for each system.  Figure 8-1 presents the flowchart




used to determine treatment  costs for  PAIs, and Figure  8-2 presents the




flowchart used to determine  treatment  costs for priority pollutants.









            Pesticide Active Ingredients









            As presented in  Figure 8-1, a treatment system has been designed




for each plant handling a PAI that requires additional  treatment.  For plants




that have multiple PAIs requiring additional treatment, a treatment train (or




trains) is designed such that PAIs requiring the same type of treatment (such




as activated carbon) are commingled and fed to the same system.  This train is




then optimized, based on the wastewater flow rate through the system and




required PAI removal efficiencies, and costs are calculated for the resulting
                                      8-2

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                                     Figure  8-1

     FLOWCHART USED  TO  DETERMINE  TREATMENT  COSTS  FOR  PAIS
     UstofPAIs
    Manufactured
      a! Plant
       Is PAI
   to be regulated
       under
       BAT?
       • plant
  currently meeting
  BAT performance in
    PAI treatment?
       Do any
   other PAte made
 at plant require same
     BAT tech?
        Can
    astawater* from
different PAto be treated
     same system
 No PAI BAT Costs,
   Proceed to
 Priority PoHutam
    Analyse*
Determine flow and
 concentration of
 PAI oomam mated
   wntewater
                                     Project Combined
                                     Treatment System.
                                     Determine flow and
                                      concentration
                                  Run Cost
                                   Model
                                   for PAi
                                 Treatment
                                 Technology
                    No
       Have
    all PAto made
at Plant been analyzed
      compliance
                                             I Yea
                                          Proceed to
                                        Priority Pollutant
                                          Analyse*
                                           8-3

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                                           Figure  8-2


FLOWCHART  USED  TO  DETERMINE TREATMENT  COSTS  FOR  PRIORITY POLLUTANTS
                            Wanflfy Prtorty
                         Pollutants Produced
                         by PAI rrrig Procaaa,
                          or during PAI BAT
                             traatmant.

                         Projact Concentration
                         of Priority Pollutant in
                          Procaaa Wastewatar
                          and Plant DJaehanja
                             Priority PolL
                         below OCPSF trigger
                             for Procaaa
                             Priority Poll
                            in compteno* tf
                                Dlacnarget
                                                                 No BAT cost
                                                                 for Analynd
                                                               Priority Pollutant
                           Prtorty PolluUnt
                          require* costing tar
                            BATtrMBTiwrt

                           List atf PPoh mad*
                         in procMS which raquln
                            sain* tiMtmwit  _
                                              No
       No BAT oast
       for group of
     priority potutants
     Wai
    Ttraatm
for PPoHi)
 during OCPSF
      Did
    OCPSF
 coating induda
 capacity (or paat
                                                         Uit Priority Pollutants tor
                                                          All PM Manufacturing
                                                          Procauas - «v«Juata
                                                          oombinad traatmant
       Can
    PPolsfrom
iffarantPAIsbatr
    in combinad
      systam
                                                           Dotarmm* fbw and
                                                      Priority Pollutant concentrations
                                                           for combinad BAT
                                                           traatmant sy»tam
                                                            Datarmina flow and
                                                       Priority Pollutant concantrxtion
                                                          for procaaa spwatic BAT
                                                            traatmant ayatam
                                                  8-4

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design.  This design and cost process is repeated for any other PAIs that




require treatment at the facility.  The total treatment costs are then summed




for the facility, and individual PAI treatment costs are allocated by dividing




the applicable set of treatment costs by the PAI wastewater contribution,




which is based on daily average wastewater flow rates and annual production




days.  Finally, BAT/PSES compliance monitoring costs are calculated for each




pesticide manufacturing facility.  These monitoring costs will be incurred




regardless of whether a plant will require additional treatment.  To be




conservative, EPA estimated monitoring costs for all plants regardless of




whether a plant already conducts monitoring of PAI concentrations.









            Priority Pollutants









            Additional treatment system design specifications and costs for




the removal of priority pollutants for individual pesticide manufacturing




facilities are calculated using the same procedure as the one used to




calculate treatment system design specification and costs for the removal of




PAIs.  The only difference is that organic chemicals, plastics,  and synthetic




fibers (OCPSF) limits and treatment technologies, such as steam stripping and




distillation, are applied to the priority pollutants (with the exception of




cyanide, which has a BAT/PSES limit specific to this rule).  In some cases,




the current priority pollutant loadings for an individual facility might not




exceed OCPSF limits; however, the treatment technology installed to bring the




PAI levels within  BAT/PSES compliance may actually increase one or more of




the priority pollutant loadings to levels exceeding OCPSF limits.  One example
                                      8-5

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of this is the application of alkaline chlorination (chemical oxidation to




remove dithiocarbamate PAIs; this treatment may result in elevated levels of




chlorinated hydrocarbon priority pollutants).  In these instances, additional




treatment was designed and costed to bring these priority pollutant levels




into compliance with OCPSF limits.  In the example above, plants costed for




alkaline chlorination were also costed for steam stripping, which was designed




to remove the resulting chlorinated hydrocarbons.









8.2         COST MODELING









            This section provides a discussion of the cost model concept used




to calculate the compliance costs of the various treatment technologies.  This




section also discusses the evaluation criteria and the cost models evaluated




by the Agency, and presents an in-depth explanation of the selected cost




model.









8.2.1       Model Evaluation









            Cost Model Concept









            Cost estimates of wastewater treatment systems are required to




determine the economic impact of the regulations.   One method of estimating




costs would be to design the anticipated treatment system for each plant and




estimate the costs based on actual vendor quotes for that design.  Multiple




designs and vendor price quotes would be gathered to estimate the costs for
                                      8-6

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each treatment technology represented within the industry.  This procedure,

however, is labor intensive for more than a few plants.  A more practical  (yet

still accurate) method to estimate costs is to develop a mathematical cost

model.  In a cost model,  design and vendor information is combined to develop

equations which describe costs as a function of system parameters.  This

method permits iterative cost estimates to be calculated without requiring

detailed design and quote information for each iteration.



            EPA developed a computer-based cost model to estimate the cost for

pesticide manufacturers to comply with the wastewater effluent guidelines.

EPA designed the model to be:
                   Capable of calculating the compliance costs for the
                   guidelines;

                   Computer-based and capable of multiple iterations to cost
                   various treatment options needed to evaluate and support
                   the regulation;

                   Detailed enough to calculate compliance costs for all the
                   plants and active ingredients impacted by BAT and PSES
                   guidelines;

                   Capable of estimating compliance costs for all the proposed
                   BAT treatment technologies over a range of characteristic
                   flow rates;  and,

                   Capable of representing various treatment processes
                   individually or in combination.  The model contains
                   independent modules to represent individual wastewater
                   treatment processes.   The model is able to link the modules
                   together to represent an entire wastewater treatment
                   system.
                                     8-7

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            EPA supplemented this cost model with Lotus 1-2-3 spreadsheets set

up to calculate treatment costs for individual plants requiring activated

carbon, hydrolysis, and chemical oxidation treatment units.  Lotus

spreadsheets were also used to calculate compliance monitoring costs.



            Evaluation Criteria



            A computer-based cost model incorporates design and cost equations

which represent the desired treatment processes.  Several models currently

exist which estimate compliance costs for wastewater treatment facilities.

EPA investigated the applicability of these models to the pesticide

manufacturing industry.  These models were chosen because either they are

available in the public domain and are used for costing wastewater treatment

facilities, or they have been used by EPA to estimate compliance costs for

other wastewater effluent guidelines.



            EPA used the following criteria to evaluate seven existing cost

models for their potential use as the pesticide industry cost model:
            (1)    Does the model contain modules to represent wastewater
                   treatment technologies in use or planned for use in the
                   pesticide industry, and are the modules representative of
                   the flow rates for that industry?

            (2)    Can the model be adapted to represent the wastewater
                   treatment processes in use or planned for use in the
                   pesticide industry?

            (3)    Can the model change the base year for costs calculated in
                   the model?
                                      8-8

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            (4)    Has the model been successfully used to estimate costs for
                   actual wastewater treatment facilities?

            (5)    Is sufficient documentation available, regarding the
                   assumptions and sources of data, such that the model is
                   credible and defensible?

            (6)    Is the model structured in a manner that is usable for the
                   pesticide industry, or are only the basic design and cost
                   equations usable?
Each model evaluated is discussed below.



            Models Evaluated



            1.      CAPDET



            The Computer Assisted Procedure for the Design and Evaluation of

Wastewater Treatment Systems (CAPDET) was developed by the U.S. Army Corps of

Engineers.  The model is intended to provide planning level cost estimates to

analyze alternate design technologies for wastewater treatment plants.  The

model includes modules which represent physical, chemical, and biological unit

treatment processes.  Equations in the modules are based on rigorous engineer-

ing principles historically used for wastewater treatment system design.  The

user may link the modules into trains which represent entire treatment

processes.  The model then designs and costs various treatment trains and

ranks them with respect to present worth, capital, operating, or energy cost.
                                      8-9

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            Several of the modules within CAPDET (carbon adsorption, biologi-




cal treatment, clarification) represent treatment processes in use in the




pesticide industry.  Although originally designed to cost municipal wastewater




treatment facilities, these modules are adaptable for the pesticide




manufacturing industry by entering design parameter values that are




representative of actual data from industry.









            The cost basis for CAPDET relies on an input block of data




labelled unit costs.  These data include construction cost indices (Marshall




and Swift, Engineering News Record) and unit costs for typical construction




and operating items (concrete, piping, operator labor, basic chemical feed-




stocks) which can be entered for any desired time frame.  The program uses




these data to calculate the costs for the various modules.   The cost output




can therefore be referenced to any year for which the data can be obtained.









            EPA encourages the use of CAPDET in facilities planning and




provides for the acceptance of CAPDET generated cost estimates for POTWs.




Significant documentation (1,600 page design manual, 300 page users manual)




supports the CAPDET methodology.  Design equations for each module are clearly




stated with references and examples provided.  For these reasons, EPA selected




CAPDET as the primary model to estimate compliance costs for the pesticide




chemicals manufacturing industry.  The individual modules were modified to




account for wastewater flows encountered at pesticide facilities.
                                     8-10

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            2.     OCPSF









            The model developed by EPA to support the Organic Chemicals and




Plastics and Synthetic Fibers (OCPSF) industry effluent guidelines consists of




three Lotus 1-2-3 spreadsheets,  one each for the BPT/BAT/PSES treatment




technologies.  Each spreadsheet contains cost equations for the treatment




processes which represent these technologies.









            The cost equations were developed in the following manner.  For




each treatment process, EPA selected a design module from a previously




available cost model.  For example, CAPDET was used for carbon adsorption and




biological treatment, while a Water General Corporation cost estimation method




was used for steam stripping.  EPA then collected and averaged data (pollutant




type and loading, design constants and physical parameters) from the OCPSF




industry to use as input values for the significant design parameters involved




in the selected modules.  Using industry-specific data as input, EPA ran the




chosen module for typical wastewater flow rates and generated cost curves as a




function of flow.  Cost equations were then derived from these curves.  EPA




compared the estimated costs calculated from these equations to actual




industry costs and modified the cost equations as necessary to match the




actual data.  The base year for the cost data was 1982.  EPA then used these




modified equations in the spreadsheets.









            Although the equations in the OCPSF model represent treatment




processes found in the pesticide industry,  the equations were not used
                                     8-11

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directly in the pesticide cost model because they were derived using OCPSF




data and 1982 costs.









            3.     Wastewater Treatment System Design and Cost Model









            The Wastewater Treatment System Design and Cost Model was




developed by the EPA/EAD Metals Industry Branch.  The model was used to




determine the cost of compliance for effluent guidelines for point source




categories for the following industries:  aluminum forming, copper forming,




coil coating, non-ferrous metal forming, non-ferrous metal manufacturing




(phases I and II) and battery manufacturing.









            One module (carbon adsorption) directly represents a treatment




process commonly used in the pesticide industry; the other modules represent




treatment processes which deal primarily with the precipitation and separation




of metals from aqueous streams.  The direct application of these other modules




is therefore generally limited to metallo-organic pesticides.  The cost data




were obtained from vendors using 1982 as a base year, and no method of




changing this base is provided.









            Both this model and CAPDET represent actual wastewater treatment




systems by a combination of modules and they generate design and cost informa-




tion using this building block approach.  Although EPA followed this approach




for the pesticide industry cost model, EPA did not use the individual cost
                                     8-12

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modules included in this model because they were developed primarily for the




Metals Industry.









            4.     CORA









            The Cost of Remedial Action Model (CORA),  created by the EPA




Office of Emergency and Remedial Response, provides order of magnitude cost




estimates for remedial actions at Superfund sites.  The model consists of two




parts:  an expert system and a cost calculation program.  The expert system




helps users select technologies for sites where physical data are not




available and where a specific remedial plan has not been established.  The




costing program calculates capital, first-year operation, and site preparation




costs for various containment, removal, treatment, and disposal technologies




(modules) included in the model library.









            Because CORA was developed as a model for Superfund remedial




actions, many of the individual modules are not applicable to the pesticide




industry.  Moreover, the modules which represent treatment technologies that




are potentially applicable to the pesticide manufacturing industry, such as




carbon adsorption, biological treatment, and off-site landfill, are not




designed to handle flow rates and wastewater characteristics typical in the




pesticide manufacturing industry.  For these reasons,  EPA did not use this




model to estimate compliance costs for the pesticide manufacturing industry.
                                     8-13

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            5.     ESE Cost Estimation Method









            Previous work in developing effluent guidelines for the pesticide




industry included cost of compliance estimates.  The estimates consisted of a




set of sizing and cost equations for each of the treatment processes used in




the pesticide industry.









            However, no direct sources of data were provided for the sizing




and cost equations, nor was a method provided to vary the equations for a




different time period.  For these reasons, EPA did not use these cost of




compliance estimates to develop the pesticide industry model.









            6.     RCRA Risk-Cost Model









            The RCRA Risk-Cost Model was developed by EPA.  The model is




designed to facilitate the development of regulations governing hazardous




waste treatment, storage, and disposal facilities.  The model consists of a




database which can be viewed as a three-dimensional matrix.  Each cell within




the matrix contains information related to a combination of wastes, an




environment, and a management practice (not facility).









            Although the technologies for the model include carbon adsorption




and biological treatment, the equations for design and costing are too general




to be of specific use for the pesticide industry.  Therefore, EPA did not use




this model to develop the pesticide industry cost model.
                                     8-14

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            7.     ASPEN









            The Advanced System for Process Engineering (ASPEN) was developed




at the Massachusetts Institute of Technology.  The model is a computer aided




design package for chemical plants that performs engineering calculations to




either design a system or evaluate an existing one.  Because the model is




primarily intended as a process simulation tool, it requires too much detailed




site-specific information for its design calculations to be useful in develop-




ing the overall cost estimates which will be required from the pesticide cost




model.  In addition, steam stripping is the only applicable unit process for




the pesticide industry.  For these reasons, EPA did not use ASPEN in the




development of the new pesticide cost model.









8.2.2       CAPDET









            Based on the evaluation of existing models, CAPDET was judged to




be the most suitable for use in the development of a cost model for the




pesticide industry.  EPA supplemented the CAPDET modules with Lotus 1-2-3




spreadsheets set up to calculate treatment costs for plants requiring




activated carbon, hydrolysis, and chemical oxidation treatment units.  CAPDET




does not contain modules for hydrolysis nor chemical oxidation, and the Lotus




spreadsheet developed to estimate costs associated with activated carbon




systems is better suited to the pesticide industry than the CAPDET module.
                                     8-15

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            General Structure









            The general structure of CAPDET includes independent programs




called modules which design and estimate the cost for various individual




wastewater treatment technologies.  The model can combine these individual




modules to represent an entire treatment system and can estimate the costs for




that system.  The model can also design several different systems and can rank




these systems with respect to construction, capital, annual operating, or




energy costs.  The model includes input data files for influent and effluent




stream characteristics, cost data, and process specifications for individual




treatment technologies to further define the physical system which is to be




modelled.  This general structure meets the requirements for the pesticide




industry cost model.









            Design Methodology









            Each module within CAPDET represents a specific wastewater




treatment technology.  For each technology, the representative module is based




on specific equipment that accomplishes the desired treatment.  Each module




includes a set of process design equations which mathematically represents the




physical and chemical processes which occur in the technology.  The module




then calculates the number and size of the specific equipment, structural,




building, and piping items necessary to perform the physical and chemical




processes.  These equations are based on general engineering principles




related to the individual treatment technology.
                                     8-16

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            For example, a. typical carbon adsorption system includes two steel




towers, filled with granular activated carbon, arranged in series flow.  These




towers and associated feed, backwash, and carbon handling equipment comprise




the physical system required to perform carbon adsorption treatment of




wastewater.  The CAPDET module for carbon adsorption therefore includes this




equipment.  Based on the input data for a given system and the design




equations, the module determines the number of parallel pairs of adsorbers




required and sizes the individual towers.  The module also designs the feed,




backwash,  and carbon handling equipment.   After the equipment is designed, the




module generates a cost estimate.  (This  methodology was followed in the Lotus




spreadsheets used to calculate activated carbon treatment costs for some of




the PAIs.)









            Cost Methodology









            The CAPDET model estimates the costs of purchasing, constructing,




operating, and maintaining wastewater treatment systems.  To determine these




costs, CAPDET uses a combination of parametric and unit cost estimating




techniques.  Parametric cost estimation calculates costs based on the price of




similar equipment at other locations, using equations in which the costs of




different sizes of equipment are calculated as a function of the wastewater




flow rate.  Unit cost estimation calculates costs for individual elements by




multiplying the unit price for the element by the quantity of that element




used in the specific treatment technology, and then totalling the costs for




all of the various elements.  For example, if CAPDET determines that multiple
                                     8-17

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hydrolysis vessels are required at a plant, the model will estimate the cost




of one vessel based on the plant flow rate and multiply that cost by the




number of vessels required.









            In CAPDET, the costs of constructing a wastewater treatment




facility are divided into three categories:  unit process construction costs,




other direct construction costs, and indirect project costs.  Unit process




construction costs account for the purchase and construction of all the




equipment and associated structures and buildings for a treatment technology




within battery limits.  The battery limits are assumed to be the physical




dimensions of the treatment technology plus 5 feet.  For example, the battery




limits for the activated carbon module include the carbon adsorption towers




and the feed, backwash and carbon handling systems.  The unit process




construction costs for activated carbon therefore include the purchase and




construction of these items.  Other direct construction costs are site-




specific items used to connect treatment technologies together to form a total




facility.  Unit process construction costs and other direct construction costs




account for total construction costs.  Indirect project costs are non-




construction costs including planning, design, administrative and legal




services, and other contingency factors.  Indirect project costs are




calculated as a percentage of total construction costs.









            To estimate unit process construction costs, CAPDET uses the




results of the process design calculations discussed in the design methodology




section.  For each module, these calculations identify the following major
                                      8-18

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items:  (1) concrete and structures, (2) installed equipment, (3) buildings




and housings, and (4) piping and insulation.  These items comprise




approximately 75% of the unit process construction costs, therefore, each of




these items is estimated separately.  Electrical, control systems, and other




facilities costs are calculated as a factor of the major costs.









            Concrete and structural items include reinforced concrete,




earthwork removal, and structural steel.  CAPDET estimates these items by




multiplying the quantities required by the appropriate unit costs.  Equipment




items include the purchase and installation of individual pieces of equipment,




along with the minor electrical work, minor piping, foundations, and painting




required for a complete installation.  CAPDET uses parametric cost equations




to estimate the cost of equipment items.  Buildings are based on the area




required for the given equipment.  The area required multiplied by the unit




costs then provides the building cost estimate.  Piping items include the




purchase and installation of piping, valves, fittings, and insulation.  CAPDET




estimates these costs by multiplying the quantities required by the unit




costs.









            CAPDET also calculates the operation and maintenance costs for a




facility after construction.  The following items for each treatment




technology are considered:  (1) labor requirements, (2) electrical energy for




operation, (3) materials,  (4) chemicals and other supplies, and (5) the




replacement schedule.  For each item in each technology, an equation relates




the amount of the item required to the flow rate used for the technology.
                                     8-19

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CAPDET then multiplies the unit costs for the items by the calculated quantity




of the items to estimate operating and maintenance costs for a treatment




technology.  For example, if CAPDET determines that 500 man-hours are required




annually to operate an activated carbon system at a specific flow rate, an




estimated hourly salary will be multiplied by 500 to account for annual labor




costs.









            CAPDET accounts for cost changes over time using two methods.




First, if the actual costs for a specific item at a specific time are known,




the user may enter these costs in the model.  These costs will then be used in




the cost estimating equations.  Second, for unit costs that are not entered by




the user, the model multiplies the default value of the unit cost by a ratio




of a construction index.  This ratio uses the values of the index for a




desired year and the default year.  By multiplying the unit cost by this




ratio, CAPDET adjusts the default information to the base year desired by the




user.  The following is a list of sources of where current, or relevant, year




data may be obtained:









            (1)    Dodge Guide for Estimating Public Works Construction Costs;




            (2)    Means Building Construction Cost Data;




            (3)    "Chemical Engineering," a bi-weekly magazine;




            (4)    "Journal Water Pollution Control Federation;" and




            (5)    "Engineering News Record."
                                     8-20

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            Input/Output









            Various types of input data are required for the model to design




and estimate costs for wastewater treatment systems.  To operate the model, a




user enters information into eight different input sections, which are:









            (1)    Facility selection:  CAPDET design and cost modules are




separated by flow rate:  large facilities that generate wastewater at flow




rates greater than 0.5 million gallons per day (MGD),  and small facilities




that generate wastewater at flow rates below 0.5 MGD.   The two flow ranges




include some but not all of the same modules.  The user must select the




applicable facility size.









            (2)    Unit process specification:  The CAPDET model contains




design and costing modules for 69 treatment technologies for large facilities




and 27 treatment technologies for small facilities (Tables 8-1 and 8-2) (The




pesticide cost model only uses a subset of these treatment technologies.)  The




model labels these technologies "unit processes."  In this section of input




data, the user may enter specific values for the design parameters in the




design equations for each of the individual modules.  Because each module has




its own set of design equations, each module also has its own list of




parameters.  If design parameter values are not entered by the user, default




data are provided by the module.
                                     8-21

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                                 Table 8-1




                    CAPDET  LARGE  FACILITY UNIT PROCESSES
1.    Flotation thickening
2.    Secondary  clarification (activated  sludge)
3.    Aerated lagoon
4.   Aerobic  digestion
5.   Anaerobic  digestion
6 .    Anion exchange
7 .    Attached growth denitrification
8.    Belt  filter  for  sludge  dewatering
9.     Carbon adsorption
10.   Cation exchange
11.   Centrifugation
12.   Chlorination
13.   Secondary clarification (user-specified)
14.   Coagulation
15.    Comminution
16.    Complete  mix  activated sludge
17.   Contact  stabilization activated  sludge
18.  User-specified costs  for unit processes
19.   Counter  current  ammonia  stripping
20.   Cross  current  ammonia  stripping
21.   Denitrification (suspended  growth)
22.   Secondary  clarification  (suspended growth denitrification)



23.   Drying beds



24.   User-specified  liquid process



25.   Equalization



26.   Extended aeration  activated  sludge
                                    8-22

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       Table  8-1  (Continued)




CAPDET LARGE FACILITY UNIT PROCESSES
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
Filtration

First stage recarbonation (lime treatment)
Flocculation
Flotation
Filter press



Fluidized bed incineration
Gravity thickening
Grit removal
Sludge hauling and land


filling
High rate activated sludge
Primary clarification (two-step lime clarification)
Lagoons (stabilization ponds)
Microscreening

Multiple hearth incineration
Secondary clarification
Neutralization
Nitrification (suspended
(suspended growth nitrification)

growth)
Nitrification (rotating biological contactor)
Nitrification (trickling
Secondary clarification
filter)
(oxidation ditch)
Overland flow land treatment
Oxidation ditch

Plug flow activated sludge
Postaeration
Primary clarification
Secondary clarification


(pure oxygen)
                8-23

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                           Table 8-1 (Continued)




                    CAPDET  LARGE  FACILITY UNIT PROCESSES
53.    Intermediate  pumping
54.    Pure  oxygen  activated  sludge
55.  Rapid  infiltration  land  treatment
56.  Raw  sewage  pumping
57.   Rotating  biological  contactor
58.   Recarbonation
59.   Secondary  clarification  (RBC)
60.   Screening
61.   Second stage  recarbonation  (lime  treatment)
62.   Slow infiltration land  treatment
63.   Sludge  drying lagoons
64.   Step  aeration activated sludge
65.   Secondary clarification (trickling  filters)
66.   Trickling filtration
67.  User-specified sludge  process
68.  Vacuum filtration
69.   Wet  oxidation
                                    8-24

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                                 Table 8-2




                    CAPDET  SMALL  FACILITY UNIT PROCESSES
1.   Activated  sludge
2.   Aerated  lagoon
3.    Bar  screens
4.    Chlorination
5.    Coagulation
6.   User-specified  costs  for unit processes
7.     Drying beds
8.   User-specified  liquid process
9.    Equalization
10.   Filtration
11.   Flotation
12.   Intermittent  sand  filtration
13.    Lagoons
14.   Secondary  clarification  (oxidation  ditch)
15.    Overland  flow  land  treatment
16.   Oxidation  ditch
17.   Postaeration
18.   Primary  clarification
19.   Intermediate pumping
20.  Rapid  infiltration  land  treatment
21.  Raw  sewage pumping
22.   Secondary  clarification  (trickling  filter)
23.   Septic  tanks  and  tile  fields
24.   Slow  infiltration  land  treatment
25.   Sludge  drying  lagoons
26.   Trickling   filtration
27.  User-specified  sludge process
                                    8-25

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      (3)   Title card:  The user may select a title for individual computer




runs and enter this title in this section of input data.  The output data




sheets will then be identified by this title.









      (4)   Scheme descriptions:  In this data section, the user may combine




several unit processes which, when taken together, simulate an entire




wastewater treatment system.  The model will design and cost this combination




of unit processes as one scheme.  If desired, a user may enter a total of four




different schemes for design and costing at one time.









      (5)   Waste influent characteristics:  The CAPDET model manipulates and




tracks 20 characteristics of the wastewater as the treatment system is




designed (Table 8-3).  The user may enter specific values for these




characteristics in the influent stream, or the model will enter default data




based on municipal wastes.  The user must enter a value for the influent flow




rate, as no default value for this characteristic is provided.









      (6)   Desired effluent characteristics:  The same 21 characteristics




that are discussed above may also be used to specify the effluent.  The user




may specify values for these characteristics in the effluent if desired,




otherwise the values for them will be determined during the design of the




system.   No default data are provided by the model for effluent stream




characteristics.
                                     8-26

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                                   Table  8-3

                        WASTE INFLUENT CHARACTERISTICS
Characteristics
Minimum Flow
Average Flow
Final/Initial
Maximum Flow
Temperature Summer/Winter
Suspended Solids
Volatile Solids
Settleable Solids
BODS
SBOD (Soluble)
COD
SCOD (Soluble)
pH
Cations
Anions
P04 (as P)
TKN (as N)
NH3 (as N)
N02 (as N)
N03 (as N)
Oil and Grease
Units
MGD
MGD
MGD
DEC C
MG/L
% of Suspended
ML/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
Default Values1
	
	
	
23/10
200
60
15
250
75
500
400
7.6
160
160
18
45
25
0
0
80
'Default values  are  from  original  CAPDET model, based on municipal waste.
Default values were used if the default values accurately represented the
actual wastewater characteristics.  Where the actual wastewater
characteristics were significantly different, the actual characteristics were
used instead of the default values.
                                     8-27

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      (7)   Unit cost data:  The user may enter values for a total of 38




different cost indices, construction unit costs, operating unit costs, and




indirect cost category parameters (Table 8-4).  Default values are provided




for each of these parameters, with the values being valid for 1989 in the




current version of the CAPDET program.  The base year for the cost estimates




for the regulation is 1986; EPA therefore entered 1986 data for these unit




costs.









      (8)   Program control:  The last section of input data provides the user




with a choice of determining the types of output that the model will generate




for a particular run  (Table 8-5).  The user may select various control




statements that will  then provide the desired output data.  Material balance




information, design information for the individual unit processes, and




summaries of cost information can all be generated by the model.









            After the user enters the above data, the model executes the




design and cost estimating programs and generates the requested output.









8.2.3       Pesticide Industry Cost Model









            After EPA evaluated the CAPDET model and determined that it could




serve as a suitable basis for the pesticide industry cost model, the Agency




adapted CAPDET to estimate costs for the installation of treatment




technologies in the pesticide manufacturing industry.  EPA developed and added
                                     8-28

-------
   Table  8-4
UNIT COST DATA
Unit Cost
1.
2.
3.
4.
5.
6.
7-
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
Building Cost
Excavation
Wall Concrete
Slab Concrete
Marshall & Swift Index
Crane Rental
EPA Construction Cost Index
Canopy Roof
Labor Rate
Operator Class II Labor Rate
Electricity
Lime
ENR Cost Index
Handrail
Pipe Cost Index
Pipe Installation Labor Rate
8" Cast Iron Pipe
8" Cast Iron Pipe Bend
8" Cast Iron Pipe Tee
8" Cast Iron Plug Valve
Small City EPA Index
Land Cost
Miscellaneous Nonconstruction Cost
Administrative/Legal Cost
201 Planning Cost
1986 Value
$51.39/sf
4.19/cy
477.37/cy
105.04/cy
797.6
112.09/hr
403.0
8.61/sf
19.52/hr
16.32/hr
0 . 049/kWh
0.03/lb
4,290.51
40.94/lf
373.4
22.16/hr
36.00/lf
131.09 ea
156.09 ea
1,104.63 ea
228.7
*
5.00%
2.00%
3.50%
     8-29

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

                                UNIT COST DATA
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
Inspection Cost
Contingency Cost
Profit and Overhead Cost
Technical Cost
Aluminum
Iron
Polymer
Blowers, rotary positive displacement
Blowers, multistage centrifugal
Blowers, single stage centrifugal
Replacement life for blowers (33)
Replacement life for blowers (34)
Replacement life for blowers (35)
2.00%
8.00%
22.00%
2.00%
**
**
**
**
**
**
**
**
**
*Land costs are calculated using a separate Lotus spreadsheet.
**These items are included in CAPDET, but are not required for pesticide
waste-water treatment modules.
                                     8-30

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           Table  8-5




PROGRAM CONTROL/OUTPUT SELECTION
Statement
Analyze
List Total
Present Worth
Construction
Project
Energy
Operation and Maintenance
Output Quantities
Summary
GO
Output
Prints unit process design data as program
is executed.
1. Prints schematic of trains.
2. Prints total costs of trains.
Prints unit process design data and
expected effluent data for different
trains, ranked by present worth cost.
Prints unit process design data and
expected effluent data for different
trains, ranked by total construction costs.
Prints unit process design data and
expected effluent data for different
trains, ranked by total project costs.
Prints unit process design data and
expected effluent data for different
trains, ranked by total energy costs.
Prints unit process design data and
expected effluent data for different
trains, ranked by operation and maintenance
costs .
Prints calculated quantities used to
estimate costs for each unit process.
Suppresses printing of design data, prints
only influent and effluent data and the
cost summary of each train.
No output is generated; however, this card
initiates the execution of the program and
it must be included as program control
input .
              8-31

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modules for treatment technologies that were not part of the original CAPDET




model but were applicable treatment technologies for wastewater treatment in




the pesticide manufacturing industry.  EPA also created three Lotus 1-2-3




spreadsheets for use in calculating treatment technology costs for activated




carbon, chemical oxidation, and hydrolysis systems.  EPA also created a Lotus




spreadsheet for use in calculating compliance monitoring costs.









            EPA obtained the necessary input data, design parameters, and unit




costs from industry sources, engineering references, and the public domain and




entered them into the model to generate the cost estimates for the pesticide




industry.









            The following sections describe the design and cost methodologies




for the treatment technologies used in the pesticide manufacturing industry.









8.3         TREATMENT TECHNOLOGIES









            Section 7A identified and described the wastewater control and




treatment technologies used or available for use to reduce or remove PAIs and




priority pollutants from wastewater discharged by pesticide chemical




manufacturers.  This section describes how the cost model represents each of




these treatment technologies.  Specific assumptions regarding equipment used,




flow ranges, input and design parameters, design and cost calculations, and
                                      8-32

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disposal cost estimates for each technology are included for the following

technologies:
                  Activated carbon;
                  Biological treatment;
                  Chemical oxidation;
                  Contract hauling and incineration;
                  Distillation;
                  Equalization;
                  Filtration;
                  Hydrolysis;
                  Hydroxide precipitation;
                  Resin adsorption; and
                  Steam stripping.
This section also discusses how EPA estimated monitoring costs for compliance.



            Individual plant treatment costs, for pesticide manufacturing

plants that will require additional treatment to meet the BAT/PSES limits

specified in Option 1, are listed on Table 8-6.   The table lists the treatment

costs estimated for each plant, broken down by capital, operating and

maintenance, land, and residual waste disposal costs.
                                     8-33

-------
                 Table  8-6




PESTICIDES OPTION 1   TOTAL COSTS BY PLANT
Plant ID
0028
0046
0180
0288
0402
0448
0563
0705
1063
1189
1287
1562
1606
1624
1820
1848
1900
2008
2080
2160
2302
2446
2507
Total Capital
Cost($)
2,613,673
0
0
0
468,626
0
0
0
450,379
3,761,850
0
0
0
0
0
1,628,512
0
0
0
218,295
40,697
0
2,546,993
Total O&M
Cost ($/yr)
1,932,135
40,730
31,785
13,680
57,470
83,690
47,200
4,760
35,193
2,105,966
1,920
55,550
1,180
6,540
23,920
1,662,363
34,860
15,540
25,880
79,825
248,904
35,580
1,162,428
Total Land
Cost ($/yr)
8,250
0
0
0
17,176
0
0
0
7,695
1,469
0
0
0
0
0
6,480
0
0
0
2,000
1,280
0
17,853
Residual
Waste
Disposal
Cost ($/yr)
303,602
0
0
0
134,534
0
0
0
26,000
102,200
0
0
0
0
0
107,959
0
0
0
0
0
0
633,374
                   8-34

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          Table  8-6  (Continued)




PESTICIDES OPTION 1   TOTAL COSTS BY PLANT
Plant ID
2543
2561
2605
2767
2847
2865
3043
3061
3141
3169
3187
3203
3285
3329
3560
3668
3828
3864
3908
3944
3962
4024
4060
Total Capital
Cost($)
1,026,950
23,402
0
0
0
0
0
713,335
254,190
597,495
0
19,583
0
0
0
0
0
446,229
0
0
1,464,209
0
596,408
Total O&M
Cost ($/yr)
1,176,142
10,189
5,280
21,160
22,660
6,160
42,380
222,625
207,090
89,462
4,620
46,847
11,520
6,840
26,660
21,580
7,440
48,415
1,180
33,080
248,361
2,860
69,344
Total Land
Cost ($/yr)
5,400
0
0
0
0
0
0
5,970
2,600
5,970
0
17,660
0
0
0
0
0
6,480
0
0
9,740
0
3,588
Residual
Waste
Disposal
Cost ($/yr)
107,062
0
0
0
0
0
0
228,360
0
20,426
0
994
0
0
0
0
0
77,132
0
0
104,448
0
1,398
                   8-35

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           Table  8-6  (Continued)




PESTICIDES OPTION 1   TOTAL COSTS BY PLANT
Plant ID
4168
4220
4248
4284
4462
4505
4863
4881
4989
5005
5247
5283
5461
5504
5522
Total Capital
Cost($)
0
925,987
0
663,692
2,488,845
119,012
0
555,136
175,015
45,734
2,346,222
0
0
0
0
Total O&M
Cost ($/yr)
8,500
300,262
12,098
154,689
3,207,192
18,043
1,180
404,795
62,351
82,413
367,481
48,880
27,340
10,620
31,605
Total Land
Cost ($/yr)
0
4,050
800
5,188
15,367
12,787
0
2,403
2,403
3,856
1,492
0
0
0
0
Residual
Waste
Disposal
Cost ($/yr)
0
6,169
0
120,888
8,410
7,000
0
0
0
75,189
0
0
0
0
0
                   8-36

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8.3.1       Activated Carbon









            Activated carbon adsorption is a physical separation process in




which highly porous carbon particles remove a variety of substances from




water.  Activated carbon can be used both as an in-plant process for the




recovery of organics from individual waste streams and as an end-of-pipe




treatment for the removal of dilute concentrations of organics from




wastewaters prior to discharge or recycle.  Activated carbon can be used to




remove both PAIs and priority pollutants.









            PhyslealEquipment









            The activated carbon module in the pesticide industry cost model




is based on vendor information for packaged activated carbon adsorption units.




The module includes a packaged unit which consists of three skid-mounted




adsorption towers and the necessary pumps and piping for filling, feeding,




backwashing, and emptying the towers.  In addition to the packaged equipment,




the module includes a feed tank for wastewater influent and a separate tank




for treated water to be stored for backwashing requirements.









            Input and Design Parameters









            EPA used the CAPDET activated carbon module to calculate costs for




activated carbon treatment systems designed to remove priority pollutants, and




the Lotus spreadsheet module to calculate costs for activated carbon treatment
                                     8-37

-------
systems designed to remove PAIs.  The CAPDET activated carbon module uses




influent flow rate and influent and effluent Chemical Oxygen Demand (COD)




concentrations as input for the cost estimation methodology.  The Lotus




spreadsheet module uses influent flow rates and PAI concentrations (labelled




"COD" in the module) from the Facility Census submittals or from EPA sampling




data as input for the cost estimation methodology.  Effluent COD




concentrations were set at the detection limit for the specific PAI in the




treated matrix.  The adsorber capacity and the empty bed residence time were




used as design parameters.  Values for empty bed residence time (EBRT) and




adsorption capacities were obtained from treatability studies, on waters




containing the specific PAI to be removed.









            The modules determine the size of the activated carbon system as a




function of flow rate, influent and effluent concentrations, and empty bed




residence time.  Adsorber capacity is used to determine the exhaustion rate of




the carbon given the flow rate and concentration difference.  After the system




is sized, the modules then estimate the cost of the system, including




auxiliaries.









            Cost Calculations









            The modules calculate the capital and O&M costs of the activated




carbon system components as a function of the size of the system.  Parametric




equations relate tower cost, pump costs, etc. to the system flow rate.  The




results of the design calculations provide the sizes of the packaged unit and
                                      8-38

-------
auxiliary equipment.  Vendor supplied information was used to generate




equations that set costs as a function of size for these pieces of equipment.




With the sizes of the equipment determined from the design calculations, the




individual equipment costs were then calculated.   The modules then summed the




individual costs and multiplied the total by a contingency factor to account




for miscellaneous other costs.  These overall totals were the capital and




operation costs for the activated carbon system.









            In these analyses, the activated carbon system capital costs




include influent surge tank and pumps;  package granular activated carbon




system; backwash system and pumps, and enclosure for system.   The O&M costs




account for operation and maintenance labor, energy requirements, materials




and supplies, and replacement carbon.  The costs for each of these elements of




the O&M cost were developed from the vendor data associated with specific




activated carbon pre-packaged units.  The activated carbon O&M costs include




operation and maintenance labor; maintenance materials; electricity or other




energy requirements; and replacement activated carbon (including regeneration




or disposal).  Operation and maintenance costs were calculated on a PAI basis




and summed for total O&M cost.









8.3.2       Biological Treatment









            Biological treatment is used in industrial wastewater treatment to




remove organic chemicals from wastewater streams through the use of biological




media.  The biological treatment process used to develop compliance costs for
                                     8-39

-------
the pesticide industry cost model is an extended aeration activated sludge




system.









            Physical Equipment









            The CAPDET module for extended aeration activated sludge was used




to calculate the compliance costs for the installation and operation and




maintenance of biological treatment processes for the pesticide chemical




manufacturers.  In the extended aeration activated sludge module, the CAPDET




model  assumes that a package unit can be provided to accomplish the entire




treatment process.  The unit includes the necessary components,  such as the




aeration tank, settling tank, sludge recycle equipment, and aeration piping to




perform the treatment.  Foundations are not included in the package unit;




however, the module calculates these costs independently and adds them to the




cost for the package unit.  The extended aeration activated sludge process is




better suited for facilities with small flow rates as it is easier to operate




than other modifications of the activated sludge process and does not require




as highly skilled operators.









            Input and Design Parameters









            For the extended aeration activated sludge module, the input




values are influent stream characteristics, including; flow rate, Biological




Oxygen Demand (BOD), Chemical Oxygen Demand (COD), suspended solids, volatile




suspended solids, non-biodegradable fraction of volatile suspended solids, pH,
                                     8-40

-------
acidity, nitrogen, phosphorous, oil and grease, toxic or special




characteristics, heavy metals, and temperature.  Design parameters include




hydraulic and solid detention times, a metabolism constant, a synthesis




factor, the endogenous respiration factor, and a temperature correction




coefficient.  Values for the flow rate were obtained from census data from the




specific plant sites.  Influent BOD concentrations were obtained from the




census data or from data generated during sampling activities at the




facilities.  Values for the remaining input data and design parameters were




taken from average values developed for the same cost module for the OCPSF




industry.  Since no better data are available for the pesticide industry, the




Agency is using the average values from the OCPSF industry data for these




design parameters.  The design parameters for the biological treatment module




are presented in Table 8-7.









            Design Calculations









            The CAPDET module for extended aeration activated sludge




determines the size of the packaged system as a function of the input data and




design parameters.  The volume of the aeration tank is calculated from the




detention time and flow rate.  Solids generation,  sludge recycle requirements,




and effluent conditions are calculated as functions of the design parameters




and the calculated aeration tank volume.   After these variables have been




calculated, the module uses them to estimate the costs of a package biological




treatment unit.
                                     8-41

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                                 Table 8-7
               DESIGN PARAMETERS  FOR THE  BIOLOGICAL TREATMENT
                                COST MODULE
           Design Parameter
     Units
Default Values
Reaction rate constant

Fraction BOD synthesized

Fraction BOD oxidized

Air requirement

Endogenous respiration rate
  (sludge basis)

Endogenous respiration rate
  (oxygen basis)

Nonbiodegradable fraction of
  volatile suspended solids in
 influent

Degradable fraction of the mixed
  liquor volatile suspended solids

Oxygen transfer ratio

Oxygen saturation ratio

Horsepower

Food/microorganism ratio

Standard transfer efficiency
    L/mg/hr
scfm/1,000 gal

     L/day


     L/day
 hp/1,000 gal

Ib BOD/lb MLVSS

  Ib 02/hp hr
      0.00135

      0.73

      0.52

     20

      0.057


      0.15


      0.5



      0.53



      0.9

      0.9



      0.5

      6
                                    8-42

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            Cost Calculations



            For the packaged extended aeration system, the costs are

determined parametrically,  based on vendor information for standard sized

packaged units.



            The total capital costs include the packaged unit and the

necessary foundations.  The operation and maintenance costs include:
            •     Operation and Maintenance Labor;
            •     Materials;
            •     Energy;
            •     Sludge Disposal O&M costs; and
            •     Sludge Disposal.
The capital costs for the extended aeration system are expressed as a function

of flow rate and tank volume and the operation and maintenance costs are

expressed as a function of flow rate.  The costs for the foundations are

determined from the size of the foundation (calculated in the design

calculations section) and the unit cost of concrete.  Other miscellaneous

costs are assumed to be a factor of the calculated costs.  Land costs are the

product of the regional unit price per acre cost and the amount of land

required.
                                     8-43

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            Sludge Disposal from Biological Treatment









            The use of biological treatment as a wastewater treatment




technology results in the generation of wasted biological treatment sludge




from the clarification step.  Dewatering equipment costs were calculated for




plants with a flowrate greater than 50,000 gpd.  In the cost estimation module




for the pesticide industry, packaged rotary drum vacuum filters are used as




the mechanical dewatering equipment for sludges generated by the packaged




extended aeration system.  EPA determined that it is not cost efficient for




plants with a wastewater flow rate less than 50,000 gpd to install dewatering




equipment and, therefore, costs were estimated for these facilities to




transport sludge without dewatering.  Off-site incineration is the sludge




disposal method since the volumes of sludge generated are below the volumes




needed to justify the capital investment of an on-site incinerator.









            The cost for sludge disposal for plants with a flowrate greater




than 50,000 gpd includes the capital cost for the mechanical dewatering




equipment, the O&M costs for the mechanical dewatering equipment, and the




disposal costs at an off-site incinerator.  The packaged rotary drum vacuum




filters are skid-mounted units that include filter, vacuum pump, filtrate




pump, pre-coat mix tank with agitator, and dust collection for the pre-coat




(pre-coat material is usually diatomaceous earth).  The packaged unit does not




include equipment for storage or slurry of feed sludge.  Base prices for the




packaged dewatering units were obtained from vendors and are a function of the




sludge generation rate from the extended aeration system.
                                     8-44

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            Operation and maintenance costs include labor and supervision,




energy, chemical conditioning, maintenance and miscellaneous overhead for




operating the filter on a continuous basis.  Disposal of the sludge after




mechanical dewatering will require shipment to an off-site incinerator.   For




the pesticide industry biological treatment cost module, the sludges are




considered hazardous.  The disposal costs include transportation costs and the




disposal fee.









8.3.3       Chemical Oxidation









            For the pesticide manufacturing industry, a packaged chemical




oxidation-alkaline chlorination system is used.  The model specifies chlorine




as the oxidizing agent because chlorine is frequently used and sufficient data




is available to calculate cost estimates.  Costs were developed for this




module based on a vendor quote from an application developed for the organic




chemicals, plastics, and synthetic fiber industry.  Parametric equations were




developed based on capital and O&M costs calculated at different flows for




flow rates above 5,000 gpd.  Capital costs for plants with wastewater flow




rates below 5,000 gpd were assumed to be the same as those for the 5,000 gpd




system.  However, O&M costs were adjusted based on the actual flow rate.









            The physical equipment included in this application are a




chlorinator, bulk storage tank, chemical feed pump, caustic feed module, and




electric control panel.  Design parameters for this module include influent




flow rate, reactor retention time, and chemical feed system size.
                                     8-45

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            Capital costs include the purchase and installation costs of the

alkaline chlorination system and auxiliary equipment.  The base purchase costs

are multiplied by factors to adjust for indirect costs and cost indices to

bring the costs to 1986 basis.  O&M costs for continuously operating systems

include operating labor, maintenance, power, miscellaneous, and chemical

costs.  O&M costs for batch systems are the same as continuous systems, except

that they are multiplied by a ratio of the actual flow rate to the minimum

flow rate for continuous operation, 5,000 gpd.



8.3.4       Off-Site Incineration



            The off-site incineration module consists of cost estimate

calculations for storage on-site, transportation to an incineration facility,

and incinerator/disposal costs.



            Assumptions for the off-site incineration disposal module include

the following:
                  All wastes are treated as hazardous liquids and are disposed
                  of by incineration;

                  5,000 gallon tank trucks are used for hauling wastewater to
                  a disposal site, and only one tank truck will visit a site
                  at a time;

                  Wastes are stored on-site no longer than 45 days in a 10,000
                  gallon storage tank; and,

                  The pumping station is only operated while loading the tank
                  truck.
                                     8-46

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            Capital equipment costs and operational and maintenance costs are




determined parametrically through the use of cost curves.  Transportation and




disposal costs are determined by multiplying the calculated quantities of




wastewaters by appropriate transportation and disposal fees.









            Physical Equipment









            Equipment for storing the waste on-site includes a 10,000 gallon




vertical atmospheric tank (tank containing liquid with an approximate vapor




pressure of 15 psia).   The tank is made of carbon steel with a flat top and




bottom.  A package high service pumping station is used to transfer liquids




from the storage tank to the hauling vehicle.  A 70 gpm pump is used because




it can empty a 10,000 gallon tank in approximately two hours.  Equipment used




in the operation and maintenance of the tank and the transportation and




disposal of the waste are factored into those specific costs.









            Storage time is determined by dividing tank size (5,000 gallons)




by the flow rate in gallons per day.  If storage time is less than 45 days per




year (flows greater than 111 gal/day), costs are calculated based on a 5,000




gallon tank truck hauling waste away once every interval of the storage time.




If storage time is greater than 45 days (flows less than 111 gal/day),  then




costs are calculated based on the wastes being stored in 55 gallon drums and




the drums being hauled away once every interval of storage time with a maximum




storage time of 90 days.
                                     8-47

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            The RCRA limit for storing hazardous wastes is 90 days.  The




division between whether a facility will use drum storage or tank storage is




whether there is enough wastewater to fill up one tank truck within 45 days.




If a facility can fill a tank truck within 45 days, then the pesticide




manufacturing facility would have a 10,000 gallon tank and a pumping system,




and the waste would be hauled in tanker trucks.  If not, the facility would




store the waste in 55 gallon drums.  A truck would stop by when there were




enough drums to fill a truck, at least once every 90 days.









            Input Data/Design Parameters









            The only input for this module is waste water flow in million




gallons per day (MGD).  Design parameters include size of equipment, time of




operation, distance travelled, and unit prices.  Equipment size parameters




include the size of the storage tank and tank truck, the capacity of the




pumping station, and drum capacity per truck load.  Operation time parameters




include the number of production days for the plant, the time to connect and




disconnect the pump and tank truck, and the time to inspect the equipment.




Travel distance parameters are the unloaded distance from the disposal site to




the pesticide manufacturing facility and the loaded distance from the facility




to the disposal site.  The module uses the default value of 500 miles for




travel distance.  Cost parameters include the drum purchase price, bulk and




drum disposal fees, demurrage fee, tank truck costs and sample analysis fees.
                                      8-48

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            Design Calculations









            The storage time was determined by dividing the capacity of the




truck by the wastewater flow rate of the facility.  With a 5,000 gallon tank




truck, a facility would need a flow of at least 111 gallons per day to require




a 10,000 gallon tank.  If a facility can use drum storage, the storage time




was determined by dividing drum capacity by the wastewater flow rate.  The




maximum allowable storage time was 90 days.









            Cost Calculations









            Compliance costs are made up of capital and annual costs.  Capital




costs include the purchase of equipment.  Annual costs include operation and




maintenance of equipment, and transportation and disposal of the waste.









            No capital costs were calculated for facilities storing their




waste in 55 gallon drums.  Capital costs for plants storing their wastes in




10,000 gallon tanks include in the purchase of the tanks and pumping systems.




Costs for this equipment are determined parametrically by cost curves




dependent on capacity, tank capacity, and pumping capacity.









            Annual costs for plants storing their waste in 55 gallon drums




includes drum replacement, drum inspection, drum transportation, drum




disposal, labor, and disposal by incineration.  Annual costs for plants




storing their waste in 10,000 gallon tanks includes operation and maintenance
                                     8-49

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of tanks, pumping station, and trucks; labor; transportation of waste; and




disposal by incineration.









            Costs for the operation and maintenance of equipment are




determined parametrically by cost equations dependent on the capacity of the




equipment.  These costs account for inspection, operation, energy usage,




upkeep, and repair of the equipment.









            Transportation costs include the loading and distance costs




multiplied by the frequency of trips.  Loading costs are equal to the time it




takes to load the truck multiplied by a demurrage fee.  Distance costs include




both the unloaded travel to the pesticide manufacturing plant and the loaded




return to the disposal facility.









            Disposal costs are the costs to sample and incinerate the waste




multiplied by the frequency of trips.  Disposal and sampling fees are




dependent on the quantities and type of waste disposal.









8.3.5       Distillation









            A small distillation system, designed to handle solvent recovery,




can be used in the separation of water and alcohol to facilitate the reuse of




esterification reaction water.  Distilling reaction wastewater by controlling




the temperatures used during evaporation of solvent and water from the




reaction mixture yields water suitable for use in salt formations.   Plants can
                                     8-50

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reduce or even eliminate their discharge of pesticide active ingredients and




alcohol contaminated wastewater by reusing the esterification wastewater.









            The contaminant mixture is first pumped into the distillation




chamber.  The unit then burns thermal oil to heat the mixture and vaporize the




solvent.  During heating, a pure solvent vapor, consisting of the alcohol used




in manufacturing the specific phenoxy ester, enters the water cooled condenser




and is liquefied.  The purified alcohol is then piped to storage drums while




the water remains in the distillation chamber and is automatically discharged




and available for reuse.  Reuse of the esterification reaction waste water is




dependent upon the separation of the alcohol from the water.









            It has been demonstrated at several pesticide manufacturing plants




that distillation of esterification reaction water to recover alcohols for




recycle in the esterification process and reuse of the water recovered from




the distillation is technically feasible.









            Distillation capital costs included purchase and installation of




equipment.  Installation includes electrical hookups for control panel In




nonhazardous area,  transportation,  assembly, and initial labor to install the




equipment.  Operation and maintenance costs include energy, electricity for




power supply,  thermal oil for heating, labor,  and supplies.  Land costs are




negligible.
                                     8-51

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8.3.6       Equalization









            Flow equalization design calculations consisted of determining the




required additional capacity, sizing the feed tank, and calculating capital,




O&M, and land costs.









            The required equalization capacity was determined by multiplying




the maximum daily feed rate by the required storage time.   The required number




of feed tanks was determined by dividing required storage time by the largest




feed tank size available.









            The capital cost includes purchase and installation of the feed




tanks and is calculated by multiplying the number of feed tanks by the net




cost of each tank.  Additional operation and maintenance costs due to the feed




tanks was assumed negligible in comparison with overall plant operations and




maintenance cost.  Land cost was calculated by multiplying the unit land cost




for the respective state by the required area.









8.3.7       Filtration









            Filtration is the removal of suspended solids through a porous




medium.  For the pesticide manufacturing industry, two types of filters were




costed for wastewater treatment:  multimedia filtration, and filter presses.
                                     8-52

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            Physical Equipment









            In general,  the equipment required for a filtration system




includes the filter frame (usually concrete or steel) and the filtration media




(usually sand).  In addition, the filter press requires a plate shifter, the




press itself, a conveyor system,  and a roof to prevent rain from contacting




the squeezed cake.









            Input and Design Parameters









            The input parameter for the multimedia filter cost estimates from




CAPDET was the wastewater flow rate.  Default values were used for other




design parameters, such as hydraulic loading rate, sand size and shape, bed




size, and filter media characteristics.  Design parameters for the filter




press were specified in a treatability study for the plant.









            Design and Cost Calculations









            Design calculations for the filters were based on the filter




requirements; effluent characteristics; quantities of supplies, materials, and




equipment; energy and other operation and maintenance requirements.  Capital




costs for the multimedia filter were based on purchase and installation costs




for the filter and auxiliary equipment.  Capital costs for the filter press




were based on vendor quotes.  O&M costs for the multimedia filter and the




filter press were based on purchasing filter supplies and material and running
                                     8-53

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the equipment.  Additional land costs were assumed negligible in comparison to




existing wastewater treatment systems at the plant.









8.3.8       Hydrolysis









            Treatment of pesticide active ingredients by hydrolysis is common




in the pesticide industry.  This wastewater treatment technology uses hydroxyl




ions to catalyze hydrolysis of the PAIs in the wastewater.  The Facility




Census shows that hydrolysis treatment may be conducted either continuously or




on a batch basis.









            A typical hydrolysis system consists of a hydrolysis vessel, a




storage and delivery system for caustic, heat exchange equipment, and




associated pumps and piping.  The wastewater is heated to 60°C (140°F) either




prior to treatment or during treatment to increase the rate of reaction.




Sodium hydroxide is added to the wastewater to increase the pH to




approximately 12.  Many plants use higher temperatures and higher pH to




further increase the rate of hydrolysis.  After the desired retention time in




the hydrolysis vessel at basic pH and high temperature, the treated wastewater




is then pumped out of the hydrolysis vessel and discharged for further




treatment or disposal.
                                     8-54

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            Physical Equipment









            The Agency was unable to identify an existing cost model that




provided adequate design and cost information for hydrolysis treatment.   A




costing module was therefore developed using existing operating hydrolysis




units for reference.  The design is based on treatment of wastewater at




elevated temperatures and at a basic pH.  The successful reduction of PAI




concentrations from actual influent to desired effluent requires the




wastewater to be maintained at the temperature and pH conditions for a




sufficient period of time.  This residence time is determined by the kinetics




of the hydrolysis chemical reaction and the influent and effluent




concentrations.  A more detailed discussion of hydrolysis is presented in




Section 7.0.









            Inputand Design Parameters









            The hydrolysis module requires wastewater flow rates for design




and costing.   Design parameters such as rate constants for the hydrolysis




reactions for individual active ingredients, batch cycle time, influent




concentrations, desired effluent concentrations, and the mode of operation




(continuous or batch) are also required.  Other parameters such as caustic and




steam addition rates (to bring the wastewater to a pH of 12 and a temperature




of 60°C) are fixed in the module.
                                     8-55

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            Design Calculations









            The hydrolysis cost module calculates the vessel volume as a




function of the wastewater flow rate and the necessary residence time.  The




length of the residence time  is a function of influent concentrations,




pollutant half-lifes, rate constants, and the desired effluent concentrations.




The module calculates the necessary residence time to achieve the very low




effluent levels, and accordingly determines the size and number of hydrolysis




vessels based on the batch flow rate and batch cycle time of wastewater.




Other equipment in the system are sized as a function of the wastewater flow




rate.









            Cost Calculations









            After the individual equipment items are designed, the hydrolysis




module calculates the costs for each item.  For each item, parametric cost




equations were either obtained from existing literature sources or developed




from vendor data.  These parametric equations calculate the capital cost of




the equipment as a function of the size of the equipment.  The costs for each




item were then added together and multiplied by a factor to include other




miscellaneous capital costs not specifically calculated.  The resulting total




represents the capital cost of a hydrolysis system.  The hydrolysis capital




costs include sodium hydroxide storage and delivery systems; heat exchanger;




hydrolysis vessel(s); pumps (including feed and transfer pumps); and other
                                     8-56

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miscellaneous items including structural steel, concrete, piping, electrical




supply, etc.









            Operating and maintenance costs were calculated by first




determining the quantity of utilities, manpower, materials, and supplies




required for the operation of the design hydrolysis system.  The quantities




were then multiplied by their respective unit costs and summed to generate a




total O&M cost.  The O&M costs include operation and maintenance labor;




maintenance materials; steam; energy; and supplies/chemicals.









8.3.9       Hydroxide Precipitation









            Precipitation using lime (or NaOH) is used for removal of metals




from solution.   Metal ions in solution react with the hydroxyl ions as the pH




is raised to form insoluble metal hydroxides.  Polymer is added to aid the




flocculation of the precipitate.









            Three operating modes of the hydroxide precipitation process are




accommodated by the computer model:  continuous, batch, and low-flow batch.




Selection of the appropriate treatment mode is based on the magnitude of the




influent flow rate.  Because of the low flow rates at PAI plants requiring




this technology, compliance costs for this treatment technology were estimated




using only the low-flow batch regime.  In low-flow batch chemical




precipitation, sufficient retention time is allowed for solids settling to




occur in the reaction vessel.  Therefore, the treated effluent stream is the
                                     8-57

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clarified overflow from the reaction vessel.  Another stream requiring




disposal is the underflow (settled solids),  which are dewatered and




subsequently disposed as a hazardous waste.









            Equations for this module were based on the chemical precipitation




module used in developing compliance costs for the metals and machinery branch




effluent guidelines.  Inputs into the module include the wastewater flow rate




and the number of wastewater productions days.  Design parameters include the




residence time and the design safety factor.  Computations made include the




volume and rate of lime addition, size of physical equipment, and sludge




disposal costs.









            Capital costs are the purchase and installation costs of the




fiberglass batch tank, agitators, and pumps multiplied by factors for




engineering/administration/legal and contingencies/contractor costs.




Operation and maintenance costs are the cost of the lime, the labor, and




maintenance on the physical equipment, and insurance costs.  Land costs were




assumed to be negligible because of the low wastewater flows and size of




equipment.  Sludge production was a. factor of the volume of lime added to the




process multiplied by a unit disposal cost.









8.3.10      Resin Adsorption









            Compliance costs were estimated for resin adsorption at a specific




plant to increase the frequency of regeneration of the resin column.
                                     8-58

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Regeneration of the resin bed is done through washing the bed with methanol.




Additional resin bed regeneration can be completed with existing equipment.




Therefore, no additional capital or land costs will be incurred as a result of




increasing the frequency of regeneration.   Additional methanol and methanol




disposal will be required to increase the  frequency of regeneration.  For this




reason, additional operation and maintenance costs will be incurred.  Purchase




price of the methanol was calculated by determining the amount of additional




methanol needed and multiplying by a unit  cost for methanol.   Additional




disposal cost was calculated by multiplying the quantity of additional




methanol needed by a unit disposal cost.  Additional purchase and disposal




costs were summed to yield the additional  O&M cost.









8.3.11      Steam Stripping









            Steam stripping is used in industrial chemical production for




recovery and/or recycle and in industrial  waste treatment to remove volatile




organic chemicals from wastewater streams  by discharging steam into a tray or




packed distillation column.  For the pesticide manufacturing industry, steam




stripping is used to remove volatile priority pollutants from pesticide




wastewater.









            Physical Equipment









            EPA used the Water General Corporation model (Process Design




Manual for the Stripping of Organics, EPA-600/2-84-139) for the design of the
                                     8-59

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steam stripping systems for the pesticide industry.  EPA previously used this




model to design steam stripping systems for the development of effluent




guidelines for the Organic Chemicals and Plastics and Synthetic Fibers (OCPSF)




industry.  This model defines the steam stripping process as a steam stripping




column (tray or packed), the associated heat transfer equipment (reboiler,




condenser, and feed heat exchanger), and fluid transfer equipment (pumps).




Although packed towers are less expensive than sieve tray columns, sieve tray




columns operate more efficiently, can operate for a wider range of liquid flow




rates, and are more easily cleaned.  For these reasons, costs were estimated




for steam stripping systems with sieve tray columns.  Feed tanks for the




equalization of wastewater influent are also included for this model.  To




satisfy practical design constraints, a minimum column diameter of 1 foot and




a minimum column height of 10 feet was established.









            The minimum column size of 1 foot in diameter and 10 feet in




height corresponds to a daily flow rate of approximately 35,000 gallons of




wastewater influent per day.  For plants with flow rates below 35,000 gallons




per day, the module calculated capital costs for the minimum sized system,




35,000 gallons and decreased the operation costs by a ratio of the actual flow




to the minimum flow.









            Input and Design Parameters









            Twenty-two input variables are used in the Water General




Corporation steam stripping model, including physical properties such as
                                     8-60

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specific heat, activity coefficients, densities and viscosities; operating

characteristics such as feed flow rate, steam flow rate, and temperature; and

mechanical characteristics such as column tray type.  The feed flow rate and

influent and effluent concentrations affect the size of the steam stripping

system; these variables were therefore used as input parameters for the plants

costed.



            An important characteristic that determines the effectiveness of

steam stripping and the design of the column is the relative volatility or

vapor pressure of the organic(s) that is being stripped form the wastewater.

About one third of the 126 priority pollutant chemicals have vapor pressures

high enough to be effectively stripped from aqueous waste streams.  For

aqueous mixtures, this vapor-liquid equilibrium can be expressed by Henry's

Law Constant.  The Water General design uses a stripping factor (S) to

determine the tower specifications;  this factor is related to the Henry's Law

Constant of the pollutant to be stripped,  as shown below.


S = KV      Where K     «=        Henry's Law Constant (atm)    _ Henry's Law Constant
                               Tower Operating Pressure (atm)           1.0 atm
                  V     =     Vapor Rate (Ib/hr)
                  L     =     Liquid Rate (Ib/hr)
                  Tower Operating Pressure = 1.0 atm



            Given the direct relationship between tower dimensions and

pollutant Henry's Law Constant, and the relationship between tower dimensions

and costs,  EPA decided to divide the priority pollutants into two groups (high

strippability and medium strippability) by their Henry's Law Constant values
                                     8-61

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for the purposes of costing  (see Table 8-8),  A representative pollutant from




each group was used in the cost study; benzene represents the high Henry's Law




Constant pollutants, and hexachlorobenzene represents the medium Henry's Law




Constant pollutants.









            The design parameters for the steam stripping cost module and the




parameter values for the representative high and medium Henry's Law Constant




pollutants are presented in  Table 8-9.  The Agency used these values for the




design parameters for the steam stripping module.









            Design Calculations









            The Water General steam stripping module methodology designs the




stripping column and auxiliary equipment by determining a material and energy




balance for the system, the  number of equilibrium stages required for the




separation, the stage efficiency, and the pressure drop across the column.




The method follows standard  distillation column design practice and provides




the results of a column diameter and height that will accomplish the




separation and achieve the required effluent quality.









            Cost Calculations









            EPA obtained size and cost information for actual steam stripping




units within the OCPSF industry.  To provide a basis for the development of
                                     8-62

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                                   Table 8-8
             PRIORITY POLLUTANTS DIVIDED INTO GROUPS ACCORDING  TO
                          HENRY'S  LAW CONSTANT VALUES
High
3 x 102 to 10-1
Benzene
Carbon Tetrachloride
Chlorobenzene
1,1, 1-Trichloroethane
Chloroethane
1 , 1 - Dichloroe thane
Chloroform
Chlorome thane
Toluene
Vinyl Chloride
1 , 1-Dichloroethene
1 , 2-Trans-dichloroethene
Trichloroethene
Tetrachloroethene
Hexachloro -1,3 -butadiene
Hexachlorocyclopentadiene
Bromome thane
Dichlorobromome thane
1 , 3 -Dichlorobenzene
1 ,4-Dichlorobenzene
Ethylbenzene





Medium
10-2 to 10-3
Acenaphthene
Acrylonitrile
1 , 2-Dichloroethane
Hexachloroe thane
1, 1,2-Trichloroethane
1, 1,2,2-Tetrachloroethane
Methylene Chloride
1 , 2 -Dichloropropane
1 , 3-Dichloropropene
1,1, 1-Tribromoethane
Bis(2-Chloroisopropyl) Ether
4-Chlorophenyl Phenyl Ether
4-Bromophenyl Phenyl Ether
1 , 2 -Dichlorobenzene
1 , 2 , 4-Trichlorobenzene
Hexachlorobenzene
4-Nitrophenol
4, 6-Dinitro-o-cresol
Acenaphthylene
Anthracene
Benzo (k) f luoranthene
Fluorene
Naphthalene
Phenanthrene
Dimethyl Nitrosamine
Diphenyl Nitrosamine
Henry s Law constant units are mg/mymg/nv}.
                                      8-63

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                                                       Table 8-9




                         STEAM STRIPPING DESIGN PARAMETERS FOR HENRY'S LAW CONSTANT PARAMETERS
Design Parameter
Representative Pollutant
CP = Specific heat of reflux
DIFL = Liquid-phase diffusivity
DIFV = Gas -phase diffusivity of pollutant into
water vapor
FC = Final concentration of organic
G = Steam rate into tower
GAMD = Activity coefficient of pollutant in
aqueous phase
GAMS •= Activity coefficient of pollutant in
aqueous phase
1C = Initial concentration of organic
K — Vapor- liquid equilibrium constant
L — Liquid feed into tower
LPRIM = Latent heat of steam
MU = Gas -phase viscosity
PSI = Fractional entrainment mass fraction
Units

cal/g-°K
ft2/hr
ftVhr
mg/1
MGD
unitless
unitless
mg/1
atm/atm
MGD
cal/g
Ib/ft-hr
mole/mole
Medium Strippabillty
Hexachlorobenzene
1.0
9.918 x 10-5
0.311
Option I - 1.0
Option II = 0.01
0.10 x L
1.0
3.775 x 106
390
37.3
0.01-1.00
542.0
294.3 x lO'3
0.008
High Strippability
Benzene
1.0
1.623 x 10*
0.501
Option I - 1.0
Option II - 0.01
0.10 x L
1.0
660
390
253.3
0.01-1.00
542.0
294.3 x lO'3
0.008
CD

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                                                       Table 8-9




                                                      (Continued)
; Design Parameter
Representative Pollutant
PR «= Operating pressure of column
REFLUX - Reflux ratio
RHOG - Vapor density
RHOL - Liquid density
SAFE - Safety factor for Vm
SIGL - Liquid surface tension
TB - Boiling point of aqueous reflux
TR - Reflux temperature
XPRF = Tray construction indicator
Units

atm
unitless
ib.yft*
ib.yfe
unitless
dyne/cm
°C
°C
unitless
Medium Strlppabllity
Hexachlorobenzene
1.0
0.0
0.037
60
0.75
58.9
100
9
Perforated
High Strippabillty
Benzene
1.0
0.0
0.037
60
0.75
58.9
100
9
Perforated
CO

-------
steam stripping costs, data were extracted from the OCPSF Supplemental 308




Questionnaires submitted by those facilities utilizing steam strippers on




their waste streams.  The capital and O&M costs taken from the Questionnaires




were scaled up using the appropriate economic indices.  Where installation




costs were not provided, they were assumed to be 50% of the capital costs.









            EPA analyzed these data to determine the relationship between the




capital and O&M costs and significant steam stripper design parameters.  The




analysis shows that capital costs are best related to the diameter (D) and




height (H) of the distillation column, while O&M costs are best related to the




diameter of the distillation column and wastewater flow (F).









            The costs calculated by these equations are then converted to the




1986 year basis by multiplying them by the ratio of cost indices for 1982 and




1986.









            In these analyses, the steam stripper capital costs include




purchase and installation for a feed tank (with approximately a 24-hour




detention time); a feed heat exchanger; a reboiler; a distillation column




(tray type); a condenser; and pumps.









            The steam stripper operation and maintenance costs include




operation and maintenance labor; maintenance materials; steam energy;




electricity; and steam stripper overhead disposal costs.
                                     8-66

-------
            For plants with flow rates below 35,000 gallons per day, the O&M




costs were multiplied by the ratio of the actual flow to 35,000 gal/day.  This




reduction in O&M cost reflect the operation of the minimum sized column (1




foot in diameter, 10 feet in height) on a batch basis.  EPA assumed that




plants with small wastewater streams requiring steam stripping would install




the minimum sized system and operate it batchwise as the wastewater




accumulated.









            Steam Stripping Overhead Disposal Cost Estimates









            The use of steam stripping as a wastewater treatment technology




results in the generation of an organic stream from the column overhead.  This




organic waste stream must be disposed of, and this disposal represents




additional costs for the operation of the steam stripper.  Based on steam




stripper manufacturers' information, this overhead waste stream flow is




estimated to be 1% of the total waste stream flow.  For the pesticide




industry, disposal of the organic stream from steam stripping is based on off-




site incineration, as the size of the stripping units does not require an on-




site incinerator.  Estimates of the cost incurred for the disposal of steam




stripper overhead were developed based on vendor quotations.









            For plants utilizing steam stripping at higher flow rates




(>50,000 gpd),  costs for disposing the steam stripper overhead were very high.




While disposal costs increase directly with increasing flow, capital costs of




steam strippers increase at a much slower rate with increasing flows.  EPA
                                     8-67

-------
determined that it is therefore cost efficient to install a second-stage steam




stripper to treat the overhead from the primary steam stripper.  Although




capital costs essentially doubled, disposal costs decreased by a factor of




100.  The net result of the second steam stripper represented a substantial




savings.









8.3.12      Monitoring for Compliance









            To ensure compliance with the regulations,  plants will sample and




test their wastewater treatment for regulated PAIs and priority pollutants.




Testing methods have been developed and promulgated for all PAIs and priority




pollutants proposed for regulation.  The monitoring costs incurred by




facilities depend on the method employed to analyze their effluent wastewaters




and the number of times monitoring occurs annually.  To estimate monitoring




costs, EPA assumed that the proposed analytical methods will be used for each




regulated PAI.  Costs for analytical methods proposed for individual PAIs do




not vary significantly; thus, in cases which the proposal allows several




analytical methods to be used, EPA estimated monitoring costs assuming one




method would be used.  For the priority pollutants, EPA assumed that Methods




624 and 625 will be used to analyze volatile and semivolatile pollutants




respectively, and Method 200.7 is assumed to be used for all metals except




cyanide for which Method 335  is to be used.  EPA assumed that the permitting




authority would require monitoring of regulated PAIs and limited priority




pollutants at least once per  week of production.  EPA also, assumed that plants




would be required to monitor  all priority pollutants at least once per day of
                                     8-68

-------
production.  Next, the cost of each method of analysis was determined in 1986




dollars by using cost indices to factor current costs back to 1986.   The




annual cost for each facility was determined by multiplying the cost of each




method by the frequency of each method used at that facility.  Then the costs




for each method of analysis were summed.   To be conservative, EPA estimated




monitoring costs for all plants regardless of whether a plant already




conducted monitoring of PAIs or priority pollutants.
                                     8-69

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                                   SECTION  9




                   BEST  PRACTICABLE CONTROL TECHNOLOGY  (BPT)









9.0         INTRODUCTION









             The Agency promulgated effluent limitations based on the best




practicable control technology (BPT) currently available for the Pesticide




Chemicals Point Source Category on April 25,  1978 (43 FR 17776) and




September 29, 1978 (43 FR 44846).  BPT effluent limitations guidelines




promulgated in 1978 for Subcategory A are presented in Table 9-1, and these




guidelines excluded from coverage discharges resulting from the manufacture of




25  PAIs and classes of PAIs.  These PAIs, presented in Table 9-2, were




excluded from coverage due to a lack of treatment data available in 1978.




Since then, the Agency has collected  effluent data on 15 organic PAIs within




the group of 25 PAIs and classes of PAIs.  The Agency is proposing to amend




the applicability of BPT to include these 15 organic PAIs and organo-tin PAIs.









9.1         BPT APPLICABILITY









            Effluent data were originally collected by the manufacturing




facilities themselves in order to monitor their discharges.  The organic PAIs




for which EPA has collected these data are ametryn, prometon, prometryn,




terbutryn, cyanazine, atrazine, propazine,  simazine, terbuthylazine,




glyphosate, phenylphenol, hexazinone, sodium phenlyphenate, biphenyl, and
                                      9-1

-------
                                   Table  9-1

                   EXISTING  BPT  EFFLUENT  LIMITATIONS  FOR THE
          PESTICIDE CHEMICALS  POINT SOURCE  CATEGORY  (40 CFR PART 455)
ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY:
Effluent
Characteristic
COD
BOD5
TSS
Total Pesticides
pH
Maximum for
any 1 day**
13.000
7.400
6.100
0.010
*
Average of daily values for 30
consecutive days shall not exceed **
9.0000
1.6000
1.8000
0.0018
*
*Within the range 6.0 to 9.0.

**Metric units: Kilogram/1,000 kg of PAI produced; English units: Pound/1,000
Ib of PAI produced; established on the basis of pesticide production.
METALLO-ORGANIC PESTICIDE CHEMICALS MANUFACTURING SUBCATEGORY:

            There shall be no discharge of process wastewater pollutants to
            navigable waters.

PESTICIDE CHEMICALS FORMULATING AND PACKAGING SUBCATEGORY:

            There shall be no discharge of process wastewater pollutants to
            navigable waters.
                                      9-2

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                                   Table  9-2

                     ORGANIC  PESTICIDE  CHEMICALS  EXCLUDED
                  FROM THE 1978 BPT SUBCATEGORY A GUIDELINES
PAI Code
057
064
067
	
037
043
	
114
123
102
	
138
157
	
211
216
225
	
164
233
235
244
211.05
	
265
PAI
Allethrin
Benzyl Benzoate
Biphenyl
Bisethylxanthogen1
Chlorophacinone
Coumafuryl
Dimethyl Phthalate1
Diphacinone
Endothall Acid
EXD (Herbisan)
Gibberellic Acid1
Glyphosate
Methoprene
Naphthalene Acetic Acid1
Phenylphenol
Piperonyl Butoxide
Propargite
1, 8-Naphthalic Anhydride1
Quinomethionate
Resmethrin
Rotenone
Sulfoxide
Sodium Phenylphenate
Triazines2
Warfarin
1 Not  included  in  the  list  of  270  PAIs  considered  for  this  regulation.
2 Includes  14 specific triazine  PAIs.
                                      9-3

-------
methoprene.  EPA has also developed analytical methods and data for organo-tin




pesticides, which were not covered in the BPT guidelines.









            EPA believes that the 15 organic PAIs listed above and the organo-




tin pesticides should be covered by BPT because the NPDES permits for these




facilities were based on BPT, and the data and engineering judgement indicate




the facilities are capable of achieving the limitations.









            EPA is therefore proposing to amend the BPT applicability




provision for Subcategory A to include the 15 previously excluded PAIs listed




in Section 9.0 and the organo-tin pesticides.  Table 9-3 presents these 15




PAIs and the organo-tin PAIs.









            EPA is not proposing to make the BPT total pesticide limitations




guideline for the organic pesticide chemicals manufacturing subcategory (which




applies to the combined discharge of 49 specified PAIs) applicable to these




PAIs, because new BAT limitations are being proposed today that will apply to




each of them individually.









            The effect of this proposed amendment is to set the BPT




limitations at the performance level achievable by these facilities under




their NPDES permits and to establish a baseline on which to evaluate




incremental costs of candidate BCT technologies.  Because the facilities are




in compliance with NPDES permits that are already based on these BPT
                                      9-4

-------
                 Table 9-3




PAIS PROPOSED TODAY FOR INCLUSION UNDER BPT
PAI Code
025
058
060
067
138
142
157
192
211
211.05
223
224
226
239
256
257
PAI
Cyanazine
Ametryn
Atrazine
Biphenyl
Glyphosate
Hexazinone
Methoprene
Organo-tin Pesticides
Pheny Ipheno 1
Sodium Phenylphenate
Prometon
Prometryn
Propazine
Simazine
Terbuthy laz ine
Terbutryn
                    9-5

-------
limitations, EPA projects that there will be no costs incurred by any of




thesefacilities in connection with today's proposed rule.  Plants




manufacturing three of the PAIs proposed to be included in BPT are currently




meeting BPT limitations through no discharge of process wastewater:   one




plant's process is dry and the two other plant's processes do not discharge




any wastewater generated to waters of the United States.
                                      9-6

-------
                                  SECTION 10




            BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)









10.0        INTRODUCTION









            The factors considered in establishing the best available




technology economically achievable (BAT) level of control include:  the age of




process equipment and facilities, the processes employed, process changes, the




engineering aspects of applying various types of control techniques, the costs




of applying the control technology, non-water quality environmental impacts




such as energy requirements, air pollution and solid waste generation,  and




such other factors as the Administrator deems appropriate (Section




304(b)(2)(B) of the Act).  In general, the BAT technology level represents the




best existing economically achievable performance among plants with shared




characteristics.  Where existing wastewater treatment performance is uniformly




inadequate, BAT technology may be transferred from a different subcategory or




industrial category.  BAT may also include process changes or internal plant




controls which are not common industry practice.









            This section summarizes the proposed BAT guidelines.  Specific




discussions regarding their development are included in Section 6 (Pollutant




Selection), Section 7 (Technology Selection and Limits Development), and




Section 8  (Cost and Effluent Reduction Benefits).
                                     10-1

-------
10-1        SUMMARY OF BAT EFFLUENT LIMITATIONS GUIDELINES









            The Agency considered 126 priority pollutants and 144 PAIs and




classes of PAIs (178 individual PAIs) for regulation under the BAT effluent




limitations guidelines for the organic pesticide chemicals manufacturing




subcategory.  A complete discussion of pollutant selection for BAT are




discussed in Sections 6.2 and 6.3.  EPA is proposing to establish limitations




for 28 priority pollutants and 91 PAIs and classes of PAIs (a total of 122




individual PAIs).









            The Agency considered two regulatory options in developing BAT




effluent limitations:  (1) limitations based on the use of hydrolysis,




activated carbon, chemical oxidation, resin adsorption, and/or incineration;




and (2) no discharge of process wastewater pollutants.  The BAT limits




established must be economically achievable.  In making this determination,




the Agency takes into consideration factors such as plant closures, product




line closures, and total cost effectiveness (dollar per pound-equivalent




removal).  Although costs are considered in this manner, the primary




determinant of BAT is the effluent reduction capability of the control




technology.   A complete discussion of the two options considered for BAT are




discussed in Sections 7.4.2 and 7.5.2, along with the option selected for




regulation.









            As described in Section 8, the Agency estimated the engineering




cost of compliance with the proposed BAT effluent limitations guidelines
                                     10-2

-------
options and the associated pollutant reduction benefits.  For Option 1, which




the Agency is proposing to adopt, EPA estimates that the proposed BAT




regulation will result in the incremental removal (beyond that achieved by




BPT) of 160,000 pounds per year (Ibs./yr.) of PAIs and 14,000 Ibs./yr.  of




priority pollutants.  EPA estimates that costs for compliance with the




proposed Option 1 BAT are capital costs of $14.5 million and annualized costs




of $14.8 million (in 1986 dollars).  (See "Economic Impact Analysis of




Effluent Limitations and Standards of the Pesticide Manufacturers").









10.2        IMPLEMENTATION OF THE BAT EFFLUENT LIMITATIONS GUIDELINES









10.2.1      National Pollutant Discharge Elimination System (NPDES) Permit




            Limitations









            The proposed BAT effluent limitations guidelines for organic PAIs




are mass-based limitations.  No discharge of process wastewater pollutants




means, as a practical matter, that the regulated pollutant is not detectable




at the final outfall from a facility (i.e., at end-of-pipe).  However,  because




some facilities provide employee showers and laundry facilities, which are not




covered by this proposed rule, the permit writer or POTW may need to require




in plant monitoring of PAI process wastewaters prior to commingling with these




other streams to effectively determine compliance.  In the case where a




facility may manufacture a parent acid with a numerical limit, such as  2,4-D,




r.nd a salt or ester of that PAI, with a limitation of no discharge, compliance




might be determined by a total plant limit based solely on the 2,4-D acid
                                     10-3

-------
limit (since the method for 2,4-D does not differentiate between 2,4-D and its




salts and esters).









            PAIs that have numerical limits may be monitored for compliance




either in plant or at end-of-pipe (EOF).  If treatment to destroy the PAI is




so efficient at the plant that the PAI would be reduced to about the detection




limit, then dilution with other plant wastewater after this point would render




compliance monitoring meaningless.  Therefore, in these cases, monitoring for




compliance should be done at the exit of the in-plant treatment system prior




to dilution.  Otherwise, compliance at EOP is calculated as the mass




limitation multiplied by the facility's daily production while in operation,




to determine the acceptable daily mass discharge.









            The proposed BAT effluent limitations guidelines for priority




pollutants are concentration-based limits and the permit writer must use a




reasonable estimate of pesticide plant process wastewater flow for each PAI




and the concentration limitations to develop mass limitations.  In most cases,




plants that manufacture more than one regulated PAI do not manufacture them




simultaneously.  The permit writer should ascertain what production has been




demonstrated to occur simultaneously and sum those flows.  The limit can then




be calculated by multiplying the concentration-based limitation by flow and




the appropriate conversion factors to obtain the acceptable daily mass




discharge.
                                     10-4

-------
            For facilities that also generate process wastewater from OCPSF




operations (more than half of the pesticide plants),  23 of the regulated




priority pollutants are the same.  For those priority pollutants that are




different, the discharger should provide additional priority pollutant




characterization data to show which wastestreams (pesticides or OCPSF) are




dilution water.









            These BAT limitations, once promulgated,  will be included in the




National Pollutant Discharge Elimination System (NPDES) permit issued to




direct discharges [see 40 CFR §122.44(a)].   The final NPDES permit limitations




will include mass effluent limitations for pesticide  chemicals manufacturing,




as well as non-pesticide chemicals manufacturing and nonprocess wastewater




discharges.









10.2.2      NPDES Monitoring Requirements









            The NPDES regulations provide guidelines  setting forth minimum




monitoring and reporting requirements for NPDES dischargers.   Section 122.48




requires that each permit specify requirements regarding monitoring type,




intervals, and frequency sufficient to yield data that are representative of




the monitored activity.   Sections 122.41, 122.44,  and 122.48 contain numerous




other requirements concerning monitoring and reporting.  Therefore, this




proposed rule does not establish monitoring requirements.  As stated in




Section 8, EPA assumed a monitoring frequency of once per week for all limited
                                     10-5

-------
PAI pollutants and once per month for all limited priority pollutants in




estimating monitoring costs.









10.3        BAT EFFLUENT LIMITATIONS GUIDELINES









            The proposed BAT effluent limitations for organic PAIs and classes




of PAIs and priority pollutants under the organic pesticide chemicals




manufacturing subcategory (Subcategory A) are listed in Tables 10-1, 10-2, and




10-3.
                                     10-6

-------
                               Table 10-1




BAT EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDE ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient (PAI)
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acif luorfen
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Busan 403 [Potassium N-
hydroxymethyl -N-
methyldithiocarbamate ]
Busan 853 [Potassium
dimethyldithiocarbamate ]
BAT effluent, limitations
Daily Maximum Shall Not Exceed Lb./ 1,000 Ib. PAI
production
1.19 x 10-4
Honthly
Average Shall
not Exceed
lb./l,000 Ub.
FAX production
3.40 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.32 x 10-2
8.82 x 10"
7.23 x 10-4
2.10 x 10-3
2.56 x 10-3
2.74 x lO'2
3.22 x W-4
1.91 x 10-'
8.79 x 10-3
2.68 x 10"
3.12 x 10"
9.14 x 10"
1.02 x 10-3
1.41 x lO'2
1.09 x 10"
5.14 x 10-2
No discharge of process wastewater pollutants
1.69 x 10-2
8.72 x 10-3
No discharge of process wastewater pollutants
1.24 x 10-1
3.95 x 10-3
3.95 x 10-3
5.74 x ID'3
5.74 x 10-3
4.18 x 10-2
1.27 x 10-3
1.27 x 10-3
1.87 x 10-3
1.87 x 10-3
                                  10-7

-------
Table 10-1




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Butachlor
Captafol
Carbarn S3 [Sodium
dimethyldithiocarbamate ]
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cy anaz ine
Dazomet3
DCPA
DEF
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
BAT effluent limitations
Daily Maximum Shall Hot Exceed Lb./ 1,000 It. PAI
production
3.53 x 1C'3
Monthly
Average Shall
not Exceed
Ib. /I, 000 Ib.
PAI production
1.09 x 10-3
No discharge of process wastewater pollutants
5.74 x lO'3
1.60 x ID'3
1.18 x 10"
8.16 x 10-2
1.51 x 10'3
3.27 x 10"
1.63 x lO"3
5.74 x lO'3
7.79 x 10-2
1.15 x lO'2
2.82 x lO'3
1.87 x 10-3
7.30 x 10"
2.80 x ID'5
3.31 x 10-2
4.57 x 10"
9.96 x ID'5
8.11 x 10"
1.87 x lO'3
2.64 x 10-2
5.58 x lO'3
1.12 x lO'3
No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x 10-2
7.33 x ID'3
3.15 x lO'2
2.95 x lO'5
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x 10-2
No discharge of process wastewater pollutants
2.20 x lO'2
5.10 x 10-3
    10-8

-------
Table 10-1




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Ethalfluralin1-2
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Me thoxy ch lor
Metribuzin
Mevinphos
Nab am3
Nabonate3
BAT effluent limitations
Daily Maximum Shall Hot Exceed lb./ 1,000 Ib. FAI
production
3.22 x 10*
7.37 x 10-4
1.02 x 10-'
1.48 x 10-2
1.83 x lO'2
5.40 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 Ub.
FAI production
1.09 x 10"
2.99 x 10*
3.61 x lO'2
7.64 x lO'3
9.45 x 10-3
2.08 x 10-3
No discharge of process wastewater pollutants
8.80 x 10-3
7.06 x ID'3
5.74 x 10-3
2.69 x 10-3
2.35 x 10*
2.90 x 10-3
2.49 x lO'3
1.87 x 10-3
1.94 x 10-3
9.55 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.46 x ID'2
3.82 x 10-3
3.23 x ID'3
1.36 x lO'2
1.44 x 10*
5.74 x lO'3
5.74 x 10-3
5.58 x lO'3
7.53 x 10-3
1.76 x 10-3
1.31 x lO'3
7.04 x 10-3
5.10 x 10-5
1.87 x 10-3
1.87 x 10-3
   10-9

-------
Table 10-1




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Naled
Norf lurazon
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendime thai in
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
BAT effluent limitations
Daily Maximum Shall Hot Exceed lb./ 1,000 li>. PAI
production
Monthly
Average Shall
not Exceed
lb./l,000 lb.
PAI production
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.72 x 10-2
7.72 x IQ-4 •
1 .72 x 10-4
5.75 x 10-4
3.21 x lO'3
2.32 x 10-4
2.51 x 10"4
7.42 x ID'3
3.43 x 10^
3.43 x 10-1
1.90 x lO"4
1.06 x 10-3
6.06 x 10-5
7.53 x 10-4
No discharge of process wastewater pollutants
2.10 x 10-3
2.10 x 10-3
2.00 x W*
5.34 x 10-3
1.06 x 10-3
2.10 x 10-3
9.14 x 10-4
9.14 x 10-4
6.90 x 10-5
1.66 x 10-3
4.84 x 10^
9.14 x lO-4
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.10 x 10-3
4.10 x lO'3
2.88 x lO"4
9.78 x ID'2
1.51 x 10-'
9.14 x W-4
1.35 x 10'3
8.96 x 10-5
3.40 x 1C'2
5.12 x lO'2
   10-10

-------
                                  Table 10-1

                                  (Continued)
Organic Pesticide Active
Ingredient (PAI)
Terbufos
Terbuthylaz ine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [Sodium
methyldithiocarbamate ]
Ziram3 [Zinc
dimethyldithiocarbamate ]
BAT effluent limitations
Daily Maximum Shall Rot Exceed Ib./ 1,000 U>. PAI
production
4.09 x 10^
2.10 x 10-3
2.10 x 10-3
1.02 x 10-2
6.52 x 10-2
3.22 x 10^
5.74 x lO'3
5.74 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 li.
PAI production
1.06 x 10"
9.14 x 10-4
9.14 x 10-4
3.71 x 10-3
3.41 x 10-2
1.09 x 10"
1.87 x 10-3
1.87 x 10°
'Monitor and comply after in-plant treatment before mixing with other
 wastewaters.

2Monitor and report as total toluidine PAIs, as Trifluralin.

3 Monitor  and  report  as  total  dithiocarbamates,  as  Ziram.

4 Monitor  and  report  as  total  tin.

5 Applies  to purification by recrystalization portion  of  the process.
                                     10-11

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                                  Table 10-2

BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR DIRECT DISCHARGE
           POINT SOURCES THAT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 ,2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
2-Chlorophenol
1 , 2 -Diehlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
2 , 4-Dichlorophenol
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 , 4 - D ime thy Ipheno 1
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT effluent limitations1
Hair! «mim for
Any One Day
Gtg/U
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
25
59
89
211
59
26
Ma-^mnn. £Or Monthly
Average
(MS/I)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
16
22
40
68
22
15
                                     10-12

-------
                                  Table 10-2

                                  (Continued)
Priority Pollutant
Tetrachloroethylene
Total Cyanide
Total Lead2
BAT effluent limitations1
Maximum for
Any One Day
<«5/L)
56
640
690
Maiinnsn for Monthly
Average
(W5/IO
22
220
320
'All  units  are  micrograms  per  liter.

2Metals  limitations  apply  only to  noncomplexed metal-bearing waste  streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
                                     10-13

-------
                                  Table 10-3

BAT EFFLUENT LIMITATIONS AND NSPS FOR PRIORITY POLLUTANTS FOR DIRECT DISCHARGE
       POINT SOURCES THAT DO NOT USE END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1, 2-Dichloroethane
1,1, 1-Trichloroe thane
Trichlorome thane
1 , 2 -Dichlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Ch 1 o r ome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
BAT effluent limitations1
Ma-ri imim for
Any One Day
C/ig/L)
134
380
380
574 -
59
46
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Ma-r-imum for Monthly
Average
(06/L)
57
142
142
180
22
21
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
                                     10-14

-------
                                  Table 10-3

                                  (Continued)
Priority Pollutant
Total Cyanide
Total Lead2
BAT effluent limitations1
Maximum for
Any One Day
(«5/U
640
690
Maximum for Monthly
Average
(MJ/U
220
320
'All  units  are  micrograms  per  liter.

2Metals  limitations  apply  only to  noncomplexed metal-bearing waste  streams.
Discharges of lead from complexed metal-bearing process wastewater are not
subject to these limitations.
                                     10-15

-------
                                  SECTION 11




                    NEW SOURCE  PERFORMANCE STANDARDS  (NSPS)









11.0        INTRODUCTION









            New source performance standards (NSPS) under Section 306 of the




Clean Water Act represent the most stringent numerical values attainable




through the application of the best available demonstrated control technology




for all pollutants  (conventional, nonconventional,  and priority pollutants).









            This section summarizes the proposed NSPS guidelines.  The




specific discussions regarding their development are included in Section 6




(Pollutant Selection),  Section 7 (Technology Selection and Limit Development),




and Section 8 (Cost and Effluent Reduction Benefits).









11.1        SUMMARY OF NSPS EFFLUENT LIMITATIONS GUIDELINES









            The Agency based NSPS for conventional pollutants and COD on the




promulgated BPT limitations and for organic PAIs and priority pollutants on




the performance of BAT technologies.  The Agency determined that limitations




that are more stringent than BAT limitations proposed for existing plants can




be achieved and are justified in some cases; in the remaining cases, NSPS is




proposed to be set equal to BAT.  BAT limits were modified to reflect the




capability for wastewater flow reduction at new facilities.  The Agency is
                                     11-1

-------
proposing to transfer the organic pesticide chemicals manufacturing




subcategory NSPS for 23 priority pollutants from the OCPSF point source




category and is developing NSPS for four brominated priority pollutants and




total cyanide.









            The Agency considered four technology options in developing NSPS:




basing NSPS on the BAT limits with no additional flow reduction, transference




of BAT limits for organic PAIs after incorporation of a 28% flow reduction,




flow reduction plus membrane filtration, and no discharge of process




wastewater pollutants.  In the assessment of these NSPS options, the Agency




considered the reasonableness of costs to implement these treatment




technologies.  A complete discussion of the four options considered for NSPS




are discussed in Sections 7.4.4 and 7.5.4, along with the option selected for




regulation.









11.2        IMPLEMENTATION OF THE NSPS EFFLUENT LIMITATIONS GUIDELINES









11.2.1      National Pollutant Discharge Elimination System (NPDES) Permit




            Limitations









            The proposed NSPS for conventional pollutant parameters, COD, and




organic PAIs are mass-based limitations and the proposed NSPS for priority




pollutants are concentration-based limits.  Limitations should be developed




using guidance given for the implementation of BAT effluent limitations




guidelines (see Section 10.2.1).
                                     11-2

-------
            These NSPS, once promulgated, will be included in the National




Pollutant Discharge Elimination System (NPDES) permit issued to direct




dischargers [see 40 CFR §122.44(a)].   The final NPDES permit limitations will




include mass effluent limitations for pesticide chemicals manufacturing, as




well as non-pesticide chemicals manufacturing and nonprocess wastewater




discharges.









11.2.2      Monitoring Requirements









            The NPDES regulations provide guidelines setting forth minimum




monitoring and reporting requirements for NPDES dischargers.  Section 122.48




requires that each permit specify requirements regarding monitoring type,




intervals, and frequency sufficient to yield data that are representative of




the monitored activity.  Sections 122.41, 122.44, and 122.48 contain numerous




other requirements concerning monitoring and reporting.  Therefore, the




proposed rule does not establish monitoring requirements.  As stated in




Section 8, EPA assumed a monitoring frequency of once per week for all limited




PAI pollutants and once per month for all limited priority pollutants in




estimating monitoring costs.









11.3        NEW SOURCE PERFORMANCE STANDARDS (NSPS)









            The proposed NSPS for conventional pollutants, organic PAIs and




classes of PAIs, and priority pollutants under the organic pesticide chemicals
                                     11-3

-------
manufacturing subcategory  (Subcategory A) are listed in Tables 11-1, 11-2,  11




3, and 11-4.
                                      11-4

-------
                                  Table 11-1

         NSPS  EFFLUENT  LIMITATIONS  FOR  CONVENTIONAL  POLLUTANTS AND  COD
Effluent
Characteristic
COD
BOD5
TSS
pH
Maximum for Any
1 Day
9.36
5.33
4.39
*
Average of Daily Values
Consecutive Days Shall Not
for 30
Exceed**
6.48
1.15
1.30
*
'These  standards  incorporate  a  28 percent  flow  reduction  achievable by  new
sources.

*Within the range 6.0 to 9.0.

**Metric units:  Kilogram/1,000 kg of PAI produced; English units:
Pound/1,000 Ib of PAI produced; established on the basis of pesticide
production.
                                     11-5

-------
                                Table 11-2




PSNS EFFLUENT LIMITATIONS FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Ac if luorfen1
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 403
Busan 853
Butachlor
New Source Performance Standards (NSPS)
Daily Maximum Shall Hot Exceed Uo./l.OOO
IB. PAI production
8.51 x ID'5
Monthly Average
Shall Hot Exceed
lb./l,000 It. PAI
production
2.42 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.67 x 10-2
6.35 x 10"
5.21 x 10-*
1.52 x 10-3
1.84 x ID'3
1.97 x 10-2
2.32 x 10"
1.37 x 10-'
6.33 x lO'3
1.93 x 10"
2.25 x 10"
6.59 x 10"
7.33 x 10"
1.02 x 10-2
7.82 x 10-5
3.70 x 10-2
No discharge of process wastewater pollutants
1.21 x 10-2
6.28 x 10-3
No discharge of process wastewater pollutants
8.90 x ID'2
2.84 x 10-3
2.84 x ID'3
4.13 x 10-3
4.13 x 10-3
2.54 x 10-3
3.00 x 10-2
9.11 x 10"
9.11 x 10"
1.35 x 10-3
1.35 x 10-3
7.90 x 10"
                                   11-6

-------
Table 11-2




(Continued)
Organic Pesticide Active
Ingredient
Captafol
Carbarn S3
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cyanazine
Dazomet
DCPA
DEF [S,S,S-Tributyl
phosphorotri thioate ]
Diazinon1
Dichlorprop , salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
New Source Performance Standards (NSPS)
Daily Maximum Shall Hot Exceed It. /I, 000
11. PAI production
Monthly Average
Shall Hot Exceed
It. /I, ODD It. PAI
production
No discharge of process wastewater pollutants
4.10 x lO'3
1.18 x 10-3
1.18 x 10"
5.87 x 10-2
1.08 x 10-3
2.35 x 10"
1.18 x 10-3
4.10 x ID'3
5.60 x 10-2
1.15 x 10-2
2.04 x 10-3
1.37 x 10-3
5.24 x 10"
2.80 x 10-5
2.38 x 10-2
3.29 x 10"
7.19 x 10-5
5.84 x W-4
1.37 x 10-3
1.90 x 10-2
5.58 x 10-3
8.13 x 10"
No discharge of process wastewater pollutants
6.91 x 10-5
3.41
2.44 x 10-2
5.27 x 10-3
2.27 x 10-2
2.11 x 10-5
1.03
9.31 x 10-3
2.73 x 10-3
1.01 x 10-2
No discharge of process wastewater pollutants
1.57 x 10-2
2.32 x 10"
3.69 x 10-3
7.82 x 10-5
   11-7

-------
Table 11-2




(Continued)
Organic Pesticide Active
Ingredient
Ethion
Fenarimol
Fensulfothion
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Methoxychlor
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norflurazon
New Source Performance Standards (NSPS)
Daily Maximum Shall Hot Exceed lb./ 1,000
Lb. PAI production
5.31 x 10-»
7.33 x 10-2
1.06 x 10-2
1.31 x lO'2
3.90 x 10-3
Monthly Average
Shall Not Exceed
It. 11, 000 lb. PAI
production
2.15 x 10"4
2.62 x lO'2
5.50 x 10-3
6.80 x 10-3
1.50 x 10-3
No discharge of process wastewater pollutants
6.31 x ID'3
5.07 x 10-3
4.13 x 10-3
1.94 x 10-3
1.69 x 10-4
2.06 x 10-3
1.82 x 10-3
1.35 x 10-3
1.40 x 10-3
6.88 x 10-»
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x lO'2
1.05 x ID'2
2.76 x 10-3
2.32 x 10-3
9.79 x lO'3
1.03 x 10-4
4.10 x 10-3
4.13 x 10-3
5.58 x 10-3
5.42 x 10-3
1.27 x lO'3
9.45 x 10"4
5.06 x 10-3
3.65 x lO'5
1.37 x 10-3
1.35 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
    11-8

-------
Table 11-2




(Continued)
Organic Pesticide Active
Ingredient
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Pentachlorophenol, salts
and esters
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
New Source Performance Standards (NSPS)
Daily Maximum Shall Not Exceed li./ 1,000
Il>. PAI production
1.25 x ID'2
5.55 x 10"
5.55 x 10"
4.16 x 10"
2.31 x 10-3
Monthly Average
Shall Hot Exceed
Ib./l.OOO li. PAI
production
5.35 x 10-3
2.47 x 10"
2.47 x 10"
1.38 x 10"
7.64 x 10"
No discharge of process wastewater pollutants
1.68 x 10"
1.81 x 10"
4.38 x lO'5
5.42 x ID'5
No discharge of process wastewater pollutants
1.52 x 10-3
1.52 x 10-3
1.44 x 10"
3.85 x ID'3
7.64 x 10"
1.52 x 10-3
6.59 x 10"
6.59 x 10"
4.97 x ID'5
1.19 x 10-3
3.49 x 10"
6.59 x 10"
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.52 x 10-3
2.95 x 10-3
2.07 x 10"
7.05 x lO-2
1.09 x 10-'
2.95 x 10"
6.59 x 10"
9.72 x 10"
6.45 x lO'5
2.45 x 10-2
3.68 x 10-2
7.59 x 10-5
   11-9

-------
                                  Table 11-2

                                  (Continued)
Organic Pesticide Active
Ingredient
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin'-2
Vapam3 [ Sodium
methyldithiocarbamate]
Ziram3 [Zinc
dimethyldi thiocarbamate ]
New Source Performance Standards (NSPS)
Dally Maximum Shall Not Exceed 11, / 1,000
Ib. PAX production
1.52 x 10-3
1.52 x 10-3
7.34 x 10-3
4.70 x 10-2
2.32 x 10"
4.13 x ID'3
4.13 x 10-3
Monthly Average
Shall Hot Exceed
lb./l,000 Ib. PAI
production
6.59 x 10-4
6.59 x 10"
2.67 x 1C'3
2.46 x ID'2
7.82 x 10-5
1.35 x 10-3
1.35 x 10-3
'Monitor and comply after in-plant treatment before mixing with other
 wastewaters.

2Monitor and report as total toluidine PAIs, as Trifluralin.

3Monitor and report as total dithiocarbamates,  as Ziram.

4Monitor and report as total tin.

5Applies to purification by recrystallization portion of the  process.
                                     11-10

-------
                                  Table 11-3




NSPS FOR PRIORITY POLLUTANTS FOR PLANTS WITH END-OF-PIPE BIOLOGICAL TREATMENT
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
2-Chlorophenol
1,2- Dichlorobenzene
1 ,4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-trans-Dichloroethylene
2 ,4-Dichlorophenol
1, 2-DIchloropropane
1, 3-Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
BAT/NSPS effluent limitations1
Maximum for
Any One Day
<«5/L)
136
38
28
211
54
46
98
163
28
25
54
112
230
44
36
108
89
190
25
59
89
211
59
Ma-riimim for Monthly
Average
C/ig/L)
37
18
15
68
21
21
31
77
15
16
21
39
153
29
18
32
40
86
16
22
40
68
22
                                     11-11

-------
                                  Table 11 3

                                  (Continued)

Priority Pollutant
Phenol
Tetrachloroethylene
Total Cyanide
Total Lead2
BAT/NSPS effluent limitations1
Maximum for
Any One Day
(W5/IO
26
56
640
690
Maximum for Monthly
Average
(W5/D
15
22
220
320
1  All  units  are  micrograms per liter.

2  Metals  limitations  apply only to noncomplexed metal-bearing waste  streams.
 Discharges of lead from complexed metal-bearing process wastewater are not
 subject to these limitations.
                                     11-12

-------
                       Table 11-4

NSPS FOR PRIORITY POLLUTANTS FOR PLANTS THAT DO NOT HAVE
            END-OF-PIPE  BIOLOGICAL  TREATMENT
Priority Pollutant
Benzene
Carbon Tetrachloride
Chlorobenzene
1 , 2 - Dichloroe thane
1,1, 1-Trichloroe thane
Chloroform
1, 2-Dichlorobenzene
1 ,4-Dichlorobenzene
1 , 1-Dichloroethylene
1 ,2-trans-Dichloroethylene
1 , 2-Dichloropropane
1 , 3 -Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Methylene Chloride
Methyl Chloride
Bromome thane
Tribromome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
BAT effluent limitations'
Ma-yiimii^ for
Any One Day
Otg/L)
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
60
47
170
574
47
47
Ma-j-itmim for Monthly
Average
<«; A.)
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
22
19
36
180
19
19
                          11-13

-------
                                  Table 11-4

                                  (Continued)
Priority Pollutant
Tetrachloroethylene
Toluene
Total Cyanide
Total Lead2
BAT effluent limitations1
Maximum for
Any One Day
(W5/IO
164
74
640
690
Maximum for Monthly
Average
Cpg/I.)
52
28
220
320
'All units are micrograms per liter.

2  Metals  limitations apply only to noncomplexed metal-bearing waste  streams.
 Discharges of lead from complexed metal-bearing process wastewater are not
 subject to these limitations.
                                     11-14

-------
                                  SECTION 12




            PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES) AND




                 PRETREATMENT  STANDARDS FOR  NEW SOURCES  (PSNS)









12.0        INTRODUCTION









            Section 307(b) of the Clean Water Act (CWA) calls for EPA to




promulgate pretreatment standards for existing sources (PSES).  PSES are




designed to prevent the discharge of pollutants that pass through, interfere




with, or are otherwise incompatible with the operation of publicly owned




treatment works  (POTWs).   The legislative history of the Clean Water Act of




1977 indicates that pretreatment standards are to be technology-based, and




analogous to the best available technology economically achievable for direct




dischargers.









            Section 307(c) of the CWA calls for EPA to promulgate pretreatment




standards for new sources (PSNS) at the same time that it promulgates new




source performance standards (NSPS).   New indirect discharging facilities,




like new direct discharging facilities, have the opportunity to incorporate




the best available demonstrated technologies, including process changes, in-




plant controls, and end-of-pipe treatment technologies, and to use plant site




selection to ensure adequate treatment system installation.
                                     12-1

-------
            General pretreatment regulations applicable to all existing and




new source indirect dischargers appear at 40 CFR Part 403.  These regulations




describe the Agency's overall policy for establishing and enforcing




pretreatment standards for new and existing users of a POTW, and delineate the




responsibilities and deadlines applicable to each party in this effort.  In




addition, 40 CFR Part 403, Section 403.5(b), outlines prohibited discharges




that apply to all users of a POTW.









            Indirect dischargers in the pesticide manufacturing industry, like




the direct dischargers,  use as raw materials,  and produce as products or




byproducts many nonconventional pollutants  (including PAIs) and priority




pollutants.  As in the case of direct dischargers, they may be expected to




discharge many of these pollutants to POTWs at significant levels.  EPA




estimates that indirect dischargers of organic pesticides annually discharge




110,000 pounds of PAIs and 29,000 pounds of priority pollutants to POTWs,









            This section summarizes the proposed PSES and PSNS guidelines.




Specific discussions regarding their development are included in Section 6




(Pollutant Selection),  Section 7 (Technology Selection and Limits




Development),  and Section 8 (Cost and Effluent Reduction Benefits).
                                     12-2

-------
12.1        SUMMARY OF PSES AND PSNS









            The Agency considered pollutants to regulate in PSES and PSNS on




the basis of whether or not they pass through,  cause an upset, or otherwise




interfere with the operation of a POTW.  EPA is proposing to develop PSES and




PSNS for 26 of the 28 priority pollutants and for the same 91 PAIs and classes




of PAIs proposed under BAT and NSPS.  Two priority pollutants, 2-chlorophenol




and 2,4-dichlorophenol,  do not pass through or interfere with POTW operation,




so PSES and PSNS are not being set for these two pollutants.









            The Agency considered the same technologies discussed for BAT and




NSPS since indirect dischargers are expected to generate wastewaters with the




same pollutant characteristics.  However, end-of-pipe biological treatment




would not be required for priority pollutants,  since the primary function of




biological treatment is to reduce BOD loadings, whether at the plant or at a




POTW.  A complete discussion of the options considered for PSES and PSNS are




included in Sections 7.4.6 and 7.5.6, along with the options selected for




regulation.









            EPA estimates that the proposed PSES regulation will result in the




incremental removal of 105,000 pounds per year of pesticide active




ingredients, and 29,000 pounds per year of priority pollutants.  EPA estimates




that cost for compliance with the proposed PSES are capital costs of $9.1




million and annualized costs of just over $6.4 million (1986 dollars).   (See
                                     12-3

-------
"Economic Impact Analysis of Effluent Limitations and Standards of the




Pesticide Manufacturers".)









12.2        PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES/PSNS)









            The proposed pretreatment standards for existing and new sources




(PSES/PSNS) for organic PAIs and classes of PAIs and priority pollutants under




the organic pesticide chemicals manufacturing subcategory (Subcategory A) are




listed in Tables 12-1, 12-2, 12-3, and 12-4.
                                      12-4

-------
                     Table 12-1




PSES FOR ORGANIC PESTICIDE ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient (PAI)
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1-2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 403 [Potassium N-
hydroxymethyl-N-
methyldithiocarbamate]
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed lb./l,000 ti>. PAI
production
1.19 x 10^
Monthly
Average Shall
not Exceed
U>./1,000 Ib.
FAI production
3.40 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.32 x 10-2
8.82 x 10-4
7.23 x 10-4
2.10 x 10-3
2.56 x 10-3
2.74 x ID'2
3.22 x 10^
1.91 x 10-'
8.79 x 10-3
2.68 x 10-*
3.12 x W-4
9.14 x 10-*
1.02 x 10-3
1.41 x 10-2
1.09 x 10-4
5.14 x 10-2
No discharge of process wastewater pollutants
1.69 x 10-2
8.72 x 10-3
No discharge of process wastewater pollutants
1.24 x 10-1
3.95 x 10-3
3.95 x 10-3
5.74 x ID'3
4.18 x 10-2
1.27 x 10-3
1.27 x lO'3
1.87 x 10-3
                        12-5

-------
Table 12-1




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Busan 853 [Potassium
dimethyldithiocarbamate ]
Butachlor
Captafol
Carbarn S3 [Sodium
dimethyldithiocarbamate ]
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cy anaz ine
Dazomet3
DCPA
DEF
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed U»./ 1,000 li. PAI
production
5.74 x 10-3
3.53 x 10-3 -
Monthly
Average Shall
not Exceed
It. /1, 000 Ib.
PAI production
1.87 x 10-3
1.09 x 10-3
No discharge of process wastewater pollutants
5.74 x 10-3
1.60 x lO'3
1.18 x 10-4
8.16 x 10-2
1.51 x 10-3
3.27 x 10-4
1.63 x 10-3
5.74 x 10-3
7.79 x 10-2
1.15 x 10-2
2.82 x 10-3
1.87 x 10-3
7.30 x 10-*
2.80 x 1C'5
3.31 x 10-2
4.57 x 10-1
9.96 x 10-5
8.11 x 10-4
1.87 x 10-3
2.64 x 10-2
5.58 x 10-3
1.12 x ID'3
No discharge of process wastewater pollutants
9.60 x 10-5
4.73
3.40 x lO'2
7.33 x 10-3
3.15 x 10-2
2.95 x 10-5
1.43
1.29 x 10-2
3.79 x 10-3
1.40 x 10-2
   12-6

-------
Table 12-1




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
Ethion
Fenarimol
Fens ul f o th i on
Fenthion
Fenvalerate
Glyphosate, salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Methamidophos
Me thorny I1
Methoxychlor
Metribuzin
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed lb./l,OOD li>. PAI
production
Monthly
Average Shall
not Exceed
IB. /1, 000 Ib.
PAI production
No discharge of process wastewater pollutants
2.20 x lO'2
3.22 x 10^
7.37 x 10-4
1.02 x 10-'
1.48 x 10-2
1.83 x 10-2
5.40 x 10-3
5.10 x lO'3
1.09 x 10-1
2.99 x W^
3.61 x 10-2
7.64 x 10-3
9.45 x lO'3
2.08 x 10-3
No discharge of process wastewater pollutants
8.80 x lO'3
7.06 x lO'3
5.74 x 10-3
2.69 x lO'3
2.35 x 10-4
2.90 x 10-3
2.49 x 10-3
1.87 x lO'3
1.94 x lO'3
9.55 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.46 x 10-2
3.82 x 10-3
3.23 x 10-3
1.36 x 10-2
5.58 x 10-3
7.53 x 10-3
1.76 x lO'3
1.31 x 10-3
7.04 x 10-3
   12-7

-------
Table 12-1




(Continued)
Organic Pesticide Active
Ingredient (PAI)
Mevinphos
Nab am3
Nabonate3
Naled
Norflurazon
Organotins4
Parathion Ethyl
Parathion Methyl
PCNB
Pendimethalin
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
Simazine
Pretreatment Standards for Existing Sources
(PSES)
Daily Haxlimm Shall Hot Exceed Ib./l.OOO lb. PAI
production
1.44 x 10*
5.74 x 10-3
5.74 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 It.
PAI production
5.10 x 10-5
1.87 x lO'3
1.87 x 10-3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.72 x 10-2
7.72 x 10"
7.72 x 10*
5.75 x 10*
3.21 x lO'3
2.32 x 10"
2.51 x 10"
7.42 x 10-3
3.43 x 10"
3.43 x 10"
1.90 x 10"
1.06 x ID'3
6.06 x 1C'5
7.53 x 10"
No discharge of process wastewater pollutants
2.10 x 10-3
2.10 x lO'3
2.00 x 10"
5.34 x lO'3
1.06 x 10-3
2.10 x 10-3
9.14 x 10"
9.14 x 10"
6.90 x lO'5
1.66 x 10-3
4.84 x 10"
9.14 x 10"
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
2.10 x lO'3
9.14 x 10"
   12-8

-------
                                  Table 12-1

                                  (Continued)
Organic Pesticide Active
Ingredient (PAI)
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthylazine
Terbutryn
Toxaphene
Triadimefon
Trifluralin1-2
Vapam3 [Sodium
methyldithiocarbamate ]
Ziram3 [Zinc
dimethyldithiocarbamate ]
Pretreatment Standards for Existing Sources
(PSES)
Daily Maximum Shall Hot Exceed Ib./l.OOO JJb. PAI
production
4.10 x lO'3
2.88 x 10"
9.78 x 1C'2
1.51 x ID'1
4.09 x 10^
2.10 x 10-3
2.10 x 1C'3
1.02 x 10-2
6.52 x 10-2
3.22 x 10-4
5.74 x 10-3
5.74 x 10-3
Monthly
Average Shall
not Exceed
lb./l,000 It.
PAI production
1.35 x lO'3
8.96 x 10-5
3.40 x 10-2
5.12 x 10-2
1.06 x 10"
9.14 x W^
9.14 x 10"4
3.71 x 10-3
3.41 x 10--
1.09 x W-4
1.87 x ID'3
1.87 x 10-3
'Monitor and comply after in-plant treatment before  mixing with other
wastewaters.

2Monitor and report as total toluidine PAIs,  as  Trifluralin.

3Monitor and report as total dithiocarbamates,  as  Ziram.

4Monitor and report as total tin.

5Applies to purification by recrystalization portion of the process.
                                     12-9

-------
         Table 12-2




PSES FOR PRIORITY POLLUTANTS
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2 -Dichloroethane
1,1, 1-Trichloroe thane
Trichlorome thane
1 , 2-Dichlorobenzene
1 ,4-Dichlorobenzene
1 , 1-Dichloroethylene
1 , 2-Trans-Dichloroethylene
1, 2-Dichloropropane
1 , 3-Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chi o r ome thane
Bromome thane
Tr ib r omome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
Pretreatment Standards
for Existing (PSES)1
Ma-rimimi £Or Any One Day
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Maximum for Monthly
Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
            12-10

-------
                                  Table 12-2

                                  (Continued)
Priority Pollutant
Total Cyanide
Total Lead2
Pretreatment Standards
for Existing (PSES)1
Maximum for Any One Day
640
690
Maximum for Monthly
Average
220
320
'All units are micrograms per liter.

2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead and zinc from complexed metal-bearing process wastewater
are not subject to these limitations.
                                     12-11

-------
                      Table  12-3




PSNS FOR ORGANIC PESTICIDES ACTIVE INGREDIENTS (PAIS)
Organic Pesticide Active
Ingredient
2, 4-D1
2, 4-D salts and esters
2,4-DB salts and esters
Acephate
Acifluorfen1
Alachlor
Aldicarb1
Ametryn
Atrazine
Azinphos Methyl
Benfluralin1'2
Benomyl1
Biphenyl
Bolstar
Bromacil, lithium
Bromacil
Bromoxynil
Bromoxynil octanoate
Bus an 403
Busan 853
Butachlor
Captafol
Carbarn S3
Pre treatment Standards for New Sources (PSNS)
Daily Maximum Shall Hot Exceed Ub./l,000
Lb, PA1 production
8.54 x lO'5
Monthly Average
Shall Mot Exceed
It, /I. 000 Ib. FAX
production
2.45 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.67 x 10-2
6.35 x 10"
5.21 x 10-4
1.51 x 10-3
1.85 x 10-3
1.97 x 10-2
2.32 x 10"
1.37 x 10-'
0
1.22 x 10-2
6.33 x 1C'3
1.93 x 10"
2.25 x 10"
6.58 x 10"
7.32 x 10"
1.02 x lO'2
7.82 x lO'5
3.70 x 10-2
0
6.27 x 10-3
No discharge of process wastewater pollutants
8.89 x 10-2
2.84 x 10-3
2.84 x 10-3
4.14 x 10-3
4.14 x 10-3
2.54 x 10-3
3.01 x 10-2
9.14 x 10"
9.11 x 10"
1.35 x 10-3
1.35 x 10-3
7.87 x 10"
No discharge of process wastewater pollutants
4.14 x 10-3
1.35 x 10-3
                        12-12

-------
Table 12-3




(Continued)
Organic Pesticide Active
Ingredient
Carbaryl1
Carbofuran
Chloroneb
Chlorothalonil
Chlorpyrifos1
Cyanazine
Dazomet
DCPA
DEF [S,S,S-Tributyl
phosphorotrithioate ]
Diazinon1
Dichlorprop, salts and
esters
Dichlorvos
Dinoseb
Dioxathion
Disulfoton
Diuron
Endothall, salts and
esters
Endrin
Ethalfluralin1-2
Ethion
Fenarimol
Fensulfothion
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Not Exceed Ub./l,000
Lb. PAX production
1.07 x 10-3
1.18 x 10^
5.87 x 10-2
1.09 x 10-3
2.35 x W-4
1.18 x 10-3
4.14 x lO-3
5.61 x 10-2
1.15 x 10-2
2.05 x 10-3
Monthly Average
Shall Not Exceed
li./l,000 li. PAI
production
4.76 x 10-4
2.80 x 10-5
2.39 x 10-2
3.29 x 10^
7.17 x 10-5
5.84 x 10"4
1.35 x lO'3
1.90 x lO'2
5.58 x 10-3
8.13 x 10-4
No discharge of process wastewater pollutants
6.88 x 10-5
3.41
1.51 x 10-'
5.28 x 10-3
2.27 x 10-2
2.13 x 10-5
1.03
5.76 x 10-2
2.72 x lO'3
1.01 x 10-2
No discharge of process wastewater pollutants
1.77 x lO'2
2.32 x 10-*
5.31 x 10-4
7.31 x 10-2
1.06 x 10-2
5.25 x 10-3
7.85 x lO'5
2.15 x 10-*
2.60 x 10-2
5.50 x 10-3
   12-13

-------
Table 12-3




(Continued)
Organic Pesticide Active
Ingredient
Fenthion
Fenvalerate
Glyphosate , salts and
esters
Heptachlor
Isopropalin1
KN Methyl3
Linuron
Malathion
MCPA salts and esters
MCPP salts and esters
Merphos
Me thami dopho s
Methomyl1
Methoxychlor
Metribuzin
Mevinphos
Nab am
Nabonate
Naled
Norf lurazon
Organotins4
Parathion Ethyl
Farathion Methyl
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Kot Exceed Ub./l,000
li. PAI production
1.32 x 10-2
3.91 x 10-3
Monthly Average
Shall Not Exceed
li./l,000 IJb. PAI
production
6.79 x 10-3
1.50 x 10-3
No discharge of process wastewater pollutants
5.42 x 10-3
5.07 x 10-3
4.14 x 10-3
1.94 x 10-3
1.69 x 10"4
1.73 x lO'3
1.82 x lO'3
1.35 x lO'3
1.40 x 10-3
6.88 x 10-5
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.15 x 10-2
1.05 x 10-2
2.75 x 10-3
2.34 x 10-3
9.80 x 10-3
1.03 x 10-*
4.14 x 10-3
4.14 x 10-3
5.58 x 10-3
5.42 x ID'3
1.27 x lO'3
9.25 x 10-*
5.06 x 10-3
3.69 x 10-5
1.35 x lO'3
1.35 x lO'3
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.25 x 10-2
5.56 x W*
5.56 x 10-*
5.36 x ID'3
2.45 x W*
2.45 x 10-4
   12-14

-------
Table 12-3




(Continued)
Organic Pesticide Active
Ingredient
PCNB
Pendimethalin
Pentachlorophenol, salts
and esters
Permethrin
Phorate
Phosmet5
Prometon
Prometryn
Pronamide
Propachlor
Propanil
Propazine
Pyrethrin I
Pyrethrin II
S imaz ine
Stirofos
TCMTB
Tebuthiuron
Terbacil
Terbufos
Terbuthy laz ine
Terbutryn
Toxaphene
Pretreatment Standards for New Sources (PSNS)
Daily Maximum Shall Not Exceed li./ 1,000
li. PAI production
4.16 x 10-1
8.81 x 1C'3
Monthly Average
Shall Hot Exceed
Ub./l.OOO It. PAI
production
1.38 x 10^
2.79 x 10-3
No discharge of process wastewater pollutants
1.68 x 10-4
1.81 x W-*
4.39 x lO'5
5.43 x 10-3
No discharge of process wastewater pollutants
1.51 x 10-3
1.51 x 10-3
1.28 x 10-1
3.84 x 10-3
7.63 x 10-4
1.51 x 1C'3
6.58 x 10-*
6.58 x 10"1
4.34 x lO'5
1.19 x 10°
3.48 x 10-4
6.58 x 10^
No discharge of process wastewater pollutants
No discharge of process wastewater pollutants
1.51 x lO'3
2.95 x 10-3
2.07 x 10-4
7.04 x 10-2
1.09 x 10-'
2.95 x 10-*
1.51 x 10-3
1.51 x 10-3
7.35 x 10-3
6.58 x 10^
9.72 x 10-*
6.45 x 10-5
2.45 x 10-2
3.69 x 10-2
7.62 x 10-5
6.58 x 10^
6.58 x 10-4
2.67 x 1C'3
   12-15

-------
                                    Table 12-3

                                    (Continued)
 Organic  Pesticide Active
 Ingredient
                              Pretreatment Standards for New Sources  (PSNS)
                              Daily Maximum Shall Hot Exceed li>./1,000
                                      Lb. FAX production
                        Monthly Average
                        Shall Hot Exceed
                        tb./l.bOO li. PAI
                          production
 Triadimefon

 Trifluralin1'2

 Vapam3 [Sodium
 methyldithiocarbamate]

 Ziram3 [Zinc
 dimethyldithiocarbamate]
4.69 x 10-2

2.32 x 10*

3.86 x 10-3


4.14 x 10-3
2.46 x 10-2

7.82 x 10-5

1.39 x 10-3


1.35 x 10-3
'Monitor and comply after in-plant  treatment before mixing  with other
wastewaters.

2Monitor and report as total toluidine PAIs, as Trifluralin.

3Monitor and report as total dithiocarbamates,  as Ziram.

"Monitor and report as total tin.

5Applies to  purification by recrystallization portion of  the  process.
                                       12-16

-------
                    Table  12-4




PSNS EFFLUENT LIMITATIONS FOR PRIORITY POLLUTANTS
Priority Pollutant
Benzene
Tetrachlorome thane
Chlorobenzene
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Trichlorome thane
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
1, 1-Dichloroethylene
1, 2-Trans-Dichloroethylene
1, 2-Dichloropropane
1 , 3-Dichloropropene
2 ,4-Dimethylphenol
Ethylbenzene
Dichlorome thane
Chlorome thane
Bromome thane
Tr ib romome thane
Bromodichlorome thane
Dibromochlorome thane
Naphthalene
Phenol
Tetrachloroethylene
Toluene
Pretreatment Standards
for New Sources (PSNS)1
MaTriimim for Any One Day
134
380
380
574
59
325
794
380
60
66
794
794
47
380
170
295
25
59
89
211
47
47
164
74
Maximum for Monthly
Average
57
142
142
180
22
111
196
142
22
25
196
196
19
142
36
110
16
22
40
68
19
19
52
28
                      12-17

-------
                                  Table 12-4

                                  (Continued)
Priority Pollutant
Total Cyanide
Total Lead2
Pretreatment Standards
for New Sources (PSNS)1
Mailman for toy One Day
640
690
Maximum for Monthly
Average
220
320
'All units are micrograms per liter.

2Metals limitations apply only to noncomplexed metal-bearing waste streams.
Discharges of lead and zinc from complexed metal-bearing process wastewater
are not subject to these limitations.
                                     12-18

-------
                                  SECTION 13




             BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY (BCT)









13.0        INTRODUCTION









            The 1977 Amendments to the Clean Water Act added Section




301(b)(2)(E),  establishing "best conventional pollutant control technology"




(BCT) for the discharge of conventional pollutants from existing industrial




point sources.  Section 304(a)(4) designated the following as conventional




pollutants:  BOD5, TSS,  fecal  coliform, pH,  and  any additional  pollutants




defined by the Administrator as conventional.  On July 30, 1979 (44 FR 44501),




the Administrator designated oil and grease as a conventional pollutant.









            The BCT effluent limitations guidelines are not additional




guidelines, but instead, replace guidelines based on the application of the




"best available technology economically achievable" (BAT) for the control of




conventional pollutants.  BAT effluent limitations guidelines remain in effect




for nonconventional and toxic pollutants.   Effluent limitations based on BCT




may not be less stringent than the limitations based on "best practicable




control technology currently available" (BPT).  Thus,  BPT limitations are a




"floor" below which BCT limitations cannot be established.









            In addition to other factors specified in Section 304(b)(4)(B),




the CWA requires that the BCT effluent limitations guidelines be assessed  in




light of a two-part "cost-reasonableness" test  [see American Paper Institute
                                     13-1

-------
   EPA. 660 F 2d 954  (4th Cir. 1981)].  The first test compares the cost for
private industry to reduce its discharge of conventional pollutants with the




cost to publicly owned treatment works  (POTWs) for similar levels of reduction




in their discharge of these pollutants.  The second test examines the cost-




effectiveness of additional industrial  treatment beyond BPT.  EPA must find




that the limitations are  "reasonable" under both tests before establishing




them as BCT.  If the BCT  technology fails the first test, there is no need to




conduct the second test,  because the technology must pass both tests.  EPA




promulgated a methodology for establishing BCT effluent "limitations guidelines




on July 9, 1986 (51 FR 24974).









13.1        JULY 9, 1986  BCT METHODOLOGY









            The BCT methodology promulgated in 1986 addressed the costs that




the EPA must consider when deciding whether to establish BCT effluent




limitations guidelines.   EPA evaluates  BCT candidate technologies (those that




are technologically feasible) by applying a two-part cost test including: (1)




the POTW test; and (2) the industry cost effectiveness test.









            To "pass" the POTW test, EPA must determine that the cost per




pound of conventional pollutant removed by industrial dischargers in upgrading




from BPT to a BCT candidate technology  is less than the cost per pound of




conventional pollutant removed in upgrading POTWs from secondary treatment to




advanced secondary treatment.  The upgrade cost to industry must be less than




the POTW benchmark of $0.25 per pound in 1976 dollars for industries whose
                                     13-2

-------
cost per pound is based on long-term performance data (Tier I POTW benchmark),




or less than $0.14 per pound for industries whose cost per pound is not based




on long-term performance data (Tier II POTW benchmark).









            If a candidate technology passes the POTW cost test, the industry




cost-effectiveness test is then applied.  For each industry subcategory, EPA




computes a ratio of two incremental costs.  The first is the cost per pound of




conventional pollutants removed by the BCT candidate technology relative to




BPT; the second is the cost per pound of conventional pollutants removed by




BPT relative to no treatment (i.e., the second cost compares raw wasteload to




pollutant load after application of BPT).   The ratio of the first cost divided




by the second is a measure of the candidate technology's cost-effectiveness.




The ratio is compared to an industry cost benchmark, which is based on POTW




cost and pollutant removal data.  The benchmark, like the measure for a




candidate technology, is a ratio of two incremental costs:  the cost per pound




to upgrade a POTW from secondary treatment to advanced secondary treatment




divided by the cost per pound to initially achieve secondary treatment from




raw wasteload.  If the industry ratio is lower than the benchmark,  the




candidate technology passes the industry cost-effectiveness test.  The Tier I




benchmark for industries whose ratio is based on long-term performance data is




1.29.  The Tier II benchmark for industries whose ratio is not based on long-




term performance data is 0.68.









            In calculating this ratio, EPA considers any BCT cost per pound




less than $0.01 to be the equivalent of zero costs.  There may be cases where
                                     13-3

-------
the numerator for the industry cost ratio and therefore the entire ratio is




taken to be zero.  EPA believes any zero cost per pound for a candidate BCT




technology meets Congressional intent concerning the concept of reasonableness




for purpose of the second test.









            If a candidate technology fails the POTW test or passes the POTW




test and fails the industry cost-effectiveness test, then that technology is




not used as the basis of BCT.









13.2        BCT TECHNOLOGY OPTIONS









            The primary technology option the Agency identified to attain




further TSS and BOD reduction for the organic pesticide chemicals subcategory




was the addition of multi-media filtration to existing BPT systems.









            The Agency also considered the options of carbon adsorption,




membrane filtration, incineration, evaporation, additional biological




oxidation (above the level required to meet BPT). and clarification through




the use of settling ponds.









            Both carbon adsorption and membrane filtration require filtration




of wastewater prior to treatment; therefore, the cost of filtration plus




carbon adsorption or membrane filtration would be more than the cost of




filtration alone.  In addition, while these two technologies can be effective




in removing specific compounds from wastewater, they may not be particularly
                                     13-4

-------
effective in removing those materials exerting biochemical oxygen demand.




Incineration and evaporation were projected to have much higher costs than




multi-media filtration due to the need to purchase fuel.  Therefore, due to




their costs, the Agency excluded both incineration and evaporation from




further consideration.  Biological oxidation and clarification were used as




the basis for BPT, and there are no data to demonstrate that higher effluent




quality could be achieved for PAI manufacturing wastewaters by increasing




biological residence time, increasing mixed liquor suspended solids, or




through the addition of settling ponds,  and so these options were rejected.




Finally, the Agency studied the use of polymers and coagulants to enhance




clarification.   While some facilities use these chemical agents on specific




pesticide-containing wastewaters to enhance treatment system performance,




there was no data available to demonstrate additional removal of the




conventional pollutants.  Therefore,  this option was rejected for lack of




data.  Therefore, only multi-media filtration was considered further as a BCT




technology upgrade for the organic pesticide subcategory.









            EPA is reserving BCT for Subcategory B because BPT limitations




already require zero discharge of process wastewater pollutants.  This is the




most stringent limitation possible; there is no need for BCT regulations




reflecting more stringent control techniques.
                                     13-5

-------
13.3        BCT COST TEST ANALYSIS



            The Agency evaluated multi-media filtration technology to

determine whether it passed the POTW test  (and if necessary the industry cost

effectiveness test).



13.3.1      The POTW Cost Test



            To determine the cost per pound of conventional pollutants removed

for a technology upgrade from BPT to BCT for the organic pesticide chemicals

subcategory, the Agency calculated:
                  The increase in the total annual cost for the BPT to BCT
                  technology upgrade.  Total annual costs include capital
                  costs, interest, and operation and maintenance costs.
                  Capital costs are amortized over 30 years at a 10 percent
                  interest rate.  The cost estimates were indexed to 1976
                  dollars for a consistent comparison to the POTW benchmark.
                  (51 FR 24982)

                  The increase in the removal of conventional pollutants for
                  the BPT to BCT technology upgrade.  The increase in removal
                  is expressed as the yearly increase in the total pounds of
                  BODj and TSS  removed,  due to  the  upgrade.   Conventionals
                  considered in the total include BOD5 and TSS.
The increase in the total annual cost was then divided by the increase in

conventionals removed and this result ($/lb) was compared to the Tier I  ($0.25

per pound) POTW benchmark.
                                     13-6

-------
13.3.2      Application to the Organic Pesticide Chemicals Manufacturing

            Subcategory



            The Agency used the CAPDET cost model for costing the multi-media

filtration technology upgrade considered for BCT.  Input parameters to the

filtration module include:
            •     Flow;
            •     Influent BOD and TSS concentrations; and
            •     Effluent BOD and TSS concentrations.
The module runs in two modes; high flow (flow greater than 0.5 million gallons

per day (MGD)) and low flow (flow less than 0.5 MGD).   The unit cost of

treatment would be lower at the high flow plant due to economics of scale.



            Pesticide facilities with information on PAI wastewater flows and

PAI production rates were split into either the high flow or low flow

categories.   A median flow and yearly PAI production rate were then determined

for each flow category.  Only one facility fell into the high flow category;

the remaining facilities fell into the low flow category.



            Long-term BPT data for BOD and TSS were used to determine the

influent BOD and TSS concentrations to the multi-media filter.  Since these

BOD and TSS data are mass based (i.e. 1.12 Ib. BOD/1000 Ibs. of production and

1.31 Ib. TSS/1000 Ibs. of production), the high flow and low flow production
                                     13-7

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values and flows were used with the mass-based long-term data to determine BOD




and TSS influent concentrations.









            To determine the effluent BOD and TSS concentrations for the




CAPDET module, BOD and TSS removal efficiencies through a multi-media filter




were estimated from available sampling data on a filtration unit (Pesticide




Sampling Episode 1332).  These removal data represent a settling pond followed




by a sand filter system.  It was assumed, for the purpose of this analysis,




that all of the BOD and TSS removal that occurred was due to the sand filter;




this assumption provides the sand filter with the best chance of passing the




cost test (since during the sampling episode, some removal probably occurred




due to the settling pond).  This assumption will overestimate the removal




efficiency of the sand filter and will also yield a cost effectiveness for the




filter that is as low as possible since the cost of the sand filter alone must




be less than the cost of a sand filter plus a settling pond.  The BOD and TSS




removals from the combined sand filter/settling pond system during sampling




were 48 percent BOD removal and 53 percent TSS removal.









            Using the flows and the influent and effluent BOD and TSS




concentrations discussed above in the CAPDET module, annualized costs (in 1976




dollars) for the technology upgrade from BPT to BCT were calculated.  The




yearly pounds of conventional pollutants removed by the technology upgrade




from BPT to BCT was then determined for both the high and low flow categories.




The conventionals considered in this calculation were BOD and TSS.
                                     13-8

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            Finally, a. removal cost ($/lbs. of conventional pollutants




removed) was determined by dividing the incremental annual cost by the BOD and




TSS removal for each flow category.  Since long-term data were available for




Subcategory A, the removal costs for each flow scenario were compared to the




Tier I POTW test value of $0.25/lb. of conventional pollutants removed.  The




results of the POTW cost test, including the annual costs ($/yr),  BOD and TSS




removals (Ib/yr),  and removal costs ($/lb), are presented in Table 13-1.









13.4        CONCLUSIONS









            As seen in Table 13-1, the proposed BCT technology,  multi-media




filtration, fails the POTW cost test.   Therefore,  multi-media filtration is




not a technology basis for BCT in the organic pesticide chemicals




manufacturing subcategory and the Agency is proposing to set BCT equal to BPT




for this subcategory.









            EPA is reserving BCT for the metallo-organic pesticide chemicals




manufacturing subcategory.
                                     13-9

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                                  Table 13-1

                        POTW COST TEST RESULTS FOR THE
             ORGANIC  PESTICIDE  CHEMICALS MANUFACTURING  SUBCATEGORY
Facility
Type
High Flow
Low Flow
($/yr)
Annual Cost
1976 $
87,622
45,116
(Ib/yr)
BOD & TSS
Removal
200,800
23,061
($/lb)
Removal
Cost
0.44
1.96
POTW
Test
Pass/Fail*
Fail
Fail
*The removal costs ($/lb.) were compared against $0.25/lb. of conventional
pollutant removed.  This POTW removal cost represents the Tier I value which
is used when long-term data are available for an industry.
                                     13-10

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                                  SECTION 14




        METALLO-ORGANIC  PESTICIDE  CHEMICALS MANUFACTURING  SUBCATEGORY
            The Agency is proposing to reserve BCT, BAT, NSPS,  PSES ,  and PSNS for




the metallo-organic  pesticide  chemicals  manufacturing subcategory.   In 1986,




there were only eight facilities producing pesticides in this subcategory,  and




no facility was manufacturing organo-cadmium pesticides.   Current BPT requires




no discharge of process wastewater pollutants from facilities producing metallo-




organic pesticides containing arsenic, copper, cadmium, or mercury.  Therefore,




BCT, BAT and NSPS regulations for Subcategory B are unnecessary.









            Metallo-organic pesticide processes generate much  smaller volumes of




wastewater  than organic  pesticide   processes.   As  discussed  in Section  5,




Subcategory B processes generated only about 3 million gallons of wastewater in




1986 compared to about 1.5 billion gallons from Subcategory A processes.  Only




about 600,000  gallons of this Subcategory B wastewater were discharged to POTWs.




In addition, the Agency estimates that current discharges of metallo-organic PAIs




and priority pollutants in  Subcategory B  wastewaters total only  60 pounds  per




year.  (Since there are no analytical methods for the specific metallo-organic




PAIs, these compounds  are monitored  by measuring the amount  of total arsenic,




copper, or mercury present in the wastewater.)









            The  Agency considered proposing  PSES  requiring no  discharge  of




process wastewater pollutants,  but determined that the only way the facilities




could  achieve  this standard is  by  off-site disposal.   Off-site  disposal was
                                     14-1

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determined not to be  economically achievable because two of the five indirect




discharging facilities in this subcategory are projected to close if forced to




meet  that  standard.    Other  options,  such  as  imposing  treated  discharge




requirements, were considered unnecessary since the existing indirect dischargers




are already subject to  locally imposed pretreatment limits  which EPA believes




provide  adequate protection  for the  POTW  and the  environment.    Imposing




additional controls based on the BAT technologies would result  in the additional




removal of only  three of  the 60 pounds of priority pollutants currently being




discharged annually by these five facilities.  In light of the relatively small




amount of pollutants being discharged,  EPA proposes not to establish regulations




for existing  indirect dischargers in this subcategory.









            Concerning PSNS, the Agency believes it is unlikely  that there will




be  any  new  manufacturers  of   metallo-organic  pesticides  currently  being




manufactured.  New manufacturing plants,  to the extent there  are  any, would very




likely produce only new pesticides not  registered in 1986. EPA believes that no




new producers of metallo-organic pesticides are likely since there have been no




new plants and no new  me tallo-organic PAIs produced in this subcategory for more




than 20 years.
                                     14-2

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                                  SECTION 15




                    NON-WATER QUALITY  ENVIRONMENTAL IMPACTS









15.0        INTRODUCTION









            The elimination or reduction of one form of pollution may create




or aggravate other environmental problems.   Therefore,  Sections 304(b) and 306




of the Clean Water Act call for EPA to consider the non-water quality




environmental impacts of certain regulations.   Pursuant to these provisions,




EPA has considered the effect of the BAT regulations on air pollution, solid




waste generation, and energy consumption.









            The non-water quality environmental impacts associated with this




regulation are described in subsections 15.1 to 15.3.









15.1        AIR POLLUTION









            Pesticide facilities generate wastewaters that contain significant




concentrations of organic compounds, some of which are  also on the list of




Hazardous Air Pollutants (HAP) in Title 3 of the Clean Air Questionnaire




(CAAA) of 1990.  These wastewaters typically pass through a series of




collection and treatment units that are open to the atmosphere and allow




wastewaters containing organic compounds to contact ambient air.  Atmospheric




exposure of these organic-containing wastewaters may result in significant
                                     15-1

-------
volatilization  of both  volatile  organic  compounds  (VOC), which contribute to




the  formation of ambient  ozone,  and HAP  from  the wastewater.









            VOC and  HAP are  emitted from wastewater beginning at the point




where  the wastewater first contacts ambient air.   Thus, VOC and HAP from




wastewater may  be of concern immediately as the wastewater is discharged from




the  process unit.  Emissions occur from  wastewater collection units such as




process  drains, manholes, trenches, sumps, junction boxes, and from wastewater




treatment units such as screens,  settling basins,  equalization basins,




biological aeration  basins,  air  or stream strippers lacking air emission




control  devices, and any  other units where the wastewater is in contact with




the  air.









            The proposed  regulations are based on  the use of steam stripping




rather than air stripping as an  in-plant technique for controlling volatile




organic  compounds.   Also, steam  strippers are proposed in conjunction with




chemical oxidations  systems  as a combined BAT-level technology to prevent air




emissions of chlorinated  priority pollutants  from  the chemical oxidation




effluent.









            No  negative air  pollution impacts are  expected due to the proposed




regulations.  Instead,  the implementation of  steam stripping as an in-plant




control technique should  decrease air emissions of volatile wastewater




pollutants.  Based on raw wastewater loading  estimates, air emissions of




volatile priority pollutants would decrease by about 6 million pounds per year
                                     15-2

-------
due to steam stripping when used as an in-plant control technology.  Also,




steam strippers are proposed in conjunction with chemical oxidation systems to




ensure no air emissions of chlorinated priority pollutants from the chemical




oxidation effluent.  The proposed regulation, however, does not require steam




stripping or any specific technology, but only establishes the amount of




pollutant that can be discharged to navigable waters.









      The Agency in the OCPSF rule concluded that the issue of volatile air




emissions is best addressed under laws that specifically direct EPA to control




air emissions.  (EPA notes, however, that all of the pesticides manufacturing




plants that currently use stripping are using steam strippers and not air




strippers.)  There are, in fact, activities underway under the Clean Air Act




to address emissions of VOCs from industrial wastewater.  Specifically, the




Agency plans to issue a Control Techniques Guideline (CTG) for Industrial




Wastewater (IWW) under Section 110 of the CAA (Title 1 of the 1990 CAAA).   The




Pesticide Chemicals Industry is one of several industries that would be




covered by the IWW CTG.  The IW¥ CTG will provide guidance to the States in




recommending reasonably available control technology (RACT) for VOC emissions




from industrial wastewater at facilities located in areas failing to attain




the National Ambient Air Quality Standards for ozone.   The Agency also plans




to issue a National Emission Standard for Hazardous Air Pollutants (NESHAP)




under Section 112 of the CAA to address air emissions of the HAP listed in




Title 3 of the 1990 CAAA.  This NESHAP will define maximum achievable control




technology (MACT).   MACT standards are technology-based standards.  The 1990




CAAA set maximum control requirements on which MACT can be based for new and
                                     15-3

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existing sources.  RACT for the CTG and MACT for the NESHAP will be based on

the same control strategy.  That control strategy is:


      1.    Identify wastewater streams requiring control;

      2.    Control the conveyance of the wastewater to the treatment unit
            (hardpipe, control vents and openings);

      3.    Treat the wastewater to remove or destroy the organic compound
            (e.g. steam stripping);

      4.    Control air emissions from the treatment unit; and

      5.    Control residuals removed during treatment.



            In view of the upcoming air emission guidelines and standards, the

Agency encourages facilities to consider integrated multi-media approaches

when designing methods of complying with the upcoming pesticide effluent

guidelines.  Combining compliance with the effluent guidelines and upcoming

CAA regulations will be more economical than individual compliance with each

rule.



            No significant increase in air emissions are expected due to

implementation of biological treatment as a BAT since volatile pollutants, if

present in significant quantities, would be removed prior to biotreatment by

in-plant steam stripping.  There is also no significant impact in air

emissions expected due to incineration because of the small volume of

wastewater (less than 50,000 gallons per year) estimated to be disposed of in

this manner.
                                     15-4

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15.2        SOLID WASTE









            Solid waste would be generated due to the following technologies,




if implemented to meet proposed regulations:  steam stripping, hydroxide




precipitation, and biotreatment.   The solid wastes generated due to the




implementation of the technologies discussed above were costed for disposal by




off-site incineration.  These costs were included in the economic evaluation




of the proposed technologies.









            The overhead stream from steam stripping is assumed to represent




an organic waste and was costed for disposal.   In some cases,  due to the large




volume of the overhead stream, the Agency costed two steam strippers in




series, with the second steam stripper treating the overheads stream from the




first stripper.  In these cases,  the only organic waste that would need




disposal is the overheads from the second steam stripper.   EPA estimates that




about 12 million pounds per year of organic waste would be generated due to




steam stripping.  While EPA believes that much of this may be amenable to




recovery and reuse, EPA was unable to quantify the amount that could be




recovered and therefore assumed that all would be incinerated.  To provide




perspective on the potential incremental increase in solid waste generation




due to the proposed rule, EPA reviewed national capacity for organic waste




disposal.  The national incinerator capacity,  including kilns and boilers, is




estimated by EPA to be greater than 3 billion pounds per year.
                                     15-5

-------
      Hydroxide precipitation  technology utilizes calcium hydroxide or a




similar chemical reagent  to  treat metal-containing wastewaters.  The




precipitated  solids represent  a  solid waste.  It is estimated that 31 thousand




pounds per year of precipitated  solids would be generated due to the




implementation of hydroxide  precipitation at one facility.  For comparison,




EPA estimates from the Toxic Release Inventory (TRI) database that 445 million




pounds of toxic chemicals were disposed in landfills in 1989.









            Biotreatment  is  the  proposed technology for controlling PAI




wastewater discharges at  two facilities.  Biosludge is continuously generated




during biotreatment, and  part  of the sludge must be discharged from the




treatment system to ensure proper operation.  It is estimated that 48,000




pounds per year of biosludge will be generated due to the proposed




regulations.  For comparison,  EPA estimates that 15,000 POTWs generate almost




8 million tons of sludge  annually, while compliance with OCPSF BAT effluent




guidelines is projected to increase solid waste generation by over 22,000 tons




annually.









15.3        ENERGY REQUIREMENTS









            Energy requirements  will increase minimally due to pumping needs




associated with the proposed technologies.  However, the main energy




requirement in this regulation is due to steam use by the proposed steam




strippers.  Steam provides the heat energy necessary to separate volatile




pollutants from wastewater streams treated by this technology.  It is
                                     15-6

-------
estimated that about 800 million pounds  per year  of  steam would be  required by




steam strippers;  this amounts to an estimated use of 187,000 barrels  per  year




of fuel oil; the  United Stated currently consumes about  19 million  barrels  per




day.
                                     15-7

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                                  SECTION 16




                              ANALYTICAL METHODS









16.0        REGULATORY BACKGROUND AND REQUIREMENTS









16.1        CLEAN WATER ACT (CWA)









            Under the Clean Water Act,  EPA promulgates guidelines establishing




test procedures for the analysis of pollutants (see 304(h),  33 U.S.C.  Section




1314(h)).  The Administrator has made these procedures applicable to




monitoring and reporting of National Pollutant Discharge Elimination System




(NPDES) permits and to implementation of pretreatment standards.









            Under the Clean Water Act,  the Agency regulates  three broad




categories of pollutants:   conventional pollutants,  toxic pollutants,  and non-




conventional pollutants.









            The pollutants designated as conventional pollutants  under Section




304(a)(4) of the CWA are:   (1) Biological Oxygen Demand (BOD), (2) Total




Suspended Solids (TSS),  (3) Fecal Coliforms,  (4)  pH,  and (5)  Oil  and Grease.




The list of these pollutants has been promulgated at 40 CFR  Part  401.16.









            The pollutants designated as toxic pollutants under Section




307(a)(l) of the CWA are the list of 65 compounds and classes of  compounds
                                     16-1

-------
promulgated at 40 CFR 401.15, and expanded to the list of 126 "Priority




Pollutants" presented at 40 CFR Part 423, Appendix A.









            The pollutants designated as non-conventional pollutants under the




CWA are those pollutants not -identified as either conventional pollutants or




toxic pollutants.









            Pesticides industry wastewaters contain conventional pollutants




and many of the toxic pollutants, and most active ingredients are non-




conventional pollutants.









            Analytical methods for conventional pollutants, toxic pollutants,




and some non-conventional pollutants have been promulgated under Section




304(h) of the CWA at 40 CFR Part 136.  In addition to the methods developed by




EPA and promulgated at 40 CFR Part 136, certain methods developed by other




Agencies and by associations such as the American Public Health Association




which publishes "Standard Methods for the Examination of Water and Wastewater"




have been incorporated by reference into 40 CFR Part 136.









            Many of the currently approved promulgated methods for PAIs do not




include the most recent advances in technology, particularly the clean-up




procedures necessary to eliminate interferences and improve reliability, nor




do they account for the latest and most sensitive detection devices, which




permit accurate detection of PAI pollutants at very low concentrations.   This




latest technology is used by many companies to monitor wastewaters, and was
                                     16-2

-------
used by EPA in its sampling of pesticide manufacturing industry wastewaters.




All of the PAI pollutant data EPA is relying on for the proposed effluent




limitations used analytical methods employing the latest in analytical




technology.  EPA is proposing that compliance monitoring of effluent from the




manufacture of the 122 PAIs proposed for regulation must employ methods listed




in Table 16-1, and will not be permitted to use the methods promulgated at




40 CFR Part 136 (except where the Part 136 method is identical to the proposed




method in Part 455).









16.1.1      Safe Drinking Water Act (SDWA)









            The SDWA authorizes the Agency to set primary drinking water




regulations for public water suppliers.   Public water suppliers are required




to perform routine monitoring to demonstrate compliance with these




regulations.  To support this monitoring,  EPA has provided a set of test




procedures for measurement of pollutants in drinking water.  These procedures




have been promulgated at 40 CFR Part 136.









            Publications containing methods for the determination of many




pesticide active ingredients are EPA/600/4-88/039 "Methods for Determination




of Organic Compounds in Drinking Water"  (December 1988),  and EPA/600/4-90/020




"Methods for Determination of Organic Compounds in Drinking Water




Supplement I" (July 1990).  EPA is proposing to allow use of these drinking




water methods in monitoring pesticide active ingredients in pesticide industry




wastewaters.
                                     16-3

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                  Table  16-1




TEST METHODS FOR PESTICIDE ACTIVE INGREDIENTS
EPA
Survey
Code
8
12
16
17
22
25
26
27
30
31
35

39
41
45
52
53
54
Pesticide Name
Triadimefon
Dichlorvos
2,4-D; 2,4-D Salts and
Esters [2,4-
Dichlorophenoxyacetic acid]
2,4-DB; 2,4-DB Salts and
Esters [2,4-
Dichlorophenoxybutyric acid]
Mevinphos
Cyanazine
Propachlor
MCPA; MCPA Salts and Esters
[2-Methyl-4-
chlorophenoxyacetic acid]
Dichlorprop; Dichlorprop
Salts and Esters [2- (2, 4-
Dichlorophenoxy) propionic
acid]
MCPP; MCPP Salts and Esters
[2-(2-Methyl-4-
chlorophenoxy) propionic
acid]
TCMTB [2-
(Thiocyanomethylthio)
benzothiazole ]
Pronamide
Propanil
Metribuzin
Acephate
Acifluorfen
Alachlor
CAS Number
43121-43-3
00062-73-7
00094-75-7
00094-82-6
07786-34-7
21725-46-2
01918-16-7
00094-74-6
00120-36-5
00093-65-2
21564-17-0

23950-58-5
00709-98-8
21087-64-9
30560-19-1
50594-66-6
15972-60-8
EPA Analytical
Method Number (s)
507/633/525.1
1657/507/622/525.1
1658/515.1/615
1658/515.1/615
1657/507/622/525.1
629
508/608.1/525.1
1658/615
1658/515.1/615
1618/615
637

525.1
632.1
507/633/525.1/1656
1656
515.1/1656
505/507/645/525 . 1/1656
                     16-4

-------
Table 16-1




(Continued)
EPA
Survey
Code
55
58
60
62
67
68
69
69
70
73
75
76
80
82
84
86
90
103
107
110
112
113
118
119
Pesticide Name
Aldicarb
Ametryn
Atrazine
Benomyl
Biphenyl
Bromacil; Bromacil Salts and
Esters
Bromoxynil
Bromoxynil octanoate
Butachlor
Captafol
Carbaryl [Sevin]
Garb o fur an
Chloroneb
Chlorothalonil
Stirofos
Chlorpyrifos
Fenvalerate
Diazinon
Parathion methyl
DCPA [Dimethyl 2,3,5,6-
tetrachloroterephthalate ]
Dinoseb
Dioxathion
Nabonate [Disodium
cyanodithioimidocarbonate ]
Diuron
CAS Number
00116-06-3
00834-12-8
01912-24-9
17804-35-2
00092-52-4
00314-40-9
01689-84-5
01689-99-2
23184-66-9
02425-06-1
00063-25-2
01563-66-2
02675-77-6
01897-45-6
00961-11-5
02921-88-2
51630-58-1
00333-41-5
00298-00-0
01861-32-1
00088-85-7
00078-34-2
00138-93-2
00330-54-1
EPA Analytical
Method Number (s)
531.1
507/619/525.1
505/507/619/525.1/1656
631
1625/642
507/633/525.1/1656
1661/1625
1656
507/645/525.1/1656
1618
531.1/632
531.1/632
508/608.1/525.1
508/608.2/525.1/1656
1657/507/622/525.1
1657/508/622
1660
1657/507/614/622/525.1
1657/614/622
508/608.2/525.1/1656
1658/515.1/615
614.1
630.1
632
   16-5

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Table 16-1




(Continued)
EPA
Survey
Code
123
124
125
126
127
132
133
138
140
144
148
150
154
156
158
172
173
175
178
182
183
185
186
192
Pesticide Name
Endothall
Endrin
Ethalfluralin
Ethion
Ethoprop
Fenarimol
Fenthion
Glyphosate [N-
(Phosphonomethyl) glycine]
Heptachlor
Isopropalin
Linuron
Malathion
Me thami dopho s
Me thorny 1
Methoxychlor
Nab am
Naled
Norflurazon
Benfluralin
Fensulfothion
Disulfoton
Phosmet
Azinphos Methyl
Organo-tin pesticides
CAS Number
00145-73-3
00072-20-8
55283-68-6
00563-12-2
13194-48-4
60168-88-9
00055-38-9
01071-83-6
00076-44-8
33820-53-0
00330-55-2
00121-75-5
10265-92-6
16752-77-5
00072-43-5
00142-59-6
00300-76-5
27314-13-2
01861-40-1
00115-90-2
00298-04-4
00732-11-6
00086-50-0
12379-54-3
EPA Analytical
Method Number (s)
548
1656/505/508/608/617/5
25.1
627*/1656*
1657/614/614.1
1657/507/622
507/633.1/525.1/1656
1657/622
547/140A
1656/505/508/608
/617/525.1
627/1656
632
1657/614
1657
531.1/632
1656/505/508/608.2
/617/525.1
630/630.1
1657/622
507/645/525.1/1656
627*/1656*
1657/622
1657/507/614/622/525 . 1
1657/622.1
1657/614/622
200. 7/200. 9/IND-01
   16-6

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Table 16-1




(Continued)
EPA
Survey
Code
197
203
204
205
206
208
212
218
219
220
223
22"4
226
230
232
236
239
241
243
252
254
Pesticide Name
Bolster
Parathion
Pendimethalin
Pentachloronitrobenzene
Pentachlorophenol
Permethrin
Phorate
Busan 85 [Potassium
dimethyldithioearbamate ]
Busan 40 [Potassium N-
hydr oxyme thy 1 - N -
methyldithiocarbamate ]
KN Methyl [Potassium N-
methyldithiocarbamate ]
Prometon
Prometryn
Propazine
Pyrethrin I
Pyrethrin II
DEF [S,S,S-Tributyl
phosphorotrithioate ]
Simazine
Carbarn- S [Sodium
dimethyldithiocarbanate ]
Vapam [Sodium
methyldithiocarbamate ]
Tebuthiuron
Terbacil
GAS Number
35400-43-2
00056-38-2
40487-42-1
00082-68-8
00087-86-5
52645-53-1
00298-02-2
00128-03-0
51026-28-9
00137-41-7
01610-18-0
07287-19-6
00139-40-2
00121-21-1
00121-29-9
00078-48-8
00122-34-9
00128-04-1
00137-42-8
34014-18-1
05902-51-2
EPA Analytical
Method Number (s)
622
1657/614
1656
1656/608.1/617
625/1625
608.2/508/525.1/1656
/1660
1657/622
630/630.1
630/630.1
630/630.1
507/619/525.1
507/619/525.1
507/619/525.1
508/1660
508/1660
1657/1618
505/507/619/525.1
630/630.1
630/630.1
507/525.1
507/633/525.1
    16-7

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                    Table 16-1




                    (Continued)
EPA
Survey
Code
255
256
257
259
262
263
264
268
Pesticide Name
Terbufos
Terbuthy laz ine
Terbutryn
Dazomet
Toxaphene
Merphos [Tributyl
phosphorotrithioate ]
Trifluralin
Ziram [Zinc
dimethyldithiocarbamate ]
CAS Number
13071-79-9
05915-41-3
00886-50-0
00533-74-4
08001-35-2
00150-50-5
01582-09-8
00137-30-4
EPA Analytical
Method Number (s)
1657/507/614.1/525.1
619
507/619/525.1
131/630/630.1/1659
1656/505/508/608/617
1657/1618/525.1
1656/508/617/627/525 . 1
630/630.1
Monitor and report as total Trifluralin.
                       16-8

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16.2        PROPOSED METHODS









16.2.1      Methods for PAI Pollutants









            EPA has not previously promulgated methods for most of the PAI




pollutants in the proposed rule.  In 1985, as part of the promulgation of




effluent limitations guidelines and standards for the Pesticide Industry, FPA




promulgated methods for 61 PAIs (50 FR 40672, October 4,  1985).  These methods




were contained in a methods compendium titled "Methods for Nonconventional




Pesticides Chemicals Analysis   Municipal and Industrial  Wastewater," EPA




440/1-83/079-C.  This document is presently out of print  and unavailable




except in photocopy form.  The methods  were also published in their entirety




in the October 4, 1985, Federal Register.  The promulgated methods were




withdrawn as a part of the withdrawal of the 1985 proposed rule to allow for




further testing and possible revision.









            Since 1986, EPA has conducted additional methods development for




PAI pollutants to incorporate the most recent advances in technology,




particularly the clean-up procedures necessary to eliminate interferences and




improve reliability, and to account for the latest and most sensitive




detection devices,  which permit accurate detection of PAI pollutants at very




low concentrations.  In addition,  EPA requested and received new analytical




methods from pesticide manufacturing facilities which monitor their




wastewater.  EPA is proposing that all of these methods be available for




compliance monitoring of effluent from the manufacture of the 122 PAIs
                                     16-9

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proposed for regulation; for many PAIs, more than one analytical method is




being proposed.  The availability of more than one method for a specific PAI




allows flexibility to the analyst to select the analytical method that




provides the most accurate results; proposal of alternative methods also




allows commenters to provide comparative data which may lead to further




improvements in methods or to rejection of some of the proposed methods where




data demonstrates that the proposed method is inadequate.









            The proposed analytical methods will be used by pesticide




manufacturers, by regulatory agencies including POTWs,  by commercial testing




laboratories, and by others, to determine compliance with the proposed




effluent limitations guidelines and standards.  There is at least one method




for each PAI, at least two methods for most PAIs, and three methods for many




PAIs.  EPA's intent in proposing multiple methods is to permit as much




flexibility as possible while controlling the quality of the methods approved.




In addition to flexibility in method selection, a certain amount of




flexibility within each method is permitted.  This flexibility was detailed in




the preamble to 40 CFR Part 136 wastewater methods [49 FR 43234, October 26,




1984] and allows modification of the method to overcome interference problems.




These alternate procedures and techniques may be employed provided that the




quality control (QC) criteria within the method are all met.
                                     16-10

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16.2.2      Methods for Metals









            EPA's Environmental Monitoring Systems Laboratory in Cincinnati,




Ohio (EMSL-Ci) has recently developed a set of methods titled "Methods for the




Determination of Metals in Environmental Samples" (EPA 600/4-91/010).   This




methods set includes techniques such as inductively coupled plasma/atomic




emission spectrometry (Method 200.7) and stabilized temperature graphite




furnace atomic absorption spectrometry (Method 200.9)  to measure metals at low




levels.  EPA proposes to permit the use of Methods 200.7, 200.9, and industry




method IND-01 for the measurement of organo-tin compounds in pesticides




industry wastewaters.









16.2.3      Development of Methods









            Since the previous methods set was published, the trend of




pesticides and herbicides produced and applied in the U.S. has continued from




chlorinated compounds to phosphorus-containing compounds and other molecules




found  to be less persistent in the environment.  This change has necessitated




the development of analytical methods to measure these compounds in wastewater




discharges and in other environmental samples.  EPA has  therefore developed




additional methods as a part  of its data gathering efforts for the1 proposed





rule.









            Where possible, EPA avoids development of a  new method by  testing




existing methods to  determine if  an active  ingredient can be measured  by  these
                                     16-11

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existing methods.  If these tests are successful, EPA revises the method to




incorporate the new analyte.  In addition, EPA has attempted to consolidate




multiple methods for the same analyte by selecting a given method or writing a




revised or new method and including as many analytes as possible in this




method.  For example, EPA has used wide-bore, fused silica capillary columns




in recently developed gas chromatography (GC) methods for pesticide active




ingredients to increase resolving power so that more analytes can be measured




simultaneously and so that these analytes can be measured at lower levels.




Drinking water methods 507^ 508, 515.1, and wastewater methods 1656, 1657, and




1658 represent GC methods that encompass a large number of analytes.









            On the other hand, it is frequently not possible to include an




analyte or group of analytes in an existing method because the nature of the




molecule(s) does not lend itself to the techniques in the method.  In these




instances, an entirely separate method must be developed.  In the methods




proposed for the rule, Method 1659 for Dazomet, Method 1660 for the Pyrethrins




and Pyrethroids, and Method 1661 for Bromoxynil represent examples of methods




that were developed.  The method for Dazomet employs a base hydrolysis to




convert Dazomet to methyl isothiocyanate (MITC) and gas chromatography with a




fused silica capillary column and nitrogen/phosphorous detector for selective




detection of MITC.  The method for the Pyrethrins and Pyrethroids employs




acetonitrile extraction of a salt-saturated wastewater sample and high-




performance liquid chromatography (HPLC) for selective detection of these




analytes.  The method for Bromoxynil employs direct aqueous injection HPLC.
                                     16-12

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16-2.4      Procedures for Development and Modification of Methods









            In many instances, EPA has combined method development with data




gathering to support the effluent limitations and guidelines in the proposed




rule.  In this process, commercial analytical laboratories compete to apply an




existing method, modify an existing method, or develop a new method under




"Special Analytical Services" contracts.   EPA then works closely with the




laboratory selected to assure that all quality assurance program requirements




will be met.  The laboratory outlines the exact tests to be undertaken to




modify the method (if required) or to develop a new procedure.   EPA approves




the approach before samples are collected.









            Samples are collected at the facility that manufactures the given




active ingredient or group of pesticides.  Frequently, multiple pesticides




requiring different procedures are required.  In this instance, more than one




laboratory may be involved in the determination of multiple pesticides.




Samples collected are of in-process wastewater, untreated effluent, treated




effluent, and other streams.  The samples are preserved and shipped to the




laboratory.









            After receipt at the laboratory, analysts attempt to measure the




active ingredient in each waste stream type using the method specified by EPA




or with the modification approved by EPA.  If the attempt is successful,




routine analysis of the samples beings; if unsuccessful, EPA works closely




with its scientific consultants and the laboratory to try other approaches.
                                     16-13

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Frequently, the industry is consulted as to how to solve an analytical problem




because industry scientists are often most familiar with the measurement of a




given active ingredient in their particular wastewater.  When an approach is




successful, the laboratory documents the approach and performs an initial




precision and recovery study to demonstrate the accuracy and reproducability




of the method.  The requirement for an initial precision and recovery study




forms one of the cornerstones of the wastewater methods, and is described in




detail in the preamble to the proposal and promulgation of these methods




(e.g., 49 FR 43234).









            After completing the initial precision and recovery study, the




laboratory begins analysis of wastewater samples using the procedure specified




by EPA or with the modification as approved by EPA.  In addition to analyzing




the samples directly, a sample of each wastewater type is spiked (fortified)




with the active ingredient of interest.  This spiked samples is then analyzed




to determine the recovery of the analyte from the actual sample, and assures




that the active ingredient can be measured accurately in each type of




wastewater sample.









            After all samples are analyzed, the laboratory prepares a report




containing a "Narrative" of exactly what modifications were required in order




to apply a method or modification to a given sample.  The report also contains




result summaries,  run chronologies (showing that analyses were performed in




the correct order on a calibrated instrument), and includes raw data so that
                                     16-14

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EPA can reconstruct the results as a part of the audit process.  The report is




then submitted to EPA by the laboratory.









            EPA has its audit team review the report and obtained from the




laboratory any missing or incomplete results.  EPA also audits the data




submitted for adherence to method specifications and consistency with data




collected from other laboratories.  Deficiencies are corrected by the




laboratory and the data are included in the package for guideline development.









16.2.5      Method Writing and Modification









            After data are collected and reviewed by EPA,  methods are written




or modified to include the active ingredient.  For example,  the active




ingredient Methamidophos is highly soluble in water but not soluble in organic




solvents.  The procedure suggested by industry for extraction of Methamidophos




used a combination of saturating the water with salt and a powerful solvent




combination for the extraction.  The laboratory applied this technique and




found that Methamidophos could be recovered at 95 percent.  Further, the




laboratory found that pre-extraction of the sample with an organic solvent




could be used to remove nearly all potential interferents from the sample, so




that the aggressive extraction would result in only Methamidophos and similar




highly water-soluble molecules in the final extract.  EPA then modified Method




1657 to incorporate the pre-extraction and aggressive extraction procedure for




highly water-soluble analytes.
                                     16-15

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16.3        INVESTIGATION OF OTHER ANALYTICAL TECHNIQUES









            In addition to methods developed for the proposed rule, EPA is




investigating other methods and other analytical techniques to aid in the




determination of non-conventional pesticides and other analytes of concern.




EPA is interested in simplifying methods where possible and in reducing the




potential pollution threat caused by the volumes of solvents used in some




methods.  An example of a simplification technique is the use of an




immunoassay specific to a given analyte (such as a pesticide) or analyte group




(such as the phenoxyacid herbicides) to allow EPA to screen rapidly for these




analytes in discharges and in other environmental samples.   EPA is also




investigating the use of "solid phase extraction" (liquid-solid extraction)  as




a means of reducing the amount of solvent used in conventional extraction




procedures.  Solid phase extraction (SPE) has been successfully applied to




drinking water matrices, but initial tests with wastewaters containing high




dissolved solids yielded low recoveries of the analytes of concern.  More




recent materials have yielded recoveries more consistent with conventional




extraction techniques.   EPA will continue to investigate these and other




analytical techniques with the objective of producing lower cost, more rapid,




and potentially less environmentally damaging analytical methods.
                                     16-16

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                                  SECTION 17

                                   GLOSSARY
Act   The Clean Water Act

Agency   U.S. Environmental Protection Agency.

BAT - The best available technology economically achievable, applicable to
effluent limitations to be achieved by July 1, 1984, for industrial discharges
to surface waters, as defined by sec. 304(b)(2)(B) of the Act.

BCT   The best conventional pollutant control technology, applicable to
discharges of conventional pollutants from existing industrial points sources,
as defined by sec. 304(b)(4) of the Act.

BMP   Best management practices, as defined by sec. 304(e) of the Act.

BPT   The best practicable control technology currently available, applicable
to effluent limitations to be achieved by July 1, 1977, for industrial
discharges to surface waters, as defined by sec. 304(b)(l) of the Act.

Clean Water Act   The Federal Water Pollution Control Act Amendments of 1972
(33 U.S.C. 1251 et seq.), as amended by the Clean Water Act of 1977 (Pub.  L.
95-217), and the Water Quality Act of 1987 (Pub.L. 100-4).

Conventional Pollutants   Constituents of wastewater as determined by sec.
304(a)(4) of the Act, including, but not limited to, pollutants classified as
biochemical oxygen demand, suspended solids, oil and grease, fecal coliform,
and pH.

Direct Discharger   An industrial discharger that introduces wastewater to a
receiving body of water with or without treatment by the discharger.

Effluent Limitation   A maximum amount, per unit of time, production or other
unit, of each specific constituent of the effluent that is subject to
limitation from an existing point source.  Allowed pollutant discharge may be
expressed as a mass loading in pound per 1,000 pound PAI produced or as a
concentration in milligrams per liter.

End-of-Pipe Treatment (EOP)   Refers to those processes that treat a  plant
waste stream for pollutant removal prior to discharge.  EOP technologies
covered are classified as primary (physical separation processes), secondary
(biological processes), and tertiary (treatment following secondary)
processes.  Different combinations of these treatment technologies may be used
depending on the nature of the pollutants to be removed and the degree of
removal required.
                                     17-1

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Indirect Discharger - An industrial discharger that introduces wastewater into
a publicly-owned treatment works.

In-Plant Control or Treatment Technologies   Controls or measures applied
within the manufacturing process to reduce or eliminate pollutant and
hydraulic loadings of raw wastewater.  Typical in-plant control measures
include process modification, instrumentation, recovery of raw materials,
solvents, products or by-products, and water recycle.

Nonconventional Pollutants   Parameters selected for use in developing
effluent limitation guidelines and new source performance standards which have
not been previously designated as either conventional pollutants or priority
pollutants.

Non-Water Environmental Quality Impact   Deleterious aspects of control and
treatment technologies applicable to point source category wastes, including,
but not limited to air pollution, noise, radiation, sludge and solid waste
generation, and energy used.

NPDES   National Pollutant Discharge Elimination System, a Federal program
requiring industry and municipalities to obtain permits to discharge
pollutants to the nation's waters, under sec. 402 of the Act.

NSPS   New source performance standards, applicable to industrial facilities
whose construction is begun after the publication of the proposed regulations,
as defined by sec. 306 of the Act.

QCPSF   Organic chemicals, plastics, and synthetic fibers manufacturing point
source category.

Point Source Category   A collection of industrial sources with similar
function or product, established by sec. 306(b)(l)(A) of the Federal Water
Pollution Control Act, as amended for the purpose of establishing Federal
standards for the disposal of wastewater.

POTW   Publicly-owned treatment works.  Facilities that collect, treat, or
otherwise dispose of wastewaters, owned and operated by a village, town,
county, authority or other public agency.

Pretreatment Standard   Industrial wastewater effluent quality required for
discharge to a publicly-owned treatment works.

Priority Pollutants   The toxic pollutants listed in 40 CFR Part 423, Appendix
A.

PSES   Pretreatment Standards for existing sources of indirect discharges,
under sec. 307(b) of the Act.

PSNS   Pretreatment standards for new sources of indirect discharges under
sec. 307(b) and (c) of the Act.
                                     17-2

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SIC   Standard Industrial Classification,  a numerical categorization scheme
used by the U.S. Department of Commerce to denote segments of industry.

Technical Development Document   Development Document for Proposed Effluent
Limitations Guidelines and Standards for the Pesticides Chemicals
Manufacturing Point Source Category.
                                      17-3

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                                  SECTION 18

                                  REFERENCES


1-          Aly, 0. M.,  and M. A. El-Dib, "Studies on the Persistence of Some
            Carbamate Insecticides in the Aquatic Environment - I   Hydrolysis
            of Sevin, Baygon, Pyrolan, and Dimethilan in Waters", Water
            Research. 5(12):1191-1205, 1971.

2.          American Paper Institute v. EPA. 660 F.  2d 954 (4th Cir. 1980).

3.          BASF Wyandotte Corp. v. Costle.  614 F. 2d 21 (1st Cir. 1980).

4.          BASF Wvandotte Corp. v. Costle.  596 F. 2d 637 (1st Cir. 1979),
            cert, denied.

5.          Biello, L. J., et al., "Final Report of Laboratory Study of
            Pesticides Wastewater Treatability", Environmental Science and
            Health. B12(2):129-146, 1977.

6.          Brown, N. P. H.,   and B. T. Graysen, "Base-Catalyzed Hydrolysis of
            (E)   and (Z)   Mevinphos", Pesticide Science.  14(6):547-549,
            1983.

7.          Budavari, Susan,  editor, The Merck Index:  An Encyclopedia of
            Chemicals. Drugs and Biologicals - Eleventh Addition. Merck & Co,
            Rahway, NJ,  1989.

8.          The Bureau of National Affairs,  Pesticides:  State and Federal
            Regulation.  Bureau of National Affairs,  Rockville, MD, 1987.

9.          Callahan, M. A.,  et al., Water-Related Environmental Fate of 129
            Priority Pollutants. Volume I:  Introduction and Technical
            Background.  Metals and Inorganics. Pesticides and PCBs. EPA-44/4-
            79-029a, United States Environmental Protection Agency, Washington
            DC, 1979.

10.         Chau, Alfred S. Y.,  and B. K. Afghan, Analysis of Pesticides in
            Water. Volumes I. II. and III. CRC Press, Boca Raton, FL, 1982.

11.         Chemical Specialities Manufacturers Association, et. al., v. EPA.
            (86-8024).

12.         Cowart, R. P., F. L. Bonner, and E. A. Epps, Jr., "Rate of
            Hydrolysis of Seven Organophosphate Pesticides", Bulletin of
            Environmental Contamination and Toxicology. 6(3):231-234, 1971.
                                     18-1

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                                 REFEREENCES

                                  (Continued)

13-         Crittenden, J.  C., J. K. Berrigan, and D. W. Hand, "Design of
            Rapid  Small-Scale Adsorption Tests for a Constant Diffusivity",
            Journal WPCF. Volume 58, Number 4, April 1986.

14-         Dennis, W. H.,  Jr., Methods of Chemical Degradation of Pesticides
            and Herbicides  - A Review. USAMEERU No. 73-04, United States Army
            Medical Envionmental Engineering Research Unit, Edgewood Arsenal,
            Maryland,  1972.

15.         Dobbs, Richard  A., and Jesse M. Cohen, "Carbon Adsorption
            Isotherms  for Toxic Organics", EPA Report Number EPA-60/8-80-023.
            April  1980.

16.         "Domestic  Sewage Study", DSS - Report to Congress on the Discharge
            of Hazardous Waste to Publicly Owned Treatment Works. EPA/530-SW-
            86-004, February 1986.

17.         Drevenkar, V.,  et al., "The Fate of Pesticides in Aquatic
            Environment II  - Hydrolysis of Dichlorvos in a Model System and  in
            River  Water"  (translation of "Archivza Higijenu Rada"),
            Toksikolgigu 27(4) 297-305, 1976.

18.         El-Dib, M. A.,  and 0. A. Aly, "Persistance of Some Phenylamide
            Pesticides in the Aquatic Environment   I   Hydrolysis", Water
            Research.  10(12):1047-1050, 1976.

19.         Eli Lilly v. Costle. 444 U.S. 1096, 1980.

20.         "EPA Method 632", Federal Register. Volume 50, No. 193, October  4,
            1985.

21.         Eto, M., Organophosphorus Pesticides:  Organic and Biological
            Chemistry. CRC  Press, Cleveland, OH, 1974.

22.         Faust, S. D., and H. M. Gomaa, "Chemical Hydrolysis of Some
            Organic Phosphorus and Carbamate Pesticides in Aquatic
            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.
                                     18-2

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                                 REFEREENCES

                                  (Continued)

25.          Gardner, David A., and Gregory L.  Huibregtse,  Radian Corporation,
            and Thomas J. Holdsworth,  Glenn M.  Shaul,  Kenneth M. Dostal,  Water
            and Hazardous Wastes Treatment Research Division, Risk Reduction
            Engineering Laboratory,  Accelerated Column Testing of Pesticide
            ManufacturinE Wastewaters.  EPA Contract No.  68-03-3371,  December
            1990.

26.          Gardner, D. A., Radian Corporation,  and G.  M.  Shaul and K.  A.
            Dostal, Water and Hazardous Wastes Treatment Research Division,
            Risk Reduction Engineering Laboratory,   Activated Carbon Isotherms
            for Pesticides. EPA Contract No. 68-03-3371,  September 1989.


27.          Gomaa, H. M., I. H. Suffet, and S.  D.  Faust,  "Kinetics of
            Hydrolysis of Diazinon and Diozoxan",  Residual Review. 29:171 190,
            1969.

28.          Hand, D. W., J. C. Crittenden, and W.  E. Thacker, "Simplified
            Models for Design of Fixed-Bed Adsorption Systems", Journal of the
            American Society of Civil Engineers, Environmental Engineering
            Division. 110(2):440-456,  April 1985.

29.          Hineline, D. W., J. C. Crittenden,  and D.  W.  Hand, "Use of Rapid
            Small-Scale Column Tests to Predict Full-Scale Adsorption Capacity
            and Performance", Proceedings of the AWWA Annual Meeting. Kansas
            City, MO, June 1987.

30.          Hinton, J. F.,  Hydrolytic and Photochemical Degradation of
            Organophosphorus Pesticides. Publication No.  63, University of
            Arkansas, Fayetteville, AK, 1978.

31.          Houghton, Mary J., The Clean Waters Act Amendments of 1987,  The
            Bureau of National Affairs, Washington DC,  1987.

32.          Kuhr, R. J., and H. W. Dorough, Carbamate Insecticides:
            Chemistry. Biochemistry and Toxicology. CRC Press, Cleveland, OH,
            1976.

33.          Lande, S. S., Identification and Description of Chemical
            Deactivation/Detoxification Methods for the Safe Disposal of
            Selected Pesticides SW-165C, United States Environmental
            Protection Agency, Washington DC, 1978.
                                     18-3

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                                  REFEREENCES

                                  (Continued)

 3^-          Lemley,  A.  T.,  et al.,  "Investigation of  Degradation Rates of
             Carbamate Pesticides    Exploring  a New Detoxification Method", ASC
             Symposium Series.  259 (Treatment  and Disposal  of  Pesticide
             Wastes):  245-259,  1984.

 35.          Macalady,  D.  L.,  and  N.  L.  Wolfe,  "New Perspectives on the
             Hydrolytic Degradation  of the  Organophosphorothioate Insecticide
             Chlorpyrifos",  Journal  of Agricultural Food  Chemicals. 31(6):1139-
             1147,  1983.

 36.          Mahoney,  William  D.,  Means Site Work Cost Data 1989. R. S. Means
             Company,  Inc.,  Kingston,  MA, 1988.

 37.          Marehenko,  P. V.,  A.  V.  Grechki and E.  V.  Kravets, "Application of
             the  Hydrolysis  of Organophosphorus Pesticides  in  the Purification
             of Effluents",  Soviet Journal  of  Water Chemistry  and Technology.
             3(5):62-65,  1981.

 38.          Marco, Gino J., Robert  M.  Hollingsworth,  and Jack R. Plummer,
             editors,  Regulation of  Agrochemicals:   A  Driving  Force in Their
             Evolution.  American Chemical Society,  Washington  DC, 1991.

 39.          Melnikov,  N.  N.,  "Decomposition of Organophosphorus Pesticides",
             (translation of "Khimiya v Seskom Khosyaistve"),  Pesticides and
             the  Environment.  12(3):49-57,  1975.

 40.          "Methods  for Chemical Analysis for Water  and Wastes", EPA-600/4-
             79/020,  EMSL, 1983.

 41.          NRDC.  et.  al..  v.  Reillv.  Civ. No.  89-2980.

 42.          Pereira,  Percival  E., Dodge Construction  Cost  Information System
             1986. McGraw-Hill  Information  Systems,  Princeton, NJ, 1985.

 43.          Perry, Robert H.,  and Don Green,  Perry's  Chemical Engineer's
             Handbook, McGraw-Hill Book Company,  New York,  1984.

 44.          Radian Corporation, Alkaline Chlorination and  Alkaline Hydrolysis
             Treatability  Study of Pesticide Manufacturing  Wastewaters. EPA
             Contract No.  68-C8-0008,  July  1991.

45.          Radian Corporation, Draft Pesticide  Manufacturers Database Report,
             EPA  Contract No. 68-C8-0008, March 1990.
                                     18-4

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                                 REFEREENCES

                                  (Continued)

46.         Radian Corporation, Hydrolysis Treatability Study Final Report.
            EPA Contract No. 68-C8-0008, July 1991.

47.         Radian Corporation, Membrane Filtration Treatability Study Final
            Report. EPA Contract No. 68-C8-0008, April 1990.

48.         Sieber, J. N.,  M. P. Catahan, and C. R. Barril,  "Loss of
            Carbofuran from Rice Paddy Water:  Chemical and Physical Factors",
            Journal of Environmental Science and Health.  B13(2):131 148,  1978.

49.         Sine, Charlotte, editorial director, Farm Chemicals Handbook '90.
            Meister Publishing Company, Willoughby, OH, 1990.

50.         Sittig, Marshall, editor, Pesticide Manufacturing and Toxic
            Materials Control Encyclopedia. Noyes Data Corporation, Park
            Ridge, NJ, 1980.

51.         Sontheimer, H., J. C. Crittenden, and R. S. Summers,  Activated
            Carbon for Water Treatment. 2nd Edition, DVGW Forschurgsstelle,
            Karlsruhu, West Germany, Distributed by AWWA Research Foundation,
            Denver, CO, 1988.

52.         Speth, T. F.,  and R. S. Miltner, "Adsorption Capacity of GAG for
            Synthetic Organics", AWWA Research Foundation. 82(2):72-75,
            February 1990.

53.         "Standard Methods for the Examination of Water and Wastewater",
            15th Edition,  American Public Health Association, Washington DC,
            1981.

54.         Summers, R. S., and J. C. Crittenden, The Use of Mini-Columns for
            the Prediction of Full-Scale GAG Behavior Design and Use of
            Granular Activated Carbon:  Practical Aspects, AWWA Research
            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.
                                     18-5

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                                 REFEREENCES

                                  (Continued)

58.         United States Congress, The Pollution Prevention Act of 1990.
            Public Law  101-508.

59.         United States Environmental Protection Agency, Development
            Document  for Effluent Limitations Guidelines and Standards for the
            Organic Chemicals. Plastics, and Synthetic Fibers - Point Source
            Category. Volumes  I and II. United States Environmental Protection
            Agency 440/1-87/009, Washington DC, 1987.

60.         United States Environmental Protection Agency, Development
            Document  for Effluent Limitations Guidelines and Standards for the
            Pesticide (Final)  Point Source Category. United States
            Environmental Protection Agency, Washington DC 1985.

61.         United States Environmental Protection Agency, Effluent Guidelines
            Division, EPA Method 630. Washington DC, January 1983.

62.         United States Environmental Protection Agency, EPA Method 637.
            Effluent  Guidelines Division, Washington DC, October 1985.

63.         United States Environmental Protection Agency, Effluent Guidelines
            Division, EPA Method 1613A. Washington DC, March 1989.

64.         United States Environmental Protection Agency, Office of Water
            Regulations and Standards, EPA Method 1916. Sample Control Center,
            Alexandria, VA.

65.         United States Environmental Protection Agency, Effluent Guidelines
            Division, EPA Method 1624/1625. Washington DC, July 1988.

66.         United States Environmental Protection Agency, Office of Drinking
            Water Health Advisories, Drinking Water Health Advisory:
            Pesticides. Lewis  Publishers, Chelsea, MI, 1989.

67.         United States Environmental Protection Agency, "Best Conventional
            Polluntant  Control Technology; Effluent Limitations Guidelines
            Final Rule", 40 CFR Parts 405, 406, 407, 408, 409, 411, 412, 418,
            422, 424, 426, and 432, Federal Register. FRL 2941-9, Volume 51,
            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.
                                     18-6

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                                 REFEREENCES

                                  (Continued)

69.          United States Environmental Protection Agency,  "General
            Pretreatment Regulations for Existing and New Sources   Final
            Rule" 40 CFR Part 403, Federal Register. OW-FRL 3006-4, Volume 52,
            No. 9, January 14, 1987.

70.          United States Environmental Protection Agency.  FIFRA and TSCA
            Enforcement System (FATES) Database. National Library of Medicine.

71.          United States Environmental Protection Agency,  "Guidelines
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