TECHNICAL DEVELOPMENT DOCUMENT
FOR THE
PESTICIDE FORMULATING, PACKAGING, AND REPACKAGING
EFFLUENT LIMITATIONS GUIDELINES,
PRETREATMENT STANDARDS, AND
NEW SOURCE PERFORMANCE STANDARDS
Carol M. Browner
Administrator
Robert Perciasepe
Administrator, Office of Water
Sheila Frace
Acting Director, Engineering and Analysis Division
Marvin B. Rubin
Chief, Energy Branch
Shari Zuskin
Project Officer
Engineering and Analysis Division
Office of Science and Technology
U.S. Environmental Protection Agency
Washington, D.C. 20460
September 30, 1996
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ACKNOWLEDGEMENT AND DISCLAIMER
This report has been reviewed and approved for publication by the Engineering
and Analysis Division, Office of Science and Technology. This report was prepared with the
support of Eastern Research Group (Contract No. 68-C5-0023) under the direction and review
of the Office of Science and Technology. Neither the United States Government nor any of
its employees, contractors, subcontractors, or their employees make any warrant, expressed or
implied, or assumes any legal liability or responsibility for any third party's use of or the
results of such use of any information, apparatus, product, or process discussed in this report,
or represents that its use by such party would not infringe on privately owned rights.
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TABLE OF CONTENTS
Page
FOREWORD xi
SECTION 1 INTRODUCTION 1-1
1.1 Legal Authority 1-1
1.2 Background 1-1
1.2.1 Clean Water Act 1-1
1.2.2 Section 304(m) Requirements and Litigation 1-4
1.2.3 Pollution Prevention Act (PPA) 1-4
1.2.4 Prior Regulation and Litigation for the Pesticide
Chemicals Category 1-4
1.3 Scope of Final Rule 1-6
SECTION 2 SUMMARY 2-1
2.1 Introduction 2-1
2.2 Overview of the Industry 2-1
2.3 Applicability of the Final Regulations 2-2
2.3.1 PFPR Operations 2-2
2.3.2 PFPR Process Wastewater 2-4
2.3.3 PFPR Products 2-4
2.4 Final Regulation for Subcategory C: PFPR and
PFPR/Manufacturers 2-8
2.4.1 BPT 2-8
2.4.2 BCT 2-10
2.4.3 BAT 2-11
2.4.4 NSPS 2-11
2.4.5 PSES . 2-11
2.4.6 PSNS 2-11
2.5 Final Regulation for Subcategory E: Refilling
Establishments 2-12
2.5.1 BPT 2-12
2.5.2 BCT 2-12
2.5.3 BAT 2-12
2.5.4 NSPS 2-13
2.5.5 PSES 2-13
2.5.6 PSNS 2-13
2.6 References 2-13
SECTION 3 INDUSTRY DESCRIPTION 3-1
3.1 Introduction 3-1
3.2 Data Collection Activities 3-1
3.2.1 The Pesticide Formulating, Packaging, and
Repackaging Facility Survey for 1988 3-2
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TABLE OF CONTENTS (Continued)
Page
3.2.2 EPA's Site Visit and Wastewater Sampling
Programs 3-7
3.2.3 Industry-Supplied Data 3-11
3.2.4 EPA Bench- and Pilot-Scale Treatability Studies 3-12
3.2.5 Treatability Data Transfers 3-12
3.3 Overview of the Industry 3-14
3.3.1 Type of Operations 3-15
3.3.2 Geographic Location 3-15
3.3.3 Ownership Type 3-15
. 3.3.4 Product Types 3-16
3.3.5 Production 3-16
3.4 Pesticide Formulating, Packaging, and Repackaging
Processes 3-18
3.4.1 General Process Descriptions 3-18
3.4.2 Production Lines 3-24
3.4.3 Trends in the Industry 3-25
3.5 References 3-26
SECTION 4 INDUSTRY SUBCATEGORIZATION 4-1
4.1 Introduction 4-1
4.2 Background 4-2
4.3 Current Subcategorization Basis 4-3
4.3.1 Product Type 4-4
4.3.2' Raw Materials 4-4
4.3.3 Type of Operations Performed: Formulating,
Packaging, and Repackaging Operations 4-4
4.3.4 Nature of Waste Generated 4-5
4.3.5 Dominant Product 4-6
4.3.6 Plant Size 4-6
4.3.7 Plant Age 4-6
4.3.8 Plant Location 4-7
4.3.9 Non-Water Quality Characteristics 4-7
4.3.10 Treatment Costs and Energy Requirements 4-8
4.4 Final Subcategories 4-8
SECTION 5 WATER USE AND WASTEWATER CHARACTERIZATION 5-1
5.1 Introduction 5-1
5.2 Sources of Wastewater in the PFPR Industry 5-1
5.2.1 Interior Wastewater Sources 5-2
5.2.2 Exterior Wastewater Sources 5-2
5.2.3 Other PFPR Wastewater Sources 5-3
n
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TABLE OF CONTENTS (Continued)
Page
5.3 Overview of Water Use in the PFPR Industry 5-4
5.3.1 Annual Water Use 5-5
5.3.2 Production Normalized Water Volumes 5-5
5.4 Overview of Wastewater Discharge and Disposal 5-7
5.4.1 Definitions 5-7
5.4.2 Discharge Status of the PFPR Industry 5-16
5.4.3 Wastewater Destinations 5-18
5.5 Wastewater Characterization Data 5-18
5.5.1 Industry-Supplied Self-Monitoring Data 5-22
5.5.2 EPA PFPR Sampling Program 5-24
SECTION 6 POLLUTANT PARAMETERS SELECTED FOR REGULATION 6-1
6.1 Introduction 6-1
6.2 Conventional Pollutants 6-2
6.3 Priority Pollutants 6-3
6.4 Pesticide Active Ingredients 6-6
SECTION 7 TECHNOLOGY SELECTION AND METHODS TO ACHIEVE THE
EFFLUENT LIMITATIONS 7-1
7.1 Introduction 7-1
7.2 Wastewater Treatment Technologies Applicable to the
PFPR Industry 7-1
7.2.1 Activated Carbon Adsorption 7-2
7.2.2 Hydrolysis 7-3
7.2.3 Chemical Oxidation 7-4
7.2.4 Membrane Filtration 7-5
7.2.5 Emulsion Breaking 7-7
7.2.6 Chemical Precipitation/Separation 7-10
7.2.7 Equalization, Neutralization, Filtration, and
Clarification ....'. 7-11
7.2.8 Disposal of Solid Residue from Treatment 7-13
7.3 Wastewater Sampling 7-14
7.3.1 Treatment System Performance 7-14
7.3.2 Reuse of Treated Wastewater 7-29
7.4 Treatability Studies 7-39
7.4.1 Emulsion Breaking Study 7-39
7.4.2 Universal Treatment System Treatability Studies 7-41
7.4.3 Hydrolysis and Activated Carbon Tests 7-51
7.4.4 Membrane Separation 7-52
7.5 Treatability Database and Treatment Technology
Transfers 7-59
7.5.1 PFPR Treatability Database 7-60
in
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TABLE OF CONTENTS (Continued)
Page
7.5.2 Treatability Data Transfers 7-62
7.6 P2, Recycle, and Reuse Practices 7-65
7.6.1 Pollution Prevention Act of 1990 7-65
7.6.2 P2 Data-Gathering Efforts 7-66
7.6.3 P2, Recycle/Reuse, and Water Conservation
Practices Found at PFPR Facilities 7-67
7.6.4 Applying P2 Practices to Shipping
Container/Drum Cleaning Operations 7-68
7.6.5 Applying P2 Practices to BulkoTank Cleaning 7-70
7.6.6 Applying P2 Practices to Equipment Interior
Cleaning 7-70
7.6.7 Applying P2 Practices to Floor/Wall/Equipment
Exterior Cleaning 7-73
7.6.8 Applying P2 Practices to Leaks and Spills Clean-
Up 7-74
7.6.9 Applying P2 Practices to Aerosol Container
(DOT) Leak Testing 7-75
7.6.10 Applying P2 Practices to Air Pollution or Odor
Control Scrubbers 7-76
7.6.11 Other P2 Practices Observed at PFPR Facilities 7-77
7.6.12 Applying P2 Practices at Refilling Establishments 7-78
7.7 References -. 7-79
SECTION 8 ENGINEERING COSTS 8-1
8.1 Introduction 8-1
8.2 Regulatory Options 8-1
8.3 Engineering Costing Methodology 8-3
8.4 Development of PFPR Cost Model and Input Datasets 8-4
8.4.1 Development of the PFPR Cost Model from the
Pesticide Manufacturing Cost Model 8-4
8.4.2 PFPR Cost Model 8-5
8.4.3 Cost Model Input Datasets 8-9
8.5 UTS Module Design and Cost Algorithm 8-18
8.5.1 Wastewater Storage Design and Cost 8-19
8.5.2 Process Vessel(s) Design and Cost 8-20
8.5.3 Carbon Adsorption Unit 8-28
8.5.4 Pumps and Strainers Design and Costs 8-30
8.5.5 Containment System Design and Cost 8-31
8.5.6 Waste Disposal Design and Cost 8-33
8.5.7 Land Cost 8-34
8.5.8 Monitoring 8-34
8.5.9 Ultrafiltration 8-35
IV
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TABLE OF CONTENTS (Continued)
Page
8.6 Storage and Reuse Cost Module 8-36
8.6.1 Storage Design 8-36
8.6.2 Containment Design 8-37
8.6.3 Capital Costs 8-37
8.6.4 O&M Costs 8-37
8.7 Off-Site Disposal Cost Module 8-37
8.7.1 System Design - Tank Storage 8-38
8.7.2 System Design - Drum Storage 8-42
8.8 Costing Methodology for Subcategory E (Refilling
Establishments) 8-45
8.9 References 8-45
SECTION 9 BEST PRACTICABLE CONTROL TECHNOLOGY (BPT) 9-1
9.1 Introduction 9-1
9.2 BPT Applicability 9-1
9.2.1 Revisions to BPT 9-1
9.2.2 Applicability of Final BPT Regulations 9-3
SECTION 10 BEST CONVENTIONAL POLLUTANT CONTROL
TECHNOLOGY (BCT) 10-1
10.1 Introduction 10-1
10.2 Summary of Final BCT Limitations 10-2
10.2.1 Pesticide Formulating, Packaging, and
Repackaging (Subcategory C) 10-2
10.2.2 Refilling Establishments (Subcategory E) 10-2
SECTION 11 BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
(BAT) 11-1
11.1 Introduction 11-1
11.2 Summary of Final BAT Limitations 11-1
11.2.1 Pesticide Formulating, Packaging, and
Repackaging (Subcategory C) 11-1
11.2.2 Refilling Establishments (Subcategory E) 11-2
SECTION 12 PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES) 12-1
12.1 Introduction 12-1
12.2 Summary of Final PSES Standards 12-1
12.2.1 Pesticide Formulating, Packaging, and
Repackaging (Subcategory C) 12-1
12.2.2 Refilling Establishments (Subcategory E) 12-3
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TABLE OF CONTENTS (Continued)
Page
SECTION 13 NEW SOURCE PERFORMANCE STANDARDS (NSPS) AND
PRETREATMENT STANDARDS FOR NEW SOURCES (PSNS) . . . 13-1
13.1 Introduction 13-1
13.2 Summary of Final NSPS and PSNS Standards 13-1
13.2.1 Pesticide Formulating, Packaging, and
Repackaging (Subcategory C) 13-1
13.2.2 Refilling Establishments (Subcategory E) 13-2
SECTION 14 REGULATORY IMPLEMENTATION 14-1
14.1 Introduction 14-1
14.2 Implementation of the Final PFPR Limitations and
Standards for Subcategory C Facilities 14-1
14.2.1 Direct Dischargers 14-2
14.2.2 Indirect Dischargers 14-3
14.2.3 Necessary Paperwork for the P2 Alternative 14-4
14.2.4 Compliance Dates 14-5
14.3 Implementation of the Final PFPR Limitations and
Standards for Subcategory E Facilities 14-6
14.4 Upset and Bypass Provisions 14-6
14.5 Variances and Modifications 14-7
14.5.1 Fundamentally Different Factors Variances 14-7
14.5.2 Removal Credits 14-8
14.6 Analytical Methods 14-11
14.7 References 14-12
SECTION 15 WATER QUALITY ANALYSIS 15-1
15.1 Introduction 15-1
15.2 Soil and Groundwater Contamination at Refilling
Establishments 15-1
15.3 Water Quality Benefits of Control of Indirect Discharges 15-1
15.4 Water Quality Benefits of Control of Direct Discharges 15-2
15.5 References 15-3
SECTION 16 NON-WATER QUALITY ENVIRONMENTAL IMPACTS . 16-1
16.1 Introduction 16-1
16.2 Summary of Non-Water Quality Impacts of the Final
PFPR Rule 16-1
16.3 Air Pollution 16-3
16.3.1 Criteria Air Pollutants 16-3
16.3.2 Volatile Priority Pollutants 16-3
16.4 Solid Waste 16-5
16.5 Energy Requirements 16-6
VI
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TABLE OF CONTENTS (Continued)
16.6 References
SECTION 17 GLOSSARY OF TERMS
Page
16-6
17-1
Appendix A: FINAL REGULATION
Appendix B: PESTICIDE PRODUCT CODES AND DEFINITIONS
Appendix C: PRIORITY POLLUTANT LIST
Appendix D: TRANSFER OF TREATABILITY DATA
vn
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LIST OF TABLES
2-1
3-1
3-2
5-1
5-2
5-3
5-4
5-5
5-6
5-7
6-1
6-2
6-3
6-4
6-5
6-6
Page
Group 2 Mixtures 2-7
Distribution of Site Visits by Subgroup 3-9
Distribution of Pesticide Production 3-17
National Estimates of Water Use by Wastewater Source
(gallons/yr) 5-6
National Estimates of Water-Using Facilities by Discharge Mode
and Subcategory 5-17
Total Process Wastewater Volume by Destination and
Subcategory (gallons/yr) 5-19
Total Process Wastewater Volume for Zero Discharge Facilities
by Destination and Subcategory (gallons/yr) 5-20
Total Process Wastewater Volume by Destination and Subgroup
(gallons/yr) 5-21
PAIs for Which Self-Monitoring Data Were Submitted 5-23
Summary Statistics of the Raw Wastewater Characterization Data
from EPA Sampling Episodes 5-26
Priority Pollutants for Which No Self-Monitoring Data Were
Submitted 6-4
Priority Pollutants Measured Above Detection Limit in Self-
Monitoring Data 6-4
Priority Pollutants in Wastewater at Sampled PFPR Facilities 6-5
Priority Pollutants Reported By PFPR Facilities 6-7
PAIs Found Above Detection Limits in Raw PFPR Wastewaters 6-9
PAIs Found Above Detection Limits in the PFPR Self-
Monitoring Database 6-10
Vlll
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LIST OF TABLES (Continued)
7-1
7-2
7-3
7-4
7-5
7-6
7-7
7-8
7-9
7-10
7-11
7-12
7-13
7-14
7-15
7-16
16-1
Page
PAI Percent Removals Achieved By Treatment System #1, First
Sampling Episode 7-16
PAI Percent Removals Achieved By Treatment System #1,
Second Sampling Episode 7-17
PAI Percent Removals Achieved By Treatment System #2 7-19
PAI Percent Removals Achieved By Treatment System #3 7-21
PAI Percent Removals Achieved By Treatment System #4 7-22
PAI Percent Removals Achieved By Treatment System #5 7-24
PAI Percent Removals Achieved By Treatment System #6 7-26
PAI Percent Removals Achieved By Treatment System #7 7-28
Achievable Effluent Concentrations Used for Estimating
Compliance Costs for PAIs from PFPR Sampling 7-31
Comparison of the Estimated LTA to Achievable Effluent Data
from the Sampling of Treat and Reuse Systems 7-33
Facility A Overall UTS Performance Results 7-45
Facility B Overall UTS Performance Results 7-48
Facility C Overall UTS Performance Results 7-49
Summary of Results for Membrane (UF/RO) Separation
Treatability Study 7-54
Interior Equipment Rinsate Wastewater Test Results 7-57
DOT Test Bath Water Test Results 7-58
Criteria Air Pollutant Emissions (Ib/yr) 16-4
IX
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LIST OF FIGURES
3-1
3-2
5-1
5-2
5-3
5-4
5-5
5-6
5-7
5-8
7-1
7-2
7-3
7-4
8-1
8-2
Page
Typical Liquid Formulation Process 3-19
Typical Dry Formulation Processes 3-20
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Drum/Shipping Container Rinsate 5-8
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Interior Equipment Cleaning 5-9
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Air Pollution Control 5-10
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Spills and Leaks Cleanup 5-11
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Exterior Equipment/Floor Wash 5-12
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Safety Equipment Rinsate 5-13
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: DOT Testing 5-14
Distribution of Facilities by Ranges of Production Normalized
Volumes, Water Source: Bulk Tank Rinsate 5-15
Oil and Grease Effluent Concentrations at Reuse Facilities 7-35
COD Effluent Concentrations at Reuse Facilities 7-36
TOC Effluent Concentrations at Reuse Facilities 7-37
Acetone Effluent Concentrations at Reuse Facilities 7-38
Small UTS System Design 8-22
Large UTS System Design 8-23
x
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FOREWORD
This document delineates the development arid implementation of the final
effluent guidelines and standards for the Pesticide Formulating, Packaging, and Repackaging
(PFPR) Industry (Subcategories C and E of the Pesticide Chemicals Manufacturing Point
Source Category). Throughout the document, the Agency refers to many commonly used
titles and phrases by their acronyms to avoid spelling them out each tune. As an aid to the
reader, the Agency has included in Section 17 a glossary of commonly used acronyms and
definitions of terms used throughout the document.
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Section 1 - Introduction
SECTION 1
INTRODUCTION
1.1
Legal Authority
This regulation for the pesticide formulating, packaging, and repackaging
(PFPR) industry is being promulgated under the authorities of Sections 301, 304, 306, 307,
and 501 of the Clean Water Act (the Federal Water Pollution Control Act Amendments of
1972, 33 U.S.C. 1251 et seq., as amended by the Clean Water Act of 1977, Pub. L. 95-217,
and the Water Quality Act of 1987, Pub. L. 100-4), also referred to as "the Act."
1.2
1.2.1
Background
Clean Water Act
The Federal Water Pollution Control Act Amendments of 1972 established a
comprehensive program to "restore and maintain the chemical, physical, and biological
integrity of the Nation's waters" (Section 101(a)). To implement the Act, EPA is to issue
effluent limitations guidelines, pretreatment standards, and new source performance standards
for industrial dischargers.
These guidelines and standards are summarized briefly below:
1. Best Practicable Control Technology Currently Available (BPT)
(Section 304(b)(l) of the Act).
BPT effluent limitations guidelines are generally based on the average
of the best existing performance by plants of various sizes, ages, and
unit processes within the category or subcategory for control of
pollutants.
In establishing BPT effluent limitations guidelines, EPA considers the
total cost of achieving effluent reductions in relation to the effluent
reduction benefits, the age of equipment and facilities involved, the
processes employed, process changes required, engineering aspects of
the control technologies, non-water quality environmental impacts
(including energy requirements) and other factors as the EPA
Administrator deems appropriate (Section 304(b)(l)(B) of the Act). The
Agency considers the category or subcategory-wide cost of applying the
technology in relation to the effluent reduction benefits. Where existing
performance is uniformly inadequate, BPT may be transferred from a
different subcategory or category.
1-1
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Section 1 - Introduction
2. Best Available Technology Economically Achievable (BAT) (Sections
304(b)(2)(B) and 307(a)(2) of the Act).
In general, BAT effluent limitations represent the best existing
economically achievable performance of plants in the industrial
subcategory or category. The Act establishes BAT as the principal
national means of controlling the direct discharge of priority pollutants
and nonconventional 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 (BCD (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
(BOD5), 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).
BCT is not an additional limitation, but replaces BAT for the control of
conventional pollutants. In addition to other factors specified in Section
304(b)(4)(B), the Act requires that BCT limitations be established in
light of a two part "cost-reasonableness" test. [American Paper Institute
v. EPA. 660 F.2d 954 (4th Cir. 1981)]. EPA's current methodology for
the general development of BCT limitations was issued in 1986 (51 FR
24974; July 9, 1986).
4. New Source Performance Standards (NSPS) (Section 306 of the Act).
NSPS are based on the best available demonstrated treatment
technology. New plants have the opportunity to install the best and
most efficient production processes and wastewater treatment
technologies. As a result, NSPS should represent the most stringent
numerical values attainable through the application of the best available
1-2
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Section 1 - Introduction
demonstrated 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.
Pretreatment Standards for Existing Sources CPSES~) (Section 307(b) of
the Act).
PSES are designed to prevent the discharge of pollutants that pass
through, interfere with, or are otherwise incompatible with the operation
of publicly owned treatment works (POTWs). The Act requires
pretreatment standards for pollutants that pass through POTWs or
interfere with POTWs' treatment processes or sludge disposal methods.
The legislative history of 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 detemiining 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 nationwide 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 (52 FR 1586; January 14, 1987).
Pretreatment Standards for New Sources CPSNS) (Section 307(b) of the
Act).
Like PSES, PSNS are designed to prevent the discharges of pollutants
that pass through, interfere with, or are otherwise incompatible with the
operation of POTWs. PSNS are to be issued at the same time as NSPS.
New indirect dischargers, like the new direct dischargers, have the
opportunity to incorporate into their plants the best available
demonstrated technologies. The Agency considers the same factors in
promulgating PSNS as it considers in promulgating NSPS.
1-3
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Section 1 - Introduction
1.2.2
Section 304(m) Requirements and Litigation
Section 304(m) of the Clean Water Act (33 U.S.C. 1314(m)), added by the
Water Quality Act of 1987, requires EPA to establish schedules for (i) reviewing and revising
existing effluent limitations guidelines and standards ("effluent guidelines"), and (ii)
promulgating new effluent guidelines. On January 2, 1990, EPA published an Effluent
Guidelines Plan (55 FR 80), in which schedules were established for developing new and
revised effluent guidelines for several industrial 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, as modified, requires, among other
things, that EPA propose effluent guidelines for the PFPR subcategories of the Pesticide
Chemicals Category by March 1994, and take final action by September 1996.
1.2.3
Pollution Prevention Act (PPA)
In the Pollution Prevention Act of 1990 (42 U.S.C. 13101 et seq., Pub.L.
101-508, November 5, 1990), Congress declared pollution prevention to be the national policy
of the United States. The Act declares that pollution should be prevented or reduced
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.
The PPA directs the Agency to, among other things, "review regulations of the Agency prior
and subsequent to their proposal to determine their effect on source reduction" (Sec. 6604; 42
U.S.C. 13103(b)(2)). This directive led the Agency to implement a pilot project called the
Source Reduction Review Project that would facilitate the integration of source reduction in
the Agency's regulations, including the technology-based effluent guidelines and standards.
This effluent guideline for the PFPR industry was reviewed for its incorporation of pollution
prevention as part of this Agency effort.
1.2.4
Prior Regulation and Litigation for the Pesticide Chemicals Category
EPA promulgated BPT for the Pesticide Chemicals Category on April 25, 1978
(43 FR 17776; 40 CFR Part 455), and September 29, 1978 (43 FR 44846; 40 CFR Part 455).
BPT limitations requiring zero discharge of process wastewater pollutants to navigable waters
were set for all pesticide formulating and packaging operations (Subcategory C).
At that time, BPT effluent limitations guidelines were also established for two
manufacturing subcategories: Organic Pesticide Chemicals Manufacturing (Subcategory A)
and Metallo-Organic Pesticide Chemicals Manufacturing (Subcategory B). The BPT effluent
guidelines established limitations for chemical oxygen demand (COD), biochemical oxygen
1-4
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Section 1 - Introduction
demand (BOD5), total suspended solids (TSS), and pH for wastewaters discharged from
Subcategory A, except that discharges of these pollutants resulting from the manufacture of 25
organic pesticide active ingredients (PAIs) and classes of PAIs were specifically excluded
from the limitations. In addition, BPT limitations were set for Subcategory A on total
pesticide discharge which were applicable to the manufacture of 49 specifically listed organic
PAIs. BPT limitations requiring zero discharge of process wastewater pollutants were set for
metallo-organic PAIs containing arsenic, mercury, cadmium, or copper.
Several industry members challenged the BPT regulation on April 26, 1978 and
the U.S. Court of Appeals remanded them on two minor issues [BASF Wyandotte Corp. v.
Costle. 596 F.2d 637 (1st Cir. 1979), cert, denied. Eli Lilly v. Costle. 444 U.S. 1096 (1980)].
The Agency subsequently addressed the two issues on remand and the Court upheld the
regulations in their entirety [BASF Wvandotte 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 pesticide chemicals manufacturing segment, and the formulating/packaging
segment of the pesticide chemicals industry. In addition, the Agency proposed guidelines on
February 10, 1983 for test procedures to analyze the nonconventional pesticide pollutants
covered by these regulations (48 FR 8250).
Based on the new information collected by EPA in response to the comments
on the November 30, 1982 proposal, EPA published a Notice of Availability (NOA) of new
information on June 13, 1984 (49 FR 24492). In this NOA, the Agency indicated it was
considering changing its approach to developing regulations for this industry. EPA requested
comments on the data. EPA published a second NOA of new information on January 24,
1985, which primarily made available for public review technical and economic data which
had previously been claimed confidential by industry.
EPA issued a final rule on October 4, 1985 that limited the discharge of
pollutants into navigable waters and into POTWs (50 FR 40672). The regulation included
effluent limitations guidelines and standards for the BAT, NSPS, PSES, and PSNS levels of
control for new and existing facilities that were engaged in the manufacture and/or
formulation and packaging of pesticides. The regulation also established analytical methods
for 61 PAIs for which the Agency had not previously promulgated approved test procedures.
Several parties filed petitions in the Court of Appeals challenging various
aspects of the pesticide regulation [Chemical Specialties Manufacturers Association, et al.. v.
EPA (86-8024)]. After a review of the database supporting the regulation, the Agency found
flaws in the basis for these effluent limitations guidelines and standards. Subsequently, the
Agency and the parties filed a joint motion for a voluntary remand of the regulation in the
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Section 1 - Introduction
Eleventh Circuit Court of Appeals. The Court dismissed the case on July 25, 1986, in
response to the Joint Motion.
Upon consideration of the parties' motion to modify the dismissal, on
August 29, 1986, the Court modified its order to clarify the terms of the dismissal. The
Eleventh Circuit Court of Appeals ordered that: (1) the effluent limitation guidelines and
standards for the pesticide chemicals industry be remanded to EPA for reconsideration and
further rulemaking; and (2) EPA publish a Federal Register notice removing the remanded
pesticide regulation from the Code of Federal Regulations (CFR).
EPA formally withdrew the regulations from the CFR 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. To redevelop the additional
effluent guidelines for the pesticide chemicals industry, EPA split the project into two parts.
EPA first promulgated effluent guidelines for the pesticide manufacturing industry (58 FR
50638; September 28, 1993). These promulgated regulations for the PFPR industry comprise
the second part of tibis effort.
1.3
Scope of Final Rule
The final regulation sets forth an innovative and flexible, yet environmentally
protective, approach for the establishment of effluent limitations and pretreatment standards
under the Clean Water Act for two formulating, packaging, and repackaging subcategories of
the pesticide chemicals industry:
• Subcategory C: Pesticide formulating, packaging, and repackaging
(PFPR), including pesticide formulating, packaging, and repackaging
occurring at pesticide manufacturing facilities (PFPR/Manufacturers) and
at stand-alone PFPR facilities; and
• Subcategory E: Repackaging of agricultural pesticide products at
refilling establishments (refilling establishments).
For Subcategory C, EPA is establishing effluent limitations and pretreatment
standards which allow each facility a choice: to meet a zero discharge limitation or to comply
with a pollution prevention (P2) alternative that authorizes discharge of PAIs and priority
pollutants after various P2 practices are followed and treatment is conducted as needed (now
characterized as the Zero/P2 Alternative option). This rule also establishes a zero discharge
limitation and pretreatment standard for Subcategory E.
Under the Zero/P2 Alternative option, each owner or operator of a PFPR
facility in Subcategory C will initially choose whether the facility will meet zero discharge or
comply with the P2 alternative. This choice can be made on a product family/process
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Section 1 - Introduction
line/process unit basis rather than a facility-wide basis.;, If the zero discharge option is chosen,
the facility owner/operator will need to do whatever is necessary (e.g., reuse or recycle the
wastewater, either with or without treatment, haul the wastewater for incineration off site or
underground injection, or incinerate on site) so that zero discharge of PAIs and priority
pollutants in the wastewater is achieved.
If the P2 alternative is chosen for a particular PAI product family/process
line/process unit, then the owner/operator of the facility must agree to comply with the P2
practices for that PFPR family/line/unit delineated in Table 8 to Part 455 of the final rule,
which can be found in Appendix A to this document. This agreement to comply with the P2
practices and any necessary treatment would be contained in the NPDES permit for direct
discharging PFPR facilities or in an individual control mechanism with the control authority
(i.e., the POTW, for indirect discharging PFPR facilities (see Section 17 for the definition of
control authority)). In general, PFPR facilities choosing the P2 alternative need only submit a
small portion of the paperwork to a permitting or control authority (e.g., initial and periodic
certification statements). See 40 CFR 455.4 or Appendix A for the definitions of initial and
periodic certification statements.
The final scope of the rule does not cover the formulation, packaging, and/or
repackaging of products that contain PAIs that are sanitizers"(including pool chemicals); PAIs
that are microorganisms (such as Bacillus thuringiensis (B.t.)); Group 1 mixtures that are
common food constituents or nontoxic household items, are GRAS (generally recognized as
safe), or are exempt from FIFRA under 40 CFR 152.25; and Group 2 mixtures that are
substances whose treatment technology has not been identified. The pretreatment standards
(i.e., PSES and PSNS) do not apply to one PAI and three priority pollutants which EPA has
determined will not pass through or interfere with POTWs. In addition, certain wastewater
sources that may be associated with PFPR operations are not covered by this rule, including
storm water, on-site employee showers, on-site laundries, fire equipment test water, water
from the testing and emergency operation of eye washes and safety showers, certain
Department of Transportation (DOT) aerosol leak test bath water, laboratory water,
wastewater from research and development laboratories, and wastewater resulting from the
formulation, packaging, and/or repackaging of certain liquid chemical sterilants. Section 2.3
contains a more detailed discussion of the applicability of the final regulations.
For Subcategory E, EPA is establishing a zero discharge effluent limitation and
pretreatment standard.
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Section 2 - Summary
SECTION 2
SUMMARY
2.1
Introduction
The final regulations for the pesticide formulating, packaging, and repackaging
(PFPR) industry include effluent limitations guidelines and standards for the control of
wastewater pollutants. This section presents a summary of the final rule. Section 2.2 presents
an overview of the industry, Section 2.3 describes the applicability of the final regulations,
and Sections 2.4 and 2.5 summarize the final effluent limitations guidelines and standards.
References are included in Section 2.6.
2.2
Overview of the Industry
The PFPR industry is made up of two distinct types of activities, which were
the basis of subcategorization for this industry. The two resulting subcategories are referred
to as:
• Subcategory C: Pesticide formulating, packaging, and repackaging,
including pesticide formulating, packaging, and repackaging occurring at
pesticide manufacturing facilities (PFPR/Manufacturers) and at stand-
alone PFPR facilities; and
• Subcategory E: Repackaging of agricultural pesticide products at
refilling establishments (refilling establishments).
Section 4 discusses in detail the subcategorization of the PFPR industry.
The PFPR industry covered by this rulemaking is made up of an estimated
2,631 in-scope facilities. These facilities are located throughout the country, with greater
concentrations of refilling establishments located in the midwestern and southeastern states to
serve the agricultural market. Section 3 discusses in detail the industry profile and data
sources used to characterize the PFPR industry.
Typically, facilities use batch operations when formulating, packaging, or
repackaging pesticide products. Because the production at these facilities is not continuous
and most equipment is not dedicated to production of a single product, the equipment is
cleaned when changing over to the next product formulation. Also, many facilities operate
on the principle of "just-in-time" production, which reduces inventory and the associated
storage space. However, when operating under "just-in-time" production, the schedule is
constantly changing according to customer demand and may increase the number of cleanouts
of production equipment.
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Section 2 - Summary
The PFPR industry uses a relatively small amount of water in their formulating,
packaging, and repackaging operations. Wastewaters are not generated by the actual
formulating, packaging, or repackaging process (as they are in pesticide manufacturing). The
main sources of process wastewater at PFPR facilities are equipment cleaning waters. The
wastewaters generated at PFPR facilities are typically recycled (on or off site), discharged to a
POTW (publicly owned treatment works), or sent off site to an incinerator.
Approximately 80% of the facilities in this industry achieve zero discharge,
while 19% indirectly discharge (to POTWs) and <1% directly discharge. The direct
dischargers seem to present an inconsistency with the 1978 promulgated BPT limitations
which call for zero discharge of wastewater pollutants to navigable waters. However, a small
number of PFPR/Manufacturers combine their PFPR wastewaters with their pesticide
manufacturing wastewaters and discharge the combined wastewater. Their permit limitations
offer no allowance for the pollutants in the PFPR wastewater in their permits (i.e., limitations
were derived based on their pesticide manufacturing wastewater only). These facilities can
discharge certain quantities of PFPR wastewaters as long as their permit limitations are met.
Section 5 presents a detailed discussion of water use in the PFPR industry.
The PFPR industry uses a wide range of raw materials, producing a variety of
pesticide types (e.g., fungicide, insecticide, herbicide) and formulation types (e.g., solutions,
emulsifiable concentrate granule). The inert ingredients that are typically mixed with PAIs
during the formulation of pesticide products include water, surfactants, and organic solvents
for liquid products, and clay and talc or other carrier materials for dry products. These
materials contribute to the wide range of pollutants that are found in the wastewaters of this
industry, including conventional pollutants (e.g, BOD5, oil and grease, and TSS), a variety of
priority pollutants, and a large number of nonconventional pollutants (e.g., COD and the
specific PAIs). Section 5 discusses PFPR wastewater characterization, while Section 6
describes the selection of pollutants chosen for regulation.
2.3
Applicability of the Final Regulations
The final PFPR regulations apply to process wastewater discharges from
existing and new pesticide formulating, packaging, and repackaging operations. PFPR
operations are defined in Section 2.3.1 and PFPR process wastewater is defined in Section
2.3.2. In addition, EPA defines the applicability of this regulation to include the formulating,
packaging, or repackaging of all pesticide products, with the exceptions noted in Section
2.3.3.
2.3.1
PFPR Operations
PFPR operations include formulating, packaging, and repackaging of pesticide
products and may occur at several types of facilities other than stand-alone PFPR facilities,
including PFPR/Manufacturers, refilling establishments, and research and development (R&D)
laboratories (see Section 17 for definitions). Additional clarification of these facilities is
provided below.
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Section 2 - Summary
PFPR/Manufacturers
Pesticide manufacturing operations are covered by 40 CFR Part 455,
Subparts A and B. However, close to 50 pesticide manufacturers also perform PFPR
operations at their facility, and are referred to in this rule as "PFPR/Manufacturers." Pesticide
manufacturers may sometimes add a solvent (organic or aqueous) to a manufactured pesticide
active ingredient (PAI) or intermediate to stabilize the product (e.g., for transport or storage).
The Pesticide Manufacturing Final Technical Development Document (1) states that dilution
of the manufactured active ingredient is only covered by the Pesticide Manufacturing rule
when it is "a necessary step following a chemical reaction to stabilize the product." Thus,
EPA would like to clarify that manufacturers can perform such operations without being
subject to the PFPR effluent guidelines as long as it is a necessary step to stabilize the product
following a chemical reaction. Typically, such operations are performed without placing the
pesticide in a marketable container (i.e., they are shipped in bulk via tank truck, rail car, or
tote tank). However, PFPR facilities should not conclude that they can receive PAIs that they
do not manufacture, even in bulk quantities, and dilute it with solvent or other carrier without
being subject to the PFPR effluent guidelines, as this would be considered formulating under
Section 455.10.
Refilling Establishments
"Refilling establishment" (Subpart E of the PFPR final rule) is defined as an
establishment where the pesticide product is repackaged into refillable containers. However,
the limitations and standards of Subpart E apply only to the repackaging of pesticide products
performed by refilling establishments: (a) that repackage agricultural pesticides; (b) whose
primary business is wholesale or retail sales; and (c) where no pesticide manufacturing,
formulating, or packaging occurs. Subpart E is not applicable to custom applicators.
On-Site and Stand-Alone R&D Laboratories
The final PFPR effluent guidelines and standards do not apply to wastewater
generated from the development of new formulations of pesticide products and the associated
efficacy and field testing (where the resulting product is not manufactured for sale). This
exemption applies to such wastewaters generated at stand-alone R&D laboratories as well as
at R&D laboratories located on site at PFPR facilities.
EPA believes that wastewaters generated at these R&D laboratories have
extremely limited reuse potential due to their experimental nature, as such formulations may
only be produced once or, at most, for one set of trials. In addition, many of the pollution
prevention (P2) practices used in this industry (e.g., reuse of interior rinsates in future
formulation) are not amenable to these one-time wastewaters. Experiments also require the
use of experimental controls. One commenter on the proposed rulemaking stated that the
addition of rinsates into the "experimental design could alter the results of the experiment and
render the data obtained useless."(2) Based on these reasons and because the wastewaters that
are discharged from these operations typically contain low quantities of PAIs, EPA believes
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Section 2 - Summary
that the wastewaters generated by experimental formulation, efficacy, and field testing can be
adequately addressed in permits and pretreatment agreements through Best Professional
Judgment (BPJ) and Best Engineering Judgment (BEJ), respectively.
2.3.2
PFPR Process Wastewater
EPA has separated the PFPR industry process wastewater sources into two
groups: interior sources and noninterior sources. Below is a list of the process wastewaters
generated from these two sources:
• Interior sources:
Drum/shipping container rinsate,
Bulk container rinsate,
Equipment interior wash water, and
Contact cooling water;
• Exterior sources:
Floor/wall/equipment exterior wash water,
Leak and spill cleanup water,
Air or odor pollution control scrubber water,
Safety equipment wash water,
DOT leak test bath water when cans have burst, and
Retain sample container rinsate (initial rinse).
These regulations do not apply to water from on-site employee showers, on-site
laundries, and testing of fire protection equipment; storm water1; water used for testing and
emergency operation of safety showers and eye washes; DOT leak test bath water from non-
continuous overflow baths (i.e., batch baths) where no cans have burst from the time of the
last water change out; and water used for cleaning analytical equipment and glassware and for
rinsing the retain sample container in on-site laboratories. However, the initial rinse of the
retain sample container is considered a process wastewater source for the final regulation.
(See the Comment Response Document (3) for a discussion on the exclusion of these
wastewaters).
2.3.3
PFPR Products
The final PFPR regulation applies to the formulation, packaging, and/or
repackaging of all pesticide products, with the exception of the following six groups of
products:
Storm water at PEPR facilities and refilling establishments is covered by the Storm Water Regulations Phases I
and n, respectively.
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Section 2 - Summary
1. Sanitizer products (including pool chemicals);
2. Microorganisms;
3. Group 1 and Group 2 mixtures;
4. Inorganic wastewater treatment chemicals;
5. Chemicals that do not pass through POTWs; and
6. Certain liquid chemical sterilants.
Additional clarification of each group is provided below.
Sanitizer Products (Including Pool Chemicals)
For the final PFPR rule, sanitizer products have been completely excluded from
Subcategory C; the exemption covers both interior and exterior wastewater sources. This
exclusion is based on the following reasons: (1) sanitizer products are formulated for the
purposes of their labeled end use to "go down the drain;" (2) sanitizer active ingredients are
more likely to be sent to POTWs in greater concentrations and volumes from their labeled
end use than from rinsing formulating equipment at the PFPR facility; (3) biodegradation data
received with comments on some of these sanitizer active ingredients support the hypothesis
that they do not pass through POTWs; (4) these sanitizer active ingredients represent a large
portion of the low toxicity PAIs considered for regulation at the time of proposal; and
(5) many sanitizer solutions containing these active ingredients are cleared by the Food &
Drug Administration (FDA) as indirect food additives under 21 CFR 178.1010.
Sanitizer products are defined in Appendix A, and include pool chemicals, as
well as home use, institutional, and most commercial antimicrobial active ingredients. The
Agency feels that pool chemicals, which are defined separately from sanitizer products, should
also be classified as sanitizer active ingredients. Therefore, to avoid possible confusion, EPA
has decided to incorporate pool chemicals into the definition for sanitizer active ingredients.
Because of this, EPA has included pool chemicals hi the sanitizer exemption.
As with the sanitizer chemicals, pool chemicals are not exempted via a list, but are instead
exempted by definition. The sanitizer products exemption does not include liquid chemical
sterilants (including sporicidals), industrial preservatives, and water treatment microbiocides
other than pool chemicals.
Microorganisms
As discussed in the Supplemental Notice and in the Comment Response
Document (3), microorganisms that are considered PAIs under FIFRA will not be covered by
this regulation and will be excluded by definition (see Appendix A). Based on available
information on the formulation, packaging, and repackaging of such microorganisms and the
generation and characteristics of wastewaters from such operations, EPA believes these
pesticides are not formulated in a similar fashion as other PAIs covered by this rule.
Microorganisms which have registered pesticidal uses are generally created through a
fermentation process, similar to those found in some food processing or pharmaceutical plants.
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Section 2 - Summary
Fermentation is a biological process, whereas other pesticides are manufactured and
formulated through chemical and physical processes.
In addition, almost all the microorganisms registered as pesticide products are
exempt from the requirement of obtaining a (residue) tolerance for pesticides in or on raw
agricultural commodities (40 CFR 180.1001). Part 180 Subpart D - Exemptions From
Tolerance - states that "an exemption from a tolerance shall be granted when it appears that
the total quantity of the pesticide chemical in or on all raw agricultural commodities for
which it is useful under conditions of use currently prevailing or proposed will involve no
hazard to the public health."
Group 1 and Group 2 Mixtures
A group of chemicals, referred to in the final rule as "Group 1 mixtures" and
defined in Appendix A, are excluded from this regulation. This group includes many herbs
and spices (e.g., rosemary, thyme, peppermint, cloves), foods/food constituents, plants/plant
extracts (excluding pyrethrins), and chemicals that are considered to be GRAS (generally
recognized as safe) by the Food and Drug Administration, as well as those products exempt
from FIFRA under 40 CFR Part 152.25 (61 FR 8876; March 6, 1996).
A second group of mixtures, "Group 2 mixtures," are also being excluded from
the regulation. EPA has not been able to transfer treatability data for many of these Group 2
mixtures because the physical characteristics that EPA uses for technology transfer are not
easily identified (e.g., molecular weights, solubilities, and aromaticity). For example, within a
given structural group, PAIs that are aromatic, have high molecular weights, or low solubility
in water have been found to be amenable to activated carbon adsorption. However, when
such characteristics cannot be identified, EPA cannot transfer treatability data for carbon
adsorption.
In addition, most of the Group 2 mixtures are used as inert rather than active
ingredients in pesticide products, and the total volume of these mixtures in use in pesticide
products is very small (i.e., Group 2 mixture PAIs only represent approximately 8% of all
pesticide products). EPA was not able to develop a definition to cover all the chemicals in
this group due to the lack of homogeneity among the chemicals. Therefore, Group 2 mixtures
are excluded from the scope of the final rule by list as opposed to by definition. Table 2-1
presents a list of these Group 2 mixtures.
Nonpersistence Chemicals
Based on comments and data collected for the PFPR Treatability Database
Report Addendum (4), EPA has also exempted certain PAIs that do not persist in sanitary
streams long enough to reach POTWs. These PAIs are: dry ice, silica gel, silicon dioxide,
and liquid nitrogen.
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Section 2 - Summary
Table 2-1
Group 2 Mixtures1
Shaughnessey Code
Chemical Harae
002201
006501
006602
022003
025001
025003
025004
031801
055601
063501
063502
063503
063506
067003
067205
067207
067302
069152
070801
071004
071501
079014
079021
079029
079034
079059
086803
107302
107303
107304
116902
117001
128888
129029
224600
505200
Sabadilla alkaloids
Aromatic petroleum derivative solvent
Heavy aromatic naphtha
Coal tar
Coal tar neutral oils'
Creosote oil (Note: Derived from any source)
Coal tar creosote
Ammonium salts of C8-18 and C18' fatty acids
BNOA
Kerosene
Mineral oil - includes paraffin oil from 063503
Petroleum distillate, oils, solvent, or hydrocarbons; also p
Mineral spirits
Terpineols ( unspec.)
Pine tar oil
Ester gum
Amines, N-coco alkyltrimethylenedi-, acetates
Amines, coco alkyl, hydrochlorides
Red Squill glycoside
Cube Resins other than rotenone
Ryania speciosa, powdered stems of
Turkey red oil
Potassium salts of fatty acids
Fatty alcohols (52-61% CIO, 39-46% C8, 0-3% C6, 0-3%C12)
Methyl esters of fatty acids (100% C8 - C12)
Fatty alcohols (54.5% CIO, 45.1% C8, 0.4% C6)
Xylene range aromatic solvent
Polyhedral inclusion bodies of Douglas fir tussock moth nucl
Polyhedral inclusion bodies of gypsy moth nucleopolyhedrosis
Polyhedral inclusion bodies of n. sertifer
Gibberellin A4 mixt. with Gibberellin A7
Nosema locustae
Lactofen (ANSI)
Bergamot Oil
Diethanolamides of the fatty acids of coconut oil (coded 079
Isoparaffinic hydrocarbons
1This information is contained in Table 9 to Part 455 of the final regulation for the PFPR industry (presented in
Appendix A of this document).
2Shaughnessey codes and chemical names are taken directly from the FATES database. Several chemical names
are truncated because the chemical names listed in the FATES database are limited to 60 characters.
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Section 2 - Summary
Inorganic Wastewater Treatment Chemicals
Based on comments and data collected for the PFPR Treatability Database
Report Addendum (4), EPA is excluding from the scope of the final regulation inorganic
chemicals that are commonly used as wastewater treatment chemicals (e.g., ferric sulfate,
potassium permanganate, sulfuric acid, carbon, chlorine). (See the Comment Response
Document (3) for a discussion on the rationale behind this exclusion.) Many of these
chemicals are also excluded under the sanitizer/pool chemicals exemption. Again, these
chemicals will be excluded by definition (see Appendix A for definitions).
Chemicals That Do Not Pass Through POTWs
The four chemicals that are excluded from the pretreatment standards (i.e.,
PSES and PSNS) because EPA determined that they do not pass through POTWs are phenol,
2-chlorophenol, 2,4-dichlorophenol, and 2,4-dimethylphenol. Phenol, as a constituent in
sanitizer products, is excluded from the rule as it was excluded under the proposed sanitizer
exemption due to disproportionate economic impacts. See the Comment Response Document
(3) for a discussion on the decision to exclude these chemicals.
Certain Liquid Chemical Sterilants
Section 221 of the Food Quality Protection Act of 1996 (P.L. 104-170)
amended the definition of "pesticide" in FIFRA to exclude liquid chemical sterilant products
(including any sterilant or subordinate disinfectant claims on such products) which are used on
a critical or semi-critical device (as defined in Section 201 of the Federal Food, Drug, and.
Cosmetic Act ("FFDCS") (21 U.S.C. 321) (see 7 U.S.C. §136(u), as amended). Because
Congress has chosen to exclude such sterilant products from the definition of "pesticide," EPA
has modified the applicability provisions of this rule so that the effluent limitations and
pretreatment standards do not cover the wastewater discharges from the formulation,
packaging, and/or repackaging of liquid chemical sterilants for use on critical devices or semi-
critical devices as these terms are now defined in FFDCA Section 201 and FIFRA Section
2(u) (see 40 CFR 455.40(f)). However, facilities that formulate, package, or repackage
products containing liquid chemical sterilants into other types of products (e.g., pesticide
products which are not used on critical or semi-critical devices introduced directly into the
human body) should be aware that the wastewaters resulting from the formulating, packaging,
and repackaging activities are covered by this rule.
2.4
2.4.1
Final Regulation for Subcatesorv C: PFPR and PFPR/Manufacturers
BPT
In 1978, EPA promulgated BPT effluent limitations guidelines (43 FR 17776;
43 FR 44846; 40 CFR Part 455) applicable to pesticide chemicals formulating and packaging
processes. The BPT limitations require that there be no discharge of process wastewater
pollutants to navigable waters. Under the final rule, EPA is amending the 1978 BPT
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Section 2 - Summary
limitation by establishing a zero discharge limitation with a compliance alternative which
provides for a P2 allowable discharge to surface waters (referred to as the Zero/P2 Alternative
option).
Under the Zero/P2 Alternative option, each owner or operator of a PFPR
facility in Subcategory C will make an initial choice of whether the facility will meet zero
discharge or comply with the P2 alternative. This choice can be made on a product
family/process line/process unit basis rather than a facility-wide basis. If the zero discharge
option is chosen, the facility owner/operator will need to do whatever is necessary (e.g., reuse
or recycle the wastewater (either with or without treatment), incinerate the wastewater on site,
or haul it for off-site incineration or underground injection) to ensure zero discharge of PAIs
and priority pollutants in the wastewater.
If the P2 alternative portion of the option is chosen for a particular PAI product
family/process line/process unit, then the owner/operator of the facility must agree to comply
with the P2 practices for that PFPR family/line/unit identified in Table 8 to Part 455 of the
final rule, which can be found in Appendix A to this document. This agreement to comply
with the P2 practices and any necessary treatment would be included in the NPDES permit
for direct discharging PFPR facilities. In general, PFPR facilities choosing the P2 alternative
need only submit a small portion of the paperwork to a permitting or control authority (e.g.,
initial and periodic certification statements). (See Section 9 for a more detailed discussion of
the final BPT guidelines.)
Stand-Alone PFPR Facilities
EPA is establishing a zero discharge limitation with a compliance alternative
for a P2 allowable discharge for PFPR facilities where no pesticide manufacturing occurs or
where pesticide manufacturing process wastewaters are not commingled with PFPR process
wastewaters. The zero discharge limitation is based on pollution prevention, recycle and reuse
practices and, when necessary, treatment and reuse for those PAIs that are formulated,
packaged, and/or repackaged but are not also manufactured at the facility. The basis also
includes some amount of contract hauling for off-site incineration. EPA believes that
although the stand-alone PFPR facilities are already achieving zero discharge, in compliance
with the 1978 BPT, the methods they are using may potentially result in cross-media impacts
that the use of the P2 alternative would potentially reduce. If they do not already have a
permit, facilities choosing the P2 alternative will have to apply for an NPDES permit in
which they agree to comply with the P2 alternative.
PFPR/Manufacturing Facilities
Zero discharge (as implemented through zero allowance) is established for
PFPR/Manufacturers for those pesticides that are formulated, packaged, and/or repackaged and
manufactured at the facility. Zero allowance is based on pollution prevention, recycle and
reuse practices, and treatment and discharge through the manufacturer's wastewater treatment
system within the pesticide manufacturing production-based numeric limitations (i.e., giving
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Section 2 - Summary
no allowance for the PFPR wastewater or its production). This is consistent with how the
existing 1978 BPT zero discharge requirements have been implemented by permit writers.
The final PFPR rule will allow PFPR/Manufacturers to discharge PFPR
wastewaters in two specific ways. For those facilities choosing to comply with zero discharge
(as opposed to the P2 alternative), their permits should incorporate the zero allowance
approach for the PFPR portion of their operations for the PAIs that they manufacture. For
those PAIs formulated and not manufactured at the facility, the permit should apply a strict
zero discharge. In part, this is because their pesticide manufacturing wastewater treatment
system may not consist of the appropriate treatment technologies for such PAIs or the
treatment system may not be designed to treat the additional volumes and/or concentrations of
the "nonmanufactured" PAIs.
However, PFPR/Manufacturers can choose the P2 alternative to zero discharge.
Such facilities would not have to achieve zero discharge or zero allowance of their PFPR
wastewaters. Instead, these facilities would comply with the practices specified in the P2
alternative and would receive a "P2 discharge allowance" following treatment (see
Appendix A for the definition of P2 allowable discharge). The P2 discharge allowance can be
applied to pesticides that are formulated, packaged, and/or repackaged and manufactured as
well as those that are not manufactured on site.
The treatment system used to treat the combined PFPR and pesticide
manufacturing wastewaters must incorporate treatment that is appropriate for those PAIs
which are not also manufactured on site (i.e., those PAIs for which individual pesticide
manufacturing production-based limitations are not contained hi the NPDES permit).
Treatment is deemed appropriate through the use of treatability studies found in literature or
performed by the facility, long-term monitoring data, or listed in Table 10 of Appendix A.
These changes will make BPT consistent with BAT (and PSES) while
essentially achieving the same pollutant removals and potentially decreasing cross-media
impacts associated with various off-site disposal methods. In addition, the change to the BPT
limitation that is being promulgated for PFPR/Manufacturers will clarify that the method by
which the zero discharge limitation has been implemented (i.e., use of a zero allowance) is
appropriate.
2.4.2
BCT
Under the final rule, the Agency is setting BCT equal to BPT for conventional
pollutants under Subcategory C. BPT and BAT established zero discharge with a compliance
alternative for a P2 allowable discharge and BCT can be no less stringent than BPT and no
more stringent than BAT. Section 10 discusses the final BCT guidelines in greater detail.
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Section 2 - Summary
2.4.3
BAT
EPA is establishing BAT limitations that are equivalent to the limitations
established for BPT for PFPR/Manufacturers and stand-alone PFPR facilities.
Under the final rule, existing direct discharging Subcategory C facilities will
have a choice of either complying with a zero discharge limitation or the P2 alternative.
However, the rule clarifies that in meeting the zero discharge limitation, permitting authorities
may authorize the commingling of pesticide manufacturing and PFPR process wastewaters to
meet the pertinent BAT limitations for pesticide manufacturers with a zero allowance for PAIs
in PFPR wastewaters. Section 11 discusses the final BAT guidelines hi greater detail.
2.4.4
NSPS
EPA is establishing NSPS limitations equivalent to the limitations that are
established for BPT and BAT. Since EPA found the Zero/P2 alternative to be economically
achievable for existing facilities under BPT and BAT on a facility basis and since new
facilities will be able to choose between zero discharge and the P2 alternative on a product
family/process line/process unit basis, EPA believes that this NSPS standard does not create a
barrier to entry. Section 13 discusses the final NSPS standards hi greater detail.
2.4.5
PSES
EPA is establishing a zero discharge pretreatment standard with a P2 alternative
which allows a discharge to POTWs. The zero discharge standard is based on pollution
prevention, recycle and reuse practices, and, when necessary, treatment for reuse (using the
Universal Treatment System - see Section 7 for a more detailed discussion of this system).
The basis also includes some amount of contract hauling for off-site incineration which may
be necessary to achieve zero discharge. Compliance with the P2 alternative is based on
performing specific pollution prevention, recycle, reuse, and water conservation practices (as
listed hi Table 8 of Appendix A) followed by a P2 allowable discharge which requires
treatment of interior wastewater sources (including drum rinsates), leak/spill cleanup water,
and floor wash prior to discharge to a POTW2. Section 12 discusses the final PSES
standards in greater detail.
2.4.6
PSNS
EPA is establishing PSNS standards for this subcategory that are equivalent to
the standards established for PSES (i.e., zero discharge with a compliance alternative for a P2
In individual cases, the requirement of wastewater pretreatment prior to discharge to the POTW may be
removed for floor wash or the final rinse of a non-reusable triple rinse by the control authority when the facility
has demonstrated that the levels of PAIs and priority pollutants in such wastewaters are at a level that is too low
to be effectively pretreated at the facility and have been shown to neither pass through nor interfere with the
operations of the POTW.
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Section 2 - Summary •
allowable discharge). EPA believes that the standards established for PSNS will not create a
barrier to entry as they are equivalent to PSES, which were found to be economically
achievable. Section 13 discusses the final PSNS standards in greater detail.
2.5
2.5.1
Final Regulation for Subcategorv Ei Refilling Establishments
BPT
The existing BPT regulations did not cover refilling establishments. As
discussed in the proposed rule (59 FR 17870), the practice of refilling minibulks did not begin
until the late 1980s (i.e., after the original BPT regulation was promulgated hi 1978). Based
on a survey of the industry (discussed further in Section 3), 98% of the existing refilling
establishments achieve zero discharge. EPA proposed zero discharge of process wastewater
pollutants as the BPT limitations for refilling establishments.
In the final regulation, EPA is establishing a BPT limitation for existing
refilling establishments at zero discharge of pollutants hi process wastewaters to waters of the
U.S. This limitation is based on collection and storage of process wastewaters, including
rinsates from cleaning minibulk containers and then: ancillary equipment and wastewaters
from secondary containment and loading pads. The collected process wastewater would be
reused as make-up water for application to fields hi accordance with the product label. Since
greater man 98% of these facilities already achieve zero discharge and the remaining facilities
discharge to POTWs, the costs associated for BPT have been estimated to be nearly zero.
Section 9 discusses the final BPT guidelines hi greater detail.
2.5.2
BCT
EPA is establishing BCT limitations for this subcategory that are equivalent to
the limitations established for BPT. Since BPT requires zero discharge of process wastewater
pollutants and 98% of the existing refilling establishments already achieve zero discharge,
EPA believes an equivalent technology basis is appropriate for BCT. Section 10 discusses the
final BCT guidelines in greater detail.
2.5.3
BAT
EPA is establishing BAT limitations for this subcategory that are equivalent to
the limitations established for BPT. Since BPT requires zero discharge of process wastewater
pollutants and 98% of the existing refilling establishments already achieve zero discharge,
EPA believes the same technology basis and discharge prohibition is appropriate and
economically achievable for BAT. Section 11 discusses the final BAT guidelines in greater
detail.
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Section 2 - Summary
2.5.4
NSPS
EPA is establishing NSPS standards for this subcategory that are equivalent to
the limitations established for BPT and BAT. Since BPT requires zero discharge of process
wastewater pollutants and 98% of the existing refilling establishments already achieve zero
discharge, EPA believes an equivalent technology basis is appropriate for NSPS and will not
create a barrier to entry. Section 13 discusses the final NSPS standards in greater detail.
2.5.5
PSES
EPA is establishing PSES standards for this subcategory at zero discharge of
pollutants in process wastewaters to POTWs. These standards are based on collection and
storage of process wastewaters followed by reuse of the wastewaters as make-up water for
application to fields in accordance with the product label. Based on a survey of the industry,
98% of the existing refilling establishments already achieve zero discharge; only a small
number of refilling establishments are indirect dischargers, and EPA has estimated that they
can comply with the final pretreatment standards at nearly zero cost. Section 12 discusses the
final PSES standards hi greater detail.
2.5.6
PSNS
EPA is establishing PSNS standards for this subcategory that are equivalent to
the limitations established for PSES (i.e., zero discharge). In addition, BPT, BAT, and NSPS
also require zero discharge of process wastewater pollutants, and 98% of the existing refilling
establishments already achieve zero discharge; thus, EPA believes an equivalent technology
basis is appropriate for PSNS and will not create a barrier to entry. Section 13 discusses the
final PSNS standards in greater detail.
2.6
1.
2.
3.
References3
United States Environmental Protection Agency. Development Document for
Effluent Limitations Guidelines. Pretreatment Standards, and New Source
Performance Standards for the Pesticide Chemicals Manufacturing Point Source
Category. EPA-821-R-93-016, Washington, DC, 1993.
Comment Letter #118 from the American Crop Protection Association
(DCN F7646).
U.S. Environmental Protection Agency. Comment Response Document.
Washington, DC, September 30, 1996 (DCN F7945).
For those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
2-13
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4.
Section 2 - Summary
Radian Corporation. Pesticide Formulators. Packagers, and Repackagers
Treatabilitv Database Report Addendum. Prepared for the U.S. Environmental
Protection Agency, Office of Water, Washington, DC, September 1995 (DCN
7700).
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Section 3 - Industry Description
SECTION 3
INDUSTRY DESCRIPTION
3.1
Introduction
This section describes the pesticide formulating, packaging, and repackaging
(PFPR) industry by presenting a summary of the data and information EPA has gathered from
previous EPA rulemaking efforts along with data collected as part of this effort to develop
revised effluent limitations guidelines and standards. The following topics are discussed in this
section:
• Section 3.2 discusses EPA's data collection methods and information
sources;
• Section 3.3 presents an overview of the industry and a discussion of
how survey results were extrapolated;
• Section 3.4 discusses PFPR processes and trends observed in the
industry; and
3.2
• Section 3.5 lists references.
Data Collection Activities
EPA has gathered and evaluated technical data from various sources in the
course of developing the effluent limitations guidelines and standards for the PFPR industry.
These data sources include:
• Responses to EPA's questionnaire entitled "Pesticide Formulating,
Packaging, and Repackaging Facility Survey for 1988";
• EPA's 1990-1995 site visit and wastewater sampling program at selected
PFPR facilities;
• Industry self-monitoring data;
• EPA treatability studies;
• Previous EPA Office of Water studies of the Pesticide Chemicals
Category;
• Literature data;
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Section 3 - Industry Description
• Data transferred from the Pesticide Chemicals Manufacturing
Rulemaking including industry treatability studies, EPA treatability
studies, and EPA's sampling of selected manufacturers;
• Office of Pesticide Programs (OPP) data;
• Other EPA studies of the Pesticide Chemicals Category; and
• Data submitted during and after the comment periods for the proposed
rule and supplemental notice.
EPA used data from these sources to profile the industry with respect to: pesticide production;
PFPR processes; geographical distribution; water usage; and wastewater generation, pollution
prevention practices, treatment, and disposal. EPA then characterized the wastewater
generated by PFPR operations through an evaluation of water use, type of discharge or
disposal, and the occurrence of conventional, nonconventional, and priority pollutants. An
overview of the industry is presented in Section 3.3. Water use and wastewater
characterization are discussed in Section 5.
3.2.1
The Pesticide Formulating, Packaging, and Repackaging Facility Survey
for 1988
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.
This section summarizes the development and distribution of EPA's
questionnaire, entitled "Pesticide Formulating, Packaging, and Repackaging Facility Survey
for 1988" (1), as well as the types of data collected and the calculation of national estimates
from the collected survey data.
Identification of Industry Population
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 a pesticide "active
ingredient" (PAI) and "inert" diluents. Each formulation has a distinct registration.
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Section 3 - Industry Description
Mandatory reporting of annual pesticide production is required by FIFRA as
part of the pesticide registration process. Pesticide-producing establishments, including PFPR
facilities, are required to provide to EPA information on registered pesticide products, such as
product registration numbers, product classification, type and use, and production rates. These
data are submitted as part of the "Pesticide Report for Pesticide-Producing Establishments"
(EPA Form 3540-16) and are stored in the FIFRA and TSCA (Toxic Substances Control
Act) Enforcement System (FATES) database administered by EPA's Office of Pollution
Prevention and Toxics (OPPT). The FATES database was created in the fall of 1979 by the
EPA Office of Enforcement, Pesticide and Toxic Substances Enforcement Division; it has
since been renamed the Section Seven Tracking System.
Development of the Questionnaire
EPA used its experience with previous questionnaires, including the
questionnaire distributed to the pesticide manufacturing portion of the pesticide chemicals
industry, to develop a detailed questionnaire for the evaluation of the PFPR industry. The
questionnaire surveyed operations producing pesticide products containing one or more of the
same 272 PAIs or classes of PAIs that were the focus of EPA's pesticide manufacturing
effluent guidelines rulemaking (58 FR 50638). Since the development of the questionnaire,
EPA has excluded 7 of the 272 PAIs from the scope of the rule (see Section 2.3 for a detailed
discussion of rule applicability).
The questionnaire was reviewed by pesticide industry trade associations,
environmental public interest groups, and a number of individual PFPR facilities, and was
subsequently revised by EPA. The revised draft questionnaire was again distributed for
comment to the industry and trade associations and, in 1989, it was pretested at nine PFPR
facilities. After facility personnel returned completed questionnaires to EPA, EPA and its
contractors visited the facilities to evaluate the accuracy and completeness of responses, to
estimate the burden on the respondents, and to learn which sections respondents found
difficult or confusing. In response to the facilities' comments, EPA revised the questionnaire
again.
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 (OMB) for
review, and published a notice in the Federal Register that the questionnaire was available for
review and comment. EPA estimated that the public reporting burden for completion of the
questionnaire was an average of 55 hours per response. EPA also redistributed 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 final changes to the questionnaire. OMB cleared the questionnaire for distribution
on January 30, 1990 without comment (OMB control number 2040-0139).
3-3
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Section 3 - Industry Description
Development of Sample Frame
FATES data files from reporting year 1988 were accessed to identify the
facilities that made products containing one or more of the 272 PAIs that were under
consideration for the development of the pesticide manufacturing effluent guidelines. This
dataset was used to define a sampling frame of 3,241 facilities identified as formulators,
packagers, or repackagers of these PAIs. The sampling frame was partitioned into 51 strata.
The stratification was done according to annual pesticide production amount (large, medium,
small, and tiny) and pesticide type (fungicide, herbicide, insecticide, and other, and
combinations of these types for facilities that formulate, package, and/or repackage more than
one type.) The sample size for each stratum was determined statistically to minimize
coefficients of variation. Chapter 2 of the Report on Formulating, Packaging, and
Repackaging flPFPR) Facility Surveys of 1988 (2) describes the survey sample in detail.
Distribution of the Questionnaire
In 1990, following approval by OMB and under authority of Section 308 of the
Clean Water Act, EPA distributed the questionnaire to selected facilities identified as PFPR
facilities. A total of 611 facilities were selected randomly from the sampling frame to
comprise the questionnaire survey sample. These facilities are referred to as sampled
facilities. The questionnaire was also distributed to a census of 91 pesticide manufacturers,
which were identified from the "Pesticide Manufacturing Facility Census for 1986". Two of
the 611 sampled facilities and 2 of the 91 manufacturers received duplicate questionnaires, so
the actual number of facilities sent questionnaires was 609 sampled facilities and 89
manufacturers for a total of 698 surveyed facilities. EPA received responses from 676 (587
randomly sampled facilities and 89 manufacturers) of the 698 facilities that received the
questionnaire (a 97% response rate). The remaining 22 facilities did not submit
questionnaires. EPA believes most of these facilities are refilling establishments by virtue of
their stratum, the company name, and their locations.
Of the 676 facilities that responded to the survey, 262 facilities that are still
covered by the scope of the rule indicated that they formulated, packaged, or repackaged
pesticide products in 1988 that contained one or more of the 272 PAIs. Another 48 facilities
also manufactured PAIs during 1988. 'One hundred and eighty-three (183) facilities indicated
they were refilling establishments. One hundred and seventy-eight (178) facilities did not
formulate, package, or repackage pesticide products in 1988 that contained one or more of the
272 PAIs that are still in scope of the rule. Of the remaining five facilities that responded,
three had gone out of business, one was released from completing a questionnaire, and one
facility had merged with another. Based on the responses to the surveys from the randomly
sampled facilities and the census of manufacturers, quantitative estimates of PFPR activities
were estimated for the entire U.S. population of such facilities.
EPA also received questionnaires from six facilities that were not selected in
the random sample or part of the census of manufacturers. Three of these facilities had
participated in a pretest of the questionnaire but were not chosen in the sample. The
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Section 3 - Industry Description
remaining three were facilities that asked if they might submit voluntary surveys. These
voluntary questionnaires were not used for extrapolation purposes, as described in the
discussion of calculation of stratified national estimates later in this section.
Data Collected by the Questionnaire
The questionnaire specifically requested information on: (1) PFPR processes
used; (2) the quantity, destination, treatment, and disposal of wastewater generated during
PFPR operations; (3) analytical monitoring data available for PFPR wastewaters (discussed in
Section 3.2.3 of this document); (4) treatability studies performed by or for facilities
(discussed in Section 3.2.4); (5) the degree of co-treatment (treatment of PFPR wastewater
mixed with wastewater from PAI manufacturing or other industrial 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.
The questionnaire consisted of the following parts:
• Introduction;
• Part A. Technical Information;
• Part B. Financial and Economic Information; and
• Part C. Contact Information and Certification.
Based on responses to the Introduction, certain facilities were exempt from completing Part A
or B for one of the following three reasons:
1. The facility did not formulate, package, or repackage in 1988 any
registered pesticide product containing one or more of the targeted 272
PAIs;
2. The facility did not report using any water in its PFPR operations in
1988; or
3. After December 31, 1988, the facility had discontinued production of
pesticide products containing one or more of the targeted 272 PAIs.
These facilities did not have to provide information on water use
practices or wastewater characterization data, which were solicited in
Part A of the questionnaire.
In addition, certain facilities that completed the questionnaire are no longer subject to this rule
due to changes in the scope (see Section 2.3 for more detail).
Based on the final scope of the rule, 484 surveyed facilities have been
identified as being PFPR facilities in 1988. Three hundred and three (303) of these facilities
fall under Subcategory C: (PFPR and PFPR/Manufacturers); 220 of these facilities use water
3-5
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Section 3 - Industry Description
in their PFPR operations. The remaining 181 facilities were identified through their responses
as refilling establishments (Subcategory E); 132 of these facilities have been identified as
water users.
Calculation of Stratified National Estimates
Following development of the sample frame, EPA determined a weight
associated with each stratum. Each surveyed facility in a stratum represents a specific number
of facilities in the national population of the PFPR industry. For example, if a surveyed
facility falls in the "herbicide-small" stratum and the weight of that stratum is 5, the responses
received from that facility represent a total of five facilities in the overall PFPR industry
population.
Based on the responses to the surveys, weighted statistical estimates of PFPR
activities associated with production containing one or more of the 272 PAIs were computed
for the entire U.S. population of such facilities. The results of these computations are referred
to as national stratified estimates. These estimates include point estimates of totals, means
(i.e., averages), and medians (i.e., the point at which an equal number of responses are above
and below the value), and their associated standard errors. Pesticide manufacturing facilities
were assigned a weight of one, since they were part of a census. The responses to
questionnaires that were voluntarily submitted but were not part of the sample population
were reviewed for potential participation in the site visit and sampling program (described in
Section 3.2.2); however, for statistical reasons, these questionnaires were omitted from the
calculation of stratified national estimates (i.e., these facilities were assigned a weight of
zero). Details of the statistical methodology used to generate estimates are provided in
Chapter 3 of the Report on Formulating, Packaging, and Repackaging (PFPR) Facility
Surveys of 1988 (2).
Two complicating factors occurred in relation to the data received from the
PFPR survey. First, some facilities in the sample frame were originally misclassified based
on their estimated 1989 production, rather than actual 1988 production. Second, some
questionnaires were missing data because the facility did not respond to all questions in the
survey.
The misclassification of facilities required that the sample be post-stratified into
the correct 1988-based strata. Therefore, the typical formulas used to generate national
estimates of means, totals, and standard errors of these estimates are not wholly correct.
Instead, alternate formulas were used to generate national estimates of totals and standard
errors of these totals (3). Though restratification of the survey facilities often increases the
estimated standard errors, the national totals (e.g., number of facilities covered by the rule or
compliance cost estimates) themselves 'will be exactly the same mathematically, as long as the
same set of facilities is used to compute the estimates. In the PFPR project, a small number
of facilities that were included in the sample because of projected 1989 production figures did
not have any actual production in 1988. These facilities were therefore not a part of the
targeted facility universe and so were excluded from the restratified calculations. Even so, the
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Section 3 - Industry Description
overall national totals showed very minor changes (on the order of at most four to five
percent) when the restratified estimates were compared with totals based on the original strata.
The second complicating factor concerns missing responses. Because some
facilities failed to answer all the survey questions, data were imputed for missing responses.
The amount of missing data was negligible in most cases. The only case where a significant
amount of data was imputed involved wastewater volumes and production-normalized
wastewater volumes, which were reported on a line-by-line basis for each combination of
wastewater source and destination. Approximately 10% of the volume and/or production-
normalized volume entries were missing and were subsequently imputed.
3.2.2
EPA's Site Visit and Wastewater Sampling Programs
As part of the development of effluent guidelines for this industry, EPA
conducted site visits and wastewater sampling episodes at a number of PFPR facilities,
PFPR/manufacturing facilities, and refilling establishments. Typically, during effluent
guidelines development, EPA depends on a sampling program to characterize the raw
wastewater and to establish which treatment systems operate at BAT levels. However, in the
case of the PFPR industry, EPA was not able to conduct as extensive a sampling program as
for other rulemaking efforts for the following reasons: (1) only 12 facilities in the industry
survey population operated on-site treatment systems that treated only PFPR water (one of the
12 was a voluntary survey participant and not part of the sample); (2) facility operating
schedules are very unpredictable due to the batch nature of their operations and just-in-time
production philosophy; and (3) due to the nature of PFPR processes, treatment is almost
always operated on a batch basis making it very difficult to characterize long-term treatment
performance (long-term even for a 3-day period). Therefore, EPA had to implement a more
widespread and in-depth site visit program than it has with past effluent guidelines. For
example, EPA contacted over 100 facilities for potential site visits. The following discussions
provide an overview of both the PFPR industry site visit and wastewater sampling programs.
Site Visits
EPA performed site visits at 58 facilities (6 of these were not survey facilities
and, therefore, did not fill out a questionnaire). As mentioned above, these site visits
provided EPA with an in-depth look at actual PFPR operations. The purpose of an individual
site visit was to:
• Evaluate the facility's water use and discharge practices to determine the
ability to comply with the various regulatory approaches;
• Gather information on different and/or typical water use, water
conservation, pollution prevention, and best management practices in the
PFPR industry;
• Evaluate the facility's suitability for wastewater sampling; and
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Section 3 - Industry Description
• Evaluate the facility as a possible candidate for bench- or pilot-scale
treatability testing.
Following the site visit, a draft site visit report was prepared that described the PFPR
operations and water management practices. The report was sent to the facility for review
and comment, and any corrections were incorporated. Facilities also identified any
information that they considered confidential business information.
To ensure that EPA collected information from a cross-section of the industry,
facilities were selected to provide a distribution across a number of different characteristics,
including: geographical areas, facility subgroup and market types, water use types, types of
equipment cleaning sequences used, and facility type (i.e., PFPR, PFPR/Manufacturer,
refilling establishment). Facilities were also selected if they were expected to have
implemented pollution prevention practices or have on-site treatment systems (particularly
treatment systems that generated effluent that could be reused).
A large part of site visit selection was based on the "Subgroup Analysis" (4).
[Note: the subgroups are not subcategories and are not being used in the regulatory sense.]
When selecting sites to visit, EPA classified the surveyed facilities into 10 subgroups based on
the types of markets (e.g., agriculture, consumer lawn and garden, government use) that
contributed the majority of pesticide-related revenue to the facility. EPA also looked at the
types and amounts of pesticide products made at the facility. EPA analyzed the trends in
water usage, water discharge/disposal methods, and production for each subgroup and
identified facilities within the subgroups that are currently achieving zero discharge through
recycle or reuse of wastewater, as well as facilities that do not currently meet this option.
This information was used not only to select facilities for site visits, but also to coordinate
additional data-gathering activities. EPA planned to visit approximately 10% of the total
number of facilities in each subgroup. Following proposal of the rule, EPA targeted certain
facilities for site visits in response to comments and to evaluate the scope of the rule,
including pool chemical and sanitizer facilities (counted as "institutional" facilities) and pet
products facilities (counted as "aerosol" facilities). Table 3-1 presents the final distribution of
site visits by subgroup.
Refilling establishments were not included in the subgroup analysis and were
selected for site visits on a separate basis. Based on responses to the facility survey, all
refilling establishments were believed to have similar operating characteristics. EPA
conducted a telephone survey of 28 refilling establishments and visited 8 facilities. Following
proposal of the rule, EPA attempted to identify refilling establishments located outside the
midwestern U.S. that handled pesticide products used on a variety of crops (specifically,
facilities that could not comply with the proposed zero discharge rule). EPA was unable to
identify any refilling establishments meeting these criteria.
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Section 3 - Industry Description
Table 3-1
Distribution of Site Visits by Subgroup
Subgroup
Aerosol
Agriculture
Consumer Home Products
Consumer Lawn and
Garden
Industrial
Institutional2
Manufacturing
Organo-Metallic
Organo-Metallic/Industrial
Other
TOTAL
Number of
Facilities In
Subgroup1
15
77
9
30
32
67
47
13
4
33
327
Humfeer of Site
Visit* Completed
5
14
1
5
5
7
5
3
0
4
493
Percent of
Subgroup Visited
33
18
11
17
16
1.0
11
23
0 .
12
15
is column reflects only surveyed facilities (i.e., this does not include the entire PFPR
industry).
2Includes sanitizer and pool chemical facilities, which are no longer within the scope pf the
rule.
3EPA actually performed site visits at 58 facilities; however, eight facilities were refilling
establishments and one was not a PFPR facility.
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Section 3 - Industry Description
Wastewater Sampling
Eighteen sampling episodes have been conducted at 17 PFPR facilities since
1988 (one facility was sampled during two different episodes). Eight of the 18 episodes
included sampling of wastewater treatment systems and all 18 included sampling for raw
wastewater characterization. EPA has not sampled any wastewater from refilling
establishments, but, as mentioned earlier, has conducted site visits at eight refilling
establishments.
Raw wastewater characterization data were collected to provide EPA with
concentration data for PFPR wastewaters for a number of different wastewater sources. EPA
collected 83 raw wastewater samples containing 53 different PAIs at 17 different facilities.
Wastewater samples were collected for the following wastewater sources: interior equipment
cleaning from both formulating and packaging operations, exterior equipment cleaning, floor
wash water, air pollution control scrubber water, DOT test bath, drum and shipping container
rinsate, laboratory equipment cleaning water, laundry water, and employee shower water. A
number of these samples were collected to characterize wastewater mat was intended for
reuse. Samples of commingled wastewaters were also collected. Raw wastewater samples
were typically analyzed for levels of conventional pollutants, nonconventional pollutants
(including PAIs), metals, and semi-volatile and volatile organics. The results of this data
collection are discussed in Section 5.5.
Facilities were selected for sampling of their treatment systems after EPA
evaluated existing data and responses to the questionnaire and follow-up telephone
conversations. Facilities were selected for sampling if: (1) the facilities were operating an
apparently effective wastewater treatment system (especially if the water treated was intended
for reuse); (2) the treatment system was used to treat PFPR wastewater only; (3) the treatment
system was similar to a system EPA was evaluating in a treatability study (the facility
treatment system could then be used as a benchmark); (4) the expected PAIs could be
analyzed using developed analytical methods; and (5) the facility was treating wastewater that
contained PAIs (or structural groups) for which data were lacking.
The treatment technologies that were sampled to test treatment performance
include: activated carbon adsorption, membrane filtration (ultrafiltration and cross-flow
filtration), ozonation, clarification, and biological oxidation. EPA analyzed the levels of
pollutants and the overall performance of the treatment systems. In addition, EPA conducted
treatability studies with both synthetic and actual PFPR facility wastewater (collected from 8
facilities) to test the treatment performance of activated carbon adsorption, chemical oxidation
by ozone/UV, ultrafiltration and reverse osmosis, chemical precipitation, hydrolysis, and
emulsion breaking (via heat and acidification and via chemical addition). These treatability
tests are summarized in Section 3.2.4 and discussed in more detail in Section 7.4.
Prior to a sampling episode at a PFPR facility, representatives of the Agency
conducted an engineering site visit. Following the visit, a draft sampling plan was prepared
which provided the rationale for the selection of sampling locations as well as the procedures
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Section 3 - Industoy Description
to be followed during sampling. A copy of this draft plan was provided to the facility for
comments prior to any wastewater sampling to ensure that the sample locations selected would
allow proper characterization of the process wastewater and evaluation of the wastewater
treatment system. EPA also collected information from facility personnel on the PAIs that
would be present in the wastewater to allow arrangements to be made for their chemical
analyses.
During the sampling episode, teams of EPA engineers and EPA contractor
engineers and technicians collected and preserved samples and shipped them to EPA contract
laboratories for analysis. Levels of conventional pollutants, nonconventional pollutants
(including the PAIs), priority pollutants, and organic and metal nonpriority pollutants were
measured in raw wastewater and treated effluent. EPA always offered to split the samples
with the facility. When facilities chose to split samples with EPA, either the facility accepted
the split samples provided by the EPA or 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 PFPR operations and treatment processes, sampling procedures, analytical
results, QA/QC evaluation, and discussion of the raw wastewater composition and treatment
system performance. The report was provided to the sampled facility for review and
comment, and any corrections were incorporated into the report. The facilities also identified
any information in the draft report that they considered confidential business information.
3.2.3
Industry-Supplied Data
Some POTWs require indirect dischargers to monitor their effluent. To make
use of this self-monitoring data, the questionnaire requested that each respondent provide all
monitoring data available for 1988 on raw waste loads, individual process stream
measurements, pollutant concentration profiles, or any other data on pollutants associated with
the formulation, packaging, or repackaging of pesticide products containing one or more of
the 272 PAIs targeted for detailed data collection. EPA received self-monitoring data from 50
PFPR facilities with their responses to the questionnaire. Six facilities submitted data only for
conventional pollutants, while 10 of the 50 facilities submitted conventional pollutant data
along with priority pollutant and/or nonconventional pollutant data (including the PAIs). EPA
later requested a number of facilities which prepare monthly discharge reports to POTWs to
provide additional monitoring data. EPA requested that all monitoring data be provided in the
form of individual data points rather than as monthly aggregates.
Much of the self-monitoring data received were not useful in characterizing
PFPR process wastewaters and cannot be used in developing chemical-specific limitations.
Most of these facilities monitor their wastewater discharge downstream from PFPR operations.
At that point, the PFPR wastewaters have been commingled with other wastewaters, such as
wastewaters from pesticide manufacturing, organic chemicals manufacturing, or nonpesticide
product formulating operations. In many cases, only one detection was reported for a specific
pollutant. Often the data represented sampling results only at the end-of-pipe plant discharge.
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Section 3 - Industry Description
The self-monitoring data were also of limited use because many POTWs do not require PFPR
facilities to monitor specific PAIs. These POTWs are more likely to require monitoring of
conventional pollutants, COD, pH, organic constituents, or metals. As discussed in Section
5.5.1, self-monitoring data from only 10 facilities were useful in characterizing priority
pollutant discharges in raw pesticide process wastewaters containing 89 PAIs.
Pesticide wastewater treatability studies performed by or for PFPR facilities
were also requested by EPA. Twenty-four facilities supplied treatability data. Only 8 of the
24 were PFPR stand-alone facilities, while the other 16 were PFPR/manufacturers. To the
extent possible, these additional data were also considered in the development of the effluent
guidelines.
3.2.4
EPA Bench- and Pilot-Scale Treatability Studies
EPA conducted 18 bench- and pilot-scale studies to evaluate the treatability of
pesticide-containing wastewaters by various treatment technologies. Eleven of these
treatability tests were conducted solely to support development of the PFPR effluent
guidelines, while one test was conducted for use in both the pesticide manufacturing and the
PFPR rulemaking efforts. Technologies evaluated for the PFPR industry include activated
carbon adsorption, chemical oxidation by ozone accompanied by irradiation with ultraviolet
light, emulsion breaking using chemical addition, emulsion breaking using heat and
acidification, alkaline hydrolysis, membrane filtration (ultrafiltration, microfiltration, and
reverse osmosis), and settling. Treatability studies were conducted both on clean water to
which PAIs were added ("synthetic wastewaters") and on actual PFPR process wastewaters.
The treatability studies conducted to support the PFPR proposed rulemaking are
discussed in detail in Section 7.4.
3.2.5
Treatability Data Transfers
EPA evaluated PAI treatability data collected under the pesticide manufacturers
rulemaking effort, and collected substantial data on PAI-specific physical and chemical
properties to identify appropriate treatment transfers. EPA also conducted an extensive search
during the PFPR and pesticide manufacturing rulemaking efforts to identify treatability
information from technical literature, treatment technology vendors, and other sources.
Information obtained from this search includes: (1) previously published EPA documents
addressing pesticides; (2) technical journal articles containing information on the treatability
of PAIs or PAI groups; and (3) reports from technology vendors containing information about
the performance and effectiveness of their equipment in treating PAIs or PAI groups. These
sources contain information on a variety of PAI or PAI group treatment technologies;
however, only information on the treatment technologies applicable to the PFPR subcategories
were considered.
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Section 3 - Industry Description
EPA transferred treatability data from the following sources, listed in order of
preference.
1. Data used to develop BAT limitations for pesticide manufacturing PAIs
or PAI structural groups. The data were transferred from the
manufacturing database to support BAT limitations if the treatment was
based on activated carbon adsorption, chemical oxidation, hydrolysis, a
combination of these technologies, or precipitation of organo-metallic
PAIs.
2. EPA bench-scale treatability study reports.
3. EPA sampling episode reports.
4. Industry treatability study reports and literature articles, and other data
sources.
Pretreatment to remove emulsions is expected to improve the treatability of
PFPR wastewater by the BAT treatment technologies to the same or similar levels that EPA
identified for PAIs in the pesticide manufacturing rule. Therefore, treatment technologies and
associated treatability data (typically obtained from full-scale treatment systems) that were
used to establish the BAT limitations for the manufacturing subcategory may be considered
applicable to the same PAIs or PAI structural groups in the PFPR subcategory. Where such
full-scale data do not exist, it may be more difficult to determine whether a particular
technology will effectively treat a particular PAI or PAI structural group. To determine
whether technologies are effective when full-scale data are not available, EPA analyzed the
treatability data provided in treatability study reports, EPA sampling trip reports, and other
data sources. Treatability data from the pesticide manufacturing administrative record
pertaining to the treatment of the 272 PAIs by activated carbon adsorption, chemical
oxidation, hydrolysis, and precipitation are included in the Final Pesticide Formulators.
Packagers, and Repackagers Treatability Database Report (5). Treatabiliry data pertaining to
the non-272 PAIs are included in the Pesticide Formulators. Packagers, and Repackagers
Treatability Database Report Addendum (6).
The final pesticide manufacturing effluent guidelines established BAT limits for
53 PAIs based on these treatment technologies. These BAT limits are typically based on
full-scale treatability data that also apply to PFPR wastewaters (assuming similar treatability
of wastewater matrices once the wastewater has been treated through an emulsion breaking or
chemical precipitation step). For some PAIs, achievable effluent concentrations were
available for full-scale activated carbon adsorption or hydrolysis treatment systems, but the
carbon saturation loadings or hydrolysis half-lives were unknown due to a lack of influent
concentration data. Of the BAT limitations for the 53 PAIs, 24 are based on activated carbon
adsorption, 14 are based on chemical oxidation, 11 are based on hydrolysis, and 4 are based
on a combination of hydrolysis and activated carbon adsorption. None of the manufacturing
3-13
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Section 3 - Industry Description
BAT limits for PAIs are based on precipitation because the organo-metallic subcategory
(Subpart B) BAT limitations were deferred.
Hydrolysis treatability studies conducted under the current pesticide rulemaking
efforts provide data for 58 PAIs or PAT groups. Hydrolysis treatability studies conducted
under previous pesticide rulemaking efforts provide data for an additional five PAIs or PAI
groups. Activated carbon adsorption treatability studies conducted under the current pesticide
rulemaking efforts provide data for 49 PAIs or PAI groups. Chemical oxidation treatability
studies conducted under the current pesticides rulemaking efforts provide data for 11 PAIs.
The studies conducted under previous pesticides rulemaking efforts do not provide any
additional data.
EPA has transferred treatability data for activated carbon adsorption, hydrolysis,
and metals precipitation for certain PAIs. Transferred treatability data for activated carbon
adsorption are based on analyses of properties of the PAIs, such as molecular weight,
aromaticity, and solubility. Hydrolysis half-life data have been transferred within certain
chemical structural groups (e.g., carbamate pesticides), while other available hydrolysis data
have been extrapolated to optimum operating conditions (i.e., pH of 12 and 60°C).
Treatability data for chemical oxidation via alkaline chlorination were not transferred, because
there were insufficient data available upon which to base such a transfer. A detailed
discussion of the treatability transfer methodology is presented in Section 7.5.
3.3
Overview of the Industry
Based on data from the 1988 FATES database and the survey questionnaire, the
PFPR industry comprises an estimated 2,631 facilities. (The survey, the FATES database, and
the extrapolation process are described in Section 3.2.1.) EPA estimates that for all the PAIs .
covered by the final rule (i.e., in-scope 272 and non-272 PAIs), there were approximately
1,497 facilities involved in formulating, packaging, and repackaging pesticide products in
1988, and approximately 1,134 refilling establishments (7).
This section discusses some general characteristics of the PFPR industry based
on an extrapolation of 303 PFPR facilities and 181 refilling establishments that completed the
Introduction of the questionnaire and reported formulating, packaging, or repackaging in 1988
a pesticide product containing one or more of the 272 PAIs still in scope of the final rule. As
discussed below, PFPR facilities may have different ownership types, geographic locations,
water uses, and may formulate, package, or repackage different varieties of pesticide products.
Additionally, this section includes information on nine facilities (seven PFPR
facilities and two refilling establishments) that reported in the survey that they discontinued
PFPR production after December 31, 1988. These facilities were only required to respond to
the Introduction of the questionnaire; therefore, limited information is available.
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Section 3 - Industry Description
3.3.1
Type of Operations
Based on survey results and EPA site visits, most PFPR facilities conduct more
than one type of PFPR operation. The PFPR industry primarily comprises facilities that
formulate and package pesticide products or facilities that formulate, package, and repackage
pesticide products. A small group of facilities performs other combinations of these
operations (e.g., package and repackage only) as well.
All of the refilling establishments perform repackaging only and do not
formulate or package pesticide products. However, an estimated 916 refilling establishments
perform custom blending or provide application services and some also sell bulk fertilizer
products.
Approximately half of the Subcategory C facilities that discontinued PFPR
production were facilities that formulate and package pesticide products; the remaining
Subcategory C facilities that discontinued production either formulated only or formulated,
packaged, and repackaged pesticide products. All of the refilling establishments that
discontinued production were facilities that repackaged only.
3.3.2
Geographic Location
When looking at the estimated national distribution of PFPR facilities by EPA
regions, EPA found that, while PFPR facilities can be found in every geographic region of the
United States, the PFPR industry is concentrated in the midwestern and southeastern portions
of the United States. The largest concentration of PFPR facilities is in EPA Regions IV and
V where a large portion of the Subcategory C facilities are located. The refilling
establishments (including those that discontinued production) are primarily located in EPA
Regions V and VII. Subcategory C facilities that discontinued production are distributed
fairly evenly across the United States.
3.3.3
Ownership Type
Virtually all Subcategory C facilities are operated by either single-facility
companies or multiple-facility companies. Only a very small number of the PFPR facilities
are estimated to have a cooperative ownership (e.g., multiple owners who purchase and
distribute pesticide products among themselves). On the other hand, a large portion of
refilling establishments have cooperative ownerships. Refilling establishments may also be
single- or multiple-facility companies.
Approximately 68% of Subcategory C facilities that discontinued PFPR
production are estimated to be single facilities. The rest of the discontinued production
facilities in Subcategory C comprise multiple-facility companies. All refilling establishments
that discontinued PFPR production are estimated to be owned by multiple-facility companies.
None of the facilities are estimated to have a cooperative ownership.
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Section 3 - Industry Description
3.3.4
Product Types
EPA's Office of Pesticide Programs (OPP) classified each pesticide product by
pesticide type (e.g., insecticide, herbicide, nematicide, rodenticide) and formulation type (e.g.,
solution, dust, granule). Definitions of pesticide and formulation types can be found in
Appendix B.
The top three types of pesticide products are herbicides, insecticides, and
fungicides. The largest percentage of products (36%) that were formulated, packaged, or
repackaged in 1988 were classified as herbicides; these same products constitute over 40% of
the production in pounds. Herbicide products are followed by insecticides, which constitute
about 27% of the products and 23% of production. Fungicides constitute 10% of the products
and almost 17% of production.
Overall, the largest percentage of products in the industry are estimated to be
emulsifiable concentrates (31%); however, they only account for 10% of the production in
pounds. Granular products and soluble concentrates account for about 18% of the products
and each contributes about 21% of the production hi pounds (for a total of 42%).
3.3.5
Production
The pounds of 1988 production for each in-scope product were obtained from
the FATES database or from the individual facilities if production data were unavailable from
the FATES database. The repackaged amount does not include the quantity of product that
facilities may have custom blended or commercially applied. The amount of pesticide
production reported by PFPR facilities is subject to double counting (i.e., a product may be
formulated and/or packaged at one facility, and packaged or repackaged at another facility).
EPA estimates that PFPR facilities formulated, packaged, or repackaged
approximately 16,780 products in 1988; almost 14,500 products contained at least one of the
272 PAIs that were the focus of the survey questionnaire. Table 3-2 presents the distribution
of pesticide production reported in the FATES database for calendar year 1988.
EPA also analyzed the percentage of PAI present in pesticide products that
were formulated, packaged, and repackaged in 1988. These data are not available in the
FATES database, so EPA accessed the detailed data collected through the survey. The survey
data are from water-using facilities that formulated, packaged, or repackaged pesticide
products in 1988 that contain one or more of the 272 in-scope PAIs. The survey data
indicated that the percentage of PAI in a product varied from less than 1% of PAI by weight
to over 99% of PAI by weight. Individual PAI usage was determined by multiplying the
pounds of production of each in-scope product by the percentage of each individual PAI
contained in the product. The pesticide products at refilling establishments tend to be more
concentrated, due to the purpose of their end use.
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Section 3 - Industry Description
Table 3-2
Distribution of Pesticide Production
'
Products Containing Only
272 PAIs
Products Containing Only
Non-272 PAIs
Products Containing Both
272 and Non-272 PAIs
Total
Number of Products
13,751
2,283
746
16,780
Pounds of Product ;
6,096,361,828
3,206,349,943
467,994,826
9,770,706,597
3-17
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3.4
Section 3 - Industry Description
Pesticide Formulating, Packaging, and Repackaging Processes
This section describes general PFPR processes, pesticide production lines, and
trends observed in the PFPR industry. Figures 3-1 and 3-2 present generic diagrams for
liquid and dry formulation processes, respectively.
3.4.1
General Process Descriptions
Pesticide formulation involves the process of mixing, blending, or diluting one
or more PAIs with one or more other active or inert ingredients to obtain a product used for
additional processing or an end-use (retail) product. Formulation does not involve an intended
chemical reaction (i.e., manufacturing). Pesticide formulations take all forms: water-based
liquid; organic solvent-based liquid; dry products in granular, powder, and solid forms;
pressurized gases; and aerosols. The formulations can be in a concentrated form requiring
dilution before application or can be ready to apply. The packaging of the formulated
pesticide product depends on the type of formulation. Liquids generally are packaged into
jugs, cans, or drums; dry formulations generally are packaged into bags, boxes, drums, or
jugs. Pressurized gases are packaged into cylinders, and aerosols are packaged into aerosol
cans.
EPA has observed formulating, packaging, and repackaging performed in a
variety of ways, ranging from very sophisticated and automated formulating and packaging
lines to completely manual lines. General descriptions of liquid formulating and packaging,
dry formulating and packaging, aerosol packaging, pressurized gas formulating and packaging,
and repackaging operations are provided below.
Liquid Formulating and Packaging
Liquid formulations contain mixtures of several raw materials, including PAIs,
inert ingredients, and a base solvent, and may also contain emulsifiers or surfactants. The
solvent may be water or an organic chemical, such as isopropyl alcohol or petroleum
distillate. In some cases, the formulation is an emulsion and contains both water and an
organic solvent. Solid materials, such as powders or granules, may also be used as part of a
liquid formulation by dissolving or emulsifyuig the dry materials to form a liquid or
suspension. The formulated product may be in a concentrated form requiring dilution before
application, or may be ready to apply.
Typical liquid formulating lines consist of storage tanks or containers to hold
active and inert raw materials and a mixing tank for formulating the pesticide product. A
storage tank may also be used on the formulating line to hold the formulated pesticide
product, prior to a packaging step. Facilities may receive their raw materials in bulk and
store them in bulk storage tanks, or they may receive the raw materials in smaller quantities,
such as 55-gallon drums, 50-pound bags, or 250-gallon minibulk refillable containers or
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3-20
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Section 3 - Industry Description
"totes." These raw materials are either piped to the formulation vessel from bulk storage
tanks or added directly to the vessel from drums, bags, or minibulks. Typically, water or the
base solvent is added to the formulation vessel in bulk quantities.
The formulating line may also include piping and pumps for moving the raw
material from the storage tanks to the mixing tank, and for moving formulated pesticide
product to the packaging line. Other items that may be part of the line are premixing tanks,
stirrers, heaters, bottle washers, and air pollution control equipment. Some lines may also
contain refrigeration units for formulation and storage units, scales, and other equipment.
Many liquid formulations are packaged by simply transferring the final product
into containers. Small quantities of product are often manually packaged by gravity feeding
the product directly from the formulation tank into the product container. For larger
quantities, the process is often automated. Formulated product is transferred to the packaging
line through pipes or hoses, or is received from a separate formulating facility and placed hi a
filler tank. A conveyor belt is used to carry product containers, such as jugs, bottles, cans, or
drums, through the filling unit, where nozzles dispense the appropriate volume of product.
The belt then caries the containers to a capper, which may be automated or manual, and to a
labeling unit. Finally, the containers are packed into shipping cases.
Dry Formulating and Packaging
Dry formulations contain active and inert ingredients; the final product may be
in many different forms, such as powders, dusts, granules, blocks, solid objects impregnated
with pesticide (e.g., flea collars), pesticides formed into a solid shape (e.g., pressed tablets), or
microencapsulated dusts or granules. They are formulated in various ways, including:
• Mixing powdered or granular PAIs with dry inert carriers;
• Spraying or mixing a liquid active ingredient onto a dry carrier;
• ' Soaking or using pressure and heat to force active ingredients into a
solid matrix;
• Mixing active ingredients with a monomer and allowing the mixture to
polymerize into a solid; and
• Drying or hardening an active ingredient solution into a solid form.
These dry pesticide products may be designed for application in solid form or to be dissolved
or emulsified in water or solvent prior to application.
Because of the many types of dry pesticide products, dry pesticide formulating
lines can vary considerably. In general, though, dry formulating lines typically have tanks or
containers to hold the active ingredients and inert raw materials, and may include mixing
3-21
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Section 3 - Industry Description
tanks, ribbon blenders, extruding equipment, high pressure and temperature tanks for
impregnating soHds with active ingredient, vacuum or other type of drying equipment, tanks
or bins for storage of the formulated pesticide product, pelletizers, presses, milling equipment,
sieves, and sifters.
Raw materials for dry pesticide products may be liquid or solid. Liquid raw
materials may be stored in rail tank cars, tank trucks, minibulks, drums, or bottles. Dry raw
materials may be stored in silos, rail cars, tank trucks, minibulks, metal drums, fiber drums,
bags, or boxes. Liquid raw materials may be pumped, poured, or sprayed into formulation
vessels, while dry raw materials are frequently transferred to formulation equipment by screw
conveyors (consisting of a helix mounted on a shaft and turning in a trough), elevators, or by
pouring.
Dry formulating lines may also include piping and pumps to move raw
materials from storage tanks to the formulation equipment, and to move formulated pesticide
product to the packaging equipment. Other items that may be included in the dry pesticide
product line are premixing tanks, tanks for storing formulated product prior to packaging,
stirrers, heaters, refrigeration units on formulation and storage equipment, scales, and air
pollution control equipment (e.g., cyclones, filters, or baghouses). Dry pesticide products may
be packaged into rail tank cars, tank trucks, totes, and minibulks, but are typically packaged
into bags, boxes, or drums.
As with many liquid formulations, dry formulations are packaged by simply
transferring the final product into boxes, drums, jugs, or bags. Small quantities or bags are
typically packaged manually using a gravity feed from the formulating unit into the containers
or bags. Larger quantities may be packaged on an automated line, similar to liquid packaging
lines.
Aerosol Packaging
Some pesticide products (typically water- or solvent-based liquids) are
packaged as aerosols, which can be applied to surfaces or dispersed in the air. The product is
placed in spray cans that are put under pressure ,and a propellant is added, which forces the
product out of the can in an aerosol spray. An aerosol packaging line typically includes a
filler, a capper, a propellant injector, and a U.S. Department of Transportation (DOT) test
bath. In the filler, formulated pesticide product is dispensed into empty aerosol cans, in much
the same way as the liquid packaging lines fill containers. The cans are then sent to the
capper, where a cap with nozzle is placed on the can. The can enters a separate room, where
the propellent is injected into the can, a vacuum is pulled, and the c'ap is crimped to make the
can airtight. In order to comply with DOT regulations on the transport of pressurized
containers, each can must then be tested for leaks and rupturing hi a DOT test bath. The
DOT test bath is a 130°F hot water bath into which cans are submerged and observed for
leaks or ruptures. The aerosol packaging line may also include a can washer to remove
residue from can exteriors prior to entering the test bath (to reduce contaminant buildup in the
3-22
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Section 3 - Industry Description
bath), a dryer to dry can exteriors, and machinery to package aerosol cans into boxes for
shipment.
Pressurized Gas Formulating and Packaging
Some pesticide products are formulated and packaged as pressurized gases.
The active and inert ingredients are received as liquids, pressurized liquids, or gases, and are
stored in tanks, tank trucks, rail cars, or minibulk storage containers. Liquid ingredients are
placed in a holding tank prior to formulation. Formulating and packaging operations for these
products typically occurs in one step in a closed-loop system. The ingredients are metered by
weight through pressurized transfer lines into DOT-approved steel application cylinders.
Other equipment that may be included in a pressurized gas line include pump and piping, and
heating and refrigerating units to maintain gas pressures and temperatures in storage.
The cylinders may be refilled at a later date, after they have been tested to
ensure that they are still capable of containing pressurized fluids. DOT requires hydrostatic
pressure testing, as well as visual examination of the cylinder. Hydrostatic pressure testing
involves filling the tank with water to a specified pressure and volume. If more water can be
held in the cylinder than its original volume, or if the cylinder weighs less than 10% of its
original weight, it is possible that the cylinder walls are deformed, whereupon the cylinder
fails the test. Visual inspection entails purging the cylinder of its vapors using an inert gas
such as nitrogen, and inspecting the interior for pitting and other defects with a fiber optic
probe. The cylinder is then rinsed with water and dried.
Repackaging
Repackaging operations are similar to packaging operations, except the "raw
material" is an already formulated product that has been packaged for sale. Repackagers often
purchase formulated pesticide products, transfer the product to new containers with customer-
specific labeling, and sell them to distributors.
A separate type of repackaging, called refilling, is usually performed by
agrichemical facilities that transfer pesticide products from bulk storage tanks into minibulks.
These refillable containers are constructed of plastic and typically have capacities ranging
from 100 to 500 gallons. Minibulks may be owned by the refilling establishment, the
pesticide registrant, or by the end user. Production lines usually consist of a bulk storage
tank, a minibulk tank into which the product is repackaged, and any interconnecting hoses or
piping. The bulk storage tanks are usually dedicated by product and clustered together in a
diked area. The products are dispensed to the minibulks by the use of manual system or a
computer-regulated system of pumps and meters.
3-23
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Section 3 - Industry Description
3.4.2 Production Lines
The 1988 survey defines a "production line" as:
Equipment and interconnecting piping or hoses arranged in a
specific sequence to mix, blend, impregnate, or package, or
repackage pesticide products. These products contain one or
more pesticide active ingredients with other materials to impart
specific desirable physical properties for a product or device, or
to achieve a desired pesticide active ingredient concentration for
a particular product or device, or to package it into marketable
containers. The line begins with the opening of shipping
containers or the transfer of active ingredient(s) and other
materials from a manufacturer or another formulator/packager, or
from inventory of bulk storage. The line ends with the
packaging or repackaging of a product into marketable containers
or into tanks for application. (1)
As described in Section 3.4.1, production lines range from complex configurations involving
numerous formulating and packaging steps to simpler lines that transfer product from storage
to a marketable container. Typically, facilities that formulate and package products operate
lines that include one or more storage tanks, one or more formulating processes (such as
mixing, blending, grinding, milling, and filtering), and a final packaging process. Facilities
that solely package products typically transfer a product from a storage tank into a marketable
container, and facilities that solely repackage products transfer product from one marketable
container into another marketable container.
Production lines at refilling establishments typically consist of a bulk storage
tank, a minibulk tank into which the product is repackaged, and any interconnecting hoses and
piping. Typical refilling establishments utilized three repackaging lines in 1988. Facilities
that merely relabel a product container were not under scope of this survey.
Line Production
Because facilities in the PFPR industry formulate, package, and repackage a
variety of pesticide products (e.g., herbicides, insecticides, and fungicides), these facilities
typically have physical divisions between formulating and packaging operations and between
diy and liquid operations, and sometimes between herbicide and insecticide operations.
Because of the large number of pesticide products a facility may handle, most
PFPR facilities operate on the principle of "just-in-time" production. This principle basically
dictates that products are made on customer demand to reduce the space needed to keep large
inventories on hand. However, because production is tied to customer orders, the specific
products that are formulated, packaged, or repackaged can vary from day to day and hour to
3-24
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''"* Section 3 - Industry Description
hour. Therefore, facilities often use an equipment line (e.g., a liquid formulating line) to
make multiple products over the course of a day, or week, or month.
The number of products formulated, packaged, or repackaged on each line
varies from line to line and from facility to facility. Some lines are dedicated to one product,
while others may handle ten or more. Certain lines produce a variety of pesticide products
that contain the same or a similar PAI, while other lines produce pesticides that contain a
variety of PAIs. Some lines are also used to formulate, package, or repackage products that
have different formulation types.
Line Operation
Facilities typically formulate, package, or repackage these products in batches.
They also usually have the flexibility to "mix and match" equipment as needed. For example,
a facility may have two formulation mix tanks, Tank A with a capacity of 100 gallons, and
Tank B with a capacity of 500 gallons. Both mix tanks have piping connections to a product
storage tank (Tank C) with a capacity of 500 gallons. The facility can configure these tanks
two ways, depending on the amount of product to be formulated. If 100 gallons of product or
less are scheduled to be made, the facility connects Tank A with Tank C and uses Tank A to
formulate the product. If more than 100 gallons of product are scheduled to be made, the
facility connects Tank B with Tank C and uses Tank B to formulate the product. In both
cases, the facility is attempting to maximize their production while minimizing the amount of
equipment that will need to be cleaned prior to formulating a new product.
The survey requested facilities to report which months each PFPR line was in
operation in 1988, and to estimate the total number of days and hours each line was in
operation in 1988. Over half of the lines at PFPR facilities are operated 100 days or less to
produce registered products that contain one of the 272 PAIs covered by the rule. A high
proportion (21%) of lines are estimated to be in operation 15 days or less per year. Less than
10% of the lines are estimated to be in operation more than 260 days per year. At refilling
establishments, over half the lines are operated less than 45 days per year. Most lines are
operated on an as-needed basis, while other lines were reported as being operated for a short
period during the year. The majority of repackaging lines at refilling establishments were in
operation in March, April, and June.
3.4.3
Trends in the Industry
The pesticide industry is changing and efforts are being made to improve
products to meet consumer demand for less toxic and safer pesticides. For example, water-
based solutions are gradually replacing organic solvents in liquid pesticide formulating.
Developments in packaging are also underway. For example, the growing use of water-
soluble packages can reduce worker exposure to pesticides and minimize problems with
disposal of packaging materials.
3-25
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Section 3 - Industry Description
As a result of the PFPR survey (see Section 3.2.1), EPA identified a significant
population of refilling establishments. These facilities repackage agricultural pesticide
chemicals, usually herbicides, into refillable containers which are used to transport the
pesticide to the site to where it is applied. The use of refillable containers became widespread
during the 1980s to reduce the numbers of empty pesticide containers needing to be disposed
of by farmers. In general, registrants distribute large undivided quantities of pesticides to
dealerships (refilling establishments) where the products are stored in large bulk tanks. The
dealer then repackages the pesticide from the bulk storage tanks to portable minibulk
containers that generally have capacities of approximately 100 gallons. The increased use of
refillable containers led to an increased amount of herbicide stored in bulk quantities and the
need to have a secondary containment system built around the bulk storage tanks. The Office
of Pesticide Programs (OPP) has proposed a regulation to require such secondary containment
systems (59 FR 6712; February 11, 1994).
3.5
3.
4.
References1
U.S. Environmental Protection Agency. Pesticide Formulating, Packaging, and
Repackaging Facility Survey for 1988 (DCN F0093).
Science Applications International Corporation. Report on the Pesticide
Formulating, Packaging, and Repackaging (PFPR) Facility Survey. Prepared
for the U.S. Envkonmental Protection Agency, Office of Water, Washington,
DC, March 28, 1994 (DCN F7151).
Cochran. Sampling Techniques. 3rd Edition. 1977, p.143-144.
Memorandum: Development and Characteristics of PFP Subgroups, February
26, 1993 (DCN F6092).
Radian Corporation. Final Pesticide Formulators. Packagers, and Repackagers
Treatability Database Report. Prepared for U.S. Environmental Protection
Agency, Office of Water, Washington, DC, March 1994 (DCN F7185).
Radian Corporation. Pesticide Formulators. Packagers, and Repackagers
Treatabilitv Database Report Addendum. Prepared for the U.S. Environmental
Protection Agency, Office of Water, Washington, DC, September 1995 (DCN
F7700).
Memorandum: Revised Estimation of Facilities in PFPR Industry, May 30,
1996 (DCN F7888).
those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
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Section 4 - Industry Subcategorization
SECTION 4
INDUSTRY SUBCATEGORIZATION
4.1
Introduction
The division of a point source category into groups called "subcategories"
provides a mechanism for addressing variations among products, raw materials, processes, and
other parameters that result in distinctly different effluent characteristics. Regulation of a
category by subcategory ensures that each subcategory has a uniform set of effluent
limitations that take into account technological achievability and economic impacts unique to
that subcategory.
The factors that EPA considered in the subcategorization of the Pesticide
Chemicals Category include:
Product type;
Raw materials;
Type of operations performed;
Nature of waste generated;
Dominant product;
Plant size;
Plant age;
Plant location;
Non-water quality characteristics; and
Treatment costs and energy requirements.
EPA evaluated these factors and determined that subcategorization of this
category is necessary. Based on these evaluations, the Pesticide Chemicals Category has been
divided into four subcategories for the purpose of issuing effluent limitations (one subpart of
40 CFR 455 was designated for incorporation of analytical methods - Subpart D: Test
Methods for Pesticide Pollutants). These four subcategories are:
• Subcategory A (Subpart A): Organic pesticide chemicals
manufacturing;
• Subcategory B (Subpart B): Metallo-organic pesticide chemicals
manufacturing;
• Subcategory C (Subpart C): Formulators, packagers, and repackagers of
pesticide products, including formulating, packaging, and repackaging at
pesticide manufacturing facilities;
• Subcategory E (Subpart E): Repackagers of pesticide products at
refilling establishments.
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Section 4 - Industry Subcategorization
Subcategories A and B, covering the pesticide manufacturing industry, have already been
addressed in a separate rulemaking published on September 28, 1993 (58 FR 50638).
Section 4.2 briefly discusses the background of the subcategorization of the
Pesticide Chemicals Category. Section 4.3 discusses the subcategorization bases of the
pesticide formulating, packaging, and repackaging (PFPR) industry, and Section 4.4
summarizes the subcategories determined under the final PFPR rule.
4.2
Background
Under the 1978 BPT rulemaking, EPA divided the Pesticide Chemicals
Category into three subcategories: (1) Subcategory A - organic pesticide chemicals
subcategory, which applied to the manufacture of organic pesticide active ingredients (PAIs);
(2) Subcategory B - the metallo-organic pesticide chemicals subcategory, which applied to the
manufacture of metallo-organic PAIs; and (3) Subcategory C - the pesticide chemicals
formulating and packaging subcategory, which applied to the formulating and packaging of all
pesticide products. As a result of the development of the September 28, 1993 pesticide
manufacturing rulemaking (which addressed Subcategories A and B), a separate Subpart D of
the rule was identified for analytical test methods.
On April 14, 1994 (59 FR 17850), EPA proposed effluent limitations
guidelines and standards for the PFPR portion of the Pesticide Chemicals Category. This rule
proposed the following two subcategories:
• , Subcategory C: Formulaters, packagers, and repackagers of pesticide
chemicals, including formulating, packaging, and repackaging operations
at pesticide manufacturing facilities (PFPR and PFPR/Manufacturers);
and
• Subcategory E: Repackagers of agricultural pesticide chemicals at
refilling establishments (refilling establishments).
This subcategorization scheme explicitly included repackaging operations into both
subcategories and created the new Subcategory E for regulation. Refilling establishments
clearly differ from the rest of the PFPR industry population in terms of the repackaging
operations they perform, the raw materials used, water use and wastewater treatment
requirements, and costs.
EPA considered creating a third subcategory for small formulators, packagers,
and repackagers of certain PAIs that are used in sanitizer chemical products. Sanitizer
facilities are similar to the other PFPR facilities with respect to the types of operations;
however, sanitizer product facilities are different in certain market and technical
characteristics. Therefore, for existing indirect discharging facilities only, EPA proposed to
segment the pretreatment standards and provide separate limitations for sanitizers in order to
reduce the economic impacts on these small entities. These separate limitations would have
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Section 4 - Industry Subcategorization
only applied to sanitizer facilities which formulate, package, or repackage small quantities of
sanitizer products ("small sanitizer facilities").
4.3
Current Subcategorization Basis
After reviewing data collected after proposal and comments on the proposed
rule and the Supplemental Notice, EPA reevaluated the proposed Subcategorization scheme.
Based on this evaluation, the Agency still believes there are two distinct subcategories within
the PFPR industry that fall within the scope of the final rule. The subcategories are:
• Subcategory C: Pesticide formulating, packaging, and repackaging
(PFPR), including pesticide formulating, packaging, and repackaging
occurring at pesticide manufacturing facilities (PFPR/Manufacturers) and
at stand-alone PFPR facilities; and
• Subcategory E: Repackaging of agricultural pesticide products at
refilling establishments (refilling establishments).
For Subcategory C, EPA is establishing effluent limitations and pretreatment
standards which allow each facility a choice: to meet a zero discharge limitation or to comply
with a pollution prevention (P2) alternative that authorizes discharge of PAIs and priority
pollutants after various P2 practices are followed and treatment is conducted as needed (now
characterized as the Zero/P2 Alternative option). This rule also establishes a zero discharge
limitation and pretreatment standard for Subcategory E.
In the proposed rule, EPA placed small sanitizer facilities in their own
subgroup within Subcategory C. However, for the final rule, sanitizer facilities have been
excluded from Subcategory C based on a number of factors. The partial exemption for small
sanitizer facilities that was included in the proposal was largely based on disproportionate
economic impacts. Based on comments received on the proposed rule, EPA expanded the
sanitizer exemption to include additional chemicals for the following reasons: (1) sanitizer
products are formulated for the purposes of their labeled end use to "go down the drain"; (2)
sanitizer active ingredients are more likely to be sent to publicly owned treatment works
(POTWs) in greater concentrations and volumes from their labeled end use than from rinsing
formulating equipment at the PFPR facility; (3) biodegradation data received with comments
on some of these sanitizer active ingredients support the hypothesis that they do not pass
through POTWs; (4) these sanitizer active ingredients represent a large portion of the low
toxicity PAIs considered for regulation at the time of proposal; and (5) many sanitizer
solutions containing these active ingredients are cleared by the Food and Drug Administration
(FDA) as indirect food additives under 21 CFR 178.1010. The sanitizer exclusion is
discussed in more detail in Section 2.3.3.
The remainder of Section 4.3 discusses the factors considered for
Subcategorization of the PFPR industry and those that were selected as the basis of the final
subcategories.
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Section 4 - Industry Subcategorization
4.3.1
Product Type
The PFPR industry produces pesticide products that fall into four basic
pesticide types: fungicide, insecticide, herbicide, and other. These pesticide types may be
formulated into product as 16 different formulation types (e.g., solution, emulsifiable
concentrate, granular, powder) (see Appendix B for definitions of formulation types).
Combining pesticide and formulation types creates far too many groups to provide a clear
basis for subcategorization. Also, facilities in this industry change their product line
frequently in response to customer demand and, therefore, it would be difficult for permitting
authorities to keep track of the correct subcategory. But, most importantly, EPA has surveyed
and visited numerous PFPR facilities with a variety of product types and has not seen
evidence of differences in water use based on product type. Therefore, EPA did not find that
product type is an appropriate basis for subcategorization of the PFPR industry.
4.3.2
Raw Materials
This industry uses a great variety of raw materials in their operations, including
over 700 individual PAIs in over 50 structural groups; thus, it is not practical to identify
subcategories by specific raw materials or active ingredients.
EPA recognized that the raw materials used by refilling establishments are
different from the raw materials used by the PFPR facilities. Refilling establishments use
bulk registered pesticide product that is simply transferred into another container (i.e.,
minibulk). The raw materials at PFPR facilities are PAIs and inert ingredients that require
mixing to result in a registered pesticide product. Therefore, EPA believes that the
differences in raw materials contribute to the decision to group refilling establishments in a
subcategory separate from.other PFPR facilities.
4.3.3
Type of Operations Performed: Formulating, Packaging, and Repackaging
Operations
Facilities that formulate, package, and repackage pesticide products, with the
exception of the refilling establishments!, have many common characteristics. As discussed in
Sections 3.3 and 3.4, formulating and packaging operations consist of mixing (without an
intended chemical reaction) PAIs with inert ingredients and placing the product in a
marketable container. Typically, these facilities operate on a batch basis and use a
combination of equipment, including mixing vessels (which may be heated), storage tanks,
transfer hoses, and rilling equipment for liquid products, and blenders, grinders, sieves,
storage tanks, and hoppers for dry products. Wastewater at these facilities is typically
generated from cleaning operations, including rinsing of raw material containers, equipment
interiors and exteriors, and floors in the process areas. EPA has seen widespread
implementation of a variety of P2 practices at these facilities (see Section 7.6 for a discussion
on these practices). Some facilities may operate on a seasonal schedule, but many facilities
have product lines that provide them with almost yearly production. The customers of these
PFPR facilities are not the product end-users, but rather distributors or retail dealers.
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Section 4 - Industry Subcategorization
However, operations at refilling establishments (that handle agricultural
pesticide products) differ from other PFPR facilities. These refilling establishments perform
repackaging of agricultural chemicals and do not perform formulating or initial packaging of
products. Repackaging, as an operation, is inherently different from formulating or packaging
operations. Repackaging is defined as the direct transference of a single PAI or single
formulation from any marketable container (typically a stationary bulk container) to another
marketable container, without intentionally mixing in any inerts, diluents, solvents, other
active ingredients, or other materials of any sort. These facilities typically handle bulk
agricultural herbicide products (and possibly some fungicides). Similar to operations at
formulating and packaging facilities, repackaging operations are also conducted on a batch
basis; however, mere are some differences in the equipment used and the sources of
wastewater generation. Generally, refilling establishments use bulk storage tanks, transfer
piping, pumps, and refillable marketable containers (minibulks or tote tanks). At most
refilling establishments, this equipment is kept in a diked secondary containment system. Not
unlike the rest of the PFPR industry, wastewater is generated by cleaning equipment.
However, many of the process wastewater sources found hi formulating and packaging
operations are not found at refilling establishments (e.g., aerosol DOT test bath water,
pollution control scrubber water, interior cleaning rinsate from formulating mix tanks) and
vice versa. At refilling establishments, wastewater is generated by cleaning stationary bulk
tanks, triple-rinsing refillable minibulk containers upon return, and collecting product that has
leaked and spilled within the containment structure. In addition, operations at refilling
establishments are seasonal and, therefore, so is then: wastewater generation.
Another difference between the refilling establishments and the other facilities
in this industry is the customer of the product/service. By definition, this final rule for
refilling establishments applies to establishments engaged in retail and wholesale sales. The
customer of these facilities is usually the end-user of the pesticide product (i.e., farmers).
Refilling establishments may provide additional pesticide services to then- customers, such as
custom blending or custom application to fields. They may also provide fertilizer chemical
sales and services as well.
EPA believes that the refilling establishments are a homogenous group and are
sufficiently different from the other facilities hi this industry to justify Subcategorization. In
addition, EPA believes that the types of operations performed in this industry (formulating,
packaging, and/or repackaging) are an appropriate basis for Subcategorization.
4.3.4
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 PAIs) from different PFPR
facilities. Virtually all wastewater is derived from cleaning the process equipment and the
surrounding areas. The volumes of water used to perform cleaning operations vary in the
PFPR industry. PFPR facilities that also manufacture PAIs generally use more water than
other facilities in the industry, because these facilities are usually larger and produce (in
volume or pounds) more formulated pesticide products than stand-alone PFPR facilities. The
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Section 4 - Industry Subcategorization
increase in water use and wastewater generation at these PFPR/Manufacturers is relative to
their increase in production; therefore, EPA concludes that a larger volume of water can be
recycled back into the process. For more discussion, see Section 5.3.2.
The differences in the nature of the wastes generated was not considered to be
an appropriate basis for subcategorization of this industry.
4.3.5
Dominant Product
As discussed in Section 4.3.1, there are a large number of products produced in
the PFPR industry due to the variety of pesticide types and formulation types. In 1988,
facilities in the PFPR industry formulated, packaged, or repackaged over 16,000 products that
fall within the scope of the rule. Refilling establishments repackaged then: "dominant
product" (i.e., agricultural herbicides) into only 522 unique products. Because refilling
establishments serve only one market type (agricultural), most of their products are
agricultural herbicides applied to farmers' fields. PFPR facilities do not necessarily have a
dominant product. Then: products may be used as home, lawn, and garden, industrial,
institutional, or agricultural products. Therefore, EPA believes subcategorization based on
dominant product produced serves as an appropriate basis to place refilling establishments in a
subcategory separate from other PFPR facilities.
4.3.6
Plant Size
Based on data available to EPA, plant size and production capacity do not
impact characteristics of wastewater generated during the formulating, packaging, or
repackaging of pesticide products. Many facilities in this industry are not solely PFPR
facilities. They may perform pesticide manufacturing, organic chemicals manufacturing
(OCPSF), and/or formulating, packaging, or repackaging of other nonpesticide products.
Therefore, plant size is not as easily defined as it is hi an industry that strictly performs one
type of operation. The size of the plant will not affect the effectiveness of treatment
technologies (i.e., the pollutant concentrations in the effluent that can be achieved with
treatment technologies), although it can affect the cost of treatment equipment and the cost of
treatment per unit of production. EPA believes the Universal Treatment System (UTS) (see
Section 7.4 for a detailed description) is flexible enough to work both for facilities with very
small wastewater flows and for facilities with larger wastewater flows. Overall, EPA does not
believe that plant size is an appropriate method of subcategorization for the PFPR industry.
4.3.7
Plant Age
The age of a plant or a production line can sometimes have a direct bearing on
the number of product changeovers on that given line and, therefore, the volume of
wastewater generated. It is more likely that an older plant does not have segregated
equipment and, therefore, cleans lines more frequently due to product changeover. However,
EPA has visited older plants that have either switched to segregated equipment or have
implemented less expensive P2 techniques, such as adding spray nozzles to hoses or using
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* Section 4 - Industry Subcategorization
floor scrubbing machines, to reduce wastewater generation to the levels of newer plants. EPA
believes that both older and newer plants would be able to achieve zero discharge or the P2
alternative. Therefore, subcategorization on the basis of plant age is not appropriate.
4.3.8
Plant Location
As discussed in Section 3.3, the majority of PFPR facilities are located in the
midwestern and southeastern parts of the United States. Many of the refilling establishments
are located in southcentral United 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 (see Section 8 for a discussion of compliance cost estimates).
Facilities in urban areas have higher land costs and tend to have less empty or unused space
for treatment units. 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, such as drought, may affect the water use at a facility. At
the tune of the survey, California was experiencing severe drought conditions. EPA has
noticed that the lack of and cost of water in this part of the country encouraged many
innovative P2, water conservation, and reuse techniques at those facilities. However, many of
these same techniques have also been implemented in areas of net precipitation (e.g., Florida).
EPA believes that location alone is not an appropriate basis for
subcategorization.
4.3.9
Non-Water Quality Characteristics
Non-water quality environmental impacts from the PFPR industry result from
solid waste disposal, transportation of wastes to off-site locations for treatment or disposal,
and emissions of volatile organic compounds and particulates to the air. The impact from
solid waste disposal is dependent upon the treatment technology used by a facility and the
quantity and quality of solid waste generated by that facility. Contract hauling of small
volumes of wastewater from PFPR facilities may create a hazard because it involves 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 PFPR industry are somewhat related to the PAIs and
the inert ingredients used. Most PAIs are very low in volatility compared to the various
solvents added as inerts or present as contaminants of the inerts. Since many of the same
solvents are used hi formulating many different pesticide products, air pollution control
problems are not unique to any segment of this industry. For example, baghouses or wet
scrubbing devices are used to remove particulates and vapors at many facilities.
Based on these discussions, the Agency believes that subcategorization on the
basis of non-water quality characteristics is not warranted. However, EPA notes that the P2
alternative was developed to reduce potential cross-media impacts from the proposed zero
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Section 4 - Industry Subcategorization
discharge regulation for PFPR facilities. EPA did not believe it was necessary to develop
such a compliance alternative for refilling establishments as the potential cross-media impacts
are low.
4.3.10
Treatment Costs and Energy Requirements
Treatment costs and best available wastewater treatment technology are
significant factors in considering whether to subcategorize PFPR facilities and refilling
establishments. In the case of the refilling establishments, almost all facilities already achieve
zero discharge. The "best" available technology in this segment of the industry is not a
treatment technology, but is the practice of collecting and reusing rinsewater through
application to farmers' fields in accordance with the product label. The water-using refilling
establishments generate a median volume of water of approximately 720 gallons annually.
These wastewaters are collected in the containment system and loading area and stored in
tanks or containers. EPA estimated that a small number of refilling establishments (19
facilities) discharge a total estimated volume of 1,500 gallons annually to POTWs. This
represents an average volume of approximately 78 gallons per facility, which can be held in a
single minibulk container costing approximately $500 per facility.
The PFPR facilities (other than refilling establishments) are also expected to be
able to recycle/reuse wastewaters; however, some wastewater sources may require treatment
before they can be recycled or discharged. EPA has estimated the costs for storage of
wastewater and treatment through the UTS (described in detail in Section 8). The average
estimated cost of compliance for PFPR facilities is approximately $59,000 (in 1995 dollars)
annually. Therefore, EPA believes subcategorization based on treatment costs and energy
requirements is appropriate.
4.4
Final Subcategories
Based on the differences hi the raw materials used, the type of operations
performed, the dominant product, and the available treatment technology and the associated
costs, EPA has defined two subcategories for the PFPR industry:
• Subcategory C: Pesticide formulating, packaging, and repackaging
(PFPR), including pesticide formulating, packaging, and repackaging
occurring at pesticide manufacturing facilities (PFPR/Manufacrurers) and
at stand-alone PFPR facilities; and
• Subcategory E: Repackaging of agricultural pesticide products at
refilling establishments (refilling establishments).
The applicability of the final effluent limitations guidelines and standards is
described briefly below. A more detailed discussion of the applicability of the final
regulations is presented in Section 2.3 of this document.
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Section 4 - Industry Subcategorization
The final PFPR regulations apply to process wastewater discharges from
existing and new pesticide chemicals formulating, packaging, and repackaging operations. For
Subcategory C—facilities that formulate, package, or repackage pesticides—EPA is establishing
a zero discharge limitation with a compliance alternative that provides a P2 allowable
discharge. Each facility can choose to meet the zero discharge limitation or comply with a P2
alternative that, authorizes discharge of PAI and priority pollutants after various P2 practices
are followed and treatment is conducted as needed (the Zero/P2 Alternative option). This rule
also establishes a zero discharge limitation and pretreatment standard for agricultural pesticide
refilling establishments (Subcategory E).
The final scope of the rule does not cover the formulation, packaging, and/or
repackaging of products that contain PAIs that are sanitizers (including pool chemicals); PAIs
that are microorganisms (such as Bacillus thuringiensis (B.t.)); Group 1 mixtures that are
common food constituents or nontoxic household items, are GRAS (generally recognized as
safe), or are exempt from FIFRA under 40 CFR 152.25; and Group 2 mixtures that are
substances whose treatment technology has not been identified. The pretreatment standards
(i.e., PSES and PSNS) do not apply to one PAI and three priority pollutants that EPA has
determined will not pass through or interfere with POTWs. In addition, certain wastewater
sources that may be associated with PFPR operations are not covered by this rule, including
storm water, on-site employee showers, on-site laundries, fire equipment test water, water
used for testing and emergency operation of eye washes and safety showers, certain
Department of Transportation (DOT) aerosol leak test bath water, laboratory water,
wastewater from research and development laboratories, and wastewater resulting from the
formulation, packaging, and/or repackaging of certain liquid chemical sterilants.
4-9
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Section 5 - Water Use and Wastewater Characterization
SECTION 5
5.1
WATER USE AND WASTEWATER CHARACTERIZATION
Introduction
As part of the characterization of the pesticide formulating, packaging, and
repackaging (PFPR) industry, EPA assessed the way water is used in PFPR operations and
evaluated what constituents may be present in PFPR wastewater. The following topics are
discussed in this section:
• Section 5.2 presents the sources of wastewater identified in the PFPR
industry;
• Section 5.3 presents an overview of water use in the PFPR industry and
discusses how survey results were extrapolated;
• Section 5.4 presents an overview of water discharge and disposal in the
PFPR industry; and
• Section 5.5 presents wastewater characterization data collected during
the EPA sampling program and through facility self-monitoring data.
Note that the national water use estimates presented in this section (with the
exception of the sampling data discussed in Section 5.5.2) reflect only water use that falls
within the scope of the final rule, and that pertains to products containing only 272 pesticide
active ingredients (PAIs) or products containing both 272 and non-272 PAIs.
5.2
Sources of Wastewater in the PFPR Industry
Process wastewater is defined in 40 CFR 122.2 and in the PFPR questionnaire
as "any water which, during manufacturing or processing, comes into direct contact with or
results from the production or use of any raw material, byproduct, intermediate product,
finished product, or waste product." As described in Section 3.4, PFPR operations are
typically performed on liquid lines or dry lines. Liquid lines generally use mixing equipment,
where as dry lines use grinding equipment and sieves. However, when formulating with
liquid PAI that is sprayed onto a dry substrate (inert carrier), both types of equipment can be
used. Figures 3-1 and 3-2 in Section 3 present basic process flow diagrams for liquid and dry
formulation processes.
When looking at these process flow diagrams, it is not easy to locate the
wastewater sources for this industry. Wastewater generated in the PFPR industry is typically
due to cleaning of equipment and related process areas and, therefore, these sources do not
appear on process flow diagrams. Under the final PFPR rule, EPA is regulating wastewaters
referred to as "interior" wastewater sources and "exterior" wastewater sources, which are
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Section 5 - Water Use and Wastewater Characterization
defined in Sections 5.2.1 and 5.2.2. Other sources of wastewater identified in the PFPR
industry are described in Section 5.2.3.
5.2.1
5.2.2
Interior Wastewater Sources
EPA has identified the following as interior wastewater sources:
• Interior Equipment Cleaning - water used to clean the interior of any
formulating, packaging, or repackaging equipment. Cleaning operations
may include:
Routine cleaning - regular or periodic cleaning of equipment
interiors,
Product changeover cleaning - cleaning due to product
changeover (defined as changing from one pesticide product to
another pesticide product, to a nonpesticide product, or to idle
equipment condition), and
Special or nonroutine cleaning - cleaning due to situations that
do not normally occur during routine operations, such as
cleaning due to equipment failure, or cleaning following the use
of binders, dyes, carriers, and other materials that require
additional cleaning time or larger volumes of water;
• Bulk Tank Rinsate - water used to rinse bulk containers used to store
pesticide products or raw materials;
• Shipping Container Rinsate - water used to rinse containers used to ship
raw materials, finished products, and/or waste products prior to reuse or
disposal of the containers; and.
• Contact Cooling Water - cooling water that comes hi direct contact with
PAIs during the formulating, packaging, or repackaging process.
Exterior Wastewater Sources
EPA has identified the following as exterior wastewater sources:
• Floor, Wall, or Exterior Equipment Wash Water - water used to clean
floors, walls, and/or exteriors of equipment at PFPR facilities;
• Leaks and Spills Cleanup Water - water used to clean up product and/or
raw material leaks and spills that occur during PFPR operations;
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5.2.3
Section 5 - Water Use and Wastewater Characterization
• Air or Odor Pollution Control Scrubber Water - water used in air
emissions control scrubbers;
• Department of Transportation (DOT) Leak Test Water - water used to
perform aerosol leak tests for DOT requirements (EPA is not covering
DOT leak test bath water from noncontinuous overflow baths where no
cans have burst from the time of the last water change-out);
• Safety Equipment Wash Water - water used to clean personal protective
equipment (e.g., gloves, splash aprons, and air-purifying respirators) that
are worn by employees working in PFPR operations (EPA is not
covering water used for testing and emergency operation of safety
showers and eye washes); and
• Laboratory Equipment Wash Water - the initial rinse of retain sample
containers (EPA is not covering water used to clean analytical
equipment and glassware).
Other PFPR Wastewater Sources
For this regulation, EPA has decided to specifically exclude the following
wastewater sources reported in the questionnaire:
• Shower Water - shower water used by employees working in PFPR
operations;
• Laundry Water - water used for laundering clothing worn by employees
working in PFPR operations;
• Fire Protection Test Water - water used to test fire protection equipment
at PFPR facilities; and
• Contaminated Precipitation Runoff - rainwater or snow melt believed to
be contaminated with PAIs.
After carefully considering whether to include the above wastewater sources,
EPA has decided not to include them for a variety of reasons. In the case of water generated
at an on-site laundry, EPA believes- that this wastewater may be better handled by a biological
treatment unit (possibly at a POTW) and treated in combination with other sanitary wastes
from the facility. Also, EPA does not want to create potential environmental or worker
exposure problems by sending the uniforms to industrial laundries or home with the
employees. Some facilities have been able to avoid washing uniforms that may be highly
contaminated by requiring disposable Tyvek® coveralls to be worn over the uniforms when
performing operations with a high risk of splashing or airborne dust.
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Section 5 - Water Use and Wastewater Characterization
In the case of on-site showers, as with laundries, EPA does not want to
potentially increase worker exposure to pesticide contamination by discouraging the use of on-
site showers. Also, many PFPR facilities conduct operations other than PFPR operations at
the same facility and, therefore, the same employee may work on PFPR and non-PFPR
operations in the same shift. Unlike other wastewater sources that have the potential for
being combined with non-PFPR wastewaters, EPA does not believe that a facility can easily
segregate or account for the pollutants generated from the PFPR operations in the shower
water.
EPA has decided not to include fire protection test water because it is generated
on an intermittent basis at relatively low volumes and has little chance of being contaminated.
Also, fire protection test water does not appear to be a wastewater source common to the
overall industry, as it was reported by only one surveyed facility.
EPA has decided not to include storm water at both Subcategory C and E
facilities to avoid duplicative regulatory coverage. EPA reviewed the Phase I storm water
regulations and determined that storm water at PFPR facilities is already covered by the
individual or general NPDES permits issued to cover storm water from industrial activities.
For general as well as most individual permits, facilities are required to prepare a detailed P2
plan that must contain a list of site-specific best management practices, plans for employee
training, and schedules for inspections. EPA believes the P2 plan required by the storm water
regulations would contain practices similar to those outlined in the P2 alternative. In addition,
because refilling establishments (SIC Code 5191) are not covered specifically by the Phase I
regulations, refilling establishments would fall into the Phase n regulations. Phase II
regulations are being developed with the assistance of a Federal Advisory Committee and are
scheduled to be proposed by September 1997.
5.3
Overview of Water Use in the PFPR Industry
As described in Section 3.2.1, EPA distributed questionnaires to selected
facilities identified by EPA as pesticide formulators, packagers, or repackagers. Each
surveyed facility (with the exception of three voluntary submissions and three pretest
facilities) represents a specific number of facilities in the national population of the PFPR
industry; this number is referred to as the facility's "weight". PFPR/Manufacturers have a
weight of 1 because they were part of a census and not a statistically random survey. Based
on responses to the surveys, weighted statistical national estimates of PFPR activities, such as
water use, were computed for the entire U.S. PFPR industry.
However, the survey focused on PFPR operations that used one or more of the
272 PAIs that were studied for the pesticide manufacturing effluent guidelines (58 FR 50638).
As described in Section 3.4.2, facilities reported operations data on a line basis, and were
required to provide volumes of water used in 1988 for each individual process line. This
water is referred to as line-specific water. In addition, facilities were required to provide
volumes of water that could not be attributed to one specific line, but were a result of PFPR
operations. This water is referred to as non-line-specific water. The national water use
5-4
-------
* Section 5 - Water Use and Wastewater Characterization
estimates presented in this section reflect only water use that falls within the scope of the final
rule, and that pertains to products containing only 272 PAIs or products containing both 272
and non-272 PAIs.
National estimates of the questionnaire responses indicate that 2,631 facilities
were performing in-scope PFPR operations in 1988, and that 2,218 of these facilities handled
one or more of the 272 PAIs; these facilities are referred to as "272" facilities, even though
they may also handle non-272 PAIs in their products. The 272 facilities can be broken down
by water use status: 1,544 water users and 674 non-water users. The national estimates
presented in this section focus on the 1,544 water-using "272 facilities" that handled one or
more of the 272 PAIs during 1988 operations. Subcategory C includes 728 "272 facility"
water users, while Subcategory E includes 816 water users.
5.3.1
Annual Water Use
Table 5-1 presents the national estimates of water use (in gallons/year) for the
PFPR industry by wastewater source for each subcategory. In addition, water use data
pertaining to Subcategory C will be broken out by PFPR and PFPR/Manufacturing facilities.
It is important to note that "water use", as presented in this section, does not include the use
of water in formulating the product. Water that is the base of the formulation becomes
product and is not considered a possible wastewater source. It is also important to note that
the water volumes presented are annual totals, as opposed to daily flow rates. Just as
formulation or repackaging of product is a batch process, so is the generation of wastewater at
these facilities.
Table 5-1 shows mat interior equipment cleaning rinsate is the largest
wastewater source for PFPR facilities. For the PFPR/Manufacturers, the largest wastewater
source is air pollution control water (scrubber water and baghouse cleaning), followed by
drum/shipping container rinsate and exterior equipment/floor wash water. Refilling .
establishments reported their largest use of water for interior equipment cleaning operations,
followed by drum/shipping container cleaning operations. Through telephone contacts, EPA
found that many surveyed refilling establishments reported minibulk rinsate as interior
equipment cleaning while others reported it as drum rinsate.
5.3.2
Production Normalized Water Volumes
EPA was able to use the questionnaire water volume data in combination with
production data provided by the FATES database (see Section 3) or by individual facilities to
calculate production normalized volumes (PNVs) for each wastewater source at each facility.
These PNVs were extrapolated to national estimates and displayed as a distribution on bar
graphs. EPA recognizes that water use at PFPR facilities is not necessarily proportional to
production; however, using PNVs helps to provide a basis for comparison between large and
small facilities.
5-5
-------
Section 5 - Water Use and Wastewater Characterization
Table 5-1
National Estimates of Water Use by Wastewater Source1
(gallons/yr)
* ^
Wastewater Source
SirbcategoryC
FFPR Facilities
PFPK/
Manufacturers:
•"•
Sufeeategory E
Refilling
Establishments
Interior Wastewaters
Bulk Tank Rinsate
Drum/Shipping Container Rinsate
Interior Equipment Cleaning
684,400
1,575,144
12,056,827
630,145
11,046,486
4,456,152
29,676
308,068
599,429
Exterior Wastewaters
Aerosol DOT Test Bath Water
Air Pollution Control
Exterior Equipment Cleaning/Floor Wash2
Safety Equipment Rinsate
Spill and Leak Cleanup
4,308,355
464,865
2,958,537
1,975,623
596,346
25,380
14,388,169
9,064,112
634,191
600,331
0
0
224,856
34,997
31,245
The national water use estimates presented in this table reflect only water use that falls within the scope of the
final rule, and that pertains to products containing only 272 PAIs or products containing both 272 and non-272
PAIs.
f\
Exterior equipment cleaning/floor wash also includes general equipment wash and maintenance.
5-6
-------
Section 5 - Water Use and Wastewater Characterization
Figures 5-1 through 5-8 present national estimates of the PNVs by line-specific
wastewater source for PFPR, PFPR/Manufacturers, and refilling establishments. Line-specific
PNVs were calculated by dividing the reported line-specific water volume by the sum of all
in-scope production reported to be formulated, packaged, or repackaged on that line. As
shown by these figures, water use at PFPR/Manufacturers is not significantly different from
water use at PFPR facilities, when normalized by annual production.
5.4
Overview of Wastewater Discharge and Disposal
In addition to water use, surveyed facilities also reported how PFPR wastewater
is ultimately discharged or disposed of from the facility. Section 5.4.1 defines the types of
discharge and disposal options reported by PFPR facilities. Section 5.4.2 presents an
overview of the PFPR industry discharge status. Section 5.4.3 summarizes the volumes of
PFPR wastewater reported by their specific destinations.
5.4.1
Definitions
PFPR facilities reported several methods of discharging or disposing of PFPR
wastewater. The ultimate destinations of PFPR wastewater include discharge options (through
a direct or indirect discharge), recycle or reuse options, or disposal options (on or off site).
Discharge Options
Direct discharge: 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: The discharge of pollutants indirectly to waters of the
United States, through publicly owned treatment works (POTWs).
No discharge (or zero discharge): No discharge of pollutants 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 processes, or disposal on or off site (e.g., by
incineration, evaporation, or deep well injection) that does not result in a discharge to waters
of the United States.
Recycle/Reuse Options
Recycle/reuse: The recycle or reuse of wastewater on or off site in PFPR
product formulations, cleaning cycles of PFPR equipment, or non-PFPR operations.
5-7
-------
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PFPR /Manufacturers
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5-15
-------
Section 5 - Water Use and Wastewater Characterization
Disposal Options
Off-site disposal: The contract hauling of wastewater as either a wastewater or
hazardous waste to a centralized wastewater treatment facility, for deep well injection, or to
an unspecified disposal.
Incineration: The incineration of wastewater either on or off site.
Septic system: An on-site septic system to which wastewater is released.
Storage: The storage of wastewater on site for periodic removal (e.g., reuse).
Evaporation: The evaporation or percolation of wastewater from an
impoundment or pond on site.
5.4.2
Land application: The application of wastewater to a facility's land.
Discharge Status of the PFPR Industry
Of the estimated 1,544 PFPR facilities that use water in PFPR operations, there
are 18 direct dischargers, 425 indirect dischargers, and 1,101 zero dischargers. An estimated
797 of the 1,101 zero dischargers fall into Subcategory E (refilling establishments). Table 5-2
presents the breakdown by discharge mode and subcategory for the PFPR industry.
As discussed in Section 2.2, the fact that some facilities directly discharge
wastewater from PFPR operations may appear inconsistent with the 1978 BPT limitation
prohibiting all direct discharges. A small number of the pesticide manufacturers that also
formulate and package pesticides combine this pesticide manufacturing wastewaters with
PFPR wastewaters and discharge the combined waste stream. Although they are given no
allowance for the pollutants present in the PFPR wastewater, they have been able to discharge
the combined wastewater because the treatment systems reduce the pollutants in the combined
wastewater to the level that is specified in theu: NPDES permits for pollutants generated in
the pesticide manufacturing process. The pesticide manufacturing regulation (58 FR 50638;
September 28, 1993) sets production-based BAT limits for specific PAIs. These limits
supersede the previous concentration-based BPT limit for "total pesticides".
In addition to the 1,101 water-using PFPR facilities that achieve zero discharge,
there are an estimated 674 facilities that do not use process water and therefore do not
discharge. Although EPA was limited to the data that could be collected from non-water
users achieving zero discharge, EPA did collect extensive data through the questionnaire and
site visits on the practices at facilities that use water and are able to achieve zero discharge.
EPA has summarized these practices in Section 7.6 and has made available in the
administrative record the numerous site visit reports that document this information.
5-16
-------
Section 5 - Water Use and Wastewater Characterization
Table 5-2
National Estimates of Water-Using Facilities by Discharge Mode and
Subcategory1
Sabcategory
PFPR
PFPR Facilities
PFPRManufacturers
Refilling Establishments
Total
dumber of Facilities
Direct Discharger
1
17
0
18
Indirect Discharger
386
20
19
425
Zero Discharger2
296
8
797
1,101
1The national water use estimates presented in this table reflect only water use that falls within the scope of the
final rule, and that pertains to products containing only 272 PAIs or products containing both 272 and non-272
PAIs.
2In addition to the 1,101 water-using zero discharge facilities, there are 674 non-water-using zero discharge
facilities.
5-17
-------
Section 5 - Water Use and Wastewater Characterization
5.4.3
Wastewater Destinations
As mentioned in Section 5.4.1, PFPR facilities reported different destinations
for their PFPR wastewater, depending on whether they discharged, recycled/reused, or
disposed of the water. Tables 5-3 through 5-5 present the total estimated volume of PFPR
wastewater for each reported wastewater destination.
Table 5-3 presents the total national estimated volume of process wastewater by
destination and subcategory. As shown in this table, a large volume of wastewater in the
PFPR industry is either recycled or reused on or off site. This table also reflects the practice
of most refilling establishments of storing and then using their wastewater on or off site (these
facilities typically reuse rinse waters as make-up water for custom application to farmers'
fields). However, Subcategory C facilities do not show the same homogeneity by wastewater
destination.
Table 5-4 presents the total national estimated volume of process wastewater by
destination and subcategory for the 1,101 water-using zero discharging facilities. As shown in
this table, most of the wastewater at these facilities is reused or recycled. EPA realizes that
facilities that choose the zero discharge option may choose wastewater destinations other than
recycle/reuse and that these destinations may increase cross-media transfers. However, based
on what facilities are currently doing (i.e., the data presented in Table 5-4), EPA believes that
recycling on or off site is the predominant method by which zero discharge is achieved by
PFPR facilities. EPA notes that, through the use of the P2 alternative, EPA expects to reduce
the cross-media impacts associated with promulgating the zero discharge option alone and
expects to encourage the use of P2, recycle, and reuse practices.
Finally, EPA looked at the wastewater destinations by subgroup (subgroups are
discussed in Section 3.2.2). As shown in Table 5-5, most of the PFPR wastewater generated
is either recycled on or off site or discharged indirectly. The volume of wastewater recycled
on or off site is greater than or in the same range as the wastewater being discharged to
POTWs for several subgroups, including the agriculture, consumer home products, consumer
lawn and garden, and combination organo-metallic/industrial subgroups. For many subgroups,
only relatively small, volumes of wastewater are incinerated or contract hauled for disposal.
In the case of the PFPR/Manufacturers (i.e., the "Manufacturer" subgroup), a relatively large
volume of PFPR wastewater is directly discharged through NPDES permits. As discussed in
Sections 3 and 4, the subgroup analysis did not point out any large differences in water use or
wastewater discharge by any specific subgroup.
5.5
Wastewater Characterization Data
Section 3.2 described the different wastewater data-collection efforts undertaken
for development of these regulations. Characterization data for raw PFPR wastewater streams
were collected from two sources: indusitry-supplied self-monitoring data submitted with and
as a follow-up to the PFPR questionnaire (described hi Section 5.5.1), and data obtained from
EPA sampling at PFPR facilities (described hi Section 5.5.2).
5-18
-------
Section 5 - Water Use and Wastewater Characterization
Table 5-3
Total Process Wastewater Volume by Destination and Subcategory1
(gallons/yr)
Wastewater Destination
Contract Haul
Deep Well Injection
Evaporation
Incineration
Land Application
NPDES (direct discharge)
POTW (indirect discharge)
Recycle on site
Recycle off site
Septic
Storage
Suhcategory C
PEER facilities
1,693,734
581,454
135,145
355,580
1,301,500
58,888
12,709,670
7,404,312
43,556
138,909
197,351
EETPB/
Manufacturers
42,266
135,917
6,000
147,300
0
19,468,401
20,367,081
675,640
2,000
360
0
Subcategory E
Refilling
Establishments
0
0
2,615
0
0
0
1,477
92,266
916,439
882
214,591
1The national water use estimates presented in this table reflect only water use that falls within the scope of the
final rule, and that pertains to products containing only 272 PAIs or products containing both 272 and non-272
PAIs.
5-19
-------
Section 5 - Water Use and Wastewater Characterization
Table 5-4
Total Process Wastewater Volume for Zero Discharge Facilities by
Destination and Subcategory1
(gallons/yr)
' ^ V
s s ^ * ,_ f
.:''*> '•
Wastewater Desti)ttatiq» 1
Contract Haul
Deep Well Injection
Evaporation
Incineration
Land Application
NPDES (direct discharge)
POTW (indirect discharge)
Recycle on site
Recycle off site
Septic
Storage
Subcategory C
K5TK. Facilities
1,542,760
581,454
134,124
192,134
1,301,500
0
0
6,897,051
43,556
138,909
189,589
PFPR/
Manufacturers
22,367
122,830
0
0
0
0
0
104,049
2,000
360
0
Subcategory E
RefiHIng
£stabli$Jaafcttt$ i
0
0
2,224
0
0
0
0
91,778
911,794
882
214,591
national water use estimates presented in this table reflect only water use that falls within the scope of the
final rule, and that pertains to products containing only 272 PAIs or products containing both 272 and non-272
PAIs.
5-20
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5-21
-------
Section 5 - Water Use and Wastewater Characterization
5.5.1
Industry-Supplied Self-Monitoring Data
As part of the PFPR survey questionnaire, EPA requested that PFPR facilities
submit any available wastewater monitoring data and requested that these data be submitted as
individual data points (as opposed to monthly averages, for example). Thirty-four facilities
submitted self-monitoring data with their questionnaire responses/ EPA later requested
facilities with monthly discharge reports to POTWs to provide additional data. The Agency
received data for conventional and priority pollutants, as well as for PAIs and other
nonconventional pollutants, such as chemical oxygen demand (COD). However, these
monitoring data usually -represented pollutant concentrations in end-of-pipe wastewater streams
(usually commingled with pesticide manufacturing, organic chemicals manufacturing
(OCPSF), or nonpesticide formulating operations). Therefore, EPA could not determine the
true contribution of the PFPR operations to the pollutant concentrations reported. In addition,
much of the self-monitoring data were of limited use because many POTWs do not require
PFPR facilities to monitor for PAIs. Facilities typically monitor wastewater only for
conventional pollutants, COD, pH, organic compounds, and/or metals.
After inspecting the data received, the Agency included data from ten facilities
in Subcategory C hi the self-monitoring database. Two of these facilities also manufacture
PAIs and six also engage in repackaging activities. The types of pesticides that these facilities
formulate and/or package vary considerably, but all appear to be medium- or large-size
operations, with most qualifying as large. The geographical distribution of these facilities is
very representative of the industry (five in Region 7, three in Region 4 and two in
Region 9).1
Concentration data for 89 individual PAIs in facility wastewaters were received.
These concentration data were used together with EPA sampling data to help verify raw
pollutant loadings used to estimate costs for regulatory options for the PFPR industry.
Table 5-6 lists the 89 PAIs for which self-monitoring data were submitted.
Self-monitoring data were also received for 118 priority pollutants. These data
may not necessarily characterize the PFPR operations at a particular facility, because the
priority pollutants in the commingled wastewaters can be attributed to many different
processes at the facility. PAIs are more likely to only be linked to PFPR or pesticide
manufacturing operations. In addition to quantitative data on priority pollutants, EPA
collected qualitative data on priority pollutants through the questionnaire. Within the survey
population, 19 facilities reported 11 priority pollutants used in cleaning solutions; 45 facilities
reported using 42 priority pollutants in their raw materials; and 35 facilities used 14 priority
pollutants as inert ingredients. See Section 6.3 for a list of these priority pollutants. See
Appendix C for a list of all priority pollutants.
*EPA Region 7 consists of Iowa, Kansas, Missouri, and Nebraska. EPA Region 4 consists of Alabama, Florida,
Georgia, Kentucky, Mississippi, North Carolina, South Carolina, and Tennessee. EPA Region 9 consists of
Arizona, California, Hawaii, Nevada, American Samoa, and Guam.
5-22
-------
Section 5 - Water Use and Wastewater Characterization
Table 5-6
PAIs for Which Self-Monitoring Data Were Submitted
1,3-Dicbloropropene
2,4-D
Alachlor
Aldicarb
Aminocarb
Atrazine
Benfluralin
Benomyl
Bolstar
Bromacil
Bromomethane
Captan
Carbaiyl
Carbofuran
Cblordane
Chloropropham
Chloroxuroji
Chlorpyrifos
Chrotoxyplios
Cinnerin I (or Allethrin)
Coumaphos
Cycloate (or Ro-neet)
DDVP (or Dicblorvos)
DBF
Demeton (or Systox)
Diazinon
Dicamba
Dichlone
Dichloran (or DCNA)
Dicofol
Dimetboate
Dioxatbion
Diphenamid
Disulfoton
Diuron
DNBP (Dinoseb)
DNOC
Endosulfan I
Endosulfan II
Endrin
EPN (or Santox)
EPTC (or EPTAM)
Ethion
Ethoprop
Fensulfothion
Fentbion
Fluometuron
Gutbion
Heptachlor
Lindane
Linuron
Malatbion
MCPP (or Mecoprop)
Merphos (or Folex)
Metbiocarb (or Mesurol)
Methomyl
Methoxychlor
Metolachlor
Mevinphos
Mexacarbate
MGK264
Monuron
Naled
Oxamyl
Oxyfluorfen
Paratbion
Paratbion metbyl
PCNB
Pentacbloropbenol
Perthane (or Ethylan)
Phenothrin (or Sumitbrin)
Phorate
Piperonyl butoxide
Prometon (or Caparol)
Propachlor
Propbam
Propoxur
Pydrin (or Fenualerate)
Pyrethrins
Resmethrin
Ronnel (or Fenchlorphos)
Siduron (or Tupersan)
Sutan (or Butylate)
Temephos
Terbufos (or Counter)
Toxapbene
Trifluralin
Vapam®
Vemolate (or Vernam)
5-23
-------
Section 5 - Water Use and Wastewater Characterization
5.5.2
EPA PFPR Sampling Program
As discussed in Section 3.2.2, EPA was not able to conduct as extensive a
wastewater sampling program for this rule as for other rulemaking efforts for the following
reasons: (1) only 12 facilities in the sample population operated on-site treatment systems
that treat only PFPR wastewater; (2) facility operating schedules are very unpredictable due to
the batch nature of their operations and just-in-time production philosophy; and (3) due to the
nature of PFPR processes, treatment is typically conducted on a batch basis, making it
difficult to characterize long-term treatment performance. These difficulties with conducting
the sampling program are discussed in 'the following paragraphs.
, The relatively few facilities with on-site treatment not only made it difficult for
EPA to locate facilities with "BAT-level" treatment, but it also affected the collection of
samples for raw wastewater characterization. Usually facilities are selected as candidates for
wastewater sampling if they have treatment systems that demonstrate a high level of
performance. When EPA visits these facilities to sample a treatment system, additional
sampling is performed to characterize the raw wastewater from various sources that feed into
the treatment system. Because so few PFPR facilities had treatment systems, only seven full-
scale sampling efforts were conducted, limiting the number of samples taken to characterize
raw wastewaters. In an effort to supplement the raw wastewater characterization data, EPA
collected a number of one-time "grab" samples while conducting site visits or when collecting
PFPR wastewater for treatability tests.
There are two factors associated with organizing a sampling program with the
operating schedules typical of PFPR facilities that have caused EPA difficulty. First, unlike
industries with continuous production (e.g., pesticide manufacturing), the PFPR industry
typically utilizes batch production. Second, PFPR facilities do not schedule production long
term, but instead week to week, and sometimes day to day. The frequently changing
production schedules at PFPR facilities made it quite difficult for EPA to schedule sampling
episodes and to acquire EPA contract laboratories to perform the analysis, particularly for
PAIs. However, even with these difficulties, EPA did sample a variety of wastewater sources
during 18 sampling episodes at 17 facilities for raw wastewater characterization data. The
sampling episodes also allowed EPA to test analytical methods for the PAIs. Results of the
sampling program are discussed in the following paragraphs.
As previously mentioned, EPA conducted two different types of sampling
episodes. Sampling was either performed as a one-time "grab" while on a one-day site visit at
a facility or as a three day full-scale sampling episode. A total of 81 wastewater samples
were collected for a variety of PAIs from the following wastewater sources: interior
equipment rinsates, exterior equipment rinsates, floor wash, scrubber water, DOT test bath,
raw material drum/shipping container rinsate, laboratory water, laundry water, shower water,
and commingled raw wastewaters. A number of these samples were collected to characterize
wastewaters that were intended for reuse; therefore, EPA expected the concentration of PAIs
in these samples to be high. With the exception of the DOT test baths, showers, and
5-24
-------
Section 5 - Water Use and Wastewater Characterization
laundries, the wastewater sources are only generated following PFPR production during
cleanup and, therefore, are not continuous.
Typically, EPA could not conduct composite sampling or make use of
automatic sampling equipment over the three-day sampling period due to the batch nature of
both wastewater generation and treatment system operation. Instead, discrete equal volume
grab samples, or aliquots, were manually collected at equal-time intervals and added to the
compositing container (a specially cleaned 10-liter glass jar). At the end of each sampling
period, the composite sample was poured into specially cleaned individual fraction containers
for shipment to the EPA contract laboratories. These fractions included analyses for: Group I
(biochemical oxygen demand (BOD5), total suspended solids (TSS), total fluoride, and pH);
Group II (total organic carbon (TOC), COD, ammonia nitrogen, and nitrate and nitrite
nitrogen); extractable (semivolatile) organic compounds; metals; and the PAIs. The fractions
for volatile organic compounds, cyanide, and oil and grease2 analyses were not poured from
the composite containers, but were 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 cool. 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 (e.g., total copper, total mercury).
Table 5-7 presents an overall statistical summary of the raw wastewater
characterization data collected during EPA sampling episodes, including the maximum,
minimum, mean, and median concentration values for individual classical pollutants ,
individual PAIs, and individual organic priority pollutants detected hi PFPR wastewaters. The
table lists the analytical method minimum detection level for each pollutant and the
percentage of nondetects found. This table excludes pollutants detected in the following types
of wastewater samples: shower, laundry, laboratory, storm water samples, and samples
collected from on-site treatment systems. These sample types were excluded from the
summary data to provide a more accurate picture of the raw wastewater concentrations from
PFPR process wastewater sources. The concentrations of PAIs, COD, and some specific
conventional pollutants found in treated streams that are reused are discussed in Section 7.3.2.
2Prior to June 1994, samples were analyzed for oil and grease using Method 413.1; results are shown as "oil and
grease". Samples collected after June 1994 were analyzed for oil and grease using Method 1664; results are
presented as "hexane extractable material".
Classical wet chemistry parameters are ammonia as nitrogen, biochemical oxygen demand (BOD^), chemical oxygen
demand (COD), fluoride, nitrate and nitrite nitrogen, oil and grease (by Method 413.1 or Method 1664), pH, total
cyanide, total dissolved solids (IDS), total organic compounds (TOC), and total suspended solids (TSS).
5-25
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-------
Section 6 - Pollutant Parameters Selected for Regulation
SECTION 6
6.1
POLLUTANT PARAMETERS SELECTED FOR REGULATION
Introduction
The pesticide formulating, packaging, and repackaging (PFPR) industry
generates process wastewaters containing a variety of pollutants. These process wastewaters
are currently reused directly, reused after storage, reused following treatment, or indirectly
discharged to a publicly owned treatment works (POTW).
For Subcategory C, EPA is establishing effluent limitations and pretreatment
standards which allow each facility a choice: to meet a zero discharge limitation or to comply
with a pollution prevention (P2) alternative that authorizes discharge of pesticide active
ingredients (PAIs) and priority pollutants after various P2 practices are followed and treatment
is conducted as needed (the Zero/P2 Alternative option). This rule also establishes a zero
discharge limitation and pretreatment standard for Subcategory E.
Under the Zero/P2 Alternative option, each owner or operator of a PFPR
facility in Subcategory C will make an initial choice of whether the facility will meet zero
discharge or comply with the P2 alternative. This choice can be made on a product
family/process line/process unit basis rather than a facility-wide basis. If the zero discharge
option is chosen, the facility owner/operator will need to do whatever is necessary (e.g., reuse
or recycle the wastewater (either with or without treatment), incinerate the wastewater on site,
or haul it for off-site incineration or underground injection) to ensure zero discharge of PAIs
and priority pollutants in the wastewater.
If the P2 alternative portion of the option is chosen for a particular PAI product
family/process line/process unit, then the owner/operator of the facility must agree to comply
with the P2 practices for that PFPR family/Une/unit identified in Table 8 to Part 455 of the
final rule, which can be found hi Appendix A to this document. This agreement to comply
with the P2 practices and any necessary treatment would be included in the NPDES permit
for direct discharging PFPR facilities. In general, PFPR facilities choosing the P2 alternative
need only submit a small portion of the paperwork to a permitting or control authority (e.g.,
initial and periodic certification statements). (See Section 9 for a more detailed discussion of
the final BPT guidelines.)
Typically, this section sets out the rationale for either including or excluding
specific pollutants for regulation. However, this regulation calls for either zero discharge of
process wastewater pollutants or implementation of the P2 alternative; therefore, all process
wastewater pollutants are controlled by this regulation with the exception of those chemicals
that are specifically exempted (see Section 2.3.3 for more detail on the scope of the rule).
Section 6 summarizes the pollutants that have been found at PFPR facilities based on EPA's
data-gathering efforts. These data-gathering efforts include the PFPR Facility Survey for
1988 (described in Section 3.2.1), the wastewater sampling program (described in Sections
6-1
-------
Section 6 - Pollutant Parameters Selected for Regulation
3.2.2 and 5.5.2), and the facility self-monitoring database (described in Sections 3.2.3 and
5.5.1). Sections 6.2, 6.3, and 6.4 discuss wastewater characterization for conventional
pollutants, priority pollutants, and PAIs, respectively.
6.2 Conventional Pollutants
Conventional pollutants include:
• Biochemical Oxygen Demand (BOD5);
• Total Suspended Solids (TSS);
pH;
• Oil and Grease ; and
• Fecal Coliform.
The most widely used measure of general organic pollution hi wastewater is
rive-day biochemical oxygen demand (BOD5). BOD5 is the quantity of oxygen used in the
aerobic stabilization of wastewater streams. This analytical determination involves measuring
the dissolved oxygen used by microorganisms to biodegrade organic matter and varies with
the amount of biodegradable matter that can be assimilated by biological organisms under
aerobic conditions. The nature of specific chemicals discharged into wastewater affects the
BOD5 due to the differences in susceptibility of different molecular structures to
microbiological degradation. Compounds that are less susceptible 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 BQD5 values. Therefore, while BOD^ is a useful gross
measure of organic pollution, 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. TSS is the portion of the total solids that can be filtered out
of solution using a 1-micron filter. Total solids are composed of matter that is settleable, in
suspension, or in solution, and can be organic, inorganic, or a mixture of both. The TSS
content in raw wastewater depends on the PAIs and inert ingredients used, as well as the
formulation type (e.g., floor wash water from a dry formulation area may have more fine
solids than that from a liquid formulation area). It can also be a function of a number of
other external factors, including stormwater runoff and runoff from material storage areas.
Solids may be washed into collection trenches and sumps when facilities perform exterior
equipment rinsing or floor washing.
A unitless measurement, pH 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
^During the development of the final PFPR rule, the EPA-approved test method for analysis of oil and grease
was changed from Method 413.1 to Method 1664. As mentioned in Section 7.3.1, results using Method 413.1
are presented as "oil and grease" and results using Method 1664 are presented as "hexane extractable material."
6-2
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,-• Section 6 - Pollutant Parameters Selected for Regulation
into hydrogen (H*) or hydroxide (OH") ions, respectively. Raw wastewater pH is a function
of the nature of the processes contributing to the waste stream. This parameter can vary
widely from facility to facility and wastewater source to wastewater source. If necessary,
fluctuations in pH are readily reduced by equalization followed by neutralization. Control of
pH is important, regardless of the final disposition of the wastewater stream, to maintain
favorable conditions for various treatment system unit, operations or for reuse.
Raw wastewater oil and grease is an important parameter in some wastewaters
as it can interfere with the smooth operation of wastewater treatment units. Many PFPR
facilities use raw materials high in oil and grease content (e.g., hydrocarbon petroleum
distillates) as inert ingredients hi pesticide formulations. However, oil and grease does not
provide a good measure of the concentration of PAIs in the wastewater.
The drinking water standard for microbial contamination is based on coliform
bacteria. The presence in wastewater of coliform bacteria (microorganisms that reside in the
human intestinal tract) indicates that the wastewater has been contaminated with feces from
humans or other warm-blooded animals. Coliform bacteria are not expected to be present hi
the PAI-contamhiated wastewater streams generated by PFPR facilities. EPA did not pursue
any further data-collection efforts characterizing fecal coliform in PFPR wastewaters for this
regulation.
6.3
Priority Pollutants
Data characterizing priority pollutants in PFPR wastewater have been gathered
by EPA quantitatively from industry-supplied self-monitoring data and EPA sampling and
analysis episodes and qualitatively from industry responses to the 1988 PFPR questionnaire.
A complete list of priority pollutants is located hi Appendix C.
As explained hi Section 5.5.1, the self-monitoring database consists of data
collected from ten facilities. EPA has examined the data and has found that all but 11 of the
priority pollutants (including three that have been since removed from the list) were
monitored; these data have been included hi the self-monitoring database. The 11 priority
pollutants for which no self-monitoring data were submitted are listed hi Table 6-1. Of the
remaining 118 priority pollutants, 30 have been reported hi self-monitoring data above their
detection limit. These 30 pollutants are listed hi Table 6-2. EPA notes that, because the self-
monitoring data were not collected from all facilities hi the sample population, Table 6-2 may
not represent a complete list of the priority pollutants found hi the PFPR industry.
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Section 6 - Pollutant Parameters Selected for Regulation
Table 6-1
Priority Pollutants for Which No Self-Monitoring Data Were Submitted
2,3,7,8-Tetrachlorodibenzo-p-dioxin(TCDD)
Alpha-BHC
Antimony (total)
Asbestos (Fibrous)
Beryllium (total)
Beta-BHC
Butyl benzyl phthalate
Chlordane (technical mixtures and metabolites)
Pentachlorophenol
Selenium (total)
Thallium (total)
Table 6-2
Priority Pollutants Measured Above Detection Limit
in Self-Monitoring Data
1,1-Dichloroethane
1,1,1-Trichloroethane
1,3-Dichlorobenzene
2-Chloronaphthalene
4,4-DDD
4,4-DDE
4,4-E«DT
Aldrin
Arsenic
BHC-Gamma (Lindane)
Chlorodibromomethane
Chloroform
Chromium
Copper
Dichlorobromomethane
Dichloromethane
Dieldrin
Endosulfan I
Endosulfan n
Endrin
Ethylbenzene
Heptachlor
Hexachlorobenzene
Lead
Nickel
Phenol
Tetrachloroethylene
Toluene
Trichloroethylene
Zinc
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Section 6 - Pollutant Parameters Selected for Regulation
EPA was also able to examine which priority pollutants were present in PFPR
wastewater during raw wastewater characterization sampling episodes. The sampling database
contains analytical data gathered through EPA sampling episodes at 17 facilities. Thirty-four
organic priority pollutants, 13 metal priority pollutants, and one dioxin were reported above
the detection limit in raw wastewater streams covered by the final rule (see Table 6-3).
However, 15 of these pollutants were detected at only one facility (as noted in Table 6-3).
Table 6-3
Priority Pollutants in Wastewater at Sampled PFPR Facilities
1,1 -Dichloroethane1
1,1-Dichloroethene1
1,1,1 -Trichloroethane
1,1,2,2-Tetrachloroethane1
1,2-Dichloroethane
1,2-Dichloropropane
1,2-Diphenylhydrazine
1,2,4-Trichlorobenzene
2-Chlorophenol
2,3,7,8-TCDD
2,4-Dichlorophenol
2,6-Dinitrotoluene1
4-Chloro-3-methylphenol
Acrolein
Antimony
Arsenic
Benzene
Beryllium
bis(2-Ethylhexyl)phthalate
Butyl benzyl phthalate
Cadmium
Carbon tetrachloride
Chloroform
Chromium
Copper
Di-n-butyl phthalate
Di-n-octyl phthalate1
Di-n-propyhiitrosamine1
Diethyl phthalate
Dimethyl phthalate1
Ethylbenzene
Fluoranthene1
Isophorone1
Lead
Mercury
Methyl chloride
Methylene chloride
Naphthalene
Nickel
Phenol
Pyrene
Selenium
Silver
Tetrachloroethene
Thallium
Toluene
Trans-1,3-dichloropropene1
Zinc
1 These priority pollutants were detected at only one facility.
6-5
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Section 6 - Pollutant Parameters Selected for Regulation
Information was also collected on priority pollutants in the PFPR questionnaire.
Section 7 of the questionnaire requested facilities to indicate whether they used any cleaning
solutions, inert ingredients, or other raw materials containing priority pollutants when
producing products containing one or more of the 272 PAIs. Facilities were also asked to
indicate the specific priority pollutant(s) used in each case. According to the questionnaire
results, 11 priority pollutants were used in cleaning solutions at 19 facilities, 42 priority
pollutants were used as raw materials at 45 facilities, and 14 priority pollutants were used as
inert formulation ingredients at 35 facilities. Table 6-4 presents a list of these priority
pollutants.
6.4
Pesticide Active Ingredients
Most PAIs are considered nonconventional pollutants (a few are priority
pollutants). Other nonconventional pollutants (e.g., chemical oxygen demand (COD), total
organic compounds (TOC), and ammonia-nitrogen) are not discussed in this section. The
wastewater characterization of nonconventional pollutants is discussed in Section 5.5.
The self-monitoring database and the analytical sampling database provide a
good idea of the concentrations of PAIs found in PFPR wastewaters; however, these data do
not always provide a complete characterization of PFPR wastewater. As discussed in Section
3.2.2, EPA was not able to perform as extensive a sampling program as usual. Wastewaters
were analyzed for those PAIs believed to be present based on the specific product formulated,
packaged, or repackaged during the sampling episode. Therefore, if a particular PAI was not
detected during sampling or was not reported in the self-monitoring data, that does not mean
it is not present in other PFPR wastewaters. In fact, EPA assumes that all PAI(s) in a given
product will be present at some concentration in process wastewater generated during the
formulation, packaging, or repackaging of that product.
Under EPA's sampling program, PFPR wastewaters were tested for a total of
56 individual PAIs. Of the 44 PAIs that were analyzed in raw wastewater streams covered by
the final rule, 42 PAIs were found at concentrations above the detection limits. These PAIs
are listed in Table 6-5. PFPR facilities submitted self-monitoring data for 89 PAIs.
Table 6-6 lists 35 PAIs that were reported above their detection limits.
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Section 6 - Pollutant Parameters Selected for Regulation
Table 6-4
Priority Pollutants Reported By PFPR Facilities1
Priority
Pollutant
Code
P004
P006
P007
POOS
P010
P011
P016
P021
P022
P023
P025
P026
P027
P031
P032
P033
P038
P044
P045
P046
P054
P055
P064
P065
Chemical Name
Benzene
Carbon tetrachloride
Chlorobenzene
1 ,2,4-Trichlorobenzene
1 ,2-Dichloroethane
1,1,1 -Trichloroethane
Chloroethane
2,4,6-Trichlorophenol
4-Chloro-3-methylphenol
Chloroform
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
2,4-Dichlorophenol
1 ,2-Dichloropropane
trans- 1 ,3-Dichloropropene
Ethylbenzene
Methylene chloride
Methyl chloride
Bromomethane
Isophorone
Naphthalene
Pentachlorophenol
Phenol
Source of Priority Pollutant
Inert
Ingredient
X
X
X
X
X
X
X
X
Raw
Material
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Solution ..
Cleaning
X
X
X
X
X
X
X
X
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Section 6 - Pollutant Parameters Selected for Regulation
Table 6-4 (Continued)
Priority :
Pollutant
Code
P066
P067
P085
P086
P087
P088
P095
P096
P097
P100
P104
P114
P115
P118
P119
P120
P121
P122
P123
P125
P128
A
•• s s •.
- Chemical Name
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Tetrachloroethene
Toluene
Trichloroethylene
Vinyl chloride
Alpha-endosulfan
Beta-endosulfan
Endosulfan sulfate
Heptachlor
Gamma-BHC (Undane)
Antimony
Arsenic
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Selenium
Zinc
Source of Priority Pollutant
Inert
Ingredient
X
X
X
X
X
X
Raw
Material
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Solution i
Cleaning
X
X
X
1The data included in this table were reported by PFPR facilities in their responses to the
PFPR Facility Survey for 1988.
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Section 6 - Pollutant Parameters Selected for Regulation
Table 6-5
PAIs Found Above Detection Limits in Raw PFPR WastewatersJ
2,4-D
Allethrin
Atrazine
n
Benthiocarb
Bromacil2
Captan
Carbaryl
Chlorpyrifos2
Cyfluthrin
Deet
Diazinon
Dicamba
Dimethoate
Disulfoton2
Diuron2
Endosulfan I
Endosulfan II
Fenvalerate
Fluometuron
Limonene
Linalool
Maleic hydrazide
Maneb
MCPP
Methoprene
Methylene bis(thiocyanate)
Metolachlor
MGK 264
Napropamide
Permethrin cis
Permethrin trans
Piperonyl butoxide
Prometon2
Propoxur
Pyrethrinl
Pyrethrin II
Sumithrin
Tebuthiuron2
Terbufos
Tetrachlorvinphos
Tetrametlirin
Tri-organo tin
Results based on EPA's analytical sampling program conducted between 1989 and 1995.
2These PAIs were detected in commingled raw influent streams to facility treatment systems.
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Section 6 - Pollutant Parameters Selected for Regulation
Table 6-6
PAIs Found Above Detection Limits in the PFPR Self-Monitoring Database
Atrazine
Carbaryl
Carbofuran
Cycloate or Ro-neet
DBF
Diazinon
Dicamba
Dichloran or DCNA
Dimethoate
Disulfoton
DNBP (Dinoseb)
Endosulfan I
Endosulfan II
Endrin
EPTC or EPTAM
Ethion
Fluometuron
Guthion
Heptachlor
Malathion
MCPP (or Mecoprop)
Merphos or Folex
Methoxychlor
Metolachlor
Parathion
PCNB
Phorate
Propachlor
Propham
Sutan or Butylate
Temephos
Terbufos or Counter
Trifluralin
Vapam®
Vernolate or Vernam
6-10
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7.1
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
SECTION 7
TECHNOLOGY SELECTION AND METHODS TO ACHIEVE
THE EFFLUENT LIMITATIONS
Introduction
This section describes the technologies and practices used by or currently
available to the pesticide formulating, packaging, and repackaging (PFPR) industry to meet
the final effluent limitations guidelines and standards. Section 7.2 describes the treatment
technologies applicable to the PFPR industry for treatment of conventional, nonconventional
(including pesticide active ingredients (PAIs)), and priority pollutants. Disposal of solid
residues that are generated from these treatment technologies is also discussed.
Section 7.3 discusses the performance of treatment systems included in the
PFPR analytical database. This database comprises the analytical and performance data
gathered at seven PFPR facilities under the EPA sampling program. Section 7.4 discusses the
performance of the treatment technologies that were tested by EPA as part of the bench- and
pilot-scale treatability tests. Section 7.4 also includes a detailed description of the
performance and applicability of the Universal Treatment System (UTS), which is the
treatment system used in estimating costs for compliance with the final rule. Section 7.5
describes the treatability database and treatability data transfers used by EPA to identify
appropriate treatment technologies for each of the PAIs within the scope of the final rule.
Section 7.6 describes in detail the practices, including pollution prevention (P2)
and recycle/reuse, that EPA believes will enable PFPR facilities to meet the final effluent
guidelines. This section attempts to present the practices as they are currently being
implemented in industry and identifies those practices believed to be the best method for
managing a particular wastewater source. Finally, Section 7.7 lists references.
7.2
Wastewater Treatment Technologies Applicable to the PFPR Industry
As previously discussed in Section 3.2.2, the majority of PFPR facilities do not
have on-site treatment systems; however, a small number of facilities do treat their PFPR
wastewaters using some of the treatment technologies discussed in this section. The most
common technologies currently used by or applicable to facilities to treat PAIs in wastewaters
from PFPR operations are: activated carbon adsorption, hydrolysis, reverse osmosis, chemical
oxidation (by alkaline chlorination or ozone/ultra-violet light (UV)), and chemical
precipitation (for removal of metals). EPA would like to note that biological treatment
(acclimated to specific PAI-containing wastewaters) and steam stripping have also been shown
to be effective in removing some PAIs and priority pollutants that may be found in pesticide-
containing wastewaters (1), but EPA believes these technologies to be cost-prohibitive for
PFPR facilities. EPA is therefore not considering them appropriate for this industry.
Equalization and neutralization are typically used for pH adjustment or removal of suspended
solids (and not for PAI removal) prior to either discharge to a POTW or recycle/reuse. The
7-1
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
treatment technologies that are most commonly used to remove suspended solids prior to
treatment (but may also incidentally remove PAIs) are emulsion breaking, clarification,
ultrafiltration, and cross-flow filtration.
Either through EPA's sampling program or treatability studies, the following
six technologies have been demonstrated to treat pesticide-containing wastewaters effectively:
1. Activated carbon adsorption;
2. Hydrolysis;
3. Chemical oxidation;
4. Membrane filtration (reverse osmosis and ultrafiltration);
5. Emulsion breaking; and
6. Chemical precipitation/separation.
Sections 7.2.1 through 7.2.8 provide descriptions of each of these technologies,
as well as descriptions of other pretreatment technologies (e.g., equalization and
neutralization) and a discussion of the disposal of solid residue from treatment.
7.2.1
Activated Carbon Adsorption
Adsorption is the primary mechanism for removing organic pollutants from
wastewater by activated carbon. The term "activated carbon" refers to carbon materials, such
as coal or wood, that are processed through dehydration, carbonization, and oxidation to yield
a material that is highly adsorbent due to large surface area and high number of internal pores
per unit mass. Activated carbon removes organic constituents from wastewater by physical
and chemical forces that bind the constituents to the carbon surface. In general, organic
constituents possessing certain properties (e.g., low water solubility and high molecular
weight) and certain chemical structures (e.g., aromatic functional groups) are amenable to
activated carbon adsorption.
The carbon adsorption capacity (i.e., the mass of the contaminant adsorbed per
mass of carbon) for specific organic contaminants is related in part to the characteristics of the
compound. 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 (e.g., pH and
temperature), process design factors (e.g., the use of granular versus powdered carbon, the
contact time, and the number and orientation of the columns), and carbon characteristics (e.g.,
the raw material source of carbon, particle size, and pore volume) also affect adsorption
capacity.
When the adsorption capacity of the carbon is exhausted, the spent carbon is
either disposed of or regenerated; the choice is generally determined by cost. Carbon may be
regenerated by removing the adsorbed organic compounds from the carbon through steam
regeneration, thermal regeneration, or physical/chemical regeneration. The most common
methods to regenerate carbon used for wastewater treatment are thermal and steam
7-2
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
regeneration. The methods volatilize the organic compounds that had been adsorbed onto the
carbon. Afterburners are required to ensure destruction of the organic vapors; a scrubber may
also be necessary to remove particulates from the air stream. Physical/chemical regeneration
uses a solvent, which can be a water solution, to remove the organic compounds.
The most common form of activated carbon is granular; the columns operate in
either an upflow or downflow mode. Powdered activated carbon is used less frequently for
wastewater treatment due to the difficulty of regeneration and reactor system design
considerations, although it may be used in conjunction with biological treatment systems.
Carbon adsorption has been demonstrated as an effective treatment technology
for bom pesticide manufacturing and PFPR industry wastewaters. EPA sampling and
treatability studies were performed on systems with activated carbon adsorption; the results of
these studies are discussed in Sections 7.3 and 7.4.
7.2.2
Hydrolysis
Hydrolysis is a chemical reaction in which organic compounds react with a
base or water and break into smaller (and less toxic) compounds. Usually the hydroxyl group
(OET) is introduced into the reactant (i.e., the target organic compound), displacing another
group, as shown by the following reaction:
O
O
ii
(RO)2-P-O-R + OH -» (RO)2-P-OH + (OR)'
When treating PFPR wastewater, the target compound is often the PAL One
group of PAIs that are amenable to hydrolysis fall in the carbamate structural group (see the
Final Treatability Database Report (2) for a more detailed discussion of PAI structuralgroups).
In the case of carbamate hydrolysis, the acid hydronium ion (H^) enters into hydrolysis
reactions. Carbamate hydrolysis occurs by the following reaction:
O
\
Ri - N
O - R3 + H2O
R3OH
- NH
CO
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
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
generally depends on the reaction pH and temperature and the reactant molecule (for this
industry, specific PAIs). Hydrolysis reactions can he catalyzed at low pH, high pH, or both,
depending on the PAL In general, increasing the temperature will increase the hydrolysis
rate. Improving the conditions for the hydrolysis reaction results in a shorter half-life, thereby
reducing both the size of the reaction vessel required (for continuous flow systems) and the
treatment time required (for batch treatment systems).
Hydrolysis is an effective treatment technology for the destruction of PAI
contaminants in PFPR wastewater by elevating the temperature and pH. Both EPA sampling
and treatability studies were performed on systems using hydrolysis; the results of these
studies are discussed in Sections 7.3 and 7.4.
7.2.3
Chemical Oxidation
Chemical oxidation is used in wastewater treatment to modify priority
pollutants or other pollutants by the addition of an oxidizing agent. Chemical oxidation is a
reaction 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
(in the form of sodium hypochlorite) to destroy compounds such as cyanide (in the metal
finishing, inorganic chemicals, and pesticide industries) and PAIs.
The major drawback to alkaline chlorination of pesticide-containing
wastewaters (specifically, wastewaters containing dithiocarbamate PAIs) is the potential
production of chlorinated organic compounds. During development of the pesticide
manufacturing rule, three chlorinated organic compounds (chloroform, bromodichloromethane,
and dibromochloromethane) were identified that were not present in raw wastewaters treated
by alkaline chlorination, but were detected in at least two of the bench-scale test reactors after
treatment. Steam stripping, air stripping, and activated carbon adsorption are three treatment
technologies that are capable of removing chlorinated organic compounds from wastewater.
At large wastewater flow rates, steam stripping and air stripping are more economical than
carbon adsorption. Because of the cross-media impacts (i.e., air emissions) associated with air
stripping, steam stripping was chosen as the method to remove chlorinated organic pollutants
formed during alkaline chlorination of pesticide manufacturing wastewaters. However, at low
flow rates, such as those found at PFPR facilities, carbon adsorption is the more economical
treatment technology, because both steam stripping and air stripping have very high capital
costs. Therefore, the costing algorithm for the PFPR industry is based on an activated carbon
7-4
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
system to remove chlorinated oxidation products (see Section 8 for a more detailed discussion
of compliance cost estimates for the PFPR industry).
A recent oxidation technology to emerge as an option for the treatment 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 as an alternative to alkaline chlorination 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 nanometers wavelength) by ozone.
These hydroxyl radicals completely oxidize the PAI (to carbon dioxide, nitrate, sulfate, and
water), avoiding the formation of halogenated organic compounds such as those produced
during alkaline chlorination. Chemical oxidation is an effective treatment technology for the
destruction of PAI contaminants in PFPR wastewater. Both EPA sampling and treatability
studies were performed on systems using chemical oxidation; the results of these studies are
discussed in Sections 7.3 and 7.4.
7.2.4
Membrane Filtration
Membrane filtration is a term applied to a group of processes that use a
pressure-driven, semipermeable membrane to separate suspended, colloidal, and dissolved
solutes from a process wastewater. The size of the pores in the membrane is selected based
on the type of contaminant to be removed. The pore size of the membrane will be relatively
large for the removal of precipitates or suspended materials, 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, leaving the contaminants
and a portion of the feed behind. 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 stream will either be
discharged or, more likely, recycled back to the manufacturing process. The reject stream is
normally disposed of, but if the reject does not contain contaminants that would preclude its
reuse, it too can potentially be recycled back to ,the process. For example, a reject stream
from a membrane system treating wastewater generated from many different processes would
likely have to be disposed of. However, if the membrane system treated a wastestream
containing only one specific PAI, the reject stream could possibly be recycled back to the
process. Depending on the characteristics of the wastewater and the type of process used, 50
to 95% of the feed stream can be recovered for reuse 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 of >0.1 micron (3.94 x 10 niches). The
systems can be operated at feed pressures of <50 pounds per square inch gauge (psig). The
feed stream does not require extensive pretreatment, and the membrane is relatively resistant
to fouling and is easily cleaned. A microfiltration system is not an effective method of
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
treatment for pesticide-containing waste-waters unless the PAIs are insoluble or are 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 to the
wastewater prior to treatment through the membrane system. The PAIs are adsorbed or
become attached to the floe that forms, and are 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, except that a UF membrane has
smaller pores. The "tightest" UF membrane is typically capable of rejecting molecules having
diameters of >0.001 micron (3.94 x 10~8 inch) or nominal molecular weights of >2,000. The
system operates at a feed pressure of 50 to 200 psig. Some pretreatment of PFPR
wastewaters may be necessary to prevent membrane fouling. UF systems are only effective hi
removing PAIs that are insoluble or attached to other suspended material (most PAIs have
molecular weights of 150 to 500 molecular weight units). For most UF designs, adding
adsorbents or fiocculants to the feed stream is not recommended, because they may plug the
membrane module. UF systems are also capable of recovering up to 90 to 95% of the feed as
product water. During development of the PFPR rule, EPA conducted a series of pilot-scale
treatability studies that showed that UF provides effective pretreatment for RO systems by
removing larger molecules that may plug the smaller pores typical of RO membranes.
Reverse osmosis systems have the ability to reject dissolved organic and
inorganic molecules. Removal of organic (noncharged) molecules such as PAIs depends on
the membrane pore size. Typically, membranes with a pore size of 0.0001 to 0.001 micron
(3.94 x 10 to 3.94 x 10 inch) are used to remove PAIs. RO membranes have been shown
to remove most PAIs with molecular weights >200. Unlike microfiltration and ultrafiltration,
RO membranes are capable of rejecting inorganic ions. The mechanism for inorganic ion
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 a molecular weight cutoff, they are more typically rated on
their ability to reject sodium chloride. Typical sodium chloride rejection for an industrial type
membrane is 90 to 95 percent.
RO systems used in industrial applications are designed to operate at feed
pressures of 250 to 600 psig. RO membranes are very susceptible to fouling and may require
extensive pretreatment. Oxidants (which may attack the membrane) or particulates, oil,
grease, and other materials that could cause a film or scale to form must be removed by
pretreatment. The RO product water stream is usually 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 are concentrated in
the reject and may limit the opportunities for recycle. RO systems are capable of recovering
50 to 90% of the feed as product water. The dissolved solids concentration in the feed
determines the percent recovery that can be obtained as well as the required feed pressure to
operate the system.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
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 most commonly fabricated from cellulose
acetate, but can also be composed of polysulfone, polyamide, or other polymeric materials.
Although cellulose acetate membranes cost less and are not as susceptible to fouling, they
have been shown to remove only marginal amounts of some low molecular weight PAIs, such
as carbaryl, fluometuron, chloropropham, and atrazine. In addition, mass balances conducted
for short-term tests have shown that a significant amount of the PAI rejection may be due to
adsorption on the membrane as opposed to rejection by it.
Discussions and results of EPA sampling and treatability studies involving
membrane filtration systems can be found in Sections 7.3 and 7.4, respectively.
7.2.5
Emulsion Breaking
There are two types of emulsions found in PFPR wastewaters: oil in water
(O/W) and water in oil (W/O). O/W emulsions are basically oily wastewaters, where some
type of hydrophobic solvent or oil is dispersed in an aqueous medium. W/O emulsions have
an aqueous phase dispersed in oil or some other hydrophobic solvent. Facilities can use
chemical methods, thermal methods, or physical methods to break these emulsions. Although
physical and thermal methods, such as dissolved air flotation for O/W emulsions and
centrifugation for W/O emulsions, may be applicable to PFPR wastewaters, these methods
have not been observed in common use at PFPR facilities and therefore are not discussed in
this section. Chemical methods involve the addition of chemicals to break emulsions by
neutralizing repulsive charges between particles, precipitating or salting out emulsifying
agents, or altering the interfacial film between the oil and water so it is readily broken.
Emulsion breaking for oily wastewater (O/W emulsions) can be performed by
the following two chemical methods:
1. Coagulation - Coagulation breaks an emulsion through the addition of
' acid, an iron or aluminum salt, or an uncharged adsorbent (clay or lime)
to the wastewater. Acid addition will generally cause the oil to float,
allowing it to be skimmed off. The addition of an iron or aluminum
salt or an uncharged adsorbent will cause sludge formation, which
breaks the emulsion by adsorbing the oil molecules to the settled
particles. Sludge formation is then followed by flocculation for sludge
removal.
2. Addition of Organic Demulsifiers - Addition of organic demulsifiers
breaks an emulsion by forming a flocculent that adsorbs the oil
. molecules. The flocculent then settles out of the wastewater as a
sludge. A wide range of polymers is available for demulsifying oily
wastewater streams. Wastewater testing is usually required to determine
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
which demulsifier is most effective. A demulsifier's applicability is
based on its molecular weight and charge density.
Emulsion breaking for W/O emulsions can be performed by the following two
chemical methods, each requiring thorough mixing and heating to 120 to 180°F:
1. Acidification - Acidification involves adding acid to dissolve solid
materials in the emulsion that are maintaining surface tensions in the
emulsion.
2. Addition of Organic Demulsifiers - Addition of an organic demulsifying
agent with both hydrophobic and hydrophilic groups breaks emulsions
by changing the charge densities of the dispersed phase.
When using chemical emulsion breaking (followed by gravity differential
separation) the following factors are important: type of chemicals, dosage and sequence of
addition, pH, mechanical shear and agitation, and heat.
Polymers, alum, ferric chloride, and organic demulsifiers can be used hi
chemical emulsion breaking. Reactive cations (e.g., H+, Al+3, Fe+3, and cationic polymers)
are particularly effective in breaking dilute O/W emulsions. Once the charges have been
neutralized or the interfacial film broken, the small oil droplets and suspended solids will be
adsorbed on the surface of the floe that is formed, or break out and float to the top. Various
types of emulsion breaking chemicals are used for the various types of oils. If more than one
chemical is required, the sequence hi which the chemicals are added can greatly affect both
the emulsion breaking efficiency and the necessary chemical dosages.
In addition, pH plays an important role hi chemical emulsion breaking,
especially if cationic inorganic chemicals, such as alum, are used as coagulants. A depressed
pH in the range of 2 to 4 keeps the aluminum ion in its most positive state where it can
function most effectively for charge neutralization. After some of the oil is broken free and
skimmed, raising the pH into the 6 to 8 range with lime or caustic will cause the aluminum to
hydrolyze and precipitate as aluminum hydroxide. This floe entraps or adsorbs destabilized
oil droplets, which can then be separated from the water phase. Cationic polymers can break
emulsions over a wider pH range and thus avoid acid corrosion and the additional sludge
generated from neutralization; however, an inorganic fiocculent is usually required to
supplement the polymer's adsorptive properties.
Mixing is important in breaking O/W emulsions. Proper chemical feed and
dispersion is required for effective results. Mixing also causes collisions that help
agglomerate droplets and subsequently help to break the emulsion.
In all emulsions, the mix of two immiscible liquids has a specific gravity very
close to that of water. Heating lowers the viscosity and increases the apparent specific gravity
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
differential between oil and water. Heating also increases the frequency of droplet collisions,
which helps to rupture the interfacial film.
Although emulsion breaking is a pretreatment step, its importance to the
treatment of PFPR wastewaters has led EPA to consider it as a major part of the technology
train for treating PFPR wastewaters. The importance of emulsion breaking becomes apparent
when treating wastewaters containing matrices that are formed during the formulation of
certain pesticide products or when wastewaters from different pesticide products are
commingled. Many pesticide products are formulated with surfactants, emulsifiers, or
petroleum hydrocarbons as inert materials to achieve specific application characteristics.
When these "inerts" mix with wastewater, emulsions may form. These emulsions may cause
matrix interferences and reduce the performance efficiency of many treatment unit operations
(e.g., chemical oxidation, activated carbon adsorption). EPA believes that, in many situations,
an emulsion breaking step will be a necessary pretreatment step to reduce matrix interferences
and improve the removal of PAIs from PFPR wastewaters.
EPA collected actual PFPR facility wastewater to use in treatability studies on
the UTS. These studies included testing of emulsion breaking using acidification and heating
and chemically assisted emulsion breaking with various coagulants. EPA purposely collected
wastewater from four facilities where the wastewater would present a real "challenge" to the
treatment system being tested. These wastewaters were not only believed to contain a variety
of PAIs from different products (due to commingling of wastewaters), but to contain a mix of
inert materials that would create an emulsion, thereby presenting "matrix interference"
problems. EPA has also conducted a treatability test of emulsion breaking by pH adjustment
and heating, in addition to testing emulsion breaking as part of UTS treatability studies.
These studies are discussed in detail in Section 7.4.
Several PFPR facilities already have emulsion breaking operations in place.
Examples of emulsion breaking technologies at these facilities, as well as emulsion breaking
technologies discussed in the final development document for the metal molding and casting
(foundries) effluent guidelines limitations (3), include:
• One of the sampled PFPR facilities uses heat to break what appears to
be an O/W emulsion.
• One PFPR facility indicated in their questionnaire response that
acidification with sulfuric acid is used to "spring" oils from the facility's
wastewater, after which the oils are skimmed.
• Another sampled PFPR facility performs acidification (apparently for
coagulation) and flocculation followed by settling.
• One PFPR facility uses "Fenton's Process," which is an oxidation
technology using ozonation in the presence of a ferrous sulfate catalyst,
followed by pH adjustment for sludge precipitation. This process is
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
designed to oxidize oils and greases (as well as any other organic
pollutants in the wastewater) to carbon dioxide and water, as well as to
precipitate metals. A variation of this process uses microfiltration,
instead of settling, to remove suspended solids.
• Some foundries, as well as facilities in other metals industries, use
chemical emulsion breaking, in which the wastewater pH is adjusted to
between 3 and 4, iron or aluminum salt is added, the wastewater is
allowed to separate (using heat to decrease separation time), and finally
lime is added to precipitate metals.
• Some foundries, as well as facilities in other metals industries, also use
thermal emulsion breaking, in which a rotating drum is half submerged
in wastewater. Hot air is blown over the drum, evaporating the
wastewater and leaving the oil behind in the remaining wastewater. The
increased oil concentration enhances further separation, and the oil is
finally skimmed.
Very little discharge monitoring data were available characterizing the effluents
from emulsion breaking technologies found at the facilities discussed above. However, some
PFPR facilities are known to treat their wastewaters following emulsion breaking. EPA
sampled treatment systems that include a pretreatment step to break the emulsions
(pretreatment steps that were sampled include ultrafiltration prior to activated carbon
adsorption, flocculation, and clarification). Results of the sampling episodes are presented in
Section 7.3.
7.2.6
Chemical Precipitation/Separation
Chemical precipitation is a separation technology in which insoluble solid
precipitates are formed from the organic or inorganic compounds in the wastewater through
the addition of chemicals during treatment. Filtration then separates out 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.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Chemical precipitation is frequently used to precipitate metals from industrial
wastewaters. The precipitated metals may then be removed by physical means such as
clarification (settling), filtration, or centrifugation.
Hydroxide precipitation is the conventional method of removing metals from
wastewater and was identified as a BAT treatment technology for facilities manufacturing
certain metallo-organic PAIs (58 FR 50638). 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 have low solubilities and are precipitated. Sodium hydroxide is more expensive
than lime, but generates a smaller volume of sludge.
Hydrogen sulfide or soluble sulfide salts (e.g., sodium sulfide) are used to
precipitate many heavy metal sulfides. Sulfide precipitation is used in the UTS because most
metal sulfides are less soluble than metal hydroxides at alkaline pH levels, and more metal
can be removed by using sulfide rather than hydroxide as a chemical precipitant. In addition,
sulfide can precipitate most complexed metals.
Carbonate precipitation is another method of removing metals by adding
carbonate reagents such as calcium carbonate to the wastewater to precipitate metal
carbonates.
Chemical precipitation is conducted at ambient conditions and is well suited to
automatic control. Metal ions such as antimony, arsenic, trivalent chromium, copper, lead,
mercury, nickel, and zinc are best removed by hydroxide precipitation. Sulfide precipitation
is best for removal of mercury, lead, and silver and complexed metals, while carbonate
precipitation removes antimony and lead.
7.2.7
Equalization, Neutralization, Filtration, and Clarification
The pesticide industry uses equalization, neutralization, filtration, and/or
clarification to treat process wastewaters for parameters such as pH, suspended solids, and oil
and grease. These technologies may be used to condition wastewater prior to treatment to
eliminate PAIs in the wastewater or following treatment for PAIs to render the water more
suitable for reuse or discharge.
Equalization
Equalization entails mixing separate wastewaters that have varying
characteristics, or accumulating a wastewater stream whose characteristics vary over time. By
mixing the wastewaters, extreme characteristics of a particular wastewater are mitigated by the
other wastewaters whose characteristics may not be as extreme. For example, a wastewater
with a high pH may be mixed with wastewater with a low pH, resulting in a more neutral
wastewater. Equalization dampens flow and pollutant concentration variation of wastewaters
prior to subsequent downstream treatment. By reducing the variability of the raw waste
loading, equalization can significantly improve the performance of downstream treatment
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
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 typically performed 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 unit performance.
Neutralization
Neutralization adjusts either an acidic or a basic waste stream to a more neutral
pH. Neutralization is used in the following situations:
• To enhance precipitation of certain dissolved metals;
• To prevent metal corrosion and damage to other construction materials;
• To allow effective operation of a biological treatment process by acting
as a preliminary treatment;
• To provide neutral pH water for recycle uses; and/or
• To reduce detrimental effects on a facility's receiving water.
Neutralization can be performed in a collection tank, rapid mix tank, or
equalization tank by commingling acidic and alkaline wastes or by adding chemicals.
Alkaline wastewaters are typically neutralized by adding sulfuric or hydrochloric acid or
compressed carbon dioxide. Acidic wastewaters can 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 byproducts, reaction rates, and quantities of sludge formed.
The most commonly used chemicals are lime (to raise the pH) and sulfuric acid (to lower the
pH).
Filtration
Filtration is a separation technology designed to remove solids from a
wastewater stream by passing the wastewater through a material that retains the solids on or
within itself. The type of filter used can be determined 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 wastewater is being filtered
continuously or in batches);
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
• 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 accumulate to form a filter cake or are
trapped within the pores (spaces) or body of the filter).
Filtration includes membrane filtration (see Section 7.2.4) as well as other
types. Although some may be used primarily to remove PAIs (e.g., RO), most types of
filtration used at PFPR facilities are used to remove suspended solids.
Clarification
Clarification can be used as either a pre- or post-treatment step. Clarification
tanks are often referred to as primary or secondary sedimentation tanks. Clarification aids in
removing settleable solids, removing free oil and grease and other floating material, and
reducing the organic load on receiving waters or POTWs. According to Metcalf & Eddy's
Wastewater Engineering, 3rd ed., "Efficiently designed and operated primary sedimentation
tanks should remove from 50 to 70% of the suspended solids and from 25 to 45% of the
BOD5." (4) These removals represent achievable levels for domestic sewage and for
industrial pesticide-containing wastewaters.
7.2.8
Disposal of Solid Residue from Treatment
Many of the wastewater treatment processes previously discussed in this section
generate solid residues (i.e., sludges). Treatment processes generating solid residues include
chemical precipitation, emulsion breaking, and clarification. Certain membrane filtration
processes can generate a solid residue, but, in most cases, the concentrate residue is still in
liquid form and, in some instances, may be recovered for its product value. Sludge may be
treated prior to disposal to reduce its volume and to render it inoffensive (i.e., less odorous);
treatment alternatives include thickening, stabilization, conditioning, and dewatering.
However, treatment of sludge may only be economical for facilities that generate large
volumes of sludge due to the capital cost associated with sludge treatment equipment.
Therefore, EPA believes that few PFPR facilities will treat sludge prior to disposal. Sludge
disposal options include combustion (e.g., incineration) and land disposal.
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 renders sludge less odorous and reduces the
pathogenic organism content. Sludge stabilization technologies include chlorine oxidation,
lime stabilization, heat treatment, anaerobic digestion, and aerobic digestion. Conditioning
entails biologically, chemically, or physically treating a sludge to enhance subsequent
dewatering techniques. The most common methods of conditioning sludge are thermal and
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
chemical. Dewatering removes water from solids to reduce the sludge volume more than that
achieved by thickening. This process is important in preparing sludge for disposal and
reducing the sludge volume and mass to 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 is a means of ultimately disposing of organic constituents found in
sludge. Some common equipment and methods used to incinerate sludge include fluidized
bed reactors, multiple hearth furnaces, atomized spray combustion, flash drying incineration,
and wet air oxidation. Environmental impacts of combustion technology include the effects of
discharges to the atmosphere (i.e., particles and other priority pollutants or noxious
emissions), to surface waters (i.e., scrubber water discharges), and to land disposal (i.e., ash).
Land disposal of sludge may include applying the sludge on land as a soil
conditioner and as a source of fertilizer for plants. This is a typical application of sludge
from biological treatment systems. In addition, sludge can be stockpiled in landfills or
permanent lagoons. In selecting a land-disposal site, a facility should guard against pollution
of groundwater or surface water.
7.3
Wastewater Sampling
In order to obtain data on treatment system performance, EPA performed seven
sampling episodes at six PFPR facilities (one facility was sampled twice). Following proposal
of the PFPR rule, EPA conducted one additional sampling episode to evaluate treatment
performance at a pool chemicals facility. Section 7.3.1 describes the sampled treatment
systems and presents performance data obtained during the EPA sampling episodes for both
individual treatment unit operations and overall system performance. Section 7.3.2 presents
characterization data of treated effluents that are reused in PFPR operations. Additional
sampling episodes that were conducted to obtain data for raw wastewater characterization are
described in Section 5.2.
7.3.1
Treatment System Performance
As described in Section 3.2.2, EPA collected samples of wastewater from eight
different treatment systems for the purpose of evaluating treatment system performance. The
selected sampling locations were chosen to allow evaluation of individual treatment unit
operations as well as overall system performance. All samples were analyzed for the specific
PAIs believed to be present in the wastewater. In most cases, the samples were also analyzed
for classical wet chemistry parameters1, priority pollutants (listed in Appendix C), and
* Classical wet chemistry parameters are ammonia as nitrogen, biochemical oxygen demand (BOD5), chemical oxygen
demand (COD), fluoride, nitrate and nitrite nitrogen, oil and grease (by Method 413.1 or Method 1664), pH, total
cyanide, total dissolved solids (TDS), total organic compounds (TOC), and total suspended solids (TSS).
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Section 7 - Technology. Selection and Methods to Achieve the Effluent Limitations
organic and metal nonpriority pollutants. Prior to June 1994, samples were analyzed for oil
and grease using Method 413.1; these results are presented in this section as "oil and grease."
Samples collected after June 1994 were analyzed for oil and grease using Method 1664.
These results are presented in this section as "hexane extractable material." Method 1664 was
developed by EPA's Office of Science and Technology to replace the gravimetric procedures
that used Freon-113, a Class I chlorofluorocarbon (CFG), as the extraction solvent for the
determination of oil and grease.
Detailed discussions of the individual treatment technologies can be found in
Section 7.2. This section presents the treatment performance data for each of the eight
treatment systems sampled. Removal efficiencies for individual treatment steps were
calculated using the difference between the concentrations of constituents in the effluent and
the influent wastewaters in each treatment step. No removal (NR) efficiency is reported when
the effluent concentration of a constituent is greater than the influent concentration. For
constituents detected in the influent stream but not detected in the effluent stream, the removal
efficiency was calculated using the effluent detection limit as the effluent concentration and
the removal is reported as greater than (>) this value. For example, if toluene was detected at
100 /ig/L in the influent and was not detected (i.e., its concentration was below the detection
limit of 5 /xg/L) in the effluent, the removal efficiency was calculated to be >95 percent.
When indicated, the overall system percent removal was averaged over the number of
individual runs performed.
Treatment System #1
The first treatment system sampled by EPA consists of an ultrafiltration
membrane unit followed by an activated carbon unit through which process wastewater is
treated for reuse. This system was sampled during two separate episodes. During each
episode, two separate treatment runs of herbicide and insecticide wastewaters were performed.
The herbicide pesticide active ingredients (PAIs) analyzed hi the wastewater were 2,4-D,
dicamba, MCPP, and prometon, and the insecticide PAIs analyzed in the wastewater were
carbaryl, chlorpyrifos, diazinon, and disulfoton. The percentages of PAI removed during
treatment for both the individual unit operations and the overall system during the two
episodes are presented in Tables 7-1 and 7-2, respectively.
Ultrafiltration is a type of membrane filtration that is typically used to separate
suspended or colloidal solutes from wastewater and is capable of rejecting molecules with
molecular weights above 2,000. Because most PAIs have molecular weights between 150 and
500, ultrafiltration is not effective for removing dissolved PAIs; however, due to their
hydrophobic nature, many PAIs adhere to suspended solids in the wastewater that are
effectively rejected by the ultrafiltration membrane. The data from the two episodes show
that, in general, the insecticidal PAIs were removed by the ultrafiltration unit to a greater
degree than the herbicidal PAIs.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-1
PAI Percent Removals Achieved By Treatment System #1
First Sampling Episode1
PAI Name
PAI Removal by
TJltrafiltration
' (%)
PAI Removal by
Activated Carbon
e*)Y,,
Overall PAI Removal
(%)
Herbicide Run
2,4-D
Dicamba
MCPP
Prometon
39.83
2.08
61.67
19.23
99.99
>99.98
99.99
>97.85
99.99
>99.98
>99.99
>97.85
Insecticide Run
Carbaryl
Chlorpyrifos
Diazinon
Disulfoton
22.77
99.47
81.82
97.82
99.99
>41.18
80.71
>79.17
>99.99
>99.69
96.49
>99.55
'Calculated percent removals are not corrected to reflect significant figures.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-2
PAI Percent Removals Achieved By Treatment System #1
Second Sampling Episode1
PAIHame
PAI Removal fey
TJMrafiltraiwin
(%)
PAI Removal by
Activated Carbon
(%>
Overall PAI Removal '
C%)
Herbicide Run
2,4-D
Dicamba
MCPP
Prometon
MR
6.93
ND
49.10
99.99
>99.98
99.60
>99.91
99.99
>99.99
>99.29
>99.96
Insecticide Run
Carbaryl
Chlorpyrifos
Diazinon
Disulfoton
NR
>99.92
NR
59.26
99.97
ND
99.48
99.98
99.97
99.77
99.27
99.99
Calculated percent removals are not corrected to reflect significant figures.
ND - PAI concentration was less than the detection limit in the influent stream.
NR - No removal.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
In addition to the PAIs removed, the ultrafiltration unit effectively removed oil
and grease and TSS. Oil and grease removals achieved by the ultrafiltration unit for the
herbicide and insecticide wastewaters averaged 94% and 88%, respectively. In addition, TSS
removals averaged >97% and >91% from the herbicide and insecticide wastewaters,
respectively.
Following ultrafiltration, the wastewater treated through an activated carbon
treatment unit. Adsorption is the primary mechanism for removing organic constituents from
wastewater through activated- carbon treatment. The main driving force for adsorption is the
attraction of the solute to the carbon and/or the hydrophobic nature of the solute. In general,
the activated carbon unit was highly effective in removing PAIs from the sampled PFPR
wastewaters. Each of the PAIs was either reduced to below detection limits or removed in
excess of 99%, with the exception of diazinon during the first sampling episode. The overall
treatment system was effective at removing at least 96% (and in many cases >99%) of the
PAIs in the wastewater.
Treatment System #2
The second treatment system sampled by EPA consists of clarification followed
by ozonation and activated carbon. Effluent from this treatment system is also reused in
PFPR operations. EPA collected samples during three treatment runs: two runs treated
wastewaters containing atrazine and one run treated wastewater containing pendimethalin.
The percentage of PAIs removed during each treatment run is presented in Table 7-3 for the
individual unit operations and the overall system.
Clarification is commonly used to settle suspended particles from wastewater.
Clarification was very effective in removing atrazine and pendimethalin from the clarifier
influent. Atrazine and pendimethalin have low solubilities in water and are "therefore more
likely to adhere to solids in the wastewater. Because clarification is designed to reduce the
solids content of the water, PAIs that adhere to solids are effectively removed during
clarification. In contrast, the more water-soluble PAIs are not likely to be removed during
clarification since they are dissolved in the water rather than adhered to the solids. In
addition to removing >92% of the PAIs, the clarification unit removed an average of 94% of
the oil and grease and an average of 80% of the TSS during the three treatment runs.
As discussed in Section 7.2, ozonation is an aggressive oxidation process in
which one or more electrons are transferred from the ozone to the wastewater constituent. In
this episode, the ozonation unit reduced pendimethalin by 62%, while there was essentially no
change in the concentration of atrazine. However, the activated carbon unit was very
effective at removing 99% or greater of the remaining PAIs in the wastewater. The overall
system effectively removed >99.99% of the PAIs in the wastewater.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-3
PAI Percent Removals Achieved By Treatment System #2*
FAlName
E&IKeatovatby
Clarification
<%)
EAlKewovalby
Ozonation
<%)
£AI Removal by
Activated Carbon
<%)
Over j»B PAI
Removal i
<%)
Treatment Batch #1
Atrazine
93.98
14.77
99.93
>99.99
Treatment Batch #2
Atrazine
92.04
NR
99.94
99.99
Treatment Batch #3
Pendimethalin
99.96
61.67
>99.35
>99.99
Calculated percent removals are not corrected to reflect significant figures.
NR - No removal.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Treatment System #3
The third treatment system that EPA sampled is used by the facility to pretreat
their wastewater prior to discharge to a publicly owned treatment works (POTW). The
system consists of clarification followed by activated carbon. The facility allows the f
wastewater to settle for about 6 to 8 hours. Following clarification, the PFPR process line
wastewaters at this facility are commingled with pesticide manufacturing wastewaters,
laboratory rinsate, and drum rinsate prior to activated carbon treatment. One treatment run of
the clarification unit and three individual treatment runs of the activated carbon unit were
sampled by EPA. EPA analyzed the wastewater treated through the clarifier for 2,4-D only;
however, because the 2,4-D concentration increased after clarification, a removal could not be
calculated. TSS removal through the clarification unit was 84%, and oil and grease was
reduced by 68 percent.
Table 7-4 presents PAI removals achieved for the individual days of sampling
and the average percent PAI removal over the three days using activated carbon. EPA
analyzed the wastewater for 2,4-D, atrazine, carbaryl, fluometuron, metolachlor, propachlor,
and trifluralin; however, atrazine, carbaryl, and trifluralin were not detected in the
commingled raw influent to the treatment system. The four other PAIs were reduced using
activated carbon, on average, by more than 50 percent. Under the pesticide manufacturing
effluent guidelines and standards studies, the activated carbon unit at this facility was found to
be achieving less than optimal removals of the manufactured PAIs, which may account for the
lower than expected removals of the PAIs by activated carbon.
Treatment Systems #4 and #5
EPA sampled two treatment systems (referred to here as treatment systems #4
and #5), which are operated by the same facility. Treatment system #4 is used to treat
nonprocess area precipitation (i.e., storm water), and consists of a multimedia filter followed
by an activated carbon unit. This system is used to pretreat the wastewater prior to discharge
to a POTW. The nonprocess area precipitation treatment system was sampled by EPA during
one treatment run for the following PAIs: carbosulfan, chlorpyrifos, diazinon, endosulfan I,
endosulfan E, malathion, oryzalin, oxyfluorfen, and permethrin. The results from treatment
system #4 are presented in Table 7-5.
Multimedia filtration is a. technology used to separate solids from the
wastewater. There was little change in the concentrations of most of the PAIs following
multimedia filtration, although endosulfan I, endosulfan II, and permethrin were reduced by
65% or more. TSS was reduced by 79% and oil and grease by 55 percent. Activated carbon
was effective at reducing concentrations of PAIs remaining in the wastewater following
multimedia filtration, leading to overall removals of >90% for four of the PAIs.
7-20
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-4
PAI Percent Removals Achieved By Treatment System #3
PAI Name
2,4-D
Fluometuron
Metolactdor
Propachlor
Activated £arboa
FAI Removal,
Dayl
C%) :
53.85
44.83
>98.82
80.00
PAl Removal,
Day!
<%)
58.57
86.87
>96.55
82.86
PAI Removal?
Day 3
(%> ^
41.33
74.12
>98.57
79.37
Average PAI
Removal
{%)
51.25
68.61
>97.98
80.74
Calculated percent removals are not corrected to reflect significant figures.
7-21
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-5
PAI Percent Removals Achieved By Treatment System #41
PAI Name,
Carbosulfan
Chlorpyrifos
Diazinon
Endosulfan I
Endosulfan n
Malafhlon
Oiyzalin
Oxyfluorfen
Permethrin
! PAI Removal fey
Multimedia Filtration
<%)
ND
11.36
NR
65.71
83.75
47.62
NR
NC
>68.25
PAI Removal by
Activated Carbon
(%)
ND
81.03
63.16
90.00
95.13
98.33
54.74
ND
72.00
Overall PAI Removal
<*) !
~
83.18
58.82
96.57
99.21
99.13
54.74
>75.00
91.11
Calculated percent removals are not corrected to reflect significant figures.
NR - No removal.
NC - Unable to calculate removal because effluent detection limit is greater than influent concentration.
ND - PAI concentration was less than the detection limit in the influent stream.
7-22
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Treatment system #5 is used by this facility to treat process wastewater and
consists of a microfiltration unit followed by an activated carbon unit. The microfiltration
unit is a cross-flow filtration system, in which suspended matter in the wastewater, or in a
precoat solution, deposits on the inner walls of the unit. This suspended matter forms a
dynamic filter, the surface of which is continuously formed by axial flow of the wastewater
through tubes. The dynamic filter enhances the performance of the microfilter to achieve
results similar to an ultrafiltration unit. After treatment, the process wastewater in this system
is primarily reused for rinsing drums and shipping containers.
During the sampling episode, three batches of process wastewater, which
ranged hi size from 1,500 to 4,300 gallons, were treated through the microfiltration system.
The samples were analyzed for the same PAIs as the samples from the multimedia filtration
system, as well as the PAIs dimethoate and Vapam®. The results are presented as 3-day
averages in Table 7-6. In general, influent pollutant concentrations were much lower on
Day 3, resulting in lower percent removal efficiencies.
Some of the more water-soluble PAIs, such as Vapam®, showed little or no
removal through the microfiltration unit throughout the sampling episode. Other PAIs,
including chlorpyrifos, oryzalin, oxyfluorfen, and permethrin, showed little or no removal
during one or two days of the sampling episode, which significantly lowered the average
microfiltration removal. For example, on Days 1 and 2, both chlorpyrifos and permethrin had
average microfiltration removals in excess of 96 percent. Microfiltration, as with
ultrafiltration, is not effective for removing dissolved PAIs; however, due to the hydrophobic
nature of many PAIs, the PAIs adhere to suspended solids in the wastewater, which are
effectively rejected by the microfiltration unit. Carbosulfan, diazinon, dimethoate,
endosulfan I and II, and malathion were all removed to below detection limits by the
microfiltration unit.
Microfiltration was also effective at reducing the concentration of oil and
grease and TSS hi the wastewater. The 3-day average removal of oil and grease through
microfiltration was >77%; the removal on Day 1 exceeded 93 percent. No removal of TSS
occurred on Day 3 because it was present in the influent wastewater at a low concentration
(16 mg/L); however, a 2-day average removal of TSS of >64% was achieved on Days 1
and 2.
The microfiltration unit is followed by an activated carbon unit. Activated
carbon was effective at reducing the concentrations of PAIs remaining in the wastewater by
more than 90% (and in most cases, by more than 98%). The overall performance of the
microfiltration unit followed by the activated carbon unit achieved PAI removal efficiencies of
>99%, with the exceptions of chlorpyrifos, diazinon, and Vapam®. When eliminating Day 3
results (because of low influent concentrations), PAI removals were >99%, with the exception
of Vapam® (98%).
7-23
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-6
PAI Percent Removals Achieved By Treatment System #51
•= s
PAI Nafcafe \ ;
Carbosulfan
Chlorpyrifos
Diazinon
Dimethoate
Endosulfan I
Endosulfan n
Malathion
Oryzalin
Oxyfluorfen
Permethrin
Vapam®
PAI Removal by
Microfiltration
' m
>88.89
64.43
>83.81
>61.52
>99.91
>99.75
>96.58
17.52
38.05
>55.97
22.33
FAl Removal by
Activated Carbon
(%)
ND
>98.21
99.93
ND
ND
ND
ND
>99.94
98.87
>99.80
>93.48
Overall PAT Removal
e/<^
>99.89
>84.84
>84.84
>99.96
>99.99
>99.99
>99.99
>99.83
99.16
>99.90
96.78
^Calculated percent removals are not corrected to reflect significant figures and represent 3-day averages.
ND - PAI concentration was less than the detection limit in the influent stream.
7-24
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Treatment by microfiltration followed by activated carbon showed better PAI
removal than treatment by multimedia filtration followed by activated carbon. As stated
above, the process wastewater treatment system treats water to concentrations that are
acceptable for reuse, whereas the nonprocess area system pretreats precipitation prior to
discharge to a POTW. As a result, the process wastewater treatment system must have high
PAI removals, while the other system must only meet the POTW's pretreatment
concentrations. This facility does not discharge the process wastewater to the POTW because
the POTW requires that the facility meet drinking water standards (which they do not feel
they can achieve consistently). In addition, because the microfiltration system treats only
process wastewater, the influent levels to the process wastewater treatment system are much
higher than those of the nonprocess area precipitation system. An average PAI concentration
of 45,000 /ig/L was present in the process wastewater influent versus an average PAI
concentration of 25 fig/L in the nonprocess area precipitation influent. Therefore, some PAI
percent removals may look low for Treatment System #4 because the influent concentrations
were already near the detection limit.
Treatment System #6
The sixth treatment system that was sampled by EPA is very similar to
treatment system #5, discussed above. Treatment system #6 consists of a cross-flow filtration
(i.e., microfiltration) unit followed by an activated carbon unit. This unit has a newer vertical
design and treats smaller batches (100 to 300 gallons) of wastewater than the batches treated
by treatment system #5. Treated effluent is reused by the facility in PFPR operations.
EPA collected samples from this system during treatment of three batches of
process wastewater. The samples were analyzed for the following PAIs: benthiocarb,
bromacil, diuron, tebuthiuron, and terbufos. The percentages of PAI removed during
treatment are presented in Table 7-7 for both the individual unit operations and the overall
system and are presented as averages of the three treatment runs.
Diuron was not effectively removed by microfiltration; however, microfiltration
was somewhat effective in removing the remaining four PAIs analyzed. Several PAIs showed
little or no removal during one or more days of the sampling episode, which significantly
lowered the average PAI removal by microfiltration. When looking at individual daily
removals, bromacil showed removal of >40% and benthiocarb showed a removal of >60% on
Day 3; tebuthiuron and terbufos had 2-day averages of 66.59% and 76.53%, respectively.
The activated carbon unit achieved removals of >88% for two of five PAIs and >98% for the
other three PAIs. The performance-data for the overall system show high PAI removals
(>98% for three of five PAIs). As with treatment system #5, the unit performs relatively well
at removing TSS (51%).
7-25
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-7
PAI Percent Removals Achieved By Treatment System #63
PAlHame;
Benthiocarb
Bromacil
Diuron
Tebutbiuron
Terbufos
; FAE Removal by
Mierefirtration
i *' <%>
30.94
14.27
1.99
44.39
51.02
PAI Removal by
Activated Carbon
(%)
98.42
89.72
99.66
88.81
98.93
Overall PJkl Removal
<%) ' '""
98.80
88.76
99.56
88.41
98.99
Calculated percent removals are not corrected to reflect significant figures and represent 3-day averages.
7-26
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Treatment System #7
The seventh treatment system that was sampled by EPA uses a two-step system
to treat wastewater for reuse. The wastewater is first sent through a flocculation and flash
mixing unit and a lamella clarification unit, primarily to reduce TSS. Most of the clarified
wastewater is then recycled to the process areas for reuse as equipment cleaning and floor
wash water. A portion of the clarified wastewater is periodically transferred to the second
part of the treatment system, which consists of two bioreactors (Bioreactors A and B)
operated hi parallel. The bioreactors are designed primarily to reduce the concentration of
2,4-D, but may also be effective in reducing other PAIs and semivolatile organic compounds
in the wastewater prior to reuse in the facility-wide scrubber system.
During the sampling episode, the facility was producing pesticide products
containing the following PAIs: 2,4-D, atrazine, diazinon, dicamba, and MCPP. The
percentage of PAI removed during treatment is presented hi Table 7-8 for each treatment run
sampled from both systems. Three-day averages of PAI removals for each system are also
presented.
As described hi the discussion of treatment system #2, the clarifier system may
remove the less water-soluble constituents that adhere to other solids removed during
clarification. As seen in Table 7-8, the clarifier achieved low removals of atrazine on Day 1
and low removals of diazinon on both Days 1 and 2. However, the removal efficiencies for
the PAIs after clarification increased on Day 3, although the influent concentrations of each
PAI was similar from day to day (e.g., the concentration of atrazine on all three days « 8,800
jug/L). Four of the five PAIs (excluding atrazine) showed removals on Day 3 of between 28
and 58 percent.
*i
In addition to PAI removals, the clarifier was somewhat effective at reducing
the TSS in the wastewater (the 3-day average removal was >50%). However, the clarifier
achieved little or no removal of oil and grease or other conventional and nonconventional
pollutants.
Biological treatment is a destruction technology hi which toxic organic
pollutants hi wastewaters are degraded by microorganisms. These microorganisms oxidize
soluble organic compounds and agglomerate colloidal and particulate solids. In general, the
biotreatment step hi this treatment system was effective hi removing 2,4-D (>99%), diazinon
(88%), and MCPP (>99%). It is important to note that this particular facility specifically
operates the biotreatment unit until 2,4-D concentrations are below 5 mg/L.
7-27
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-8
PAI Percent Removals Achieved By Treatment System #7
PAI Name
2,4-D
Atrazine
Diazinon
Dicamba
MCPP
V f
PAI Name
2,4-D
Atrazine
Diazinon
Dicamba
MCPP
Clarification
PAI Removal,
JOay I
' <%)
MR
12.23
18.83
NR
NR
PAI Removal,
»ay2
<%)
NR
NR
26.64
NR
0.64
FAt Removal,
Day3
<%)
43.11
NR
37.56
28.74
58.30
Average £Al _
Removal
(%)
NR
3.01
27.68
NR
2.01
'• •: ' Biological Oxidation
P&I Removal,
Bioreactor A
tf ~<%>
99.86
24.65
89.94
27.40
99.70
PAI Removal,
Bioreacfor B -
Batch I
<%) -,_
>99.45
4.04
>61.37
NR
99.97
PATltemoval,
Bioreactor B -
Batch!
(%)
99.31
0.53
94.76
NR
99.95
Average PAI ,
Removal
(%)
>99.54
.9.74
>88.02
NR
99.87
Calculated percent removals are not corrected to reflect significant figures and represent 3-day averages.
NR - No removal.
7-28
-------
: Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Atrazine and dicamba were not effectively removed during biotreatment at this
facility. The removals of atrazine and dicamba in Bioreactor A were approximately 25% and
27%, respectively; however, in Bioreactor B, during both Batches 1 and 2, there was either
insignificant or no removal. This may be explained by the differences in the time of aeration
in the reactors: 90 hours in A, 67 hours in Bbatchl, and 24 hours in
The biological system achieved high removals of oil and grease (94.04%
removal on average) and moderate removals of other conventional pollutants, including
BOD5, COD, TOC, TSS, and total cyanide. (Note: Inefficient solids settling may have
contributed to lower removals in general.)
Treatment System #8
The eighth treatment system sampled by EPA treats waste generated from the
formulation, packaging, and/or repackaging of pool chemicals. EPA conducted this sampling
episode, in part, to evaluate whether to exempt pool chemicals from this rule. EPA had not
specifically excluded these chemicals at proposal because it was believed the processes were
dry.
During normal PFPR operations, small amounts of dry product may fall on the
floor or accumulate on equipment surfaces and become contaminated with ordinary dust and
dirt. These chemicals act as strong oxidizing agents and, left untreated, may pose a serious
fire and safety hazard. Facilities treat (or deactivate) these chemicals by adding water and
neutralizing chemicals, such as sodium hydroxide or sodium carbonate, to this contaminated
product. With this treatment, the available chlorine in the water is converted to a pH neutral
salt, which can be discharged to a POTW.
EPA collected influent and effluent samples from one treatment batch at a pool
chemicals facility. Chlorine, which was used as an indicator for the PAIs, was reduced from
1,200 to <0.1 mg/L, a reduction of >99.99 percent. At the same time, chloride increased
from 1,040 to 4,530 mg/L.
7.3.2
Reuse of Treated Wastewater,
As discussed in Section 7.3.1, five of the eight treatment systems sampled by
EPA produce effluent that is reused by the facility into PFPR or general facility operations.
The facilities may reuse the treated water for a specific purpose, (e.g., rinsing raw material
drums or as make-up water in the air pollution control scrubber system). Facilities may also
use the treated water for washing floors in pesticide production areas or elsewhere in the
facility. Some facilities may even return the treated wastewater to the formulations. This
section discusses the ability of faculties to reuse treated wastewaters and summarizes the
concentrations of pollutants found in treated effluents that are reused. Section 7.6 discusses
additional recycle and reuse practices that may be used by PFPR facilities.
7-29
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Comparison of PAI Effluent Concentrations
When sampling the five PFPR treat and reuse systems, EPA collected effluent
concentration data on 23 different PAIs. EPA compared these effluent concentrations to the
effluent concentrations used to develop the PFPR compliance cost estimates. The effluent
concentrations used in the costing effort were derived from the pesticide manufacturing best
available technology (BAT) performance long-term average (LTA) concentrations and through
data transfers (see Section 7.5 for a more detailed discussion of technology transfers and
Section 8 for more discussion of compliance cost development).
When costing the PFPR Industry to comply with the proposed regulation, EPA
estimated achievable PAI effluent concentrations from the Universal Treatment System (see
Sections 7.4 and 8.4). For PAIs that have pesticide manufacturing limitations that are based
on one of the UTS PAI-removal technologies (i.e., activated carbon, hydrolysis, chemical
oxidation, or chemical precipitation), achievable effluent concentrations were based on LTA
concentrations achieved by pesticide manufacturing BAT systems. For PAIs that have
pesticide manufacturing limitations that are not based on one of the four technologies
mentioned above, achievable effluent concentrations are based on treatability data. For PAIs
that do not have pesticide manufacturing limitations, EPA transferred LTA concentration data
within structural groups (using the highest LTA in the structural group). When there was no
LTA for any PAI within a given structural group, EPA transferred the 90th percentile highest
LTA.
EPA compared the LTAs presented in Table 7-9 to the concentrations of the 23
PAIs analyzed hi actual PFPR treatment system effluents. The table lists the source as well as
the concentrations of the LTAs. As mentioned in the previous paragraph, the table indicates
whether the data were derived from: a pesticide manufacturing BAT limitation; a data
transfer within the structural group; or a 90th percentile highest data transfer. For 13 of the
23 PAIs, EPA used LTA concentrations; from pesticide manufacturing BAT limitations. EPA
transferred the highest LTA concentration within the structural group for eight of the 23 PAIs.
For the remaining two PAIs, the 90th percentile highest data transfer was used.
EPA believes that estimating costs for PFPR facilities to achieve manufacturing
limitations for the purpose of reusing their wastewater is an accurate, if not conservative,
approach. However, EPA is aware that some facilities may not require treatment to these
concentrations in order to reuse their wastewater. The discussion below cites examples of
facilities that have been able to reuse wastewaters at concentrations that are higher or
approximately equal to the LTA concentrations that were used in the costing effort. Also
included in this discussion are examples of the PFPR treatment systems reducing PAI
concentrations below the LTA concentration of the pesticide manufacturing BAT performance.
The following paragraph presents a comparison of achievable effluent concentrations from
EPA's sampling program versus the LTA concentration data used for costing purposes.
7-30
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-9
Achievable Effluent Concentrations Used for Estimating Compliance Costs
for PAIs from PFPR Sampling
PAT
2,4-D
Atrazine
Bromacil
Carbaryl
Carbosulfan
Chloipyrifos
Diazinon
Dicamba
Dimeihoate
Disulfoton
Diuron
Endosulfan I
Endosulfan II
Malathion
MCPP
Oryzalin
Oxyfluorfen
Pendimethalin
Permethrin
Prometon
Tebuthiuron
Terbufos
Vapam®
Estimated LTA Concentration
Used for Costing (rag/L)
0.0020
0.0111
0.4310
0.0714
0.0085
0.0056
0.0319
0.0026
0.0072
0.0100
0.0152
0.0127
0.0127
0.0034
0.0020
0.2000
0.2000
0.0107
0.0003
0.0882
0.0040
0.0080
0.2000
Source of Concentration Data
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Transfer Within Structural Group
Transfer Within Structural Group
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Transfer Within Structural Group
Transfer Within Structural Group
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Transfer Within Structural Group
Transfer Within Structural Group
Transfer Within Structural Group
Transfer Within Structural Group
90th Percentile Highest Transfer
90th Percentile Highest Transfer
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Pesticide Manufacturing BAT
Transfer Within Structural Group
7-31
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-10 presents both, the achievable effluent concentrations from EPA's
sampling program and the estimated LTA concentration data used for costing purposes. The
sampling data are presented for each episode where the PAI was detected and may represent
the average of multiple days of sampling for a particular episode. Actual effluent data from a
particular episode have been categorized as either greater than the estimated LTA used for
costing purposes or within the same range or less than the estimated LTA. [Note: During
some sampling episodes, facilities were only able to provide EPA with limited information on
the PAIs believed to be in the wastewater that was to be treated. The reason for this is that
facilities store wastewater over a period of time prior to batch treatment and a facility may
only be able to provide EPA with a list of products produced at the facility during that time
period. Therefore, in a few cases EPA may have analyzed the wastewater for PAIs that were
not actually present. This may account for a number of the nondetects reported and the low
concentrations associated with the detection limits.]
As identified hi the previous paragraph, when comparing the actual sampling
data for effluent concentrations from treat and reuse systems, EPA found three different
patterns. First, for PAIs such as 2,4-D, atrazine, diazinon, dicamba, MCPP, tebuthiuron, and
terbufos, the actual concentration of the PAI hi the treated effluent that was able to be reused
was greater than the estimated LTA concentration. This implies that it may not be necessary
for facilities to treat the wastewater to effluent concentration values equal to or lower than the
manufacturing BAT LTA concentrations in order to reuse those wastewaters hi PFPR
operations.
Second, EPA found that, for another group of PAIs, the estimated LTA
concentrations were in the same range as the PAI average concentrations found in the reuse
water sampled at the PFPR facilities. These PAIs included carbaryl, carbosulfan, dimethoate,
diuron, malathion, permethrin, and Vapam®. These data support the assumption that
treatment systems used by PFPR facilities perform well (i.e., can achieve the manufacturing
BAT LTA concentrations) and that this water can then be reused.
Finally, EPA found that, for the remaining PAIs (bromacil, chlorpyrifos,
disulfoton, endosulfan I, endosulfan II, oryzalin, oxyfluorfen, pendimethalin, and prometon),
the PFPR treatment systems were achieving effluent concentrations that were lower than the
estimated LTA concentrations. This difference may be due to the wastewater matrices
associated with PFPR wastewaters being more conducive to treatment by the UTS, or that the
use of UF followed by activated carbon may be better suited to handle these wastewaters,
especially on a batch basis, and prepare them for reuse.
Comparison of Other Pollutants
Even when treat and reuse systems reduce PAI concentrations to very low
levels, they may not be as efficient at reducing the concentrations of other pollutants.
However, many of these facilities still reuse the treated water with relatively high
7-32
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-10 •*
Comparison of the Estimated LTA to Achievable Effluent Data from the
Sampling of Treat and Reuse Systems
FAI
2,4-D
Atrazine
Bromacil
Carbaryl
Carbosulfan
Chlorpyrifos
Diazinon
Dicamba
Dimethoate
Disulfoton
Diuron
Endosulfan I
Endosulfan n
Malafhion
MCPP
Oryzalin
Oxyfluorfen
Pendimethalin
Pennethrin
Prometon
Tebuthiuron
Terbufos
Vapam®
Estimated LTA
Concentration Used for
Costing
0.0020
0.0111
0.4310
0.0714
0.0085
0.0056
0.0319
0.0026
0.0072
0.0100
0.0152
0.0127
0.0127
0.0034
0.0020
0.2000
0.2000
0.0107
0.0003
0.0882
0.0040
0.0080
0.2000
Sampled Achievable Effluent Concentration
(mg/L)
Within Same Range or i
Less Than Estimated '•
LTA
0.0034
—
0.065
0.030
0.0010
<0.0017; O.00055
0.015
<0.00045
0.0034
O.00059
0.011
O.000067
0.000067
O.0017
—
O.00020
O.00062
0.00030
O.00020
O.00295
—
—
0.488
Greater Than
.Estimated LTA
835.961; <3.79
0.022; 8.58; 7.40
—
'
—
—
1.083; O.13
62.46; 70.25
—
—
—
—
—
—
1.195.831; 1.92; 0.051
—
—
—
—
—
2.14
0.015
—
1These PAIs were detected in the effluent from a clarification system used to treat wastewaters for reuse.
7-33
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
ij
concentrations of conventional pollutants, COD, or acetone . Therefore, in addition to
analyzing the concentration of PAIs in reuse waters, EPA looked at the following pollutants:
COD, oil and grease, TOC, and acetone.
Figures 7-1 through 7-4 display the concentrations of oil and grease, COD,
TOC, and acetone, respectively, detected in effluents from the treatment and reuse systems
discussed in Section 7.3.1.3 The systems are labelled A through E. These figures
demonstrate that PFPR facilities have found ways to reuse their wastewaters following
treatment, although some pollutants may still be detected in the effluent. Similar to the PAI
results discussed in Section 7.3.1, some treatment systems achieved very low effluent
concentrations of these pollutants while others did not. In particular, one facility treated water
on site for reuse and achieved higher effluent concentrations. Regardless, each of the effluent
streams presented are currently reused.
As shown in Figure 7-1, oil and grease effluent concentrations are generally
very low (less than 1 mg/L). However, Facility E (which uses a microfiltration system
followed by an activated carbon unit) reuses water with an oil and grease effluent
concentration as high as 62 mg/L. This facility reuses its wastewater for general facility
cleaning. Also, Facility F (not shown in the figure) has average oil and grease effluent
concentrations of 320 mg/L and 39 mg/L through the clarification unit and the bioreactors,
respectively. Again, this facility reuses its effluent water from the clarification unit for
general facility cleaning, and it reuses its effluent from the bioreactors as make up water in
the scrubber tub.
The effluent concentrations of COD fall between 750 mg/L and 1,500 mg/L
(Figure 7-2). However, at one facility that uses an ultrafiltration system followed by an
activated carbon unit; EPA measured the COD in the treated effluent to be approximately
2,550 mg/L. This facility reuses its water in the facility wherever it's needed. In addition,
Facility F had an average COD effluent concentration of 12,000 mg/L from the clarifier and
an average COD concentration of 5,325 mg/L from the bioreactors. Again, this facility is
able to reuse the clarified water in the production areas and to reuse the water that was treated
through the bioreactors in the facility-wide scrubber system.
As shown by Figure 7-3, TOC effluent concentrations generally fall between
250 mg/L and 700 mg/L. However, one facility (which uses an ultrafiltration system
followed by an activated carbon unit) is able to reuse its wastewater with a TOC
f\
Acetone is a volatile organic pollutant that has been found in PFPR wastewaters, particularly following activated
carbon treatment. (When activated carbon is riearing saturation, it may selectively desorb pollutants in order to
adsorb other pollutants for which it has a greater affinity.) Acetone is believed to be a common contaminant in
isopropyl alcohol, which is often used as a solvent or for cleaning in PFPR facilities.
The data from one facility (Facility F) that has a treat and reuse system are not represented on the bar graphs.
This facility uses a two-part system consisting of clarification for reuse followed by biological oxidation for
reuse. The concentration data from this facility were of a different order of magnitude than data from other
facilities and could not be presented on the same bar graph. The data from this facility are discussed in the text.
7-34
-------
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7-38
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
concentration at 1,500 mg/L. In addition, Facility F reuses its treated wastewater with
average TOC effluent concentrations of 4,065 mg/L and 1,650 mg/L from the clarification
unit and from the bioreactors, respectively.
Finally, as shown in Figure 7-4, the concentrations of acetone in the reuse
water fall within a wide range. The bar graph uses a logarithmic scale in order to present all
the data in one figure. The concentrations range from 50 jug/L to 9,000 jig/L. Facility B uses
ultrafiltration followed by activated carbon and is able to reuse their wastewater witii acetone
concentrations of 65,600,000 /*g/L: Acetone was not detected in the reuse water at Facility F.
In summary, EPA believes that treatment systems at PFPR facilities are able to
reduce the concentrations of pollutants in PFPR wastewaters to reusable levels. For the PAIs,
these reusable levels are typically in the same range as the achievable effluent concentrations
used for estimating compliance costs for the PFPR facilities (see Section 8 for a more detailed
discussion of achievable effluent concentrations and their relationship to reused waters).
However, as demonstrated by the data in Table 7-10, facilities have still been able to reuse
treated wastewaters even though the PAI concentrations in those waters are high when
compared to LTA concentrations used for costing. Facilities are also able to reuse these
treated wastewaters when the concentration of conventional pollutants and/or COD are not
reduced below detection limits.
7.4
Treatabilitv Studies
As part of the data-gathering effort to support development of this rale, EPA
conducted a number of bench- and pilot-scale studies to evaluate the treatability of pesticide-
containing wastewaters by various treatment technologies. The purpose of these studies was
to expand the treatability information available on various PAIs, to verify the effectiveness of
a given technology on PFPR wastewater matrices, and to evaluate the ability of some
technologies to create reusable effluent streams.
This section describes four types of treatability studies conducted by EPA.
Section 7.4.1 discusses the results of the emulsion breaking study that evaluated the
effectiveness of heat and acidification. Section 7.4.2 presents the results of the UTS studies
mat evaluated activated carbon adsorption, hydrolysis, emulsion breaking via heat and
acidification, chemical assisted clarification, chemical oxidation, and settling. Section 7.4.3
discusses the results of a pyrethrin treatability study that evaluated hydrolysis and activated
carbon treatment technologies. Section 7.4.4 discusses the results of membrane separation
studies that evaluated five separate membrane systems.
7.4.1
Emulsion Breaking Study
Pesticide products often contain emulsifiers and surfactants, which are used to
keep PAIs in solution, suspension, or emulsion when the products are mixed with water for
application. When water is used in cleaning operations at PFPR facilities, the resultant
wastewater may contain emulsified PAIs due to the presence of these emulsifiers and
7-39
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
surfactants. Therefore, EPA conducted a study to assess the effectiveness of heating and
acidification in breaking the emulsions prior to additional treatment steps to remove or destroy
PAIs. The results of this study are described in detail hi the report entitled Emulsion
Breaking Performance Study (5).
During the emulsion breaking study, off-the-shelf pesticide products were added
to tap water to simulate equipment interior cleaning rinsates. In the first test, 2-liter screening
tests (2-liter refers to the sample volume) were conducted to evaluate whether these products
would form emulsions in water and whether acid and heat would be effective in breaking the
resultant emulsions. Based on the screening test results, larger-scale tests (15-liter batch tests)
were conducted to collect sufficient sample volume for more complete analysis. A third test
was conducted on one of the products used hi the 15-liter batch test to study the effect of
detergents used hi cleaning operations on emulsion breaking performance.
Seventeen off-the-shelf pesticide products were selected for use in the 2-liter
screening tests. These products involved three product types (herbicides, insecticides, and
fungicides), four formulation types (emulsifiable concentrates, flowable concentrates, soluble
concentrates, and solutions), 25 different PAIs, and PAI concentrations of <1 to 97% hi the
products.
During the 2-liter screening tests, the wastewater was analyzed for turbidity to
assess the effectiveness of the emulsion breaking step. These tests demonstrated that, by
applying heat and adding acid, the turbidity of most of the simulated wastewater streams was
reduced. Twelve of the 17 tested pesticide products showed reduced wastewater turbidity
after the addition of heat and acid, with turbidity reductions ranging from 15 to >99 percent.
Two of the simulated wastewaters did not appear to form emulsions when the pesticide
products were added to water. Only one of the simulated wastewater streams with a turbidity
of >100 nephelometric turbidity units (NTUs) did not show a decrease hi turbidity after heat
and acid were added.
Six of the pesticide products determined to show the most reduction hi turbidity
during the 2-liter screening tests were selected for the 15-liter batch tests. Samples of the
feed (after the pesticide product was added to water) and treated effluent (the aqueous phase
after heat and acid addition) were analyzed for HEM, TDS, TOC, TSS, and turbidity. The
results of the 15-liter batch tests confirmed that heat and acid addition is an effective tool for
breaking wastewater emulsions and clarifying the aqueous phase. Consistent, significant
removals of HEM (44 to 99.9% reduction) and turbidity (54 to 96% reduction) were measured
during the 15-liter batch tests. In the two tests where TSS was present in the feed at a
concentration greater than the detection limit, it was effectively removed from the treated
effluent (68% and 89% reductions). TOC reductions ranged significantly from <1 to 99
percent. TDS reductions also varied; the concentration increased during two of the tests, most
likely due to the addition of sulfuric acid to reduce the pH of the simulated wastewater
streams.
7-40
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
In the third test of the study, one of the pesticide products, which is 97%
petroleum oil, was used to evaluate the effect of detergents used in cleaning operations on
emulsion breaking performance. During this test, a small amount of liquid detergent was
added to the tap water along with the pesticide product, and the 15-liter batch test was
repeated. The addition of detergent did degrade emulsion breaking performance, but the
reductions of HEM (98%), TDS (86%), and turbidity (87%) were still very high. The TOC
concentration, however, increased by 122% after heat and acid addition during the detergent
test.
7.4.2
Universal Treatment System Treatability Studies
Concept of the UTS
PFPR facilities often generate wastewater on multiple production lines.
Because the wastewater volumes are usually small, however, it is not practical to operate
dedicated wastewater treatment systems for individual lines. Recognizing this, EPA believes
that a centralized wastewater treatment system is more appropriate, and has conceptualized a
single BAT treatment system for PFPR facilities that the Agency is terming the Universal
Treatment System (UTS). As envisioned by EPA, the UTS would be sized to handle small
volumes of wastewater on a batch basis and would combine the most commonly used and
effective treatment technologies for PAIs (hydrolysis, chemical oxidation, activated carbon,
and sulfide precipitation (for metals)) with one or more pretreatment steps, such as emulsion
breaking, solids settling, and filtration. Each of the these treatment technologies is discussed
in more detail in Section 7.2. The BAT performance of the PAI treatment technologies is
well demonstrated and they serve as the full or partial basis for most of the pesticide
manufacturing PAI limitations4. EPA believes that the UTS, relying on these treatment
technologies, can provide treated effluent suitable for reuse in PFPR operations or as a P2
allowable discharge with respect to all PAIs (see Section 7.3.2 for discussion on pollutant
concentrations in reuse water).
Treatment systems similar to the UTS are in operation at PFPR facilities that
currently reuse treated wastewater. These facilities use activated carbon as the primary
treatment step, usually following solids settling or filtration pretreatment steps, and achieve
between 98% and 99% removal of the PAIs in most cases (see Section 7.3.1 for treatment
performance data achieved by such systems).
The Agency has developed a PAI treatability dataset, based on full-scale
treatment system data, treatability study information, and data transfers, that show that all of
the PAIs considered under this rulemaking, with the exception of 44 PAIs that are difficult to
treat, are amenable to one or more of the UTS treatment technologies. The treatability dataset
and the transfer of treatability data are discussed in Section 7.5. For some PAIs, a different
Sulfide precipitation (for metals removal) is not the basis of the recently proposed pesticide manufacturing
limitations because EPA deferred setting limitations, beyond BPT, for the organo-metallic subcategory (40 CFR
455, Subpart B).
7-41
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
treatment technology, such as resin adsorption or solvent .extraction, may have served as the
basis for the pesticide manufacturing limitation because it was in use at a given facility and
judged to represent BAT performance based on monitoring data. In some cases, the use of
these types of technologies, rather than the UTS, might be more appropriate at a PFPR facility
if the facility is only handling a PAI that requires that technology. However, the wastewater
matrix at a PFPR facility may be more complex than pesticide manufacturing wastewater
containing the same PAI; therefore, the treatment technologies identified as BAT for the
pesticide manufacturing limitations may not achieve the same levels of PAI removal without
pretreatment to remove emulsifiers/surfactants. In addition, for most PFPR facilities, the
commingled wastewater will contain multiple PAIs. EPA finds that all of these PAIs will be
amenable to the more common UTS treatment technologies for purposes of reducing the PAIs
and other pollutants to concentrations that would allow recycle or reuse at the facility, or
would qualify as a P2 allowable discharge following implementation of P2 practices.
Furthermore, a treatment system relying on a technology such as solvent extraction to remove
a PAI would still require activated carbon polishing to adsorb other wastewater constituents,
including residual extraction solvent, before the treated wastewater could be reused. Rather
than attempting to integrate these other technologies into a centralized wastewater treatment
scheme, EPA believes that the UTS offers a more consistent, simple, and cost-effective design
and represents the best available technology at PFPR facilities.
Final effluent from the UTS is expected to be suitable for reuse as general
pesticide production area cleanup water or discharge under the P2 alternative. Based on the
PAI treatability dataset and information from PFPR facilities that treat and reuse pesticide
process wastewater, the Agency believes that the UTS is applicable to, and cost-effective for,
all PFPR facilities. Therefore, EPA is basing the compliance cost estimates for the treatment
portion of the Zero/P2 Alternative option on the UTS (although facilities may choose
equivalent technologies if they so desire). Accordingly, the best available technology (BAT)
identified by EPA for the purpose of setting pretreatment standards for existing sources
(PSES) consists of either recycle/reuse practices, preceded by treatment with the UTS where
necessary, or the alternative standard of P2 practices, with treatment through the UTS
followed by discharge where allowed and when conditions are met. Application of this BAT
will enable all PFPR facilities to achieve the requirements contained in the final rule.
UTS bench- and pilot-scale studies were conducted to provide data on the
feasibility of merging the UTS unit operations into one system and was evaluated by testing
both synthetic (or clean water) and actual PFPR wastewaters.
UTS Pilot-Scale Testing
In one pilot-scale study, three technologies (emulsion breaking via heat and
acidification, alkaline hydrolysis, and activated carbon adsorption) were evaluated to
determine their effectiveness in treating wastewaters from PFPR facilities. These technologies
were selected to represent the UTS used to model compliance costs for PFPR facilities (see
Final Pesticides Formulators. Packagers, and Repackagers Cost and Loadings Report and the
7-42
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Addendum to the Final Pesticides Formulators. Packagers, and Repackagers Cost and
Loadings Report for more detail on the development of compliance costs) (6,7).
In this study, three tests were conducted using wastewaters collected from three
PFPR facilities to assess whether the UTS that formed the basis for proposed facility
compliance costs estimates would effectively treat actual PFPR wastewaters (see Pilot-Scale
Tests of the Universal Treatment System for the Pesticide Formulating. Packaging, and
Repackaging Industry) (8). The three facilities are referred to as Facilities A, B, and C, and
were selected because they generated wastewaters with characteristics that would make the
wastewaters difficult to treat. Facility A was selected because it generated a wastewater that
contained a variety of PAIs and surfactants. Facility B was selected because it generated a
wastewater that contained a high total organic carbon content. Facility C was selected
because it generated a wastewater that contained a variety of PAIs. In addition, the
wastewater from Facility C supported biological growth.
Each of the three tests involved a bench-scale pretest to determine whether that
particular wastewater was amenable to emulsion breaking via heat and acidification. In one
test, the emulsion breaking pretest also evaluated the effectiveness of alkaline conditions.
Based on the pretest results, two of the wastewaters were subjected to a pilot-scale emulsion
breaking step. The third wastewater was effectively pretreated using only a settling step,
making emulsion breaking unnecessary. All wastewaters were then subjected to alkaline
hydrolysis, followed by activated carbon treatment. Raw wastewaters and treated effluents
were analyzed for PAIs, classical wet chemistry parameters, volatile and semivolatile organic
compounds, and metals. Pollutant reductions were calculated across each treatment step and
across the entire system. Pretreatment steps were shown to be effective in all of the UTS
tests. PAI results were used to develop hydrolysis half-lives for 11 PAIs analyzed. The
concentrations of nine PAIs were reduced by 90% or more during the activated carbon
treatment step. Another two PAIs were reduced hi concentration by about 50 percent. The
pilot-scale UTS also reduced most of the classical wet chemistry parameters, except for TDS.
The tests conducted with the wastewater from these three PFPR facilities are
described in more detail below.
Facility A Treatability Test
Five separate types of wastewater were collected from Facility A: interior
equipment rinsates from the formulation of four different products, and floor wash water from
a mechanical floor scrubber. The wastewaters from Facility A contained 11 PAIs, and were
tested using a treatment train of emulsion breaking via heat and acidification, alkaline
hydrolysis, and activated carbon adsorption.
During the bench-scale emulsion breaking pretest, phase separation occurred
only in an aliquot of the floor wash water, and yielded a darker, settled sludge layer and a
lighter supernatant phase. Based on these results, pilot-scale emulsion breaking was
conducted only on the floor wash water. Following pilot-scale emulsion breaking of the floor
7-43
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
wash water, the supernatant was commingled with the four interior equipment rinsates and fed
to the hydrolysis treatment step.
The overall UTS performance results for the PAIs were somewhat mixed.
Some of the PAIs (allethrin, Umonene, piperonyl butoxide, and pyrethrin II) were effectively
reduced to low or detection-limit concentrations during hydrolysis. At the 60-liter sample
point during the activated carbon test, most of the other PAIs were reduced to concentrations
, less than their detection limits. However, the cis- and trans-permethrin concentrations were
only moderately reduced during UTS treatment. These results are somewhat surprising since
these PAIs were effectively treated by a combination of hydrolysis and activated carbon
during previous UTS testing (described below). The methoprene analyses showed moderate
removals (40 to 60%) during hydrolysis; however, the activated carbon data were difficult to
evaluate due to fluctuating concentrations, leading to inconclusive results for this PAL
The COD, HEM, and TOC concentrations were reduced during UTS treatment,
with percent removals ranging from about 40 to 60 percent. The activated carbon step
reduced the TSS parameters to a very low effluent concentration, 34.0 mg/L; however, the
overall TSS percent removal from initial feed to final effluent was 5.60 percent. TDS was
the only significant classical wet chemistry parameter to increase in concentration during the
UTS test. This increase was probably due to the pH adjustment steps, which can form salts in
the wastewater. Table 7-11 presents the analytical results for PAIs and classical wet
chemistry parameters for UTS treatability testing of Facility A wastewater. The percent
removals for the PAIs are based on the average influent concentration and the 60-liter sample
results. Percent removals for the other constituents are calculated using the influent and 240-
liter samples.
Facility B Treatability Test
An interior equipment rinsate sample containing one PAI (tetrachlorvinphos)
was collected from Facility B. No phase separation occurred during the emulsion-breaking
pretest on an aliquot of this wastewater; therefore, the pilot-scale emulsion breaking step was
not conducted. However, because the wastewater contained visible suspended solids, the
wastewater was allowed to settle without adjusting the pH or temperature. The supernatant,
which was 92% of the original wastewater volume after settling, was fed to the hydrolysis
unit. Based on the aqueous samples collected before and after settling, the PAI did not
partition to the sludge layer. However, no sludge sample was collected to confirm this
observation.
Hydrolysis effectively reduced the concentration of tetrachlorvinphos from an
initial concentration of 1,500 /zg/L to O.25 /ig/L (the detection limit). The overall percent
removal for this PAI was >99.9 percent based on the 240-liter sample (0.71
7-44
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-11
Facility A Overall UTS Performance Results
Analyte Name
Influent to
Hydrolysis
Influent to
Activated
Carbon
60-Liter
Carbon
Sample
240-Liter
Carbon
Sample
Percent
Removal*
Pesticide Active Ingredients (g/L)
Allethrin
Cyfluthrin
Fenvalerate
Limonene
Linalool
Methoprene
cis-Permethrin
trans-Permethrin
Piperonyl butoxide
Pyrethrin I
Pyrethrinll
Resmethrin
Sumithrin
Tetramethrin
3,470
123
<5
73.0
5,250
1,740
92,700
20,200
41.0
428
92.0
<15
<15
<15
<15
307
214
10.5
946
917
110,000
26,200
20.9
1,040
<5
<15
<15
1,070
<15
<15
<5
<100
<100
1,420
49,600
12,300
<100
82.0
<5
<15
<15
<15
<15
394
<5
6.60
498
543
62,400
14,900
<5
17.3
<5
<15
<15
782
>99.6
>87.8
NC
NC
>98.1
18.2
46.5
39.0
NC
80.8
>94.6
NC
NC
NC
Classical Wet Chemistry (mg/L)
Ammonia-Nitrogen
Biochemical Oxygen Demand
Chemical Oxygen Demand
Cyanide, Total
Fluoride
Hexane Extractable Material
Nitrate-Nitrogen
Nitrite-Nitrogen
pH
Total Dissolved Solids
8.80
>1,320
19,000
19.0
1.30
106
1.40
0.10
5.90
2,580
101
>1,320
10,700
51.0
1.20
48.0
1.30
0.30
11.4
2,830
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.20
>1,310
10,500
96.0
1.20
41.0
1.30
0.40
7.40
2,950
86.3
NC
44.6
NC
7.7
61.1
3.7
NC
NC
NC
7-45
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-11 (Continued)
•^s
Analyte Nam.4
Total Organic Carbon
Total Suspended Solids
Influent to
i Hydrolysis
5,200
36.0
Influent to
Activated
Carbon
2,120
198
60-LItfir
Carbon
Sample
NA
NA
240-liter
Carbon
Sample
2,180
34.0
J?er
-------
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
The Facility B wastewater contained high concentrations of BOD5, COD, TOC,
TDS, and TSS. The BOD5 concentration increased during the UTS test. This increase is
apparently due to the removal of the PAI, which appeared to inhibit biodegradation of the
other wastewater constituents. Once the PAI was hydrolyzed, the BOD5 concentration
increased from <1 mg/L to 44,600 mg/L. The COD and TOC concentrations remained
relatively unchanged during the UTS test, whereas the HEM concentration was reduced to less
than the detection limit. Changes in the TDS and TSS concentrations during the test appear
to be related to the pH level. The TDS concentration decreased as the pH was increased and
increased as the pH was decreased. The pH changes had the opposite effect on the TSS
concentration. Apparently, the wastewater pH affected the solubility of certain constituents,
causing them to either solubilize (TDS) or precipitate (TSS). Table 7-12 presents the
analytical results for PAIs and classical wet chemistry parameters for UTS treatability testing
of Facility B wastewater.
Facility C Treatabffity Test
Commingled interior and exterior equipment rinsates and floor wash water were
collected for treatability testing from Facility C. These wastewaters were commingled at the
facility prior to collection and contained five PAIs: ametryn, atrazine, cyanazine, metolachlor,
and pendimethalin. These wastewaters also supported biological growth.
During the bench-scale emulsion-breaking pretest, heat and acidification
provided the best emulsion breaking performance. Based on the results of the pretest, the
wastewater was subjected to pilot-scale emulsion breaking using heat and acidification, and a
gray flocculent formed in the wastewater. The pilot-scale emulsion breaking resulted in a
translucent yellow supernatant and a grayish sludge layer. The supernatant, which was 93%
of the original wastewater volume, was used as the influent to the hydrolysis treatment step.
The cyanazine and pendimethalin concentrations were reduced during the emulsion breaking
step, while the other PAIs were not significantly affected.
The UTS effectively reduced all of the PAIs to low or detection-limit
concentrations, with removals ranging from >99.5 to >99.9 percent. The presence of
biological growth did not appear to hinder PAI removals. Carbon breakthrough did not occur
for atrazine, cyanazine, or pendimethalin. Carbon breakthrough apparently began to occur for
ametryn and metolachlor between the 120- and 200-liter samples. However, the ametryn and
metolachlor concentrations were still low in the 200-liter sample, at 221 jtg/L and 21.6 jtg/L,
respectively.
Except for TDS, the classical wet chemistry parameters were reduced to
relatively low concentrations by the UTS. The TDS concentration increased, probably
resulting from the acid and base additions to adjust the pH. Acid and base addition can cause
salt formation in the wastewater, thereby increasing TDS measurements. Table 7-13 presents
the analytical results for PAIs and classical wet chemistry parameters for UTS treatability
testing of Facility C wastewater.
7-47
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-12
Facility B Overall UTS Performance Results
s •» ^ #
Analyte Name
Influent
Sample
Settling
Supernatant
Sample
24-Hour
Sample
240-liter
Sample
Percent
Removal'1
Pesticide Active Ingredients (g/L)
TetracHorvinphos
1,200
1,500
O.25
0.71
99.9
Classical Wet Chemistry (mg/L)
Ammonia-Nitrogen
Biochemical Oxygen Demand
Chemical Oxygen Demand
Cyanide, Total
Fluoride
Nitrate-Nitrogen
Nitrite-Nitrogen
Hexane Extractable Material
pH
Total Dissolved Solids
Total Organic Carbon
Total Suspended Solids
85.0
<1
70,700
69.0
5.60
21.5
4.10
40.0
7.57
109,000
24,200
4,940
81.0
<1
80,600
<50
0.1
28.0
4.10
22.0
5.55
86,400
24,400
2,940
91.0
<1
66,600
63.0
1.30
34.0
4.80
15.0
10.8
41,100
22,400
39,500
93.0
44,600
66,000
113
1.70
20.0
1.08
<5
7.25
189,000
19,900
880
NC
NC
6.65
NC
69.6
6.98
73.7
>87.5
—
NC
17.8
82.2
Percent removals were calculated using the 240-liter sample for all constituents.
NC - Not calculated.
7-48
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-13
Facility C Overall UTS Performance Results
Aaalyte J^ame
Influent
Sample
Emulsion
Breaking
Effluent Sample
24-Hour
Sample
120-Liter
Sample
200-Liter
Sample
Percent
Removal*
Pesticide Active Ingredients (mg/L)
Ametryn
Atrazine
Cyanazine
Ethalfluralin
MetolacMor
Pendimethalin
253,000
16,500
3,750
<10
15,700
110
318,000
22,900
714
<10
20,400
49.0
531,000
8,410
<2
<10
14,700
45.0
12.9
<10
<2
<0.1
1.26
<0.5
221
<10
<2
<0.1
21.6
<0.5
>99.9
>99.9
>99.9
NC
>99.8
>99.5
Qassical Wet Chemistry (mg/L)
Ammonia-Nitrogen
Biochemical Oxygen
Demand
Chemical Oxygen Demand
Cyanide, Total
Fluoride
Nitrate-Nitrogen
Nitrite-Nitrogen
Hexane Extractable
Material
pH
Total Dissolved Solids
Total Organic Carbon
Total Suspended Solids
32.5
<108
3,190
10
1.65
1.73
0.065
<16.5
7.18
1,880
534
334
26.0
<35
1,700
<10
1.30
0.38
0.02
56.0
1.91
3,740
534
6.00
18.0
45.0
1,380
<10
0.54
0.25
0.02
44.0
12.3
5,230
439
303
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
20.0
31.0
204
<10
0.64
1.70
<0.01
<5
7.75
6,470
63.0
<4
38.5
NC
93.6
NC
61.2
1.45
>84.6
NC
—
NC
88.2
>98.8
Percent removals were calculated using the 200-liter sample for all constituents.
NC - Not calculated.
NA - Not available.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Previous UTS Testing
EPA also conducted, a bench-scale and two pilot-scale tests of treatment trains
similar to the UTS prior to the three UTS tests described above. The bench-scale test was
conducted on synthetic wastewater, and the pilot-scale tests were conducted on wastewater
from two PFPR facilities (Facilities D and E). These tests were conducted before the
development of final PFPR industry compliance costs, and, in some cases, used technologies
different from those used to base the cost estimates. For example, one test (Facility D) used
chemically assisted clarification instead of heat and acidification as the emulsion breaking
technology.
In the bench-scale test, four PAIs were spiked into clean water to make a
synthetic wastewater for initial testing to determine if the UTS effectively removes PAIs. The
four PAIs were bromacil, tebuthiuron, propoxur, and diuron. These PAIs were selected based
on the PAIs that were expected to be present in actual facility wastewaters that were to be
collected for UTS treatability testing. The synthetic wastewaters were treated using the
following steps: hydrolysis, chemical oxidation via ozone/ultraviolet light oxidation, and
activated carbon adsorption. Emulsion breaking was not performed on these synthetic
wastewaters because they consisted only of PAIs and water and, therefore, did not contain
emulsions.
In the first pilot-scale test, actual PFPR facility wastewater (from Facility D)
was tested and analyzed for five PAIs: benthiocarb, bromacil, diuron, tebuthiuron, and
terbufos. The purpose of this test was to determine if the UTS effectively removes PAIs and
other organic pollutants present in actual PFPR wastewaters (i.e., those with potential matrix
interference problems). The wastewater was treated using the following steps: emulsion
breaking by coagulation, pH adjustment, flocculation and settling, hydrolysis, chemical
oxidation via ozone/ultraviolet light oxidation, and activated carbon adsorption. In addition,
as a separate aspect of the evaluation, the adsorption properties of these five PAIs were
determined using accelerated column tests (ACT) (ACT results are used to estimate full-scale
carbon system performance, design, and costs).
The second pilot-scale test that evaluated UTS technologies was conducted on
actual PFPR facility wastewaters (from Facility E) containing both allethrin and permethrin.
These wastewaters were treated using emulsion breaking, hydrolysis, and activated carbon
adsorption. Based on results from the previously conducted pyrethrin wastewater treatability
study (8), EPA assumed that the pyrethrins were amenable to hydrolysis treatment and,
therefore, did not require the chemical oxidation step of the treatment train.
The treated effluents from each of these tests were analyzed for PAIs, volatile
and semivolatile organics, and other wastewater parameters such as TOC, oil and grease, and
turbidity. These test results are described briefly below.
Pilot-scale test results using the PFPR wastewater collected at Facility D
indicate that the concentrations of the target PAIs (bromacil, tebuthiuron, diuron, terbufos, and
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
benthiocarb) can be reduced to less than their analytical detection limit (>99.99% removal) by
chemically assisted clarification (i.e., emulsion breaking), ozone/UV light oxidation, and
activated carbon adsorption. Chemically assisted clarification, using ferric chloride and a
polyelectrolyte, removed turbidity, a major portion of the oil and grease, and some TOC.
Bench-test data show that the PAIs were oxidized using a continuous ozone dosage of
76 mg/L/minute at a UV intensity of 3 W/L. The overall TOC, COD, oil and grease, and
TSS removals achieved for Facility D were 36.2%, 30.5%, >99.5%, and 99.2%, respectively.
Oxidation converted a portion of the soluble organics in the Facility D
wastewater into insoluble precipitates that required a second chemically assisted clarification
step prior to carbon adsorption. Results of carbon isotherm tests and a carbon adsorption
column test indicate that oxidation generates short-chained organic acids and alcohols that are
poorly adsorbed on carbon. This results in a TOC concentration of 6,000 mg/L in the final
effluent.
Pilot-scale test results for the PFPR wastewater collected at Facility E indicate
that chemically assisted clarification using ferric chloride 'and a polyelectrolyte removes most
of the allethrin and permethrin, oil and grease, and turbidity. Alkaline hydrolysis at a pH of
12 and 60°C followed by carbon adsorption decreased the concentrations of allethrin and
permethrin to less than their analytical detection limit (>99.99% removal). Carbon adsorption
effluents contained approximately 800 mg/L of TOC, of which nearly 60% was derived from
isopropyl alcohol. Isopropyl alcohol is a solvent used to clean equipment in the PFPR
facility. The overall TOC, COD, oil and grease, and TSS removals achieved for Facility E
were 84.8%, 79.1%, 98.0%, and 83.2%, respectively.
Detailed results of this treatability test can be found in a report entitled
Evaluation of the Universal Treatment System for Treatment of Pesticide Formulator/Packager
Wastewater (9).
7.4.3
Hydrolysis and Activated Carbon Tests
EPA conducted bench-scale treatability testing of the effectiveness of hydrolysis
under both the pesticide manufacturing and the PFPR effluent guidelines programs. Under the
pesticide manufacturing effluent guidelines program, synthetic wastewaters were prepared by
spiking PAIs into clean water to simulate pesticide wastewaters (10). This method of
preparing synthetic wastewaters simulates interior equipment cleaning rinsates in both the
PFPR and pesticide manufacturing industries. EPA also evaluated the effectiveness of
hydrolysis in treating actual pesticide manufacturing wastewaters containing ethion (11).
EPA also conducted bench-scale treatability tests to evaluate the effectiveness
of activated carbon adsorption on pesticide-containing wastewater. Under the pesticide
manufacturing effluent guidelines program, carbon isotherm tests were conducted on 29 PAIs
that were spilled into clean water (12). In addition, EPA conducted ACT tests on wastewaters
generated from the production of atrazine, Vapam®, chlorothalanil, and diazinon (13).
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Under the PFPR effluent guidelines development, the Agency investigated the
treatability of combined pyrethrin (the sum of pyrethrin I and pyrethrin II) in wastewater
through hydrolysis and activated carbon adsorption bench-scale testing. Pyrelhrin-containing
wastewater from a pesticide manufacturing facility was used for the bench-scale tests. A full
description of the tests and results can be found in a report entitled Pvrethrm Wastewater
Treatabilitv Study Report (14).
The effectiveness of hydrolysis treatment on pyrethrin-containing wastewater
was evaluated through bench-scale testing under two hydrolysis conditions; alkaline (pH 12)
and acidic (pH 2). Both tests were conducted at a temperature of 60°C. The test results
showed that, at an elevated temperature (60°C), pyrethrin hydrolyzes more rapidly under
alkaline conditions, with a calculated half-life value of 1.2 hours at a pH of 12. Under the
acidic conditions, the calculated half-life was 77 hours at a pH of 2. .
EPA also conducted tests on the pyrethrin-containing wastewater to determine
the effectiveness of pyrethrin removal through carbon treatment. Six different carbon dosages
were tested to develop a carbon isotherm for pyrethrin. The tests showed that the treatment
of pyrethrin-containing wastewaters with activated carbon requires high carbon dosage rates; a
5,000 mg/L carbon dosage reduced the combined pyrethrin from 100 mg/L to less than
1.0 mg/L. This means that, with a 10-gallon-per-minute flow rate, the carbon column would
have a service life of 11.4 days for combined pyrethrins at a 110 mg/L initial concentration
(the highest combined pyrethrin concentration found in untreated wastewater during the
study). Therefore, pyrethrins are adsorbed by the activated carbon column. The test results
show, however, that the more practical treatment technology (first step) for treating pyrethrin-
containing wastewaters is hydrolysis.
7.4.4
Membrane- Separation
Synthetic Wastewater Study
During development of the pesticide manufacturing rule, the Agency conducted
a pilot-scale treatability study to determine the effectiveness of membrane systems to remove
PAIs from wastewater. The study evaluated seven different types of reverse osmosis (RO)
membranes using two synthetic feed solutions containing 19 different PAIs. The study
concluded that the best overall performance was obtained with a thin film composite
membrane. The test results are summarized in a July 1991 report entitled Membrane
Filtration Treatabilitv Study (15).
During development of the PFPR rule, EPA conducted four more studies of
membrane systems conducted on actual PFPR wastewaters: RO study, RO with pretreatment
study, and two ultrafiltration (UF)/RO studies.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
RO Study
EPA conducted a follow-up study to evaluate RO treatment using actual
wastewater generated by a PFPR facility. This study used a pilot-scale RO module to
determine if membrane separation technology could be used to create a high-quality water
stream (permeate) suitable for reuse from raw PFPR wastewater. The study measured
removals for nine PAIs. Although the technology produced a "clean" permeate stream, there
were membrane fouling problems. The results of this test suggested that pretreatment
technologies should be evaluated to reduce suspended solids and oil and grease5 in PFPR
wastewaters to a concentration acceptable for long-term RO membrane operation. The test
results are presented in a report entitled Membrane Separation Study for the Pesticide
Formulator Packager Project (16).
RO with Pretreatment Study
The Agency conducted a third RO membrane pilot-scale treatability study using
actual wastewater from two PFPR facilities (referred to as Site A and Site B). During this
test, EPA evaluated the effectiveness of a pretreatment step designed to reduce fouling of the
RO membrane. Two pretreatment systems were tested: UF and chemical precipitation. One
set of tests (one run for Site A and one for Site B) consisted of UF followed by RO, while
the other set consisted of chemical precipitation jar tests followed by RO. The wastewaters
from Site A contained the following PAIs: 2,4-D, dicamba, MCPP, and prometon. The
wastewaters from Site B contained benthiocarb, bromacil, diuron, tebuthiuron, and terbufos.
As mentioned above, wastewaters from Sites A and B were run separately
through the UF/RO setup. Two separate systems were used for the ultrafiltration and reverse
osmosis tests. The pilot-scale systems were designed to use commercially available
ultrafiltration and reverse osmosis equipment, while keeping the size of the systems as small
as possible. This design approach was selected to provide results representative of a full-scale
system, while minimizing the amount of wastewater that had to be collected, shipped, and
ultimately disposed. The UF membrane used for the pilot-scale test was a tubular-type
system, which resists fouling better than either spiral-wound or hollow-fiber types. The RO
module was a spiral-wound configuration, thin-film composite membrane.
The results of the UF/RO study show this treatment sequence was effective in
removing the nine PAIs present in the wastewaters tested. In addition to high PAI removal,
UF pretreatment prevented rapid fouling of the RO membrane. Table 7-14 summarizes the
study results for Sites A and B.
5During the development of the final PFPR rule, the EPA-approved test method for analysis of oil and grease
was changed from Method 413.1 to Method 1664. As mentioned in Section 7.3.1, results using Method 413.1
are presented as "oil and grease"; results using Method 1664 are presented as "hexane extractable material."
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-14
Summary of Results for Membrane (UF/RO) Separation Treatability Study
.' '« - ';
Pollutant "- ;
Total Suspended Solids
Total Organic Carbon
Oil & Grease
Chemical Oxygen Demand
2,4-D
Dicamba
MCPP
Prometon
Bromacil
Benthiocarb
Diuron
Terbufos
Tebuthiuron
Removals : tiy tdtrafittrattoa {%)
Site A
98.2
20.2
59.4
23.9
14.5
6.7
—
30.5
SiteB
99.9
29.8
89.6
32.5
—
88.6
37
99.8
49.1
Removals Tt>y Reverse Osmosis (%)
Site A
—
95.2
>98.1
96.1
99.4
99.5
—
99.5
SifeB J
—
97.1
>94.7
97.5
98.2
98.0
98.5
96.3
99.2
Note: Removals for MCPP and TSS (for RO only) could not be calculated because the feed concentrations were
below the analytical detection limits for these pollutants parameters. Removal by TIP could not be calculated for
bromacil because the permeate concentration was greater than the feed concentration.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
The UF/RO treatment sequence achieved better than 96% removal of all but
one (MCPP) of the nine PAIs. The removal for MCPP could not be calculated because the
concentration in the feed was below the analytical detection limit. Data for bromacil indicate
that, overall, it was reduced by 98.2%; however, this percent removal may misrepresent the
treatment performance because there is some indication that the measurement of bromacil in
the untreated wastewater was affected by analytical interference. The system also achieved
high removals of TSS and oil and grease. Removals for TSS through the RO unit could not
be calculated because the UF unit reduced the TSS, for both Sites A and B, below the
analytical detection limit. The average removal of TSS achieved by the UF unit was
approximately 99 percent. The UF/RO system achieved an average oil and grease removal of
>96.4 percent.
The UF/RO treatment sequence appears to be a very effective alternative to the
UTS (at least for high molecular weight PAIs) to achieve a treated water that can be reused in
the facility. Removals of total dissolved solids (TDS) ranged from 86% to >91 percent. It is
less clear whether the concentrated waste created by either of these treatment steps can be
recovered for its product value. The samples taken from the concentrate fraction show high
concentrations of the PAIs; however, there are also high concentrations of sodium, calcium,
and total dissolved solids, which could prevent the recovery of these wastes.
As an alternative to UF, EPA tested chemical separation as the pretreatment
step to the RO module. A series of jar tests was conducted to evaluate different coagulants
and to establish an optimum dosage. Coagulants that were evaluated included alum, lime, and
ferric chloride. Polymer additions were also evaluated as a means of improving the effluent
quality. The results showed that UF was the more effective pretreatment step for removing
oil and grease. The oil and grease removal by chemical separation was 37.6%, compared to
59.4% by UF. However, the removal of TSS was high for both chemical separation (96.4%)
and UF (98.2%). In addition, chemical separation was slightly more effective than UF hi
removing most PAIs, with the exception of 2,4-D, for which the removals were comparable.
This difference is most likely due to the fact that UF membranes, due to their high molecular
weight cutoff, are not designed for PAI removal. However, good removals of TSS and oil
and grease can be achieved with UF, making it an attractive pretreatment option.
UF/RO Study
The Agency conducted a fourth membrane treatability study to determine the
efficacy of membrane separation technologies in treating specific wastewater streams from a
PFPR facility. Tests were conducted using a sample of an interior equipment rinsate stream
and a sample of the water from a Department of Transportation (DOT) test bath. These
wastewater samples were treated using a pilot-scale system consisting of a UF membrane
followed in series by an RO membrane. The UF membrane used for the pilot-scale test was a
tubular-type system and the RO module was a spiral-wound configuration, thin-film composite
membrane.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Interior Equipment Rinsate
Both the UF and RO membrane tests of the interior equipment rinsate achieved
the target of 90% product water recovery. The product water, or final permeate stream, from
the UF/RO system was very low in all pollutant concentrations compared to the raw
wastewater fed to the system. Many pollutant constituents and parameters were reduced
below their detection limits in the final system permeate. Table 7-15 summarizes results of
the UF and RO tests conducted on the interior equipment rinsate sample. MGK 264,
piperonyl butoxide, propoxur, pyrethrin I and II, and tetramethrin were detected in the interior
equipment rinsate sample. Removals of >99% were achieved for all of these PAIs (with the
exception of propoxur) by the UF membrane, and 97% removals were achieved for MGK 264
and propoxur by the RO membrane.
Removals of classical wet chemistry parameters during the UF test ranged from
>20% for COD to >99% for HEM. However, the percentages of many of the classical wet
chemistry parameters not accounted for in the mass balances for the UF test were roughly
equivalent to the percent removals. For example, the COD removal was 22.7%, and the mass
balance closure for COD was 77.5% (100 - 77.5 = 22.5%). Therefore, membrane rejection
was not the sole mechanism responsible for the removals of these parameters.
During the RO test, removals of COD, HEM, BOD5, total organic carbon
(TOC), and total dissolved solids (TDS) ranged from >86% to >95 percent. Mass balance
closures for the RO test were close to 100% for some parameters (e.g., COD - 109%) but
ranged significantly for other parameters (BOD5 - 14.3% and HEM - <875%), making it
difficult to assess the removal mechanisms.
DOT Test Bath Water
Both the UF and RO membrane tests of the DOT test bath water achieved the
target of 90% product water recovery. The DOT test bath water was much cleaner than the
interior equipment rinsate, and the UF/RO system was effective in reducing those pollutants
present in the DOT test bath water to very low concentrations in the final system permeate.
Prior to collecting a sample from the DOT bath, the Agency intentionally leaked pesticide into
the DOT bath to simulate a bursting can.
Table 7-16 summarizes 'the results of the UF and RO tests conducted on the
DOT test bath water. MGK 264 and propoxur were the only two PAIs detected in the feed
sample. The UF membrane reduced the MGK 264 concentration by 68%, but the propoxur
concentration in the UF permeate was greater than the feed concentration. The mass balance
closure for MGK 264 was 56%, indicating that membrane rejection was not the only
mechanism responsible for the removal of this PAL The mass balance closure was 545% for
propoxur, most likely due to analytical difficulties. MGK 264 and propoxur removals by the
RO membrane were >70% and >99%, respectively. The mass balance closures ranged from
52% for propoxur to <75% for MGK 264, indicating that membrane rejection was not the
only removal mechanism.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-15
Interior Equipment Rinsate Wastewater Test Results
Parameter
Feed
Concentration
BF,
Membrane
% Removal*
UFMass
Balance1
(%)
RO
Membrane %
Removal*
(i>0%
; Recovery)
RO
Mass
Balance
<%)
OT/RO
Permeate
Concentration
Pesticide Active Ingredients, pgfL
MGK 264
Piperonyl butoxide
Propoxur
PyrethrinI
Pyrethrinll
Tetramethrin
953,000
721,000
154,000
234,000
43,100
127,000
>99.9
>99.9
-
>99.9
>99.9
>99.9
12.3
<15.3
167
<11.4
<56.9
<12.2
96.9
-
98.1
-
-
-
81.4
-
Ill
-
-
-
2.98
<10.00
3,000
<2.50
<2.50
<5.00
Classical Wet Chemistry Parameters, mg/L
Biochemical Oxygen
Demand (BOD5)
Total Suspended Solids
(TSS)
Chemical Oxygen
Demand (COD)
Total Organic Carbon
(TOC)
Total Dissolved Solids
(TDS)
Hexane Extractable
Material (HEM)
2,180
17.0
24,500
6,400
112
139,000
52.1
>76.5
22.7
23.0
-
100.0
44.1
<34.2
77.5
76.3
175
0.3
95.7
-
89.3
89.1
>94.4
>86.8
14.3
-
117
109
<48.9
<875
45.0
<4.00
2,020
538
<10.0
<5.00
lrThe percent removal is calculated on a concentration basis rather than a mass basis. That is, the percent removal reflects the
reduction hi concentration from the feed sample to the permeate sample but does not account for the reduced permeate volume
(<100% recovery). The mass balance calculation does account for the relative feed, permeate, and reject volumes.
Fluoride, pH, ammonia-nitrogen, nitrate-nitrogen, nitrite-nitrogen, and cyanide were detected in very low concentrations compared
to the other classical wet chemistry parameters. Therefore, the analytical results for these parameters are not summarized in this
table.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Table 7-16
DOT Test Bath Water Test Results
Parameter
" ^F«ed- ;"
Concentration
\ ^'
Membrane %
Removal*
UFMass
Balance1
(%)
R0 Membrane
% Removal
(90% Recovery)1
ROMass
Balance2
<*/o)
OT/R0
Permeate
Concentration
Pesticide Active Ingredients, /ig/L
MGK264
Propoxur
21.1
470
68.0
—
56.2
545
>70.4
99.8
<75.2
52.3
<2.00
5.10
Classical Wet Chemistry Parameters, mg/L2
Biochemical Oxygen
Demand
Total Suspended Solids
Chemical Oxygen Demand
Total Organic Carbon
Total Dissolved Solids
Hexane Extractable
Material
84.0
10.0
308
76.0
200
<5.00
—
>60.0
23.4
9.2
8.0
—
134
<197
101
110
103
—
62.1
—
84.3
>85.5
84.5
—
161
—
133
<138
127
—
33.0
<4.00
37.0
<10.0
28.5
<5.00
*The percent removal is calculated on a concentration basis rather than a mass basis. That is, the percent removal reflects the
•reduction in concentration from the feed sample to the permeate sample but does not account for the reduced permeate volume
(<100% recovery). The mass balance calculation does account for the relative feed, permeate, and reject volumes.
Fluoride, pH, ammonia-nitrogen, nitrate-nitrogen, nitrite-nitrogen, and cyanide were detected in very low concentrations compared
to the other classical wet chemistry parameters. Therefore, the analytical results for these parameters are not summarized in this
table.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
The classical wet chemistry parameter concentrations in the feed to the UF
membrane were relatively low. The TSS concentration was reduced to below its detection
limit (>60% removal) in the UF permeate. Removals ranged from 8% to 23% for COD,
TOC, and TDS; the mass balances, which ranged from 100% to 110%, confirmed membrane
rejection as the removal mechanism. The RO membrane achieved removals for BOD5, COD,
TOC, and TDS ranging from 60% to 85 percent. However, the mass balances were generally
>100%, indicating analytical discrepancies between the feed, permeate, and reject samples. A
fully detailed description of the tests and the results can be found in the report entitled Pilot-
Scale Membrane Separation Study (17).
Comparison of Treatability Study Results
In addition to the UF/RO treatability studies, EPA performed wastewater
sampling on one UF/RO system and two microfiltration systems. One of the microfiltration
systems is operated at one of the PFPR facilities whose wastewater was used for a UF/RO
treatability study. In an effort to use the full-scale system as a benchmark for the pilot-scale
system, EPA collected water containing the same PAIs for the treatability test as were present
in the treatment performance sampling episode. The treatment performance data of the pilot-
scale versus full-scale systems are compared in the discussion below.
The UF/RO pilot-scale system performed slightly better than the full-scale
microfiltration/activated carbon system at removing bromacil (98.2% vs. 89.7%) and
tebuthiuron (99.2% vs. 89.1%). However, the full-scale system achieved slightly better
removals of benthiocarb (98.0% vs. 98.4%), diuron (98.5% vs. 99.7%), and terbufos (96.3%
vs. 98.8%). The pilot-scale UF/RO removed oil and grease (>94.7% vs. 26.0%) and TSS
(99.9% vs. 51.0%) better than the full-scale system. As demonstrated by these data, the pilot-
scale UF/RO PAI removals are consistent with removals achieved by the full-scale membrane
separation system.
The performance achieved by the UF/RO system as a whole and UF alone as a
pretreatment step make them very attractive as an alternative treatment system to the more
conventional physical/chemical treatments. In particular, these systems achieve a net decrease
in TDS concentrations, while still demonstrating good removals of PAIs.
7.5
Treatability Database and Treatment Technology Transfers
Section 7.5.1 describes the treatability database constructed by the Agency
during development of the PFPR rule and used to determine the effectiveness of the UTS in
treating each PAI subject to the scope of the rule. The database was also used to provide
PAI-specific information used to estimate costs associated with treatment of PFPR
wastewaters. Treatability data are available from a variety of sources, including bench-scale
treatability studies sponsored by EPA, sampling of wastewater treatment systems at PFPR and
pesticide manufacturing facilities, treatability studies conducted by PFPR and pesticide
manufacturing facilities, treatment technology vendors, and literature searches. However,
treatability data are not available for all of the PAIs covered by the scope of the final PFPR
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
effluent guidelines. Where specific treatability data are unavailable for a PAI, the feasibility
of a treatability data transfer is evaluated, and, where appropriate, treatability data are
transferred to the PAI. The PAIs are divided into structural groups based on similarities in
the basic chemical structures and functional groups of the PAIs. Structural groupings are used
to identify appropriate treatment technologies and to assist in the transfer of treatability data.
Section 7.5.2 describes the treatability data transfer methodology.
Activated carbon adsorption treatability data transfers are based on structural
similarities and an analysis of chemical properties that indicate whether a PAI is amenable to
activated carbon adsorption treatment. Hydrolysis treatability data transfers are based on an
analysis of the chemical structure of the PAIs and the acid strength of the hydrolysis leaving
group, as measured by the negative log of the dissociation constant, pKa, or kinetically
derived relationships based on the Arrhenius equation. Transfers of precipitation treatability
data to organo-metallic PAIs are based on the use of this technology to remove organo-
metallic compounds in the PFPR and pesticide manufacturing industries and the chemical
properties common to organo-metallic PAIs that make these PAIs amenable to precipitation.
PAI treatability data and treatability data transfers are discussed in more detail in the
following reports: Final Pesticides Formulators, Packagers, and Repackagers Treatabilitv
Database Report (2) and Pesticides Formulators, Packagers, and Repackagers Treatabilitv
Database Report Addendum (18).
7.5.1
PFPR Treatability Database
This section describes the sources of PAI treatability data contained in the
PFPR administrative record for the rulemaking and the applicability of these data to the
treatment of PFPR facility wastewater. These sources include:
• Pesticide manufacturing PAI or PAI group BAT limitations development
data;
• EPA treatability study reports;
• EPA sampling episode reports; and
• Industry treatability study reports, literature articles, and other data
sources.
•
In cases where sufficient pretreatment makes PFPR wastewater similar in
treatability to pesticide manufacturing wastewater^ treatment technologies and associated
treatability data (typically obtained from full-scale treatment systems) used to establish the
PAI BAT limitations for the pesticide manufacturing subcategories are considered applicable
to the same PAIs in the PFPR subcategories. Where such full-scale data do not exist, the
determination of a particular technology's application to a particular PAI relies on other
available data. Where full-scale data were not available, the treatability data provided in EPA
treatability study reports, EPA sampling trip reports, and other data sources are analyzed for
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
applicability to the PFPR industry, based on the treatment technology and the conditions and
effectiveness of the treatment.
Hydrolysis is considered an effective treatment technique for a specific PAI if
treatability data are available for that PAI demonstrating, at a temperature of 60°C or less and
a pH of 12 or less, half-lives of <720 minutes (12 hours) or a removal of 90% or greater.
Hydrolysis treatability data demonstrating a half-life of >720 minutes (12 hours) at a
temperature of 60°C and a pH of 12 are considered ineffective in treating the PAI. No
conclusion is drawn about the effectiveness of hydrolysis where treatability data show
ineffective treatment at a temperature of <60°C or a pH of less than 12, effective treatment at
temperatures >60°C or a pH greater than 12, or <90% removal. The conditions of 60°C and
pH of 12 were chosen because they were the optimum EPA treatability study conditions for
many of the PAIs tested, and they correspond with the operating conditions used by a number
of full-scale hydrolysis treatment systems at pesticide manufacturing facilities. Because
hydrolysis rates generally increase with temperature and pH (for basic solutions), it is assumed
that, when hydrolysis is shown to be effective at conditions <60°C and a pH of between 7 and
12, it will also be effective at 60°C and a pH of 12. Although hydrolysis may be effective
for some PAIs at low pH (e.g., Polyphase), most PAIs hydrolyze more rapidly at high pH. In
cases where a PAI hydrolyzes at low pH, the hydrolysis may occur during the emulsion
breaking step of the UTS, which occurs at low pH and high temperature.
Activated carbon is considered an effective PAI treatment technique if
treatability data are available that show any carbon saturation loading or a PAI removal of
90% or greater. The availability of PAI-specific saturation loading data shows that it is
possible to remove the PAI from PFPR wastewaters using activated carbon, although, for
some PAIs, a large quantity of carbon may be required. No conclusion is drawn about the
effectiveness of activated carbon adsorption where treatability data demonstrate a PAI removal
of <90 percent.
Chemical oxidation is considered an effective treatment technique for a specific
PAI if treatability data are available demonstrating a PAI removal of >90 percent. No
conclusion is drawn about the effectiveness of chemical oxidation where treatability data
demonstrate a PAI or PAI group removal of less than 90 percent.
Chemical precipitation is considered an effective treatment technique for a
specific PAI if treatability data are available demonstrating a PAI removal of >90 percent.
No conclusion is drawn about the effectiveness of chemical precipitation treatability data
demonstrating a PAI or PAI group removal of <90 percent.
Due to the large number of PAIs subject to the scope of the final PFPR rule,
treatability data from actual water treatability tests are not available for every combination of
technologies and PAIs. Where treatability data are not available for a particular
PAI/technology combination, treatability data transfers were evaluated. The transfer of
treatability data is described below.
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Treatability Data Transfers
This section discusses methodologies for transferring hydrolysis and activated
carbon data from PAI structural groups with data to those PAIs lacking data. A PAI is
deemed to require transfer of treatability data if it has no specific treatability data indicating
effective treatment. Treatability data transfers for hydrolysis and activated carbon are
discussed more fully in Appendix D.
Two types of data gaps exist within the hydrolysis treatability data. First, there
are many PAIs for which no treatability data, hydrolysis or otherwise, exist. For some of
these PAIs, hydrolysis data may be transferred from structurally similar PAIs with hydrolysis
rreatability data, based on hydrolysis rate estimation techniques (19). However, these
techniques are limited in applicability to only a few types of structures. Second, half-life data
(the common measurement unit of the hydrolysis reaction rate for a particular constituent) are
available for 31 PAIs at conditions other than those considered optimum for wastewater
treatment (in the case of the UTS, the conditions are a pH of 12 and 60°C). Data may be
transferred to these PAIs by extrapolating PAI data measured at conditions other than a pH of
12 and 60°C to these conditions using Mnetically derived relationships, provided that
sufficient data are available to calculate the pH and temperature dependency of the hydrolysis
rate constant Both types of hydrolysis transfers are discussed in detail in Appendix D.
The carbon adsorption data discussed in Section 7.5.1 consist of removal
percentages or saturation loadings. Carbon saturation loading data (the measure of the amount
of organic compounds that can be adsorbed onto a unit amount of activated carbon), overall
pollutant loadings, and pollutant concentrations in a facility's wastewater stream, are
important parameters in designing an activated carbon treatment system. The saturation
loading achievable by a carbon adsorption treatment system varies with the concentration of
the compounds being adsorbed, the wastewater pH and temperature, and the presence of other
adsorbable compounds. As a result, precise carbon saturation loadings are specific to a
facility's individual wastewater stream. Approximate carbon saturation loadings, however,
may be estimated for a faculty's wastewater stream by using treatability study data and
estimates of the pollutant concentrations in facility wastewaters. Activated carbon treatability
studies present data in the form of carbon adsorption isotherms. These isotherms are
graphical representations of the variability of the carbon saturation loading in equilibrium with
varying concentrations of the target compound being adsorbed at a constant temperature.
Thus, a carbon adsorption isotherm may be used to identify the carbon saturation loadings
over a range of target compound concentrations.
The Langmuir and the Freundlich equations are the two most commonly
encountered equations that describe carbon adsorption isotherms (20). However, the
Langmuir equation, which has a simple theoretical basis, often does not provide a good fit to
isotherms for wastewater adsorption systems (21). The empirical Freundlich equation
typically provides a better fit for adsorption from liquids (21). The Freundlich equation is
also widely used and has been found to describe adequately the adsorption process in dilute
solution (22). Therefore, Freundlich isotherms are used to characterize the effectiveness of
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activated carbon adsorption treatment on PAIs contained in PFPR wastewaters. Where
applicable, Freundlich isotherm parameters are transferred to PAIs lacking activated carbon
adsorption treatability data.
The methodology for transferring activated carbon adsorption treatability data
consists of two steps:
1. Identifying PAIs likely to be amenable to carbon adsorption; and
2. Determining Freundlich isotherm parameters for the amenable PAIs
based on data transfers from PAIs for which data are available.
The identification of PAIs likely to be amenable to carbon adsorption is based
on an analysis of each PAI's chemical structure and physical properties. The following types
of compounds are readily adsorbed onto carbon: aromatic compounds (22); high molecular
weight (in the case of PAIs, this includes PAIs with greater than four carbon atoms)
compounds (23), and compounds with low water solubility (23). The effectiveness of
activated carbon adsorption tends to increase as the PAI's molecular weight increases and the
PAI's water solubility decreases. Molecular weight, aromaticity, and solubility information,
combined with structural similarities to PAIs for which activated carbon treatability data exist,
is used to determine whether each PAI is likely to be amenable to carbon adsorption. The
following method is used to identify PAIs amenable to activated carbon adsorption:
1. If a saturation loading is available for a PAI, then the PAI is amenable
to carbon adsorption..
2. If no saturation loading data are available for a PAI, then the PAI's
structure is analyzed to determine if it falls into one of the structural
categories amenable to activated carbon. If it does, then the PAI is
considered to be amenable to activated carbon adsorption.
Experimental data identifying the Freundlich isotherm parameters K and 1/n are
not available for all PAIs amenable to activated carbon adsorption. The PFPR treatability
database contains data from a variety of sources and of varying quality. Only data from EPA-
sponsored, bench-scale treatability studies were used in transfers of K and 1/n values to ensure
that only the data subjected to the rigorous EPA QA/QC procedures were transferred. The
following hierarchy is used to identify K and 1/n values for each PAI:
1. Where K and 1/n values are available for a PAI from an EPA-sponsored,
bench-scale treatability study, or other treatability data, those K and 1/n
values describe the isotherm for that PAI.
2. If K and 1/n values are not available for a PAI that is amenable to
activated carbon, and K and 1/n values are available from an EPA-
sponsored, bench-scale treatability study for only one other PAI in the
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same structural group, then those K and 1/n values are transferred to the
PAI without K and 1/n values.
If K and 1/n values are not available for a PAI that is amenable to
activated carbon, and K and 1/n values are available from EPA-
sponsored, bench-scale treatability studies for more than one PAI in the
same structural group, then K and 1/n values for a minimum Freundlich
isotherm for the structural group are transferred to the PAI. The
minimum Freundlich isotherm is generated by plotting the lowest
saturation loading for all PAIs with experimentally determined K and 1/n
values within the structural group over a range of concentrations from
0.0001 mg/L to 1,000 mg/L. An isotherm fitted to the plotted points is
the minimum Freundlich isotherm for the structural group.
If K and 1/n values are not available for a PAI that is amenable to
activated carbon treatment, and K and 1/n values are not available for
any PAIs within the same structural group, then K and 1/n values from
the 90th percentile lowest Freundlich isotherm for all PAIs are
transferred to the PAI. The 90th percentile lowest Freundlich isotherm
is generated by plotting the 90th percentile lowest saturation loading for
all PAIs with experimentally determined K and 1/n values from EPA-
sponsored, bench-scale treatability studies over a range of concentrations
from 0.0001 mg/L to 1,000 mg/L. An isotherm fitted to the plotted
points is the 90th percentile lowest Freundlich isotherm. This 90th
percentile isotherm represents a conservatively low estimate of
saturation loadings at various concentrations while discounting outlier
values.
An analysis of the chemical structure and properties of some PAIs
indicated that, although the PAIs are amenable to activated carbon
treatment, they are not as amenable as other PAIs within the same
structural group. For example, a PAI may be more water soluble than
other PAIs within the same structural group. The PAI that is more
water soluble may be less amenable to activated carbon treatment. If K
and 1/n values are available for a PAI that is amenable to activated
carbon treatment, and K and 1/n values are available for other PAIs
within the same structural group, but analysis of chemical structures and
properties indicates that the PAI without K and 1/n values is not as
amenable to activated carbon treatment, then the K and 1/n values of the
90th percentile lowest Freundlich isotherm are transferred to the PAI.
This ensures that conservatively low K and 1/n values are transferred,
and K and 1/n values are not transferred from PAIs that are more
amenable to activated carbon treatment to PAIs that are less amenable to
activated carbon treatment.
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Activated carbon adsorption treatability data transfers were attempted for all
PAIs. For many PAIs for which activated carbon data transfers are appropriate, data
indicating effective treatment by hydrolysis or chemical oxidation are also available. In these
cases, the treatment technology is selected for the PAI in the following order: hydrolysis,
chemical oxidation, activated carbon. Appendix D discusses the activated carbon treatability
data transfers for each structural group.
7.6
P2. Recycle, and Reuse Practices
EPA has developed a list of pollution prevention, recycle, and reuse practices
for the pollution prevention (P2) alternative, which is derived from pollution prevention,
recycle, and reuse practices that have been demonstrated in the PFPR industry. These
practices reduce both the pollutant loading and the volume of the wastewater by creating
opportunities for reuse. In some instances, the water conservation aspect of the practices will
discourage the practice of diluting the wastewater so that wastewater concentrations appear to
be at an allowable level.
Section 7.6.1 describes the Pollution Prevention Act of 1990 and its
relationship to this final rule. Section 7.6.2 briefly discusses the P2 data-gathering efforts. A
general description of P2, recycle, and reuse practices that are widely practiced in the PFPR
industry is presented in Section 7.6.3. Specific discussions on how to apply P2, recycle/reuse,
and water conservation techniques to PFPR wastewater sources covered by the rule are
provided hi Sections 7.6.4 through 7.6.10, and a discussion of other P2, recycle, and reuse
practices observed in the industry is found in Section 7.6.11. The discussions of applicable
practices follow the P2 hierarchy developed by EPA — prevention, recycling, treatment, and
disposal or release. Minimization of the wastewater generated for any stream is considered to
be part of the prevention step, since pollution is being prevented or reduced at the source, as
explained in Section 6602(b) of the Pollution Prevention Act of 1990.
7.6.1
Pollution Prevention Act of 1990
In developing these guidelines and standards, EPA has addressed the Pollution
Prevention Act of 1990. Under this Act, Congress established a national policy to prevent or
reduce pollution at the source whenever feasible. This policy is referred to as pollution
prevention, or source reduction, and may include in-process recycling practices. The
following guidelines, known as the environmental management hierarchy, were set to
implement the pollution prevention policy: pollution should be prevented or reduced at the
source whenever feasible; pollution that cannot be prevented should be recycled or reused in
an environmentally safe manner whenever feasible; pollution that cannot be prevented or
recycled should be treated in an environmentally safe manner whenever feasible; pollution
should be disposed or released into the environment in an environmentally safe manner only
as a last resort.
As discussed hi Section 2, the PFPR rule sets zero discharge for PFPR and
PFPR/Manufacturers (Subcategory C) facilities and for refilling establishments (Subcategory E
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facilities). However, facilities have the option of complying with the P2 alternative, which
allows facilities a "P2 allowable discharge" if the facility incorporates specific P2 practices
into their PFPR operations. A list of the specific practices are located in Table 8 in
Appendix A. The focus of the basis for this proposed zero discharge regulation is P2, reuse,
and recycle. Both raw material and water conservation can fall under the heading of P2,
reuse, and recycle practices and both are discussed throughout this section. In addition to
describing these P2, recycle/reuse, and water conservation practices, EPA has also estimated
the savings that might be realized due to water savings and product recovery associated with
these practices (see the Economic Analysis Report (24) for a detailed discussion).
Throughout this section, EPA has noted the cases in which media transfers may
occur as a result of using certain methods that have less impact on water. This notation
illustrates EPA's interest in taking a more holistic, multimedia view of environmental
regulations. Although the use of some methods may reduce the impact to water, these
methods may not, when considered from a multimedia perspective, lead to an overall
environmental improvement. Facilities that are contemplating using any of the methods that
may result in media transfer need to carefully weigh the trade-offs before a decision is made.
EPA would like to note that it recognizes that source reduction in the context
of pesticide use generally has other important components. These components include
improving efficiency in PFPR processes, improving application efficiencies, encouraging
integrated pest management and low input sustainable agricultural practices, and encouraging
the use of safer pesticides when pesticides are necessary. Currently, EPA is pursuing efforts
in these other areas. One example is the Office of Pesticides Programs' Notice of Proposed
Rulemaking on pesticide containers and containment (59 FR 6712; February 11, 1994), which
proposes to reduce the number of pesticide containers needing disposal by setting standards
and guidelines for the use of refillable containers.
7.6.2
P2 Data-Gathering Efforts
EPA has gathered technical data on the PFPR industry, including descriptions
of pesticide production processes, water usage, and water treatment, from several sources. As
described in Section 3.2.1, EPA distributed questionnaires to selected facilities identified as
pesticide formulators, packagers, and/or repackagers. These questionnaires were intended to
survey 1988 PFPR operations and water use (including reuse and recycle practices) at the
selected facilities. Information was also collected through follow-up telephone calls and
written requests for clarification of questionnaire responses.
EPA has also gathered information about PFPR practices during site visits and
sampling episodes. Between 1989 and 1995, EPA visited 58 PFPR facilities to gather
information on production processes and P2 techniques used by these facilities, as well as
information pertaining to wastewater generation, treatment, and disposal.
EPA also conducted telephone follow-up calls to clarify the information
submitted in the 1988 questionnaire by 43 PFPR facilities that reported transporting any PFPR
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wastewater off site for disposal. These questions focused on the type of hazards present in
PFPR wastewaters that are disposed of, and the methods used to minimize generation of these
wastewaters. A more detailed discussion of these facilities is presented in the January 6, 1993
memorandum entitled "Summary of Practices at Contract Haul Facilities" (25).
7.6.3
P2, Recycle/Reuse, and Water Conservation Practices Found at PFPR
Facilities
The PFPR industry uses many P2, recycle/reuse, and water conservation
practices. Wastewaters identified at these facilities are primarily generated during cleaning
operations of the PFPR production areas and associated equipment. Because the wastewaters
are cleaning rinsates and are not, for example, waters of reaction, the P2 practices are not as
process-specific as those practices identified for the pesticide manufacturing industry.
Therefore, the Agency has been able to identify P2, recycle/reuse, and water conservation
practices that are widely accepted and practiced by this industry. It is the Agency's opinion
that some or all of these practices can be implemented at all PFPR facilities.
These P2, recycle/reuse, and water conservation practices fall into three groups:
production practices, housekeeping practices, and practices that use equipment that, by design,
promote pollution prevention. Some of these practices/equipment listed below conserve
water, others reduce the amount of PAI or pesticide product in the wastewater, and still others
may prevent the generation of a wastewater altogether. (Please note: EPA does acknowledge
that some of these practices/equipment may lead to media transfers or increased energy
consumption.)
Production practices include:
• Triple-rinsing raw material shipping containers directly into the
formulation;
• Scheduling production to minimize cleanouts;
• Segregating formulating/packaging equipment by:
Individual product,
Solvent- versus water-based formulations, and
Product "families" (products that contain similar PAIs in
different concentrations);
• Storing interior equipment rinse waters for use in future formulation of
same product;
• Packaging products directly out of formulation vessels;
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• Using raw material drums for packaging final products; and
• Dedicating equipment (possibly only mix tank or agitator) for "hard-to-
clean" formulations.
Housekeeping practices include:
• Performing preventative maintenance on all valves, fittings, and pumps;
• Placing drip pans under leaky valves and fittings or under any valves or
fittings where hoses or lines are routinely connected and disconnected;
and
• Cleaning up spills or leaks in outdoor bulk containment areas to prevent
contamination of storm water.
Equipment that promotes P2 by reducing or eliminating wastewater generation
• Low-volume/high-pressure hoses;
• Spray nozzle attachments for hoses;
• Squeegees and mops;
• Low-volume/recirculating floor scrubbing machines;
• Portable steam cleaners;
• Drum triple rinsing stations (described in Section 7.6.4); and
• Roofs over outdoor tank farms.
These practices have been identified by EPA as effective in reducing the
volume of wastewater generated during PFPR operations and have been observed in use at
PFPR facilities, PFPR/manufacturing facilities, and refilling establishments.
7.6.4
Applying P2 Practices to Shipping Container/Drum Cleaning Operations
PFPR facilities frequently receive pesticide raw materials in containers such as
55-gallon plastic or steel drums or 30-gallon fiber drams. In some cases, the empty drums
are returned to the supplier, but usually the PFPR facility is responsible for disposal of the
drums. The simplest, most cost-effective, and best approach to prevent pollution associated
with cleaning drums and shipping containers is to rinse empty pesticide drums prior to
disposal to capture the PAI residue for direct reuse in product formulations. In this way, the
facility not only eliminates a potential highly contaminated wastewater source, but is also able
to recover the product value of the raw material and avoids costs associated with storage of
the wastewaters.
Rinsing procedures for pesticide drums are provided in 40 CFR Part 165. The
most common method of drum rinsing in the PFPR industry is triple rinsing. After a drum
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containing PAIs or pesticide products is emptied, it should be triple rinsed with the solvent
(organic solvent or water) that will be used in the formulation. This method prevents the
creation of a rinsate that cannot be added directly to the formulation (e.g., a facility will not
create a water-based rinsate when producing a solvent-based product).
Some facilities use a high-pressure, low-volume wash system equipped with a
hose and a spray nozzle to triple rinse drums; volumes of 5 to 15 gallons of water per drum
have been reported. EPA has identified many facilities that reuse these rinsates directly hi
product formulations. Other facilities treat drum rinsate and reuse the effluent for further
drum or equipment rinsing. If the rinsate cannot be reused directly hi product formulations,
the Agency believes that another effective method to reduce wastewater generation during
shipping container/drum cleaning processes is the use of drum rinsing stations.
One of the facilities visited by EPA uses a three-cell station for triple rinsing
drums. The water hi the first cell is used for the first rinse, the water hi the second cell is
used for the second rinse, and the water hi the third cell is used for the final rinse. The rinse
water hi the first cell is reused until it is visually too contaminated to effectively clean the
drums. At that time, it is removed from the cell (for treatment) and the rinse water from the
second cell is transferred into the first cell. The rinse water from the third cell is transferred
into the second cell, and the third cell is refilled with treated effluent from their treatment
system. Each cell contains approximately 100 gallons of water; approximately 70 drums can
be rinsed before the first cell requires water changing.
During another site visit, EPA observed hi use a unique, closed-loop set-up for
emptying and triple rinsing raw material drums. The system was designed by the facility for
several purposes: to aid them in emptying and cleaning drums and performing the triple
rinse; to eliminate the need for storage of the water (or solvent) for reuse; and to prevent
mathematical errors by the operators during the weighing out of raw materials and water (or
solvent).
The system consists of two 55-gallon drums, a formulation tank, and
connecting hoses. One of the drums is permanently fixed on top of the formulation tank.
The formulation tank and drum are situated on a load cell (used for weighing). The second
drum, which is full of raw material, is placed on the ground next to the formulation tank. One
hose is used to vacuum out the raw material and transfer it to the drum on the. formulation
tank/load cell. The other hose is equipped with a doughnut-shaped nozzle that provides the
triple rinse by spraying the ulterior of the now empty raw material drum. The rinsate that is
created by the triple rinse procedure is automatically removed by the vacuum line and is
transferred to the drum on the formulation tank/load cell.
The load cell can be used to weigh the amount of raw material and/or rinsate
that is added to the formulation by zeroing out the weight of the tank and drum. This allows
the volume of both raw material and rinse water (or solvent) to be factored into the total
volume of water (or solvent) required in the formulation. The drum on top of the formulation
tank is equipped with a spring-loaded valve that enables the operator to take weight
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measurements prior to emptying the contents of the drum into the mix tank. This set-up has
almost completely eliminated operator math errors and related formulation specification
problems.
It is the Agency's opinion that the best and most cost-effective way to
eliminate rinse water from raw material, drum cleaning is to triple rinse the residue directly
into the formulation being produced.
7.6.5
Applying P2 Practices to Bulk Tank Cleaning
PFPR facilities sometimes produce large quantities of formulated pesticide
products and receive large quantities of raw materials used to produce pesticide products;
these products and raw materials are stored on site in bulk tanks. These tanks are typically
rinsed only when it becomes necessary to use the tank to store a different material. For
example, a facility may store bulk quantities of a pesticide product used for soybean crops
during the spring and then switch in the summer to storing a pesticide product used for corn
crops. Each time the facility switches the product stored in a bulk tank, the tank is rinsed.
Bulk tanks are sometimes also rinsed at the end of a season as a part of general maintenance.
Recovery of product value from bulk tank rinsates is a common P2 practice in
the PFPR industry. Bulk tank rinsates have been reused by some PFPR facilities in product
formulations and by some agrichemical facilities in commercial applications of pesticides (as
make-up water). Facilities can usually store this rinsate on site until the opportunity to reuse
it is available.
Another effective P2 technique is to minimize the amount of rinsate generated
during bulk tank cleaning by using high-pressure, low-volume washers. Some PFPR facilities
have also demonstrated that using squeegees reduces wastewater generation during bulk tank
cleaning. The smaller the volume of water needed to clean the bulk tank, the more readily
the entire volume can be recovered by adding to product or make-up in an application.
It is the Agency's opinion that the best and most cost-effective way to
eliminate rinse water from bulk tank rinsate is to dedicate these tanks to specific raw materials
or products. If dedication of equipment is not possible, material changeover operations should
be minimized and the bulk tank rinsates stored for reuse in future formulations or for make-up
water in custom applications.
7.6.6
Applying P2 Practices to Equipment Interior Cleaning
As discussed in Section 3.4, formulated and packaged products may be either
liquid (including emulsifiable concentrates) or solid (dry). A liquid formulating and
packaging line often consists of mix tanks; melt kettles (if necessary); transfer piping or hoses
and pumps; filters prior to packaging; and a packaging hopper and fillers operating over a
conveyor belt. A dry formulating and packaging line often consists of crushing, pulverizing,
grinding, and/or milling equipment; blenders; screening equipment; and the packaging
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equipment. Repackaging is often a simple process of transferring material manually from one
container into a container of a different size. For both liquid and dry operations, the
packaging equipment is often portable.
PFPR facilities generally do not dedicate line equipment to a specific product
because many products are made in small batches, and it is not cost-effective to dedicate a
line to a product made periodically throughout the year. Often the equipment is used for
short-term production campaigns, and can be used for both pesticide and nonpesticide
products. To ensure product quality, the production line equipment is normally cleaned
between product batches; these cleaning operations are referred to as product changeover
cleanings. Many facilities also perform routine periodic cleaning of production lines for
maintenance and, on occasion, also perform special or nonroutine cleaning due to equipment
failures or the use of materials that require additional cleaning time or cleaning solvents.
Different types of lines (e.g., lines that handle dry, liquid, or emulsifiable concentrate
products) require different cleaning methods, such as water or solvent rinsing, flushing with
solid material, mechanical abrasion, or a combination of these techniques. The cleaning
process is also determined by the product that was previously made and its relation to the next
product to be made. For example, if the products contain the same ingredients, but at varying
percentages, the facility may only require a minimal cleaning of the line (if any cleaning is
required).
Lines handling dry products are usually cleaned by flushing the line with the
solid, inert material (such as clay) used as the carrier in those products. EPA has observed
this practice at several facilities. The dry flush may be followed by a water rinse when
additional cleaning is required. Liquid lines are usually rinsed between changeovers with
either water or an organic solvent, depending on the product just completed and the next
product to be made on the line. Water cleaning is also performed for routine maintenance.
Product changeover cleanings can be eliminated or greatly reduced by
dedicating equipment to specific products or groups of products. Although entire lines are not
generally dedicated, EPA is aware of many facilities that dedicate tanks to formulation mixing
only, thereby eliminating one of the most highly contaminated wastewater streams generated
at PFPR facilities. Facilities also dedicate lines to the production of a specific product type,
such as water-based versus solvent-based products, thereby reducing the number of cleanings
required, and allowing greater reuse of the cleaning water or solvent.
Another effective P2 technique identified by EPA is to schedule production to
reduce the number of product changeovers, which reduces the number of equipment interior
cleanings required. Facilities may also reduce the number of changeover cleanings required
or the quantity of water or solvent used for cleaning by scheduling products in groups or
"families." Products may lend themselves to a particular production sequence if they have
common PAIs, assuming the products also have the same solvent base (including water). A
product with a PAI such as MCPP can be followed by a product containing 2,4-D, MCPP,
and dicamba. Where other raw material cross-contamination problems are not a concern, no
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cleaning would be required between changeovers. Facilities that have implemented this
technique have conducted testing to ensure that product quality is not adversely affected.
Scheduling production according to packaging type can reduce changeover
cleanings of packaging equipment. Packaging lines are often able to handle containers of
different sizes; a slight adjustment to one packaging line, such as adding a short length of
hose, may prevent the use of an entirely different set of packaging equipment that would also
require cleaning. Packaging can also be performed directly out of the formulation vessels,
with or without using portable filling units, to avoid using and subsequently cleaning interim
storage tanks and transfer hoses.
Another effective P2/water conservation technique to minimize the quantity of
rinse water generated by equipment interior cleaning is the use of water hoses equipped with
hand-control devices (for example, spray-gun nozzles such as those used on garden hoses).
This practice prevents the free flow of water from unattended hoses. Another technique to
conserve water is the use of high-pressure, low-volume washers instead of ordinary hoses.
One of the facilities visited indicated that, by using high-pressure washers, they reduced
typical equipment interior rinse volumes from 20 gallons per rinse to 10 gallons per rinse.
Steam cleaning can also be a particularly effective method to clean viscous
products that otherwise require considerable volumes of water and/or the addition of a
detergent to remove. Many facilities have access to steam from boilers on site; however, if
there is no existing source of steam, steam cleaning equipment can be purchased. Although
steam generation can increase energy consumption and add NOX and SOX pollutants to the
atmosphere, there are benefits to be gained. Facilities may end up creating a much smaller
volume of wastewater and may potentially avoid the need to use detergents or other cleaning
agents that could prevent product recovery. The Agency cautions that steam would be a poor
choice for cleaning applications where volatile organic solvents or inerts are part of the
product, as the steam would accelerate the volatilization of the organic compounds.
Facilities also clean equipment interiors by using squeegees to remove the
product from the formulation vessel and by using absorbent "pigs" to clean products out of
the transfer lines before equipment rinsing. These techniques minimize the quantity of
cleaning water required, although they generate a solid waste stream requiring disposal.
Regardless of whether or not residual product is removed from equipment interiors before
rinsing, equipment interior rinsate can typically be reused as make-up water the next time that
a water-based product is being formulated.
One facility that was visited by EPA uses a unique method of cleaning to
reduce the volume of water needed to clean equipment interiors. At this facility, the
production lines are hooked to dedicated product storage tanks. Prior to rinsing these
production lines, the facility uses air to "blow" the residual product hi the line back to
product storage. Not only will these lines require less water to clean, but the residual product
that is blown back to storage is not diluted and should not affect the product specifications in
any way.
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It is the Agency's opinion that the best way to eliminate rinse water from
equipment interior cleaning is to dedicate equipment. Equipment may be completely
dedicated to the production of a single product or may be dedicated to a "product family". In
addition, a facility may be able to dedicate specific pieces of equipment, such as formulation
tanks. When the generation of rinse waters cannot be avoided, the equipment should be
rinsed using a controlled water source (e.g., hoses with spray nozzles) and the rinsates should
be stored for reuse in future formulations. Also, rinse waters from formulating many dry
products can be totally eliminated by flushing production lines with the solid, inert material
(such as clay) used as the carrier for the products handled on the line. This inert material is
then stored for reuse in the next formulation of that product.
7.6.7
Applying P2 Practices to Floor/Wall/Equipment Exterior Cleaning
During formulating and packaging operations, the exteriors of equipment may
become soiled from drips, spills, and dust (especially equipment located near dry lines). The
floors in the formulating and packaging areas become dirty in the same manner and also from
normal traffic. PFPR facilities clean the equipment exteriors and floors for general
housekeeping purposes, and to keep sources of product contamination to a minimum. When
water is used, these cleaning procedures become a source of wastewater.
Equipment exteriors and floor areas of dry formulating and packaging lines are
typically cleaned without using water; instead, facilities use vacuuming, scraping, and other
mechanical means to clean the areas around these lines. Floors and equipment exteriors
associated with liquid lines, and occasionally dry lines when an especially thorough cleaning
is desired, are rinsed with water (or an appropriate organic solvent). While some facilities
routinely clean equipment exteriors and floors, or do so at all changeovers between certain
products, other facilities have indicated that equipment exterior and floor cleanings are
performed only when required after visual inspections by the operators or facility
management. Wastewater from cleaning the walls around formulating and packaging lines
appears to be rarely generated. The quantity of water used annually for equipment exterior or
floor cleaning varies widely from facility to facility, from several gallons to thousands of
gallons.
This wastewater source can be minimized through the use of high-pressure,
low-volume washers rather than ordinary water hoses. Where ordinary hoses are used,
facilities have noted that attaching spray nozzles or other devices to prevent free flow of water
from unattended hoses reduced water use. Additionally, some facilities practice steam
cleaning (see Section 7.6.6) rather than water cleaning of equipment exteriors to reduce the
amount of wastewater generated.
Instead of hosing down the exterior of a piece of equipment, the Agency has
identified some facilities that wipe equipment exteriors with rags or use a solvent cleaner,
such as a commercially available stainless steel cleaner. This practice avoids generating a
wastewater stream, but does create a solid waste that, depending on the solvent used, could be
considered a hazardous waste. Squeegees are also used to clean equipment exteriors and
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floors, and are not disposed of after single uses. It may be possible to dedicate squeegees to a
certain line or piece of equipment, but using squeegees may still require using some water.
Some PFPR facilities use automated floor scrubbers, which replace the practice
of hosing down floors. Floor scrubbers are mechanical devices that continually recirculate
cleaning water to clean flat, smooth surfaces with circulating brushes. During operation, the
scrubber collects the cleaning water in a small tank that is easily emptied after the cleaning
process, or at a later date. Using a floor scrubbing machine can require as little as 5 to 15
gallons of cleaning solution (typically water) per use. A mop and a single bucket of water
can also be used in place of a hose. Floor mopping can generate as little as 10 gallons of
water per cleaning.
EPA has visited a number of facilities which reuse their floor wash water with
and without filtering. One facility has set up its production equipment on a steel-grated
platform directly above a collection sump. Following production, the equipment and the floor
of the platform, on which the operator stands when formulating product, are rinsed down and
the water is allowed to flow into the sump. A pump and a filter have been installed in the
sump area to enable the operator to transfer this rinsate back into the formulation tank the
next time he is ready to formulate. This sump is also connected to floor trenches in the
packaging area for the same product. When the exterior of the packaging equipment and the
floors in this area are rinsed, this water is directed to the trenches and eventually ends up in
the collection sump for reuse.
It is the Agency's opinion that wastewater generated from floor and equipment
cleaning can be best reduced by the following techniques: sweeping the area before rinsing;
cleaning on visual inspection rather than routine/daily cleaning; using a floor scrubbing
machine or a mop and a bucket to clean the floors; and using a high-pressure, low-volume
hose with a spray nozzle or a steam cleaning machine to clean equipment exteriors.
7.6.8
Applying P2 Practices to Leaks and Spills Clean-Up
Leaks and spills occur during the normal course of PFPR operations. Leaks
originate at hose connections or valves, and can be reduced through preventive maintenance,
such as checking equipment and connections before use or on a regular basis. If leaks do
occur, simple measures (such as placing drip pans under the leaky equipment or placing
hoppers under packaging fillers) can either eliminate or minimize the quantity of water
required for cleanup; these measures also aid in retaining the product value.
Spills of raw materials occur from bulk storage tanks or during addition of raw
materials to mix tanks. Product spills occur from bulk storage tanks or during packaging
operations (from overfilling containers, missing the container to be filled, or tipping filled
containers before capping). Good housekeeping procedures, such as keeping work areas
uncluttered, can help prevent spills.
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Dry products that have leaked or spilled can be vacuumed or swept without
generating any wastewater. Liquid leaks and spills can be collected into a trench or sump (for
reuse, discharge, or disposal) with a squeegee, leaving only a residue to be mopped up or
hosed down if further water cleanup is required. Liquid leaks and spills can also be cleaned
up using absorbent material, such as absorbent pads or soda ash. For an acidic product, soda
ash or a similar base material will also serve to neutralize the spill. If a residue remains,
some water may be used for mopping up or hosing the area down, but methods to reduce
floor wash should be implemented whenever possible (see Section 7.6.7). EPA has observed
that many facilities clean up leaks and spills from water-based products with water and then
handle the wastewater as floor wash; however, these facilities clean up leaks and spills from
solvent-based products with absorbent materials. Using an absorbent material may be the best
practice for cleaning up small scale solvent-based leaks and spills; however, EPA does
recognize that this material then needs to be disposed of (cross-media transfer). Therefore,
good housekeeping practices may be even more important hi the case of organic solvent-based
product spills and leaks because, if not prevented, these spills and leaks may have to be
cleaned up with absorbent material and disposed of.
Direct reuse of leaks and spills is another possible P2 technique. If drip pans
or other containers are used to catch leaks and spills, the material (either water-based or
solvent-based) can be immediately reused in the product being formulated or packaged, or
stored for use in the next product batch. Collection hoppers or tubs can be installed beneath
packaging fillers to capture spills and immediately direct the spills back to the fillers. Leaks
or spills around bulk storage tanks can be contained by dikes, which, in fact, are often
required by state regulations. (EPA recently proposed federal regulations for containment
structures at agricultural refilling establishments and at certain other facilities, as discussed in
Section 3.4.3.)
It is the Agency's opinion that the amount of wastewater generated from leak
and spill clean-up activities can best be reduced by performing regular preventative.
maintenance, including checking valves and fittings for leaks. Another effective practice,
particularly in the case of dedicated filling equipment, is the use of drip pans. Collecting
leaks and spills in drip pans may enable a facility to directly reuse the collected product and
retain the product value.
7.6.9
Applying P2 Practices to Aerosol Container (DOT) Leak Testing
DOT test baths are used to test aerosol cans for leaks and weaknesses under
pressure. The leak test is performed as a requirement prior to transporting the cans (49 CFR
173.306.a.3(v)). The cans are visually examined for leaks while submerged in a 130°F hot
water bath. The water in the bath is changed periodically to reduce the buildup of
contaminants in the water. Bursting cans may contaminate the water bath with pesticide
product. Can exteriors may also contaminate the bath water since they may have product or
solvent on them from the can-filling step. According to several facilities, pesticide products
and solvents can cause visibility problems hi the bath water and leave an oily residue on the
cans exiting the bath. One of the facilities visited by EPA also indicated that rust particles hi
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the bath water can foul steam sparging equipment (used to heat the bath), requiring that the
bath water be dumped and refilled.
No method of eliminating this source of wastewater has been identified;
however, the volume of water used may be minimized by using a contained water (i.e., batch)
bath as opposed to a continuous overflow water bath. A batch water bath is completely
emptied and refilled with water when required, based upon visual inspection by the operator.
Therefore, the quantity of wastewater generated depends on the frequency of refilling and the
volume of the bath (200 gallons is a typical volume of the contained water baths at facilities
visited by EPA). One of these facilities uses a contained water bath and heats the bath with
steam to ensure that the temperature of cans reach 130°F. This facility indicated that steam
condensation causes some overflow that exits the bath via a standpipe. A continuous
overflow bath constantly replaces the water in the bath, keeping it clean; however, a constant
stream of wastewater is generated. Depending on the overflow rate of the bath, a continuous
overflow bath may generate more wastewater per production unit than a batch water bath.
One facility visited by EPA has installed a diatomaceous earth filter on one
DOT test bath. The facility recirculates the bath water through the filter to remove
contaminants such as oil and grease and suspended solids. The filtered water is then reused in
the bath, thereby extending the usefulness of the bath water. The facility anticipates they will
dispose of the filter as nonhazardous waste.
Another of the facilities visited uses a can-washing step prior to the DOT test
bath, presenting an additional source of wastewater. This can washing is performed, at
operator discretion, to reduce the quantity of contaminants entering the bath water. The
effectiveness of this step has not been quantitatively determined.
It is the Agency's opinion that the best way to reduce wastewater generated by
aerosol container (DOT) leak testing is using a batch water bath where the water is changed
out when it is determined to be "dirty" by visual inspection. Another effective P2 technique
is the installation of treatment equipment, such as filters, to remove the constituents that
visually contaminate the bath water and allow the water to be reused in the bath.
7.6.10
Applying P2 Practices to Air Pollution or Odor Control Scrubbers
Many PFPR facilities use dry air pollution control equipment, such as carbon
filters and baghouses, to reduce particulate emissions from PFPR operations. These facilities
are able to reduce air pollution without generating wastewater. Other PFPR facilities use wet
scrubbers to reduce air emissions from PFPR operations. Facilities that also perform
non-PFPR operations may use scrubbers that are not specific to PFPR operations, but instead
serve the general facility. Scrubbers can be operated with continuously recycled water until
the contaminated water needs to be replaced (as practiced by one of the facilities visited by
EPA) or they can be operated with a bleed steam (blowdown) on a continuous basis.
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Some facilities may only need a wet scrubber on one particular process (i.e., a
dedicated scrubber). These facilities have been able to reuse the scrubber blowdown or
changed-out scrubber water as make-up water in the formulation of that particular product.
Some facilities with nondedicated scrubbers have been able to use the scrubber blowdown or
changed-out scrubber water for floor or equipment exterior cleaning.
7.6.11
Other P2 Practices Observed at PFPR Facilities
Safety Equipment Cleaning
Most PFPR facilities use safety equipment, including safety showers and eye
washes, gloves, respirators, and rubber boots, to protect individuals from the dangers
associated with certain raw materials and finished products. PFPR process wastewater is
generated from rinsing boots, gloves, and respirators. Wastewater generated from routine
checks of safety showers and routine flushes of eye wash stations (to ensure the station is
clean and operable) are not considered process wastewater under the final PFPR rule.
Quantities of contaminated wastewater generated from safety equipment
cleaning are generally on the order of several gallons or tens of gallons. Some facilities
successfully avoid generating this type of wastewater by using disposable safety clothing (e.g.,
gloves, dust masks) that do not require cleaning. EPA realizes that using disposable
protective clothing may be considered a media transfer. The reduction in worker exposure
may be an important decision-making factor when considering the trade-offs using disposable
safety equipment.
Laboratory Equipment Cleaning
Many PFPR facilities operate on-site laboratories for conducting quality control
(QC) tests of raw materials and formulated products. Wastewater is generated from, these
tests and from cleaning glassware used in the tests. Although laboratory equipment cleaning
(with the exception of the first rinse of retain sample containers) is not considered a process
wastewater stream covered by the final PFPR rule, EPA observed and documented several
methods of minimizing this source.
One effective P2/reuse technique during laboratory equipment cleaning
operations is to dedicate laboratory sinks to certain products, and collect any wastewater
generated from the testing of those products either for reuse in the product or for transfer
back to the PAI manufacturer or product registrant. In the cases where the facility uses
solvents in conjunction with the QC tests performed in the laboratory, the solvent-
contaminated water may not be able to be reused in the process. One PFPR facility uses a
small activated carbon unit to treat their lab water (activated carbon is discussed in detail in
Section 7.2).
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Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Precipitation Runoff
Precipitation runoff includes all precipitation that falls on PFPR facilities that is
believed to be contaminated. Although precipitation runoff is not considered a process
wastewater stream covered by the final PFPR rule, EPA observed and documented several
methods of minimizing this source. Contaminated precipitation runoff can be prevented by
bringing all PFPR operations indoors, as many PFPR facilities have done, or by covering
outdoor storage tanks and dikes with roofs, which has also been done at many PFPR facilities.
Hie roofs would ideally extend low enough to prevent crosswinds from blowing rain into
spill-containment dikes. To prevent rainwater contamination, the drain spouts and gutters
should conduct roof runoff to areas away from PFPR operations, and the roofs should be kept
in good repair.
7.6.12 Applying P2 Practices at Refilling Establishments
Secondary Containment in the Bulk Storage Area
Containment systems enclosing the pesticide bulk liquid storage area are usually
constructed of a floor and a dike that is sufficiently high to contain the volume of the largest
tank plus an additional 10 to 25% safety factor. If the outside storage area is uncovered, the
containment system is usually designed to contain 6 inches of precipitation in addition to 110
to 125% of the volume of the largest tank. Typically, facilities construct the secondary
containment system with steel reinforced concrete that is 6 to 10 inches thick and coated with
an appropriate sealant. The floor may be slightly sloped to a sump area from which any
spillage or collected precipitation can be easily pumped.
Although precipitation that falls in the containment area is not a process
wastewater covered by the final PFPR rule, EPA gathered information on methods to reduce
or eliminate this potential source of water. Refilling establishments that provide commercial
application services are likely to collect and reuse any precipitation that accumulates in the
containment system during the spring and summer months. In fact, some refilling
establishments require such large volumes of water for their application operations that any
precipitation accumulated is pumped into application trucks for immediate use. However, it
may be difficult for other facilities that do not require large volumes of water or do not offer
any application services to reuse all the precipitation collected in the containment system.
These facilities could keep the containment system free of any spilled pesticides through good
housekeeping practices so that precipitation falling into the containment system does not
become contaminated. Some facilities house their pesticide bulk storage area inside a building
or under a covered area to eliminate precipitation from collecting in the containment system,
as well as to protect the area from vandalism and from severe weather such as cold winters.
Enclosing containment structures is not a requirement for this rulemaking, nor
is it a requirement of the Office of Pesticides Programs proposed containment rule. However,
the Agency considers roofing a bulk storage area and loading pad a prudent and pollution-
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preventing action by refilling establishments. EPA alsd recognizes that there may be barriers
in some areas to enclosing bulk storage areas under roof, such as fire code restrictions.
Containment Pad in the Loading/Unloading Area
Agrichemical dealers sometimes install loading/containment pads in the
operation area to contain and collect any product spills that may occur during pesticide
loading operations. The pad is usually installed contiguous to the bulk storage area so that it
will also contain any spills which may occur during the loading of the bulk storage tanks and
the repackaging of pesticides into smaller containers. Facilities may also conduct all their
pesticide cleaning operations, such as rinsing minibulk containers, directly on the pad in order
to contain and collect the rinsates.
The pad is normally constructed of concrete and is sloped to a sump area.
Some of the facilities contacted by EPA reported that the sump area is divided into individual
collection basins so that the facilities can segregate wastewaters contaminated by different
products and reuse these wastewaters for applications. For instance, facilities hi the Midwest
frequently have two collection basins; one basin collects wastewaters contaminated with corn
herbicides and the other collects wastewaters contaminated with soybean herbicides. As part
of this collection system, some facilities install one or more tanks to store wastewater until it
can be applied to land, while other facilities use portable minibulk tanks to store the
wastewater. When facilities collect wastewaters that must be segregated by different types of
pesticides, multiple storage tanks are used to avoid contamination.
7.7
1.
2.
3.
4.
References6
U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines, Pretreatment Standards, and New Source Performance
Standards for the Pesticide Chemicals Manufacturing Point Source Category.
EPA-821-R-93-016, September, 1993 (DCN F6442).
Radian Corporation. Final Pesticides Formulators. Packagers, and Repackagers
Treatability Database Report. Prepared for the U.S. Environmental Protection
Agency, Office of Water, Washington, DC, March 1994 (DCN F7185).
U.S. Environmental Protection Agency. Final Development Document For the
Metal Molding and Castings (Foundries) Effluent Guidelines Limitations.
EPA 440/1-85/070.
Metcalf and Eddy, Inc. Wastewater Engineering Treatment and Disposal, Third
Edition. McGraw-Hill, Inc.
For those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
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5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Eastern Research Group, Inc. Emulsion Breaking Performance Study - Final
Report. Prepared for the U.S. Environmental Protection Agency, Office of
Water, Washington, DC, August 1996 (DCN F7937).
Radian Corporation. Final Pesticides Formulators. Packagers, and Repackagers
Cost and Loadings Report. Prepared for the U.S. Environmental Protection
Agency, Office of Water, Washington, DC, March 31, 1994 (DCN F7184).
Eastern Research Group, Inc. Addendum to the Final PFPR Cost and Loadings
Report: Revisions to Costing Approach for Final Rule. Prepared for the U.S.
Environmental Protection Agency, Office of Water, Washington, DC,
September 1996 (DCN F7943).
Radian Corporation. Pilot-Scale Tests of the Universal Treatment System for
the Pesticides Formulating. Packaging, and Repackaging Industry. Prepared for
the U.S. Environmental Protection Agency, Office of Water, Washington, DC,
September 30, 1996 (DCN F7938).
Radian Corporation. Evaluation of the Universal Treatment System of
Pesticide Formulator/Packager Wastewater. Prepared for the U.S.
Environmental Protection Agency, Office of Research and Development,
Cincinnati, OH, September 1993 (DCN F6446).
Radian Corporation. Treatability of PAIs by Hydrolysis - Bench-Scale Tests.
Prepared for the U.S. Environmental Protection Agency, Office of Water,
Washington, DC, November 8, 1990 (DCN F5544).
Radian Corporation. Hydrolysis Treatabilitv Field Study. Prepared for the
U.S. Environmental Protection Agency, Office of Water, Washington, DC,
September 28, 1990 (DCN F5546).
Radian Corporation. Activated Carbon Isotherms for Pesticides. Prepared for
the U.S. Environmental Protection Agency, Office of Research and
Development, Cincinnati, OH, October 10, 1989 (DCN F5885).
Radian Corporation. Activated Column Testing - Pesticide Manufacturing
Wastewaters - Phase 2. Prepared for the U.S. Environmental Protection
Agency, Office of Research and Development, Cincinnati, OH, September 1,
1991 (DCN F5884).
Radian Corporation. Pyrethrin Wastewater Treatabilitv Report. Prepared for
the U.S. Environmental Protection Agency, Office of Water, Washington, DC,
June 1993 (DCN F6167).
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15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
Section 7 - Technology Selection and Methods to Achieve the Effluent Limitations
Radian Corporation. Membrane Filtration Treatabilitv Study. Prepared for the
U.S. Environmental Protection Agency, Office of Water, Washington, DC, July,
1991 (DCN F5541).
Radian Corporation. Membrane Separation Study for the Pesticide Formulator
Packager Project. Prepared for U.S. Environmental Protection Agency, Office
of Water, Washington, DC, 1994 (DCN F6445).
Eastern Research Group, Inc. Final Pilot-Scale Membrane Separation Study.
Prepared for the U.S. Environmental Protection Agency, Office of Water,
Washington, DC, August 1996 (DCN F7939).
Radian Corporation. Pesticide Formulators. Packagers, and Repackagers
Treatabilitv Database Report Addendum. Prepared for the U.S. Environmental
Protection Agency, Office of Water, Washington, DC, September 1995 (DCN
F7700).
Lyman, WJ. et al. Handbook of Chemical Property Estimation Methods.
McGraw-Hill Book Company, 1981.
Tchob anaglous, G. and E.D. Schroeder. Water Quality. Addison-Wesley
Publishing Company, Inc. Reading, MA, 1985.
McCabe, W.L., et al. Unit Operations of Chemical Engineering. Fourth
Edition. McGraw-Hill Book Company, New York, NY, 1985.
U.S. Environmental Protection Agency. Carbon Adsorption Isotherms for
Toxic Organics. Municipal Environmental Research Laboratory,
EPA-600/8-80-023, Cincinnati, Ohio, April 1980 (DCN F5786).
U.S. Environmental Protection Agency. Final Development Document for
Effluent Limitations Guidelines and Standards for the Organic Chemicals.
Plastics, and Synthetic Fibers Point Source Category. Volume I.
EPA 440/1-87/009, Washington, DC, October, 1987, p. VH-121.
U.S. Environmental Protection Agency. Economic Analysis of Final Effluent
Limitations Guidelines and Standards for the Pesticide Formulating. Packaging.
and Repackaging Industry. EPA 821-R-96-017, Washington, DC, September
1996.
Memorandum: Summary of Practices at Contract Haul Facilities, January 6,
1993.
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Section 8 - Engineering Costs
SECTION 8
ENGINEERING COSTS
8.1
Introduction
This section discusses the costs of compliance for the PFPR industry with the
proposed effluent guidelines. Section 8.2 reviews the regulatory options and Section 8.3
describes the engineering costing methodology used to estimate compliance costs and pollutant
loadings associated with these options. Section 8.4 describes the development of the PFPR
cost model and the facility- and PAI-specific input datasets. Sections 8.5 through 8.7,
respectively, describe in detail the design and cost algorithms used for the following costing
modules included in the cost model: Universal Treatment System, storage and reuse, and off-
site disposal. Section 8.8 presents the design and cost algorithms used to estimate compliance
costs for Subcategory E (refilling establishments) facilities and Section 8.9 lists references.
For further analysis of the costs and loadings, as they apply to the economic impact analysis,
see the Economic Analysis report (EA) (1).
8.2
Regulatory Options
EPA considered five regulatory options (for Subcategory C: PFPR and
PFPR/Manufacturers) as part of the development of the proposed effluent limitations
guidelines for the PFPR industry. These proposed options are discussed in detail in the
technical development document supporting the proposed PFPR rule (2) and in the
Supplemental Notice (60 FR 30217) to the proposed PFPR rule, and are not discussed further
in this section. After gathering additional data after proposal, and reviewing comments on the
proposed rule and the Supplemental Notice, the Agency has decided to promulgate a
regulatory option that comprises several compliance strategies. The overall option being
promulgated is referred to as the Zero/Pollution Prevention (P2) Alternative option, and gives
PFPR facilities a choice of complying with zero discharge or a P2 alternative in which
facilities incorporate specific P2 practices and treatment technologies, followed by an
allowable discharge.
The various compliance strategies that make up the Zero/P2 Alternative option
are listed below:
• Zero discharge: comprises a combination of treatment and reuse, reuse
without treatment, and contract hauling of wastewater for off-site
disposal;
• P2 alternative: comprises a combination of P2 practices, treatment and
discharge, discharge without treatment, and reuse without treatment; and
• Zero discharge based on recycle/reuse and contract hauling of
wastewater: comprises the same treatment options as the zero discharge
8-1
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Section 8 - Engineering Costs
option, except that wastewaters that are treated and reused under the
zero discharge option are contract hauled for off-site disposal under this
option.
Treatment of wastewater under these options is performed through the Universal Treatment
System (UTS). The UTS is a treatment system capable of conducting emulsion breaking,
hydrolysis, chemical oxidation, chemical precipitation, and activated carbon adsorption
treatment steps. The UTS is described in greater detail in Section 7.
The Agency prepared cost estimates for each of the compliance strategies
described above. These compliance cost estimates are based on information submitted by
facilities that were surveyed as well as data collected from sampling and site visits and the
FATES database; these cost estimates were then extrapolated to the entire PFPR industry.
EPA assumes that, after implementation of the final PFPR rule, each facility will choose the
least expensive compliance strategy for their particular situation. More detail concerning these
compliance strategies and associated cost estimates can be found in the EA (1) and in the
Addendum to the Final PFPR Cost and Loadings Report: Revisions to Costing Approach for
the Final Rule (3) prepared for this rulemaking.
Under the final PFPR rule, EPA is regulating wastewaters referred to as interior
and exterior wastewater sources (discussed further in Sections 5.2.1 and 5.2.2, respectively).
Below is a list of the process wastewaters generated from these two sources:
• Interior wastewater sources:
Drum/shipping container rinsate,
Bulk container rinsate,
Equipment interior wash water, and
Contact cooling water;
• Exterior wastewater sources:
Floor/wall/equipment exterior wash water,
Leak and spill cleanup water,
Air or odor pollution control scrubber water,
Safety equipment wash water,
DOT leak test bath water when cans have burst., and
Retain sample container rinsate.
The final scope of the rule does not cover the formulation, packaging, and/or
repackaging of products that contain PAIs that are sanitizers (including pool chemicals); PAIs
that are microorganisms (such as Bacillus thuringiensis (B.t.)); Group 1 mixtures that are
common food constituents or nontoxic household items, are GRAS (generally recognized as
safe), or are exempt from FIFRA under 40 CFR 152.25; and Group 2 mixtures that are
substances whose treatment technology has not been identified. The pretreatment standards
8-2
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Section 8 - Engineering Costs
(i.e., PSES and PSNS) do not apply to one PAI and three priority pollutants which EPA has
determined will not pass through or interfere with POTWs. In addition, certain wastewater
sources that may be associated with PFPR operations are not covered by this rule, including
storm water, on-site employee showers, on-site laundries, fire equipment test water, water
from testing and emergency operation of eye washes and safety showers, certain Department
of Transportation (DOT) aerosol leak test bath water, laboratory water, wastewater from
research and development laboratories, and wastewater resulting from the formulation,
packaging, and/or repackaging of certain liquid chemical sterilants. Therefore, these exempted
PAIs and wastewaters are not factored into the final costs and loadings estimates for this rule.
See the Addendum to the Final Pesticide Formulating, Packaging, and Repackaging Cost and
Loadings Report: Revisions to Costing Approach for the Final Rule (3) for additional
discussion of these exemptions.
8.3
Engineering Costing Methodology
In developing these regulatory options, EPA assessed the economic impact of
these options on the PFPR industry. The economic burden is a function of the estimated costs
of compliance to achieve the final effluent limitations, which may include the initial capital
cost required to construct any necessary treatment system(s) as well as the annual operating
and maintenance (O&M) costs for that system, including the cost of monitoring for
compliance with the limitations.
Estimation of these costs typically begins by identifying the P2 practices and
wastewater treatment technologies that can be used to meet a particular compliance option.
Data are then gathered from facilities within the industry already using these practices and/or
operating these treatment technologies, equipment vendors, reference guides, literature, and
other applicable sources to determine the estimated costs associated with each practice or
technology. The technology costs vary based on such design parameters as wastewater flow
rate, extent of pollutant reduction required to achieve effluent limitations, and type of
pollutant(s). Most information sources list these costs in the form of cost curves, which are
graphic representations of cost as a function of flow rate, removal efficiency, pollutant-
specific treatability parameters (such as hydrolysis half-life or carbon saturation loading), and
other design parameters. Cost curves can also be generated by varying these parameters and
estimating the associated change in the equipment and material costs. Costs for individual
facilities or groups of facilities sharing similar operating characteristics can then be calculated
based on these cost curves. A computerized model can efficiently calculate these costs based
on equations representing these cost curves.
EPA used this methodology to develop a cost model for the PFPR industry.
EPA identified P2 practices and wastewater characterization and reuse/disposal information
from the 1988 PFPR questionnaire responses, facility site visits and sampling trips, and from
the FATES database. Applicable PAI removal/destruction technologies and associated
treatability data were determined based on information contained hi the administrative record
supporting the development of effluent guidelines for the pesticide manufacturing industry and
in the administrative record for the PFPR regulation. These data sources consist of
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Section 8 - Engineering Costs
wastewater sampling analytical results, EPA- and industry-supplied treatability studies, and
literature information. Cost curves for these treatment technologies were then developed
based on the design and cost algorithms developed for the pesticide manufacturing cost model,
revised to reflect conditions specific to the PFPR industry. These cost curves were compiled
into a computerized spreadsheet cost model, which uses input datasets containing facility- and
PAI-specific data to estimate compliance costs for the surveyed facilities that: discharged
wastewater from PFPR operations in 1988. As discussed in Sections 8.5 through 8.7, the
final PFPR cost model consists of individual spreadsheet modules that calculate the costs and
loadings associated with the treatment of PFPR wastewater (the UTS module), storage and
reuse of facility wastewater streams, and off-site disposal of PFPR wastewater. Also
discussed, in Section 8.8, is the cost module used to develop compliance costs for refilling
establishments (Subcategory E).
8.4
Development of PFPR Cost Model and Input Datasets
This section describes the development and components of the PFPR cost
model. Section 8.4.1 discusses the development of the PFPR cost model from the cost model
used to estimate compliance costs for the pesticide manufacturing industry. Section 8.4.2
discusses the technical basis for the three treatment technology modules making up the PFPR
cost model: the wastewater treatment module (the UTS module), the storage and reuse
module, and the contract hauling for off-site disposal module. Section 8.4.3 discusses the
development and the function of the input datasets.
8.4.1
Development of the PFPR Cost Model from the Pesticide Manufacturing
Cost Model
Treatment technologies applicable to the removal and/or destruction of PAIs
were initially identified and characterized during development of effluent guidelines for the
pesticide manufacturing industry, and further evaluated during the PFPR proposed rule
development. These treatment technologies include activated carbon, biological treatment,
chemical oxidation, distillation, hydrolysis, hydroxide precipitation, resin adsorption, and
solvent extraction. The cost model developed for the pesticide manufacturing rulemaking
includes cost modules for each of these technologies, as well as a module for contract hauling
of wastewater for off-site incineration. EPA further identified ultrafiltration (UF) and reverse
' osmosis (RO) as treatment technologies applicable for the removal of PAIs.
The applicability of each of the pesticide manufacturing cost model treatment
technologies and UF/RO to the PFPR industry was evaluated based on data obtained from
PFPR questionnaire responses, from site visits and sampling visits conducted at PFPR
facilities, and from EPA treatability studies. These sources indicate that the most generally
applicable wastewater treatment technologies for PFPR facilities are activated carbon,
chemical oxidation, hydrolysis, and chemical (hydroxide or sulfide) precipitation. In addition,
due to the lower wastewater flow rates commonly found at PFPR facilities, contract hauling
of wastewater for off-site incineration is sometimes a more economically viable disposal
option than it is for pesticide manufacturers. Finally, these sources indicate 'that many PFPR
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Section 8 - Engineering Costs
facilities conduct wastewater recycling, some perform treatment operations, and several do
both. Wastewater recycling operations typically consist of storage and reuse of wastewater,
usually into the next production batch of the same pesticide product. PFPR facility pollution
prevention, wastewater conservation, and recycling/reuse practices are discussed in Section 7.6
of this document.
Revised versions of the activated carbon, chemical oxidation, hydrolysis,
chemical precipitation, and contract hauling for off-site incineration cost modules from the
pesticide manufacturing cost model were incorporated into the PFPR cost model. (These
treatment technologies are described in Section 7.2). In addition, new modules were
developed for inclusion in the PFPR cost model for emulsion breaking (also described in
Section 7.2) and storage/containment. These technologies were chosen for inclusion in the
PFPR cost model because they are commercially available at a scale applicable to the smaller
PFPR wastewater volumes, have been used for wastewater treatment at PFPR facilities, or are
necessary to ensure that the PFPR cost model contains technologies applicable to all PFPR
wastewater streams. The emulsion breaking cost module estimates the costs for equipment
and chemicals needed to remove oils, emulsifiers, and surfactants from PFPR wastewaters
prior to PAI treatment. A separate cost module for wastewater storage and containment is
required in lieu of the storage and containment design and cost algorithms hi the pesticide
manufacturing cost model, as the pesticide manufacturing storage and containment algorithms
are not applicable to the lower PFPR industry wastewater volumes. The revised cost curves
and design and costing algorithms used in each of these cost modules are discussed hi the
Final Pesticide Formulators. Packagers, and Repackagers Cost and Loadings Report, dated
March 31, 1994 (the "final PFPR cost report") (4).
8.4.2
PFPR Cost Model
A final PFPR cost model was developed to estimate compliance costs and
loadings specific to the regulatory options evaluated. Since the regulatory options range from
treatment and discharge of PFPR wastewater to zero discharge of PFPR wastewater, the final
PFPR cost model contains modules that can design the necessary equipment and estimate the
resulting costs for treatment, storage and reuse systems, or off-site disposal. Each module is a
compilation of computer spreadsheets driven by spreadsheet macros that automatically
calculate costs and loadings for individual PFPR facilities based on facility-specific data in the
PFPR questionnaire database. By using the appropriate inputs and combining the outputs
from these modules in different combinations, compliance costs may be estimated for each
regulatory option. These combinations are discussed in Section 8.4.3.
Wastewater Treatment Module (The "UTS" Module)
The current UTS module was developed from the individual cost modules for
each treatment technology. Test runs were conducted using the individual cost modules to
calculate treatment and discharge compliance costs for seven PFPR facilities. Analysis of
these test runs indicated that a treatment train incorporating emulsion breaking, hydrolysis,
activated carbon, chemical oxidation, and chemical precipitation would be capable of treating
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Section 8 - Engineering Costs
PFPR wastewaters to levels meeting the requirements of the P2 alternative or zero discharge.
Therefore, a standardized, or "universal," treatment system was developed that is applicable,
with minimal facility-specific modifications, to every water-using PFPR facility.
The Universal Treatment System (UTS) consists of raw wastewater storage
tanks (with capacity to hold up to three months' generation of wastewater or the facility's
maximum wastewater volume generated at one time in 1988, whichever volume is larger); a
jacketed process treatment vessel(s) in which emulsion breaking, chemical oxidation,
hydrolysis, and chemical precipitation take place; an activated carbon system consisting of a
feed storage tank, a grit pre-filter, a 3-bed absorber unit, and, if required due to size, a
backwash system; and effluent storage tanks equal in capacity to the raw wastewater storage
tanks. These wastewater treatment technologies are explained in Section 7.2 and are discussed
in relation to the UTS module in the following paragraphs. EPA points out that the model
calculates costs under the assumption that hydrolysis and chemical oxidation are carried out
only when required (based upon the treatability information described in Section 8.4).
Emulsion breaking pretreatment and activated carbon adsorption, however, are always
assumed to be carried out on the wastewater and therefore their costs are always included.
This approach is conservative, because it is likely that not all facilities will need to use
emulsion breaking or activated carbon adsorption to treat their wastewaters.
Emulsion Breaking
Many pesticide formulations involve mixing emulsifiers and other surfactants
with the PAI(s) in order to achieve specific application characteristics. Wastewater streams
containing these emulsifiers may be difficult to treat, as the emulsifiers may interfere with the
removal or destruction of PAI(s) or other pollutants. As a result, pretreatment by emulsion
breaking has been identified as the first step in the "best available technology" using the UTS
process vessel(s).
Based on information gathered on the PFPR industry through the questionnaire
and sampling, and information on equipment gathered through vendors, a design and cost
algorithm has been developed that calculates estimated treatment costs for an emulsion
breaking system based on heating and acidification of wastewater. The wastewater is heated
to 60°C (140°F) with steam, acidified to pH 3 with sulfuric acid, agitated for 1 hour, and then
allowed to settle for 23 hours. The oil layer is either skimmed off the top of the tank with a
wet vacuum pump (for small systems), or separated from the aqueous phase by pumping the
aqueous phase into a second process vessel (for, large systems). The de-emulsified wastewater
is neutralized with sodium hydroxide.
Chemical Oxidation
As described in Section 7.2, chemical oxidation is used in wastewater treatment
to destroy certain organic pollutants by the addition of an oxidizing agent (e.g., ozone,
permanganate, chlorine dioxide, or chlorine). Chemical oxidation has been demonstrated by
the pesticide industry and in EPA treatability studies to be effective at destroying alkyl halide,
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Section 8 - Engineering Costs
DDT-type, phenoxy, phosphorothioate, and dithiocarbamate PAIs in pesticide manufacturing
facility wastewaters.
Based on the available data, the UTS cost module includes a chemical
oxidation (via alkaline chlorination) design and cost algorithm. Wastewater pH is raised to 12
with sodium hydroxide, mixed with a 10% sodium hypochlorite (NaOCl) solution, held for a
four-hour residence time, and neutralized with sulfuric acid. The UTS cost module relies on
the activated carbon system to remove chlorinated oxidation products.
Hydrolysis
Hydrolysis is a chemical reaction in which organic compounds react with a
base (hydroxide compound) or water and break into smaller (and less toxic) compounds (see
Section 7.2 for detailed discussion).
Although most PAIs and classes of PAIs will hydrolyze at ambient conditions
to some extent, half-lives in many cases are measured in terms of weeks, months, or years.
Significant hydrolysis needs to occur in a relatively short period of time to be considered as a
viable treatment process. Treatability study data reported in the literature have indicated that
carbamate, phosphate, phosphorothioate, and phosphorodithioate based PAIs are subject to
fairly rapid hydrolysis under the proper conditions. EPA conducted a treatability study on 38
PAIs in these pesticide groups and in the urea group to determine hydrolysis rates at pHs of
2, 7, and 12 and at temperatures of 20°C and 60°C. At elevated temperature (60°C) and high
pH (12) conditions, most of these PAIs had half-lives of less than 30 minutes.
The UTS cost module hydrolysis design and cost algorithm calculates treatment
costs based on elevating the wastewater's pH and temperature. Wastewater is heated to 60°C
(140°F) with steam, mixed with sufficient sodium hydroxide to raise the pH to 12, agitated
for the required residence time (as determined by the longest PAI half-life), and neutralized
with sulfuric acid.
Chemical Precipitation
As described hi Section 7.2, chemical precipitation is a separation technology in
which the addition of chemicals during treatment results hi the formation of insoluble solid
precipitates. Settling or filtration then separates the solids formed from the wastewater.
The UTS cost module chemical precipitation design and cost algorithm
calculates treatment costs based on a combination of hydroxide and sulfide precipitation.
Wastewater pH is raised to 12 with sodium hydroxide, mixed with sodium sulfide, held for a
15-hour residence time to allow for settling, and neutralized with sulfuric acid. Settled solids
are drained from the process vessel, and residual solids are removed in the downstream
strainer and activated carbon system.
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Section 8 - Engineering Costs
Carbon Adsorption
Granular activated carbon (GAC) has been demonstrated to be a practical
method of removing a wide range of organic contaminants from industrial wastewater. In the
pesticide manufacturing industry, activated carbon adsorption has been used to treat
wastewater containing PAIs in the following structural groups: acetamides, aryl halides,
benzonitriles, carbamates, phenols, phosphorodithioates, pyrethrins, s-triazines, tricyclic,
toluidines, and ureas.
In addition, EPA and industry activated carbon treatability studies have
demonstrated sufficient treatability of pesticides in the acetanilide and uracil structural groups
to establish this treatment as a basis for control of specific PAIs in these groups. Carbon has
been shown in treatability studies to be an effective polishing control for thiocarbaniate PAIs.
Carbon also effectively removes high molecular weight, aromatic, and/or insoluble
compounds.
The activated carbon system consists of a feed tank, a transfer pump, three
carbon beds, and either a cartridge pre-filter or a backwash system (depending on the size of
the activated carbon beds selected). The feed tank is designed to hold the volume of
wastewater in the process vessel(s) before it is discharged to the carbon beds. The module
selects one of five activated carbon models with a configuration consisting of three carbon
beds operating in series; the five models can handle flows ranging from less than one gallon
per minute (gpm) up to 700 gpm. The three-bed design, with effluent from the second bed
monitored for breakthrough, maximizes the carbon usage efficiency of the system. New
carbon is used in the third bed to polish effluent from the second bed. When breakthrough is
detected from the second bed, the first bed is sent for off-site regeneration, the second bed
becomes the first bed, the-third bed becomes the second bed, and a fresh carbon bed is ,
brought on line as the third bed.
The activated carbon module accounts for solids removal from the wastewater
by incorporating either a cartridge pre-filter or a backwash system into the carbon system
design. A cartridge pre-filter is selected if one of the two smaller activated carbon models is
chosen and a backwash system is designed if one of the three larger activated carbon models
is chosen. The backwash system consists of a pump and two tanks, one tank to accumulate
and store treated wastewater for use as a backwash fluid and the other tank to store spent
backwash fluid. The spent backwash fluid is recycled to the raw wastewater feed tank.
Equations used to size the system, estimate the carbon usage rate, and estimate
capital and operating and maintenance costs can be found in Section 8.5.
Storage and Reuse Module
The storage and reuse cost module estimates costs associated with the storage
and containment of PFPR wastewaters prior to reuse. A facility that recycles and reuses
wastewater may store the wastewater in drums, or they may elect to install multiple tanks hi
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Section 8 - Engineering Costs
order to segregate wastewater streams contaminated with different PAIs or PAI types (i.e.,
herbicides, insecticides, etc.). This module determines, on a line-specific basis, whether drum
or tank storage is required; the number, size, and cost of the drums or tanks; and the
necessary size and resulting costs of a secondary containment system enclosing the wastewater
storage area. (See details of the design and costing algorithm in Section 8.6.)
Off-Site Disposal Module
The off-site disposal module calculates off-site disposal costs based on contract
hauling PFPR wastewater for off-site hazardous incineration. Off-site disposal costs can be
calculated for stream-specific wastewater sources or for the entire wastewater flow from a
facility. The module optimizes a storage design consisting of either a tank storage system or
a 55-gallon drum storage system. The module then calculates the associated transportation
and incineration costs. (See details of the design and costing algorithm in Section 8.7.)
8.4.3
Cost Model Input Datasets
The cost model contains separate datasets for estimated facility-specific influent
PAI concentrations; facility-specific wastewater flow rates; facility- and stream-specific
wastewater treatment and discharge status (based on the regulatory options); and PAI-specific
treatability data and achievable effluent concentrations. The actual datasets can be found in
the addendum to the final PFPR cost report (3).
Influent Concentrations
Facility-specific PAI concentration data are estimated based on questionnaire
data, sampling data, and information from the FATES database. These PAI concentrations
are estimated using facility-specific stream types and stream flow rate data obtained from the
PFPR questionnaire, stream-specific PAI concentration data obtained from EPA sampling
episodes, and FATES production data. PAI loadings are estimated for each stream at each
facility, and overall facility PAI loadings are estimated by summing the stream-specific PAI
loadings. Stream-specific PAI loadings are estimated by first identifying the PAIs that could
be in each stream (from information reported in the questionnaire and in FATES) and then
using sampling data to estimate the concentration for each of these PAIs. It is assumed that
the PAI(s) used in each pesticide product that is formulated, packaged, or repackaged on each
production line is contained in the wastewater streams generated by that line. It is also
assumed that all PAIs formulated, packaged, and repackaged by each facility are in the
facility's non-line-specific wastewater streams. The concentration of each PAI in the facility's
commingled wastewater (i.e., all line- and non-line-specific streams) is then estimated by
dividing the sum of the stream-specific loadings for each PAI by the total commingled
wastewater flow rate.
The PAI concentrations for each stream are extrapolated from the sampling
data in the PFPR analytical database. These sampling data were collected at 17 PFPR
facilities and have been sorted by stream type and PAI. For most stream types, the current
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Section 8 - Engineering Costs
sampling dataset lacks concentration data for numerous PAIs. That is, sampling data may be
available for atrazine in interior cleaning streams but not for atrazine in floor wash samples,
and data may not be available for certain other PAIs in any stream type. As a result,
extrapolated values are used for some PAI-stream type pairs, based on the following
hierarchy:
• Actual PAI concentration data are used for specific stream types when
available;
• PAI concentration data are transferred to structurally similar PAIs within
the same stream type if no actual concentration data are available; and
• Median values of all the PAI concentration data points within the same
stream type are transferred to all remaining PAIs lacking concentration
data for this stream type.
Information on the concentration of non-272 PAIs in facility wastewater
streams was not collected in the 1988 questionnaire. Therefore, data from the 1988 FATES
database was used to estimate concentrations of non-272 PAIs. Information from the 1988
FATES database indicates which facilities conducted PFPR operations using non-272 PAIs in
addition to 272 PAIs. The PFPR cost model assumes that the total concentration of non-272
PAIs in each wastewater stream is equal to the total concentration of 272 PAIs in that stream,
provided the facility formulates, packages, or repackages non-272 PAIs. For example, if the
total concentration of the 272 PAIs is 1,000 mg/L, and the facility produces non-272 pesticide
products, then the total concentration of non-272 PAIs is assumed to be 1,000 mg/L. Where
information from the FATES database indicates that the facility does not formulate, package,
or repackage non-272 PAIs, then the concentration of non-272 PAIs in all wastewater streams
at the facility is assumed to be zero. Where information from the FATES database indicates
that the facility formulates, packages, or repackages non-272 PAIs only, the PFPR cost model
was not used to estimate costs and loadings at the facility. The development of a national
cost and loadings estimates of non-272 only facilities is discussed in Appendix B of the EA of
the final rule (1).
Facility Wastewater Volumes
Comprehensive volume data are available for individual water-using PFPR
facilities in the PFPR industry sample, based on the responses and follow-up correspondence
to the 1988 PFPR questionnaire. Annual wastewater volumes for individual line-specific and
non-line-specific PFPR wastewater streams are documented in each questionnaire, along with
the destination for each stream. Based on this breakdown of the volume data, the volume of
wastewater generated by stream type (e.g., floor wash) and the total volume of PFPR
wastewater discharged in 1988 could be determined for each facility. All PFPR wastewater
sources except shower water, laundry water, fire protection test water, stormwater, and
laboratory water (which are not included for regulation) are included in the volume
calculations. (The reasons for excluding specific wastewater streams from regulation are
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Section 8 - Engineering Costs
presented in Section 5.2 of this document). Facilities reporting multiple wastewater streams
but only partial wastewater volume information are costed based on the wastewater volume
information provided. Likewise, if a facility reported generating wastewater in 1988 but did
not provide any volume data, no compliance costs are estimated for this facility. In addition,
PFPR wastewater streams that were recycled on- or off-site, contract hauled from the facility
for treatment or disposal, or handled in any manner other than being discharged hi 1988, are
not included hi the volume calculation. If a percentage of a wastewater stream was
discharged from a facility hi 1988, only the volume corresponding to that percentage is
included hi the volume calculated for mat facility.
Although EPA has identified UTS treatment technologies for all of the 272
PAIs, there is insufficient information to identify a UTS treatment technology for 44 of the
non-272 PAIs. Under each regulatory option, the management practice for wastewater
containing only these 44 PAIs differs from the management practice employed for
wastewaters containing at least one PAI that is not a PAI that lacks treatability data.
Because the 1988 PFPR questionnaire does not contain data on the wastewater
volumes associated with products containing only non-272 PAIs, wastewater volumes
associated with those products are estimated from data contained hi the 1988 FATES
database. The wastewater volumes for non-272 PAIs are further subdivided into wastewater
containing only PAIs that lack treatability data, and all other non-272 wastewater, based on
the 1988 FATES database. To determine the volume of wastewater associated with non-272
PAIs that have UTS technologies identified, the volume of wastewater associated with the 272
PAIs at each facility reported hi the 1988 PFPR questionnaire is multiplied by the ratio of the
production of products containing non-272 PAIs mat are treatable to the production of
products containing 272 PAIs.
To determine the volume of wastewater associated with PAIs that lack
treatability data, the volume of wastewater associated with the 272 PAIs at each facility
reported hi the 1988 PFPR questionnaire is multiplied by the ratio of the production of
products containing only those PAIs to the production of products containing 272 PAIs.
To optimize the design of the UTS at each facility, the cost model provides for
storage of all PFPR wastewater generated during each quarter of the year based on which
months the line was reported to be hi operation in 1988. To determine the number of
calendar quarters that each PFPR facility was in operation, the calendar year is split into four
quarters, with January through March constituting the first quarter, April through June
constituting the second quarter, July through September constituting the third quarter, and
October through December constituting the fourth quarter. If a PFPR line was hi operation in
any month of a certain quarter of 1988, the PFPR facility is considered to have been hi
operation during that quarter. Wastewater reported for a specific line in the questionnaire is
split evenly among all quarters that the line was hi operation hi 1988. For example, if a
PFPR facility operated a line hi June and December of 1988, any wastewater reported to be
generated on that line would be split evenly between the second and fourth quarters. Any
non-line-specific wastewater reported is split evenly among the quarters that the facility
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Section 8 - Engineering Costs
reported conducting PFPR operations in 1988. For example, if a PFPR facility has two lines
with the JBrst in operation during the first two quarters of 1988 and the second in operation
during the second two quarters of 1988, any non-line-specific wastewater would be split
evenly among all four quarters.
The model utilizes the quarterly volumes to determine the appropriate design
size of the wastewater storage tank(s), the batch treatment vessel, and the carbon adsorption
system. The model compares the wastewater storage capacity based on the highest quarterly
volumes with the maximum amount of wastewater discharged from any source at any one
time, in order to ensure that adequate storage is available.
Wastewater Stream Cost Codes
The cost model calculates costs and loadings on a wastewater stream-specific
basis at each PFPR facility, according to the applicability of P2 and recycle/reuse measures to
each stream. These cost codes indicate whether the water can be reused directly (without
treatment or storage), stored and reused, treated and reused, treated and discharged, discharged
without treatment, or contract hauled for disposal off site. In general, rinsates generated from
a specific line are considered reusable after storage if the product formulated on that line uses
water and is formulated multiple times over the course of the year. The stored rinsate could
then be used in the next formulation of the product. Treated wastewater (in which PAIs are
treated to concentrations equal to or less than 0.8 ppm) is considered reusable in exterior
cleaning applications.
Each stream was assigned a cost code dependant on a conservative evaluation
of the quality of wastewater generated and the ability to reuse, treat and reuse, or treat and
discharge that water. Stream cost codes may include a choice for contract hauling for off-site
incineration. This is used when costing the Zero Discharge Option (which includes some
contract hauling of streams that are difficult to reuse) and regulatory Option 4 (pollution
prevention and reuse for interior sources with contract hauling for off-site incineration for
other wastewater sources). The codes are:
• Code A: Stream is costed, for storage and reuse.
• Code B: Stream is costed for contract hauling for off-site disposal.
• Code C: Stream is costed for treatment and reuse under the zero
discharge option, or treatment and discharge under the P2 alternative
(under the proposed rule, these streams were costed for treatment and
reuse).
• Code D: Stream is costed for treatment and reuse under the zero
discharge option, or treatment and discharge under the P2 alternative
(under the proposed rule, these streams were costed for treatment and
reuse or off-site incineration).
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Section 8 - Engineering Costs
• Code E: No cost associated with the reuse of this stream.
• Code F: This code is no longer used.
• Code G: This code is no longer used.
• Code H; Stream is costed for P2 equipment and the volume of the
stream is reduced. Streams are coded H for the P2 alternative only.
In terms of costing the survey facilities, interior streams consist of non-line-
specific drum rinsates, non-line-specific bulk tank rinsates, and line-specific interior cleaning
streams. Interior streams are considered to be reusable without treatment, with the exception
of particular streams that may be difficult to reuse. Drum rinsates are assumed to be reusable
into a product formulation without storage or treatment, and therefore receive Code E. Bulk
tank rinsates are also assumed to be reusable into product formulations without treatment, and
therefore receive either Code A or Code E, depending upon whether a facility generating this
stream already reuses or contract hauls the wastewater.
Interior cleaning streams may, however, exhibit certain characteristics which
make them difficult to reuse. Interior cleaning streams were evaluated based on these
characteristics or on the process generating the rinsate. The following characteristics were
identified:
• Lines that do not formulate products: Cleaning wastewater generated on
lines that only package or repackage products cannot be reused into any
other product formulation. These streams receive Code B for the Zero
Discharge Option and Code D for the P2 alternative.
• Lines that handle dry or emulsifiable concentrate products: Cleaning
wastewater from lines that handle dry or emulsifiable concentrate
products cannot be reused in these formulations since these products do
not contain water. Since it is impossible to determine the portion of
water on the line which is due to only these products, these streams
receive Code B for the Zero Discharge Option, and Code D for the P2
alternative.
• Lines at toll formulators: These facilities may not make a product more
than once hi any given time period and therefore may not be able to
reuse cleaning water directly into product formulations. These streams
receive Code B for the Zero Discharge Option, and Code D for the P2
alternative.
• Lines that have special cleaning operations: Facilities may have
difficulty reusing cleaning wastewater from these operations directly into
product formulations since special cleanings are often unplanned and
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Section 8 - Engineering Costs
may contain many different PAIs or generate large quantities of water.
Based on facility-specific analysis of other cleaning streams on the same
line, water that can be reused into products formulated on that line is
given Code A, and the remaining water is given Code B for the Zero
Discharge Option and Code D for the P2 alternative.
Lines that use solvent combination cleaning: Facilities may have
difficulty reusing cleaning water that may contain solvents when a line
is switched from a solvent-based to a water-based product. These
streams are given Code B for the Zero Discharge Option and Code D
for the P2 alternative.
Lines that perform multiple cleaning steps: Cleaning water from lines
that use sequences of cleaning steps, including solvent cleaning and
water cleaning, may contain solvents and may be difficult to reuse.
These streams receive Code B for the Zero Discharge Option and Code
D for the P2 alternative.
Lines that perform detergent cleaning: Cleaning wastewaters that
contain detergents may be difficult to re'use into products that normally
do not contain detergents. These streams receive Code B for the Zero
Discharge Option and Code D for the P2 alternative.
Lines that perform cleaning with other substances: Lines that perform
cleaning with water in addition to cleaning with other substances (e.g.,
abrasives or dry carriers) may be difficult to reuse in products that do
not contain such substances. These streams receive Code B for the Zero
Discharge Option and Code D for the P2 alternative.
Lines that generate more wastewater than can be potentially reused:
Based on the available information, some lines were identified as
generating more water from cleaning operations than was assumed could
be reused directly into product formulations. The volume of water that
could be reused into the product formulations, was calculated as follows:
1) First, the pounds of PAI reported to be in the product was
calculated. The percent of PAI(s) provided by the facility in
Section 3 of the questionnaire were used to determine this value:
Total Pounds
of Production
x
Total % of
PAI in Product
Pounds of
PAI
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Section 8 - Engineering Costs
2) Next, the calculated pounds of PAI (from #1) were subtracted
from the total pounds of product to determine the pounds of
product remaining:
Total Pounds
of Production
Pounds of
PAI
Pounds of
Product Remaining
3) The pounds of product remaining (from #2) were converted to
gallons:
Pounds of Product
Remaining
34 pounds _ Gallons of Product
gallon Remaining
4) It was assumed that cleaning water could be used to make up
50% of this volume, which was assigned Code A:
Gallons of Product x 5Q% = Gallons of water that
Remaining ° can be reused in formulation
5) The volume of cleaning water that exceeded the volume that
could be reused was assigned Code B for the Zero Discharge
Option and Option 4, and Code D for the P2 alternative.
Line-specific interior cleaning streams that do not exhibit any of the above
characteristics are assumed to be reusable into product formulations without treatment, and
therefore receive Code A (storage and reuse).
Waste streams that were not discharged directly (via NPDES discharge point)
or indirectly (to a POTW) in 1988 are assigned Code E (no cost for the reuse of these
streams).' These streams were already either recycled or otherwise disposed of via a zero
wastewater discharge method in 1988.
PAI Treatability Dataset
For each PAI, the PFPR cost model identifies the applicable UTS treatment
technology. This treatment technology is the "BAT" treatment technology associated with the
PAI. A UTS treatment technology is applicable if treatability data demonstrating effective
treatment are available from the pesticide manufacturing or PFPR project records. Where
more than one treatment technology is applicable, the cost model designates only one
technology as applicable hi the following order: (1) precipitation1; (2) hydrolysis;
precipitation is applied to metallic PAIs only.
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Section 8 - Engineering Costs
(3) chemical oxidation; (4) activated carbon adsorption. However, treatability data are not
available for all combinations of technologies and PAIs. Where treatability data are not
available for a particular PAI, treatability data are transferred to the PAL The treatability data
transfer methods are described in Section 7 and Appendix D of this report.
Hydrolysis half-lives and activated carbon Freundlich parameters are used by
the cost model to determine batch times and carbon usage requirements. PAIs that are
treatable by precipitation or chemical oxidation trigger certain design and costing algorithms
in the cost model. These algorithms include cost functions for energy and materials which are
based on flow rate and batch volume. No PAI-specific data are used in calculating the costs
associated with precipitation and chemical oxidation treatment costs other than identifying the
PAIs amenable to these treatment technologies. A more thorough description of the available
treatability data and data transfers is contained in the Final Treatabilitv Database Report (5)
and the Addendum to the Final Treatabilitv Database Report (6).
As with the influent concentration dataset, achievable effluent concentration
data are not available for all PAIs. Therefore, achievable effluent concentrations are
extrapolated from other PAIs, based on the following methodology:
• PAIs with numerical pesticide manufacturing BAT limitations are
assumed to be treatable to the same achievable effluent: concentrations as
determined under the pesticide manufacturing rulemaking following
pretreatment to break emulsions.
• PAIs without numerical pesticide manufacturing BAT limitations that
are in the same structural group as a PAI with BAT limits are assumed
to be treatable to the same achievable effluent concentration.
• PAIs that do not have numerical pesticide manufacturing BAT
limitations and that are not structurally similar to PAIs with numerical
BAT limitations are assumed to be treatable to conservatively high
effluent concentration. This extrapolated concentration is equal to the
90th percentile highest effluent concentration of all the PAIs with
numerical BAT limitations.
• Non-272 PAIs are assumed to be treatable to the median achievable
effluent concentration for all 272 PAIs.
Each in-scope PAI identified in the FATES 1988 database has a "BAT" treatment
technology2^ associated with it, which is presented in Table 10 in Appendix A of this
document. This PAI treatability dataset is used by the cost model to determine which
treatment technologies need to be sized and costed. The achievable effluent concentration for
2Forty-four PAIs lack treatability data; therefore, pollution prevention is listed as the treatment technology on
Table 10 in Appendix A of this document.
8-16
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Section 8 - Engineering Costs
each PAI is required by the cost model to determine batch times, reagent quantities, and
carbon usage requirements. PAI hydrolysis half-lives and PAI carbon saturation loadings are
also used by the cost model to determine batch times and carbon requirements.
Cost Model Output
Each module in the cost model (the UTS module, the storage and reuse
module, and the off-site disposal module) generates capital costs and operating and
maintenance (O&M) costs. In addition, the UTS module calculates land costs (calculated for
those facilities that indicated in the questionnaire that they lack the necessary land for a
wastewater treatment unit) and monitoring costs. The final costs for each facility consist of
the combined capital costs, including the land cost, and the combined O&M cost, including
the monitoring cost from each of the modules. This section describes the combinations of
modules employed to estimate compliance costs for the four regulatory options. See the final
PFPR cost report (4) and the addendum to the final PFPR cost report (3) for more detail on
how individual costs were developed.
Revised Zero Discharge Option
Under the Revised Zero Discharge Option, facility wastewater streams coded A
are costed for storage and reuse, streams coded B are costed for off-site disposal as hazardous
waste, streams coded C and D are costed for treatment and reuse, and streams coded E are
managed at no cost through direct reuse. Therefore, the storage and reuse module is used for
the A streams, and the UTS module with 5% blowdown is used for streams coded C and D
(reduced by 5% to account for UTS blowdown), and the off-site disposal module is used for
streams coded B plus 5% of the volume of streams coded C and D.
The Revised Zero Discharge Option results in no effluent PAI loadings because
all wastewater is directly reused, stored and reused, treated and reused, or disposed off site,
resulting in zero discharge of PFPR process wastewaters.
Pollution Prevention Alternative
Under the P2 alternative, facility wastewater streams coded A are costed for
storage and reuse, streams coded C and D are costed for treatment and discharge, streams
coded H are reduced by 80% and are costed for treatment and discharge, and streams coded E
are managed at no cost through direct reuse or discharge without treatment. Therefore, the
storage and reuse module is used for the A streams, and the UTS module with 0.2%
blowdown is used for streams coded C and D. Costs associated with off-site disposal of the
UTS blowdown are calculated by the UTS module.
Estimated effluent PAI loadings for the P2 alternative consist of the PAI
loadings contained in wastewaters discharged without treatment plus the loadings from
wastewater discharged after UTS treatment. Therefore, PAI loadings are calculated as the
sum of the raw 1988 loading of wastewaters coded E that are discharged without treatment
8-17
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Section 8 - Engineering Costs
(i.e., DOT and safety equipment cleaning streams) plus the loadings from the wastewater
streams coded C and D and H after the PAI concentrations in those streams have been
reduced to the target achievable effluent concentrations. Although the volume of streams
coded H is reduced by 80% prior to UTS treatment, the total loading in these streams is not
reduced prior to UTS treatment, resulting in an increased concentration in streams coded H.
Revised Option 1
All PFPR wastewater is costed for treatment and discharge based on the PFPR
wastewater discharged in 1988. Therefore, only the UTS module with 0.2% blowdown is
used to estimate costs. Estimated effluent PAI loadings for Revised Option 1 are calculated
as loadings from discharged wastewater streams after the PAI concentrations in those streams
have been reduced to the UTS achievable effluent concentrations.
Revised Option 4
Revised Option 4 is based on the Revised Zero Discharge Option, but
substitutes off-site disposal of wastewater for streams that are coded for treatment and
discharge under the Revised Zero Discharge Option. Wastewater streams coded A are costed
for storage and reuse, streams coded C and D are costed for off-site disposal, and streams
coded E are managed at no cost through direct reuse. Therefore, the storage and reuse
module is used for the A streams, and the off-site disposal module is used for the C and D
streams.
Revised Option 4 results in no effluent PAI loadings because all wastewater is
directly reused, stored and reused, or disposed of off site, resulting in zero discharge of PFPR
process wastewaters.
8.5
UTS Module Design and Cost Algorithm
This section presents the design and cost equations in the UTS cost module.
The UTS cost module is used to determine facility-specific design parameters and associated
capital and annual O&M costs for all elements making up the UTS. These elements include:
• Wastewater storage tanks (discussed in Section 8.5.1);
• One or more process vessels in which batch physical/chemical treatment
steps (emulsion breaking, hydrolysis, chemical oxidation, and chemical
precipitation) take place (Section 8.5.2);
• An activated carbon treatment system (Section 8.5.3);
• Ancillary pumps and strainers (Section 8.5.4);
8-18
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Section 8 - Engineering Costs
• Containment for treatment system equipment and treatment chemicals
(Section 8.5.5);
• Disposal of solid waste residuals (Section 8.5.6);
• Land required for the treatment system (Section 8.5.7); and
• Effluent monitoring (Section 8.5.8).
The UTS module determines design parameters based on facility-specific
wastewater volumes and PAIs, and PAI-specific concentration and treatability data. For
Option 1, the facility- and PAI-specific input datasets are based on all PFPR wastewater
streams discharged at each facility. For the zero discharge option and the P2 alternative, the
datasets are based only on streams coded C, D, and H. Once each treatment system
component is sized, the component's costs are calculated using cost curves obtained from
vendor and literature sources. Copies of all vendor information and other design and cost
data used to develop the cost curves are contained in the final PFPR cost report (4).
Some PFPR facilities make use of various filtration technologies (such as
ultrafiltration and microfiltration) instead of physical/chemical treatment to produce reusable
effluent. Vendor and PFPR facility information indicate that ultrafiltration is a viable
technology for both emulsion breaking and for PAI removal. EPA included design and cost
equations for ultrafiltration in the UTS cost module, in order to conduct a sensitivity analysis
on the costs associated with the addition of ultrafiltration to the UTS design. These equations
are presented in Section 8.5.9. EPA concluded that ultrafiltration adds relatively small capital
costs and very small O&M costs to the overall UTS costs; however, EPA also concluded that
the incremental treatment provided by ultrafiltration to the emulsion breaking and PAI
removal steps was not required to achieve effluent suitable for reuse. As .a result,
ultrafiltration is not part of the treatment system costed for each facility requiring treatment
under Option 1, the zero discharge option, and the P2 alternative.
8.5.1
Wastewater Storage Design and Cost
The UTS module utilizes facility wastewater volume data to configure both a
raw wastewater storage system and a treated effluent wastewater holding system. The raw
wastewater storage system provides sufficient storage for the maximum size and number of
quarterly wastewater treatment batches through the process treatment tank. The effluent
wastewater holding system, set equal in volume to the raw wastewater storage system,
provides sufficient storage to test treatment performance prior to discharge or reuse, and also
to minimize the analytical monitoring costs. Both the raw wastewater and effluent wastewater
storage systems are configured with capacities equal to a design flow of 120% of the largest
of the quarterly volumes or 120% of the largest batch volume. This calculation ensures that
both storage systems have sufficient capacity to handle the largest volume of water generated
in any one quarter of a year. Tank sizes range from a minimum of 250 gallons to a
maximum of 30,000 gallons (based on vendor literature). Tanks smaller than 2,000 gallons
8-19
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Section 8 - Engineering Costs
are polyethylene tanks and tanks larger than 2,000 gallons are carbon steel tanks. Tank sizes
are rounded up to the next 100 gallons. If the design flow is larger than 30,000 gallons,
multiple storage tanks are configured for each storage system.
8.5.2
Process Vessel(s) Design and Cost
The UTS includes a process vessel for batch emulsion breaking, hydrolysis (if
required), chemical oxidation (if required), and chemical precipitation (if required). The
process vessel is a carbon steel tank equipped with a steam jacket and an agitator, and has a
capacity of between 1,000 and 3,000 gallons.
The treatment system cost model spreadsheet determines the number and size
of process vessels required to adequately treat the design flow in 90 days or less to avoid
build-up of wastewater in storage (although some facilities may need to treat water less
frequently).
The design algorithm is a function of the volume of wastewater to be treated
and the required vessel residence time. The spreadsheet calculates a residence time based on
the required time to treat the wastewater for emulsion breaking, hydrolysis, chemical
oxidation, and chemical precipitation. Six hours are allotted for the chemical oxidation step,
24 hours for the emulsion breaking step, 15 hours for chemical precipitation, and the
necessary time required for hydrolysis, based on the half-lives of the PAIs handled at the
facility that are amenable to hydrolysis (the UTS module determines the time required for
hydrolysis based on the PAI with the longest half-life). The lengths of time required to
perform the individual treatment steps are added and the total number of days (based on 24
hours per day) required to treat a batch of wastewater is calculated.
The UTS module next optimizes the process vessel size. Once the required
batch treatment time is estimated, the UTS module selects the smallest vessel that could treat
the design flow in 90 days and calculates costs associated with the selected vessel. The UTS
module then selects the next largest vessel (in 500-gallon increments) and calculates costs to
determine whether a larger vessel would be more cost-effective. A larger vessel would
require a larger capital cost but may result in lower O&M costs because fewer batches of
wastewater would have to be processed through the vessel (resulting in lower labor and
energy costs). If the larger vessel is cheaper than the smaller vessel, the UTS module then
selects the next largest size vessel and compares costs once again. This process continues
until the least expensive vessel (between 1,000 and 3,000 gallons) is chosen. In order to
compare costs of the different process vessels, the module uses annualized costs. Annualized
costs are estimated by amortizing the capital costs over ten years (assuming 10% interest) and
adding the amortized capital costs to the annual O&M costs.
If a 3,000-gallon vessel is not large enough to treat the design flow in 90 days,
multiple process vessels are included in the design. In addition, the UTS design algorithm has
both small and large system designs from which to choose. "Small" PFPR facilities (facilities
that treat fewer than five batches of wastewater per quarter) should be able to treat PFPR
8-20
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Section 8 - Engineering Costs
wastewater on a batch basis. In this case, the oil layeisfrom the emulsion breaking step is
skimmed off the top of the water in the process vessel. Additional hydrolysis, chemical
oxidation, and sulfide precipitation steps, as required, take place in the same vessel. The
facility has the flexibility of pumping the aqueous phase of the de-emulsified wastewater out
of the process vessel, removing the oil layer as a sludge for disposal, and pumping the de-
emulsified wastewater back into the process vessel for further treatment. "Large" facilities
(facilities that treat over five batches of wastewater per quarter) are assumed to treat PFPR
wastewater on an ongoing basis and may not enjoy this flexibility. As a result, the UTS
design for "large" facilities consists of two process vessels hi series. Emulsion breaking takes
place hi the first vessel and hydrolysis, chemical oxidation, and sulfide precipitation steps, as
needed, take place in the second vessel. Figures 8-1 and 8-2 are schematic diagrams of the
UTS designs for small and large PFPR facilities, respectively.
The cost equation for carbon-steel, jacketed, agitated tanks was derived from
information in Chemical Engineering Magazine (4):
Process Vessel Cost
($ per vessel)
= 2,030 + (1.4 x volume) - (2.0xlO~4 x volume2)
The final process vessel cost is the unit process vessel cost multiplied by the
number of vessels required, multiplied by a 48% delivery and installation factor (based on
information from the textbook Plant Design & Economics for Chemical Engineers (4), and
adjusted to 1988 dollars via the Marshall & Swift Index for process equipment hi Chemical
Engineering Magazine (4).
The agitator is designed based on the process vessel size. The minimum
agitator size is 0.5 hp for a 1,000-gallon vessel, and increases in size by 0.5 hp per 1,000
gallons of capacity. The agitator cost is included in the cost of the process vessel.
Treatment Requirements
The UTS module next calculates ,the amount of steam, treatment chemicals
(H2SO4, NaOH, NaOCl, and Na2S), labor, energy, and other materials required to treat the
annual wastewater volume, based on the estimated number of treatment batches required each
year. The module also calculates the area required to store a 6-month supply of treatment
chemicals on containment pallets. Lastly, the UTS module estimates the annual volume of
de-emulsified oil that would be skimmed from the wastewater after being treated hi the
process treatment vessel. This amount is based on the annual volume of wastewater and the
average concentration of oil and grease measured in PFPR wastewater samples collected by
the Agency.
8-21
-------
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8-23
-------
Section 8 - Engineering Costs
Steam Requirements
Steam heat is required for emulsion breaking and hydrolysis,. The UTS cost
module designs both treatment steps to operate at 140°F. The module assumes the influent
wastewater temperature to be 50°F, and mat negligible heat loss occurs across the process
vessel's jacket. The steam requirement (SR) is calculated by the equation:
SR I lb = Heat Required (BTU)/Heat of Vaporization (BTU/lb)
[ batch J
The heat required (HR) is calculated by the equation:
HR (BTU) - v 1VeSSf n x Temperature 8.34Jb J_ BTU
v J v«i«m*» (gai) Rise gai n, op
From steam tables, the heat of vaporization for 15 psig saturated steam at
140°F is 945 BTU/lb. Therefore:
f.
lb
SR I *" 1 = 0.794 x Vessel Volume (gal)
[ batch J
This steam requirement is summed for all emulsion breaking and hydrolysis
treatment batches to determine the annual steam requirement for each facility. The UTS
module uses a steam cost of $0.0015 per pound, adjusted from 1980 dollars to 1988 dollars,
from Plant Design & Economics for Chemical Engineers (4).
Sulfuric Acid Requirements
Sulfuric acid (H2SO4) is used to lower the pH for emulsion breaking and to
neutralize treated wastewater following hydrolysis, chemical oxidation, and chemical
precipitation steps.
According to vendor information, 49 mg/L of 100% H2SO4 are required to
adjust wastewater pH from 7 to 3. Assuming that 50% H2SO4 is used, this figure is doubled
to 98 mg/L, and multiplying this figure by a factor of 2 (to ensure sufficient acidification)
yields 196 mg/L, or 0.196 g/L. This figure converts to approximately 0.0016 lb H2SO4 per
8-24
-------
Section 8 - Engineering Costs
gallon of wastewater. As a result, the acid requirement (AR) for emulsion breaking is
calculated by:
AR
= 0.0016 Ib H2S04 x Batch Volume (gallon) x
24 V6 '
Number
of Batches
For pH neutralization following alkaline wastewater treatment steps, the same
vendor information that indicates 0.49 g/L of 100% H2SO4 are required to adjust wastewater
pH from 12 to 7 is used. Assuming 50% H2SO4 is used, this figure is doubled to 0.98 g/L,
and multiplying this figure by a factor of 2 (to ensure sufficient acidification) yields 1.96 g/L.
This figure converts to approximately 0.016 Ib H2SO4 per gallon of wastewater. As a result,
the acid requirement (AR) for the alkaline wastewater treatment steps is calculated by:
Ilh 1
_ = 0.016 Ib H2SO4 x Batch Volume (gallon)
yrj
This acid requirement is summed for all emulsion breaking and alkaline
treatment batches to determine the annual H2SO4 requirement for each facility, with a
minimum amount equal to 55 gallons (640 pounds at 50% strength). The UTS module uses a
H2SO4 cost of $0.75 per pound for 50% H2SO4, adjusted from 1992 dollars to 1988 dollars,
based on a vendor quote.
The UTS cost module also accounts for the secondary containment of drums of
H2SO4 on spill pallets. Sufficient storage is provided for a 6-month supply of acid.
Sodium Hydroxide Requirements
Sodium hydroxide (NaOH) is used to elevate the pH for hydrolysis, chemical
oxidation, and chemical precipitation, and to neutralize treated wastewater following emulsion
breaking.
According to vendor information, 0.00366 pounds of 100% NaOH are required
to adjust the pH of one gallon of wastewater from 3 to 12. Assuming 50% caustic is used,
this figure is doubled to 0.00732 pounds per gallon. As a result, the NaOH requirement (NR)
for the alkaline wastewater treatment steps is calculated by:
NR \— I = 0.00732 Ib NaOH x Batch Volume (gallons)
This NaOH requirement is summed for all alkaline treatment batches to
determine the annual NaOH requirement for each facility, with a minimum amount equal to
8-25
-------
Section 8 - Engineering Costs
55 gallons (690 pounds at 50% strength). The UTS module uses a NaOH cost of $0.16 per
pound, adjusted from 1992 dollars to 1988 dollars, based on vendor information.
The UTS cost module also accounts for the secondary containment of drums of
NaOH on spill pallets. Sufficient storage is provided for a 6-month supply.
Sodium Hvpochlorite Requirements
Sodium hypochlorite (NaOCl) is used for chemical oxidation via alkaline
chlorination. A 10% NaOCl solution is used as the chlorinating agent (NaOCl was used in
the EPA alkaline chlorination treatability study). Based on the treatabih'ty study, a
conservative estimate of 1,000 milligrams of chlorine are required for every liter of
wastewater. This results in an NaOCl feed rate of 19.2 gallons per 1,000 gallons of
wastewater. Therefore, the chlorine requirement (CR) for alkaline chlorination is calculated
by:
CR
= 19'2 gallons x Batch Volume (gallons)
1,000 gallons
This chlorine requirement is summed for all alkaline chlorination treatment
batches to determine the annual NaOCl requirement for each facility, with a minimum amount
equal to 55 gallons. The UTS module uses a NaOCl cost of $0.67 per gallon, adjusted to
1988 dollars, based on vendor information.
The UTS cost module also accounts for the secondary containment of drums of
NaOCl on spill pallets. Sufficient storage is provided for a 6-month supply.
Sodium Sulfide Requirements
Sodium sulfide (TS^S) is used when chemical precipitation is required.
Information concerning the amount of Na2S needed for precipitation was available from EPA
treatabih'ty studies and rulemaking development documents and from vendors. According to
these sources, 0.416 pounds of Na2S per 1,000 gallons of wastewater is effective in
precipitating out metals. Therefore, the sulfide requirement (SR) for chemical precipitation is
calculated by:
SR f Jb =
= 0.416 pounds x Batch
( n
yr 1,000 gallons
This sulfide requirement is summed for all chemical precipitation treatment
batches to determine the annual Na2S requirement for each facility, with a minimum amount
equal to 55 gallons. The UTS module uses a Na2S cost of $0.75 per pound, adjusted from
1992 dollars to 1988 dollars, based on vendor information.
8-26
-------
Section 8 - Engineering Costs
The UTS cost module also accounts for the secondary containment of drums of
on spill pallets. Sufficient storage is provided for a 6-month supply.
Labor Requirement
Labor is estimated on a per-batch basis. Each batch of wastewater processed is
assumed to require one hour for pumping and four hours for chemical addition, wastewater
testing, and other miscellaneous maintenance requirements. An extra hour is allocated if
chemical precipitation is required.
The labor cost is calculated at $19.15 per hour for unionized operating
engineers, adjusted from 1991 dollars to 1988 dollars, based on information from the
Richardson Construction Cost Trend Reporter (4).
Energy Requirement
The total energy requirement is the sum of the energy needed for the wet
vacuum pump (if included in the design) and the agitator (the process vessel feed pump
energy requirement is discussed in Section 8.5.4). The wet vacuum pump is 3 HP and
operates for 0.5 hours per batch, and the agitator is 0.5 HP per 1,000 gallons of process vessel
capacity and operates 8 hours per batch. With 0.746 kw-hr/HP-hr and assuming both the wet
vacuum pump and the agitator operate at 70% efficiency, the total energy requirement is
calculated by:
Total Energy (kw-hr) = Wet Vacuum Pump Energy + Agitator Energy
Wet Vacuum Pump XT ^T. * i. « ^ i. »
Energy (kw-hr) = No" of Batches x °'5 hours x 3
x 0.746 x
0.7
Agitator Energy (kw-hr) = No. of Batches x 8 hours x 0.5 HP x
Vol10.746x 1
1,000
0.7
The energy cost is calculated at $0.083 per kw-hr, in 1988 dollars, based on
U.S. Census data.
Capital Costs of the Process Vessel Batch Treatment System
Capital costs are estimated for the process vessel(s), wet vacuum pump, and
containment pallets used to store the treatment chemicals. These costs account for the actual
equipment costs as well as the delivery and installation of the equipment. An additional 3%
of equipment costs is added to account for miscellaneous costs associated with the process
vessel system, and an additional 10% of equipment costs is added to account for engineering,
administration, and legal costs.
8-27
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Section 8 - Engineering Costs
Operating and Maintenance Costs of the Process Vessel Batch Treatment
System
Annual O&M costs are estimated for labor, energy, steam, and treatment
chemical costs. An additional 3% of the total capital costs associated with the process vessel
system is added to the annual O&M costs to account for any miscellaneous O&M costs.
Another 1% of the total capital costs is added to the O&M costs to account for annual
insurance costs.
8.5.3
Carbon Adsorption Unit
This section discusses the sizing of the granular activated carbon system, the
carbon usage rate, and the capital and O&M costs of the activated carbon system.
Granular Activated Carbon System Sizing
The cost model designs and optimizes the activated carbon system using a
methodology similar to the one used to optimize the process vessel design. The spreadsheet
first identifies the smallest activated carbon model that would adequately handle the quarterly
flow at a facility (at a default empty bed residence time (EBRT) of 60 minutes) and estimates
capital and O&M costs for the system. The spreadsheet then selects the next largest model
and compares that model's annualized costs with the smaller model's annualized costs to
determine which model is more cost-effective. The larger model would have a higher capital
cost but may have lower overall costs due to fewer carbon bed change-outs. If the larger size
results in lower overall costs, the spreadsheet selects the next largest size model and compares
costs once again. This process continues until the most cost-effective of the five activated
carbon models is selected.
To determine the appropriate GAC model, the module first compares the
volume required with the volume capacity of each model. The module determines the volume
required using the following equation:
Volume Required (gal) = Flow (gpm) x EBRT (min)
Using this volume, the module selects the appropriately sized GAC model (i.e., one that will
provide volume equal to or greater than the volume required). The module also checks to
ensure that the hydraulic loading of the GAC system does not exceed the recommended rate
of 5 gpm/ft2. The module calculates the hydraulic loading by dividing the flow rate hi
gallons per minute by the cross-sectional area of the selected GAC unit. If the selected unit
does not result in a hydraulic loading of greater than 5 gpm/ft2, and provides sufficient
volume for the system flow rate and EBRT, then that unit is appropriate.
8-28
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Section 8 - Engineering Costs
Carbon Usage Rate
The carbon usage rate is calculated using the following parameters: PAI
influent concentrations, achievable PAI effluent concentrations, flow rate, and the saturated
loading (based on influent concentration) of the activated carbon for each PAI amenable to
GAC. The equation used is:
Usage Rate Ib
day
Difference in PAI cone. (mg/L) x flow (gpd) x 8.34 Ib/gal 1
1,000,000 ~ I
Saturation Loading
Ib PAI j
Ib Carbon J
In addition, the following equation was added to account for carbon used to remove other
organic constituents that may be present in the wastewater. The equation used is:
Carbon Usage =
33.3 Ib Carbon
1,000 gal Wastewater
This carbon usage rate is based on actual EPA sampling data from PFPR facilities.
Capital Costs of the Activated Carbon System
The module estimates capital costs for the feed tank(s), activated carbon beds,
and the prefilter or backwash system. The activated carbon system and backwash system
costs are based on quotes from an activated carbon unit vendor. The prefilter costs are based
on quotes from other vendors. These costs account for the actual equipment costs as well as
the delivery and installation of the equipment. To account for miscellaneous equipment
associated with the activated carbon system, 42% of the equipment costs is added. All costs
are indexed from 1990 dollars to 1988 dollars.
Operating and Maintenance Costs of the Activated Carbon System
The module estimates annual costs for carbon replacement, labor, energy, and
effluent breakthrough monitoring. Energy costs are a function of the amount of water being
processed through the activated carbon system as well as the number of calendar quarters that
the activated carbon system would be in operation. Monitoring costs, which are based on a
total organic carbon (TOC) analysis, are a function of the number of batches of wastewater
processed through the activated carbon system. An additional 3% of the total capital costs of
the activated carbon system is added to the annual O&M costs to account for any
miscellaneous O&M costs. Another 1% of the total activated carbon equipment costs is added
to the O&M costs to account for annual insurance costs. All costs are indexed to 1988
dollars.
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Section 8 - Engineering Costs
Energy Costs
Energy is required for the backwash pumping and for the building. For
backwash pump costs, the following equations are used:
Energy Usage = No. of Production Days x
24hrs
day
x Pump Power (hp) x
0.746 kw
Annual Energy Cost = Energy Usage (kw-hr/yr) x Energy Cost ($/kw-hr)
However, as the backwash pumps only operate 20 min/day the usage is reduced
by a factor of 0.014.
The cost of electricity used in this module is estimated using a unit value of
$0.10/kw-hr. The 1987 statistical abstract reports an energy cost of $0.083/kw-hr for 1984.
Using CPI Indexes, this value was indexed to the 1988 cost of $0.10/kw-hr.
Monitoring Costs
Monitoring costs are calculated by multiplying the annual number of activated
carbon treatment batches by the TOC analytical cost of $31 per analysis, based on analytical
lab quotes.
Carbon Costs
Information on carbon costs was obtained from an activated carbon unit vendor
during the development of the pesticide manufacturing cost model. For regenerated carbon,
the purchase cost was $0.65/lb in 1990 and the cost to regenerate carbon was $0.15/lb.
Freight costs were $1.50/mile when delivering 2,000-pound bulk bins and $2.50/mile when
delivering 20,000-pound bulk loads. These costs are indexed from 1990 dollars to 1988
dollars.
8.5.4
Pumps and Strainers Design and Costs
The UTS cost module also includes process vessel feed pumps, activated
carbon system feed pumps, a blowdown waste storage pump (for large systems), and in-line
strainers to filter out coarse particles. The number and sizes of the pumps and strainers is
based on the UTS size. Small systems have one process vessel, and therefore one process
vessel feed pump and one in-line strainer. Large systems have separate process vessels for
emulsion breaking pretreatment and for alkaline wastewater treatment steps. As a result, the
large UTS systems would have multiple process vessel feed pumps (i.e., one per vessel). The
large UTS systems also include two in-line strainers.
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Section 8 - Engineering Costs
Each process vessel has one centrifugal pump system. In addition, the UTS
design includes a centrifugal waste pump for transferring stored blowdown waste to tanker
trucks. Each centrifugal pump system is designed to have a capacity equivalent to the
nominal flow rate in gallons per minute of the wastewater flow rate to the UTS. If the flow
rate is less than 5 gpm, the module assumes both a minimum flow rate and pump capacity of
5 gpm. Pump capacities, power requirements, and costs are presented in the final PFPR cost
report (4). The table presents small pump and large pump cost curves; the large pump cost
curve is utilized for pump requirements exceeding 250 gpm.
Annual O&M costs for the pumps and strainers include pump energy costs and
strainer cleaning labor costs. Pump energy costs are calculated using the same equations as
the activated carbon backwash pump energy costs. Annual strainer cleaning labor is estimated
to be 15 minutes per strainer per batch. The same labor rates as noted in the process vessel
module are used in this module to determine the total labor cost.
8.5.5
Containment System Design and Cost
The treatment system design includes a concrete containment system that
encloses the wastewater storage tank(s), the process vessel(s), the activated carbon feed
tank(s), the activated carbon bed(s), the backwash system (if one is specified by the model),
and the waste disposal tank. The containment system consists of a concrete pad and a 2.5-
foot concrete dike and is designed to contain at least 125% of the volume of the largest tank
specified by the cost model.
To determine the required area and perimeter of the containment system (c/s),
the module calculates the following three quantities:
• Amount of area required for the tanks - the spreadsheet calculates the
area in square feet needed for each individual tank and then adds the
areas to determine a total space required to house the tanks. This
number is multiplied by 1.2 to provide space for other equipment (such
as pumps, etc.).
• Amount of containment provided - using the total space required, the
module then calculates the containment that this space would provide in
gallons.
Amount of Containment = [Area of c/s (sq.ft) - 2 (area displaced by
tanks) x 2.5 ft.] x 7.48 gal/ft3
• Amount of containment required - 125% of the volume of the largest
tank is required. This accounts for any precipitation that may build up
in the containment system. Thus, if the largest tank specified is a
20,000-gallon tank:
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Section 8 - Engineering Costs
Containment Required = 1.25 x 20,000 gal = 25,000 gal
If the amount of containment provided is not sufficient, then the spreadsheet
automatically determines the area required to provide sufficient containment. This is
calculated by the following equation:
Area of c/s (sq.ft.) = [(Area of c/s required (gal) x 1 :ft3/7.48 gal)/
2.5 ft.] + E (area displaced by tanks)
equation:
The perimeter of the containment system is estimated by the following
Perimeter (ft) = integers/Area of c/s (sq.ft.) +1x4
Capital Costs of the Containment System
Capital costs are estimated for the construction of a concrete pad and concrete
dike for a containment system as well as the initial application of a protective coating on the
containment system. An additional 30% of the costs of the concrete containment system is
added for fees and design costs. An additional 5% of the containment system cost and the
fees and design costs is added to account for contingency costs. All costs are indexed from
1991 dollars to 1988 dollars. Each of these costs is described below:
• Concrete Floor: An EPA/OPP report estimates a 1991 cost of $4 per
square foot of installed reinforced concrete. Thus the cost of the
concrete floor is estimated by:
1991 Cost = $4 x Area of c/s (sq. ft.)
• Concrete Dike: The EPA/OPP report estimates a cost of $16 per lineal
foot of dike for a height of 2.5 feet. Thus the cost of the concrete dike
is estimated by:
1991 Cost = $16 x Perimeter of c/s (ft)
• Floor Coating: The EPA/OPP report estimates a cost of $0.90 per
square foot to adequately coat the concrete floor with an appropriate
sealant.
1991 Cost = $0.90 x Area of c/s (sq. ft.)
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Section 8 - Engineering Costs
• Dike Coating: The EPA/OPP report estimates a cost of $0.90 per
square foot of concrete.
1991 Cost = $0.90 x Height of Dike (ft) x Perimeter of c/s (ft)
Operating and Maintenance Costs of the Containment System
The cost model estimates annual costs associated with the upkeep of the
containment system. Costs are estimated assuming that the concrete containment system
would be recoated every three years with a protective sealant. An estimated recoating cost of
$.90 per square foot is used in the module. The coating costs are amortized over three years
to estimate an annual coating cost.
1991 Recoating = $Q 9Q x f L rf _ Area Displaced by] [ Height of
Cost [^ \ -i x Tanks (sq.ft) J I Dike (sq.ft)
of Perimeter of
This cost is then indexed from 1991 dollars to 1988 dollars.
8.5.6
Waste Disposal Design and Cost
The UTS cost module includes design and cost algorithms for off-site disposal
of the reject stream from emulsion breaking and settled solids from chemical precipitation.
Off-site disposal consists of contract hauling for off-site incineration.
The size of the off-site disposal stream is calculated based on sampling data
and the facility-specific wastewater flow rate. EPA sampling data indicate an average oil and
grease concentration of 0.2% (2,000 ppm) in raw, commingled PFPR wastewater. For the P2
alternative, the UTS design assumes that this oil and grease measurement is representative of
the amount of oil and other emulsifiers in PFPR facility wastewater. The emulsion breaking
oil layer volume is therefore calculated by multiplying the wastewater flow rate by 0.2%.
The solids contribution from chemical precipitation is assumed to be equal to the mass of
sodium sulfide added to the process vessel.
Under the Revised Zero Discharge Option, PFPR facilities are costed for
off-site disposal of 5% of the wastewater treated in the UTS. This disposal represents the
amount of waste generated from the emulsion breaking step of the UTS plus additional
wastewater blowdown to prevent the accumulation of soluble salts in reused wastewater. The
5% blowdown is based on the blowdown rate at a PFPR facility that reuses commingled
interior equipment cleaning rinsate, drum and shipping container rinsate, air pollution control
scrubber water, and contaminated precipitation. The blowdown from the facility's recycle
loop varies from an estimated 2.6% to 3.5%. (Episode 4226, February 1994, EPA Contract
No. 68-CO-0081) The blowdown rate for the Revised Zero Discharge Option is higher than
the other regulatory options because reuse of the treated wastewater is required under the
] j
J J
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Section 8 - Engineering Costs
Revised Zero Discharge Option. The treatment may require additional blowdown to ensure
that water quality is sufficient for reuse.
The UTS cost module calculates costs for a storage tank sized to hold the
maximum quarterly off-site disposal stream volume. The module also calculates off-site
disposal O&M costs for the oil layer stream on a quarterly basis, and for the settled solids
stream on an annual basis. The O&M costs include the transportation and incineration costs.
These costs are discussed in detail in Section 8.7.
8.5.7
Land Cost
Land costs are calculated for the facilities that indicated in their PFPR
questionnaire response that they lack space for a wastewater treatment system. The size
required for the containment system is used as the amount of land required for the treatment
system. State-specific land costs were derived from the Industrial Real Estate Market Survey,
1989 (4). The cost module determines if land is required, identifies the facility's state,
calculates space requirements, and calculates the total land cost based on the land cost for that
state.
8.5.8
Monitoring
In addition to the TOC analytical costs associated with the operation of the
activated carbon adsorption system, PFPR facilities may incur analytical monitoring costs as
part of evaluating treatment system performance or, in the case of Option 1 being the selected
option, demonstrating compliance with numerical discharge limitations. Under the Zero/P2
Alternative option, the Agency assumes facilities will monitor wastewater after treatment and
before recycling or discharging it to ensure it has been adequately treated. The cost model
therefore contains a monitoring cost dataset, consisting of the analytical methods used to
detect individual PAIs and corresponding method costs, that is used to estimate monitoring
costs for Option 1, the zero discharge option, the P2 alternative, and Option 4.
The analytical methods dataset has been compiled primarily from the August
1993 Methods for the Determination of Nonconventional Pesticides in Municipal and
Industrial Wastewater (7), a compendium of EPA-approved analytical methods for those PAIs
where pesticide manufacturing limits were proposed. Additional PAI analytical methods
discussed in analytical reports from treatability studies and sampling episodes conducted by
EPA to support development of effluent limitations guidelines and standards for the pesticides
industry have been included when available. Finally, costs have been extrapolated for some
PAIs, based on the following methodology:
• Use of the same method(s) as for structurally similar PAIs for those
PAIs without approved methods. In cases where more than one method
is available for structurally similar PAIs, the most expensive method is
used to estimate costs.
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Section 8 - Engineering Costs
• Analytical methods are assumed to cost $200 (an approximate average
cost of PAI analytical methods) for those PAIs lacking analytical
methods and methods for structurally similar PAIs.
• Analytical methods are assumed to cost $1,000 for non-272 PAIs (the
maximum cost for a 272 PAI).
The treatment system design includes effluent storage with sufficient capacity
to hold the volume of wastewater generated by each facility each quarter. As a result,
monitoring is costed on a quarterly basis. If a facility handles several PAIs that can be
analyzed with the same method, "that analysis would only be run one time per quarter. The
model determines the minimum number of analyses required by the PAIs assumed present in
each facility's wastewater. The analytical methods and costs for each PAI are included hi the
treatability dataset and can be found in the final PFPR cost report (4).
8.5.9
Ultrafiltration
An alternative pretreatment method to remove oil and grease from PFPR
wastewater is ultrafiltration. Ultrafiltration is a type of membrane separation (filtration) in
which a pressure-driven, semipermeable membrane is used to achieve selective separations of
suspended and colloidal solutes from a process wastewater. The "tightest" ultrafiltration
membrane is typically capable of rejecting molecules having diameters greater than 0.001
micron (3.94 x 10 inch) or nominal molecular weights greater than 2000. 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. Ultrafiltration systems
operate at feed pressures of 50 to 200 pounds per square inch gauge (psig). Some
pretreatment may be necessary to prevent membrane fouling. Ultrafiltration systems are
capable of recovery of up to 90 to 95% of the feed as product water.
Although ultrafiltration is a viable technology for PFPR wastewaters, EPA is
not currently using ultrafiltration as a basis for setting limitations and standards in the
proposed effluent guidelines. However, EPA did develop a design and cost algorithm for
ultrafiltration. At present, this algorithm is not activated when running the UTS cost module.
The ultrafiltration design and cost algorithm is briefly discussed below for the purpose of
providing a complete discussion of the engineering costing work performed for this proposal.
EPA also performed a sensitivity analysis on the cost of adding the ultrafiltration unit to the
UTS, as discussed in Section 8.5.
There are two UTS designs that incorporate ultrafiltration for pretreatment.
Small UTS systems (that handle up to five treatment batches per quarter) would replace
emulsion breaking with ultrafiltration. Vendor information and limited field sampling data
indicates that ultrafiltration is effective in separating an aqueous stream from an emulsified oil
stream, with a reject rate of between 5 and 10 percent. The reject rate is specific to the
particular wastewater feed composition. Large UTS systems retain a separate emulsion
breaking step to minimize the emulsifier load on the ultrafiltration unit. This separate step
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Section 8 - Engineering Costs
also decreases the volume of the reject stream from the ultrafiltration unit. De-emulsified
wastewater treated through the second process vessel for hydrolysis, chemical oxidation,
and/or sulfide precipitation is pumped through the ultrafiltration unit a second time to remove
any solids in the effluent that did not settle out in the process vessel. This treatment reduces
the solids in the activated carbon system feed and minimizes the activated carbon system
backwash requirements.
The ultrafiltration design and cost algorithm is based on the use of one of five
ultrafiltration units at a particular vendor. The size, power requirements, and cost of these
units are presented in the final PFPR cost report. The units are sized based on the batch
volume treated through the UTS. The ultrafiltration design is based on the capacity of the
ultrafiltration unit and the number of ultrafiltration units required to handle the daily UTS
volume. The spreadsheet then determines the total capital cost (in 1988 dollars, including
delivery and installation) and O&M costs. O&M costs include labor and energy costs.
Ultrafiltration operation is assumed to require 1 hour of labor per batch, at $17.21 per hour
(in 1988 dollars).
8.6
Storage and Reuse Cost Module
This section presents a discussion of the storage and reuse (S&R) cost module.
This module accounts for all costs (in 1988 dollars) associated with the purchase and
installation of wastewater storage drums and tanks, the construction and upkeep of a
containment system, and any applicable land costs.
8.6.1
Storage Design
The S&R module first determines line-specific storage requirements for each
facility. Input data from the PFPR questionnaire database includes the number of lines at
each facility and the number of products and the annual wastewater volume on each line. The
module then calculates the number of drums or tanks (and tank sizes, if tank storage is
required) needed to store the wastewater associated with each product on each line.
The S&R module calculates a design flow and required storage capacity for
each line. The module makes the assumption that each product generates an equal amount of
wastewater on each line. The design flow is calculated by dividing the wastewater flow rate
on each line by the number of products. The required storage capacity is 120% of the design
flow. Drum storage is selected for smaller capacity requirements. Either one or two drums
per product are selected, based on the design flow. If this capacity exceeds 110 gallons (two
55-gallon tanks), then tank storage is selected for the line. For tank storage, the module also
calculates the containment area required, based on the containment algorithm discussed in
Section 8.5.5.
The S&R module also includes a 3-hp centrifugal pump for transferring
wastewater between the line equipment and the storage tanks or drums. The design is for a
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Section 8 - Engineering Costs
portable pump, so that only one should be required regardless of the number of lines or
products.
8.6.2
Containment Design
The S&R module determines the area displaced and the containment area
required for each storage tank. The module then uses the algorithm discussed in Section 8.5.5
to calculate the containment costs for a concrete pad and 2.5-foot concrete dike, as well as the
initial coating of the containment system. Containment pallets are used for drum containment.
8.6.3
Capital Costs
The capital costs consist of the tank costs, pump costs, drum costs and
containment costs. According to vendor information, each drum costs $55, which is then
indexed in the module to 1988 dollars. Containment costs are calculated for the concrete
floor, the 2.5-foot concrete dike, the floor coating, and the dike coating. All capital costs are
increased by 30% for added fees and design costs. An additional 5% is added for
miscellaneous costs.
8.6.4
O&M Costs
The O&M costs consist of the pump energy requirement and containment
system recoating. These costs are calculated using the algorithms discussed in Sections 8.5.4
and 8.5.5, with the coating costs amortized over three year periods. All costs are indexed to
1988.
8.7
Off-Site Disposal Cost Module
This section presents a discussion of the off-site disposal, or contract haul
(CH), cost module. The CH module calculates off-site disposal costs based on contract
hauling PFPR wastewater for off-site incineration.
Off-site disposal costs are calculated for stream-specific wastewater sources
(e.g., Code C and D streams for Option 4, as discussed in Section 8.4.3). The CH module
utilizes quarterly wastewater volume data to configure a wastewater storage system that has
the capacity to hold the quarterly design flow (120% of the largest of the quarterly volumes
and the large batch volume). This calculation ensures that the storage system can handle at
least the volume of water generated in any one quarter of a year.
The CH module optimizes a storage design consisting of either a tank storage
system or a 55-gallon drum storage system. For each facility, the CH module designs and
costs each storage system and then selects the less expensive design. In order to compare
costs of the tank and drum storage designs, the module annualizes total costs for each system
by amortizing capital costs over ten years (assuming 10% interest) and adding these costs to
the O&M costs.
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Section 8 - Engineering Costs
The cost of contract hauling wastewater off site for incineration depends on the
volume of wastewater being hauled and how often the wastewater must be hauled. Hauling
frequency is based on the conservative assumption that wastewater is not stored on site for
longer than 90 days. (Facilities may not have any RCRA hazardous pesticide waste and,
therefore, would be able to store/hold their waste for longer than 90 days.) Thus, if a PFPR
facility generated wastewater throughout the year, the facility would incur costs of at least one
disposal trip per quarter of operation, even if the volume of wastewater generated was very
small. For example, if a facility generated 250 gallons each quarter of the year, the facility
would incur costs for hauling 250 gallons of wastewater off site at least four times. If another
facility generated 1,000 gallons of wastewater annually but generated all the wastewater in
one quarter, this facility would incur costs for hauling the wastewater off site only once.
Although the actual incineration fees would be the same for both facilities (based on a per
gallon unit cost of incinerating hazardous pesticide wastewaters), the total costs would be
much higher for the first facility due to the additional disposal trips (mileage fees) required
and the additional sampling analyses required for each batch of wastewater being incinerated.
Some commentors on the proposed PFPR rule had concerns about additional
burden on incineration capacity and therefore higher disposal costs for facilities choosing that
option. Because EPA will provide for the discharge of some PFPR wastewater, EPA does not
believe an additional burden will be placed on incineration capacity. This is supported by a
survey, "Hazardous Waste Incineration 1994," published in the El Digest. June 1994 (8),
which showed that, while there is increasing demand for incineration, there is still great
untapped capacity. The surveyed commercial incinerators believe that market saturation,
competition with cement kilns, and successful "waste minimization efforts by industry account
for the unused capacity and the decline in the average price for incineration. (Also, see the
memorandum in the administrative record supporting the final PFPR rule entitled
"Incineration Costs for PFP Facilities" (9).)
8.7.1
System Design - Tank Storage
The CH module configures a storage system consisting of a tank and
centrifugal pump that can handle the design flow. If the design flow is larger than 30,000
gallons, multiple storage tanks are configured. Tanks having a volume of less than 2,000
gallons are constructed of polyethylene while tanks having a volume of 2,000 gallons or
greater are constructed of carbon steel. In addition to the storage tank(s), the module also
includes the cost of a centrifugal pump to transfer the wastewater from the storage tank to a
truck used to haul the wastewater. The tank sizing and cost algorithms are the same as those
discussed in Section 8.5.1. A 70-gpm pump is specified for tank storage, because it can
transfer 5,000 gallons of wastewater to a tanker truck hi under 2 hours.
The CH module next estimates the number of disposal trips that would be
required to haul a facility's wastewater off site. For the tank storage configuration, the
module assumes that all wastewater would be hauled in 5,000-gallon tank trucks.
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Section 8 - Engineering Costs
The CH module design also includes a Concrete containment system to enclose
the wastewater storage tank(s). The containment system consists of a concrete pad and
concrete dike, and is designed to contain at least 125% of the volume of the largest tank
specified.
Capital Costs of the Tank Storage Design
The CH module estimates capital costs for the storage tank(s) and the transfer
pump. These costs account for the actual equipment costs as well as the delivery and
installation of the equipment. The module also estimates costs for the construction of the
containment system. Capital costs are estimated for the construction of the concrete pad and
concrete dike as well as the initial application of a protective coating on the containment
system. The containment cost equations are presented in Section 8.5.5. An additional 30%
of the costs of the concrete containment system is added for fees and design costs. An
additional 5% of the cost of the containment system cost is added to account for contingency
costs. All costs are indexed to 1988 dollars.
Operating and Maintenance Costs of the Tank Storage Design
The CH module estimates annual O&M costs associated with the tank storage
design, which include labor, energy, transportation, and incineration costs. The labor costs
cover the labor required to routinely check the integrity of the tanks and the labor required to
transfer the wastewater from the storage tanks to the trucks used for hauling. The energy
costs cover the energy required to operate the transfer pump. Annual transportation costs are
based on the number of annual disposal trips required. The module estimates transportation
costs based on a 500-mile trip. Estimated transportation costs also account for demurrage fees
that are typically charged while a truck is being loaded. The demurrage cost is independent
of the volume of wastewater being hauled in the 5,000-gallon tank truck. In other words, the
demurrage cost estimated for transporting 500 gallons of wastewater would be the same as the
cost estimated for transporting 5,000 gallons of wastewater. Annual incineration costs are
estimated based on a unit cost per gallon of wastewater incinerated. The module also
accounts for an analysis fee typically charged by incineration facilities for each batch of
wastewater incinerated.
Tank Inspection Costs
Inspection of the integrity of the facility storage tank is estimated to take 15
minutes per day, as recommended by CAPDET, the Army Corps of Engineers wastewater
treatment cost model modified for use hi estimating compliance costs for the pesticides
manufacturing industry effluent limitations guidelines. Thus, the annual inspection tune can
be figured as follows:
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Section 8 - Engineering Costs
Annual Inspection _ f 15 min x 60 min.
Time (hrs)
day
hr
90 days No. of quarters
X i X —..ii i N
quarter
yr
To determine labor costs, the annual inspection time is multiplied by an
estimated labor rate in 1988 dollars:
Annual Inspection _ Annual Inspection 1988 Labor
Costs
Time (hrs)
Rate ($/hr)
The 1988 labor rate is estimated using a 1991 hourly rate of $19.15 for a plant
operator, indexed to $17.21 in 1988 dollars.
Truck Loading Costs
The truck loading costs include the cost of labor incurred for the time spent
loading the tank truck with wastewater. It takes approximately 3 hours to fill a 5,000-gallon
tank truck based on the following estimates:
Connect time
Disconnect time
Loading time
Total time
0.5 hr
0.5 hr
5,000 gal/70 gpm
72 min or 1.2 hr
2.2 hr
A conservative estimate of 3 hours is used. Thus, the annual truck loading costs can be
figured by the following:
Annual Costs = (Labor Rate ($/hr) x No. Loads Per Year
= $52 Per Load x No. Loads Per Year
Pump Energy Costs
The pump is assumed to operate only when the storage tank is being emptied
into a tank truck. The pump designed for this model is a 70-gpm pump requiring a 3-hp
motor. Thus, for every load, the pump requires the following amount of energy:
Energy Per Load (kw-hr) = 2 hr x 3 hp x 0.746 (kw/hp)
= 4.476 (kw-hr/load)
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Section 8 - Engineering Costs
A unit energy cost is estimated using the 1984 cost reported in a U.S. Census
Report and indexed to 1988 dollars.
Annual Pump Energy Costs =
4.476 kw-hr $0.100 No. of loads
load
kw-hr
Transportation Costs
All PFP wastewater is hauled in bulk by a 5,000-gallon tank truck when tank
storage is designed. Transportation fees include the cost per mile to haul the wastewater to an
incineration facility plus any applicable demurrage fee. The highest estimate of transportation
fees quoted from a vendor was $5.00 per loaded mile.
Transportation costs for bulk wastewater also includes a demurrage fee incurred
for each load. Most transportation services allow for two hours free demurrage time for both
loading and unloading the truck (total of four hours), and charge $80/hr thereafter (highest
quote). Because this module assumes a loading and unloading time of three hours each, a
total demurrage fee of $160 is incurred for each load.
as follows:
Thus, the annual transportation costs, indexed to 1988 dollars, can be estimated
No. of loads per year x [$5/mi x 500 mi + $160 demurrage] x 852.0/932.9
Incineration Costs
As discussed in Section 8.7, EPA does not believe that implementation of the
final rule PFPR places an additional burden on incineration capacity. Incineration costs for
the tank storage design include an incineration fee per gallon of wastewater as well as a
sampling and analysis fee per load of wastewater. The disposal fee used in this module is
$4.67 per gallon" of pesticide wastewater plus $300 sampling and analysis fee per load of
wastewater. These costs were estimated from the following sources:
1982 OCPSF Industry Information-From the 1982 Technical Development
Document for the OCPSF Industry, an estimated incineration fee of $0.90/gal is used for bulk
pesticide wastewaters.
1990 Vendor Quotes—In 1990, vendor quotes were obtained when incineration
costs were being estimated for the Pesticide Chemicals Manufacturing Industry. An estimated
incineration fee of $6.00/gal is used for bulk pesticide wastewaters.
1992 Vendor Quotes—In developing this cost module, vendor quotes were
obtained in March, 1992 for incineration fees. The highest quote obtained was $7.10 per
gallon of pesticide wastewater in bulk form.
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Section 8 - Engineering Costs
Using the estimated costs for these three years, a linear regression was
performed to estimate the 1988 incineration costs to be $4.67/gal.
Disposal costs also include a $300 sampling fee per wastewater load. This cost
was obtained from vendors and is used for a 1988 estimation.
Annual Disposal Costs = $4.67/gal x No. of gal wastewater/yr + $300 x No. of loads/yr
Containment Costs
The final costs that the CH module estimates are the annual costs associated
with the upkeep of the containment system. Costs are estimated to recoat the concrete
containment system every three years with a protective sealant. The coating costs are
amortized over three years to determine an annual coating cost. The containment system
sizing and cost algorithms are the same as those discussed hi Section 8.5.5.
8.7.2
System Design - Drum Storage
The CH module also configures a storage system designed for drum storage.
Based on the annual volume of wastewater generated at a facility and how often the
wastewater is generated, the module estimates the number of drums required to store the
wastewater and the number of disposal trips required to haul the wastewater off site for
incineration.
The only capital costs associated with the drum storage design is the purchase
of containment pallets used to store and contain drums of wastewater. According to vendor
information, each containment pallet costs $349. The model estimates costs for the
containment pallets based on the number of drums required to store the design flow. All
costs are indexed to 1988, the year of the PFPR questionnaire.
The CH module estimates annual O&M costs associated with the drum storage
design, which include drum purchase, labor, transportation, and incineration costs. The labor
costs cover the labor required to routinely check the integrity of the drums, and the labor
required to load the drums onto the trucks used for hauling. Annual transportation costs are
based on the number of annual disposal trips required. Estimated transportation costs also
account for demurrage fees that are typically charged while a truck is being loaded. Unlike
Hie transportation costs estimated for tank storage, the transportation costs estimated for drum
storage depend on the volume of wastewater being hauled each disposal trip. For instance, the
cost estimated for a truck to haul five drums would be substantially lower than the cost
estimated for a truck to haul 80 drums. Annual disposal costs are estimated based on a unit
cost per gallon of wastewater being incinerated. The module also accounts for an analysis fee
typically charged by incineration facilities for each batch of wastewater being incinerated. All
costs are indexed to 1988, the year of the PFPR questionnaire.
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Section 8 - Engineering Costs
Drum Purchase Costs
According to vendors, the typical cost of a 55-gallon, DOT-approved drum
constructed of carbon steel is $55 (including delivery) in 1992. (Refurbished drums that meet
DOT specifications may also be used to store wastewater at a lower cost). This cost is
indexed to 1988 dollars.
Annual Drum Purchase Cost = No. of Drums Per Year x $50.23/drum
Drum Inspection Costs
Similar to the tank storage design, an inspection time of 15 minutes per day is
assumed for each production day. The 1988 salary of $17.21/hr (as derived in the tank
storage design) is assumed.
Annual Inspection Cost = (15 min/day x 1 hr/60 min x No. of Prod, days/yr) x $17.21/hr
Transportation Costs
For the drum storage design, all drums are assumed to be hauled by an
appropriate size flat-bed truck or van. Transportation fees include the cost per mile to haul
the drums to an incineration facility (default value of 500 miles) plus any demurrage fee. For
transportation of drummed wastewaters, the cost depends on the number of drums being
hauled. For full truck loads (40 to 80 drums), a 1992 fee of $5.00 per loaded mile is used.
This fee, indexed to 1988 dollars, is $4.57 per loaded mile. Thus, with a default distance of
500 miles, the transportation cost of a full truckload is estimated at $2,285.
For loads that are less than 40 drums, a distribution of price by number of
drums was provided by a vendor, and these costs are used to develop an equation. The
following costs were provided:
Number of Drums
1 - 10
11 -20
21 -30
31 -40
1992 Cost (default distance of 500 miles)
$790
$900
$1,000
$1,190
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Section 8 - Engineering Costs
Using these data, transportation costs are estimated using the following
equation:
1992 Cost = 13 x number of drums + $710
1988 Cost = 852'° x (1992 Costs)
932.9
Transportation costs must also account for any demurrage fees. As in the tank
storage design, it is assumed that transportation facilities allow 2 free hours for loading and
unloading the truck (4 total hours) and charge $80 per hour thereafter. As recommended by
CAPDET, an estimated rate of 4 drums per hour is used for loading and unloading the truck.
Thus, the following equation is used to estimate loading and unloading costs:
. Annual Demurrage Fees = (2 x No. of drums per year - 4 x No. of trips per year) x $80/hr
If the equation yields a negative number, then no demurrage fee is incurred.
Incineration Costs
As discussed in Section 8.7, EPA does not believe that implementation of the
final PFPR rule places an additional burden on incineration capacity. Incineration costs for
the drum storage design include an incineration fee per gallon of wastewater as well as a
sampling and analysis fee per truck load of wastewater. The incineration fee used is $8.13
per gallon of pesticide wastewater (or $447 per drum) and a $300 sampling fee per load.
1982 OCPSF Industry Information-From the 1982 Technical Development
Document for the OCPSF Industry, an estimated incineration fee of $1.50/gal is used for
drummed pesticide wastewaters.
1990 Vendor Quotes—In 1990, vendor quotes were obtained when incineration
costs were being estimated for the Pesticide Chemicals Manufacturing Industry. An estimated
incineration fee of $10.00/gal is used for drummed pesticide wastewaters.
1992 Vendor Quotes—In developing this cost module, vendor quotes were
obtained in March, 1992 for incineration fees. The highest quote obtained was $700 per drum
or $12.73 per gallon.
Using these estimated costs for these three years, a linear regression was
performed to estimate the 1988 incineration costs to be $8.13 per gallon.
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Section 8 - Engineering Costs
Incineration costs also include a $300 sampling fee per wastewater load. This
cost was obtained from vendors and is used for a 1988 estimation.
Annual Incineration Costs = $447/drum x No. of drums/year + $300 x loads/year
8.8 Costing Methodology for Snbcategorv E (Refilling Establishments)
A total of three surveyed Subcategory E facilities reported discharging a total
of 270 gallons of wastewater in 1988. These three surveyed facilities represent 19 facilities in
the national estimates for which costs are estimated. Two regulatory options were developed
for refilling establishments. The first option, storage and reuse, was based on the observed
practice of wastewater reuse in subsequent product formulations. The second option was
based on achieving zero discharge of all PFPR wastewater via contract hauling for off-site
incineration. For the first option, the compliance costs are limited to the capital costs
associated with a 250-gallon polyethylene storage tank and a 1/2 horsepower (hp) pump. The
O&M costs, which normally include containment and pump energy, are assumed to be zero
since these containment costs would be covered under the Office of Pesticides Programs
Proposed Pesticide Containers and Secondary Containment regulations (59 FR 6712; February
11, 1994). Energy associated with the low volumes at these refilling establishments should be
negligible. The off-site disposal module (described in Section 8.7) was used to calculate costs
for the CH option.
8.9
1.
2.
3.
4.
References3
U.S. Environmental Protection Agency. Economic Analysis of Final Effluent
Limitations Guidelines and Standards for the Pesticide Formulating, Packaging.
and Repackaging Industry. EPA 821-R-96-017, September 1996.
U.S. Environmental Protection Agency. Development Document for Best
Available Technology. Pretreatment Technology, and New Source Performance
Technology for the Pesticide Formulating. Packaging, and Repackaging
Industry. EPA 821-R-94-002, March 1994 (DCN F7424).
Eastern Research Group, Inc. Addendum to the Final Pesticide Formulating.
Packaging, and Repackaging Cost and Loadings Report: Revisions to Costing
Approach for the Final Rule. Prepared for the U.S. Environmental Protection
Agency, Office of Water, Washington, D.C., September 1996 (DCN F7943).
Radian Corporation. Final Pesticides Formulators. Packagers, and Repackagers
Cost and Loadings Report. Prepared for the U.S. Environmental Protection
Agency, Office of Water, Washington, D.C., March 31, 1994 (DCN F7184).
For those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
8-45
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5.
6.
7.
8.
9.
Section 8 - Engineering Costs
Radian Corporation. Final Pesticides Formulators, Packagers, and Repackagers
Treatabilitv Database Report. Prepared for the U.S. Environmental Protection
Agency, Office of Water, Washington, D.C., March 1994 (DCN F7185).
Radian Corporation. Pesticides Formulators, Packagers, and Repackagers
Treatabilitv Database Report Addendum. Prepared for the U.S. Environmental
Protection Agency, Office of Water, Washington, D.C., September 1995, (DCN
F7700).
U.S. Environmental Protection Agency. Methods for the Determination of
Nonconventional Pesticides in Municipal and Industrial Wastewater, Volumes I
and E. EPA 821-R-93-010, Washington, D.C. 1993 (DCNs F7131 and F7132).
Hanke, J. "Hazardous Waste Incineration 1994", El Digest. June 1994
(DCNF7411).
Memorandum: Revision to Incineration Costs for PFP Facilities, October 6,
1995 (DCN F7705).
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Section 9 - Best Practicable Control Technology (BPT)
SECTION 9
9.1
BEST PRACTICABLE CONTROL TECHNOLOGY (BPT)
Introduction
Best practicable control technology (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.
This section summarizes the final BPT limitations. Specific discussions
regarding their development are included hi Section 6 (Pollutant Parameters Selected for
Regulation), Section 7 (Technology Selection and Methods to Achieve the Effluent
Limitations), and Section 8 (Engineering Costs). Implementation of these guidelines is
discussed in Section 14.
9.2
9.2.1
BPT ADDlicabilitv
Revisions to BPT
The 1978 BPT regulation (43 FR 44846; September 29, 1978) established a
zero discharge limitation for direct wastewater discharges from pesticide formulating and
packaging1 facilities (Subcategory C). This regulation included pesticide formulating,
packaging, and repackaging (PFPR) operations that occurred at direct discharging pesticide
manufacturing facilities as well as stand-alone PFPR facilities2. The basis for the 1978 zero
discharge BPT limitation was water conservation, reuse and recycle practices, with any
residual water being evaporated or hauled off site to a landfill. However, many facilities that
were direct dischargers hi 1978 switched to indirect discharge of wastewaters through POTWs
In 1978, repackaging was not included in the title of Subcategory C, but was covered by the BPT regulation
and, therefore, will be included in the title for the final rule.
fj
A stand-alone PFPR facility is a PFPR facility where either: 1) no pesticide manufacturing occurs; or 2) where
pesticide manufacturing process wastewaters are not commingled with PFPR process wastewaters. Such facilities
may formulate, package, or repackage or manufacture other nonpesticide chemical products and be considered a
"stand-alone" PFPR facility.
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Section 9 - Best Practicable Control Technology (BPT)
instead of achieving zero discharge via recycle and land filling or evaporation. Due to the
1978 BPT regulation, there should currently be no direct discharging PFPR facilities.
However, the zero discharge limitation was not interpreted or implemented in the same way
for PFPR/Manufacturers as it was for stand-alone PFPR facilities.
It is EPA's understanding that permitting authorities incorporated the BPT zero
discharge standard for PFPR wastewaters into the pesticide manufacturers' NPDES permits as
a "zero allowance." A zero allowance would let a PFPR/Manufacturer discharge PFPR
wastewaters along with their pesticide manufacturing wastewaters as long as they did not
exceed the pesticide limitations in the pesticide manufacturing rule. The 1978 pesticide
manufacturing BPT limitations were presented as a total pesticides limit for 49 specific PAIs.
However, the more recent BAT and NSPS limitations (58 FR 50638; September 28, 1993) do
not set a total pesticides limit, but instead set individual production-based limitations. Since
the pesticide manufacturing limits are based solely on the manufacturing production and do
not include the PFPR production, permits could still use a zero allowance approach to allow
discharges of PFPR wastewater from these combined facilities.
At the time of proposal, EPA did not believe it was necessary to amend the
1978 BPT because the zero discharge limitation was comparable to the proposed standard of
zero discharge3. EPA recognized that the bases for the 1978 BPT and proposed rule were
not identical and that land filling and evaporation were no longer the best options for
achieving zero discharge (59 FR 17870). However, EPA believed that since both the 1978
BPT and the proposed rule were largely based on water conservation and recycle and reuse
practices, facilities could meet BPT in a manner similar to the proposed rule.
Following proposal, EPA received many comments on and requests for revision
of the BPT regulation from the PFPR/Manufacturers and trade associations. Commenters
raised issues related to the technical feasibility of zero discharge for both the proposed rule
and the 1978 BPT rule.
Commenters believed that, because not all wastewaters were reusable as EPA
had assumed, the potential increase in cross-media impacts associated with a zero discharge
regulation in addition to the large costs associated with contract hauling for incineration made
any zero discharge regulation infeasible. The commenters requested numeric discharge
limitations and/or an acceptable discharge allowance (associated with pollution prevention
practices) for their PFPR wastewaters and that BPT be revised accordingly. Based on these
and other comments on the proposed rule, EPA developed the Zero/P2 Alternative option for
PSES and BAT (for Subcategory C facilities), which was discussed in the Supplemental
Notice (60 FR 30217) and revised based on additional comment for the final rule.
Commenters also specifically commented on the need for revision of the 1978
BPT due to: (1) certain practices on which the 1978 BPT was based (e.g., land filling and
EPA proposed a zero discharge standard for PSES based on pollution prevention, recycle/reuse, and, when
necessary, treatment and reuse and expected it to be implemented via "no flow" of process wastewater.
9-2
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Section 9 - Best Practicable Control Technology (BPT)
evaporation), which are no longer desirable because they may cause cross-media impacts or
may no longer be available; and (2) the changes in pesticide active ingredients (PAIs) and
pesticide formulation chemistries since 1978. For example, many pesticide products have
been reformulated from an organic solvent-based product to a water-based product to avoid
the generation of volatile organic compounds (VOCs). This has, in many cases, caused an
increase in the volume of wastewater generated by this industry. In addition, many facilities
are switching to safer, more "environmentally friendly" PAIs which would change the
characteristics of the wastewaters from those determined in 1978. Commenters believe that
EPA must revise BPT or account for the additional costs associated with the current practices
that would be utilized to meet the zero discharge limitation (i.e., off-site incineration).
Based on these comments, EPA decided to amend BPT for both the existing
direct discharging PFPR/Manufacturers and stand-alone PFPR facilities to allow them to
choose between zero discharge and the P2 alternative. EPA believes that, although the stand-
alone PFPR facilities are already achieving zero discharge, in compliance with the 1978 BPT,
the methods they are using may potentially result in cross-media impacts that the use of the
P2 alternative would potentially reduce.
Also, these changes will make BPT consistent with BAT (and PSES) while
essentially achieving the same pollutant removals and potentially decreasing cross-media
impacts associated with various off-site disposal methods. In addition, the change to the BPT
limitation that is being promulgated for PFPR/Manufacturers will clarify that the method by
which the zero discharge limitation has been implemented (i.e., use of a zero allowance) is
appropriate.
9.2.2
Applicability of Final BPT Regulations
Pesticide Formulating, Packaging, and Repackaging (Subcategory C)
Under the final rule, EPA is amending the 1978 BPT standard by establishing a
zero discharge limitation with a compliance alternative which provides for a P2 allowable
discharge to surface waters. The zero discharge limitation is based on P2, recycle and reuse
practices, some contract hauling for off-site incineration, and, when necessary, treatment and
reuse for those PAIs that are formulated, packaged, and/or repackaged but are not also
manufactured at the facility.
Under the Zero/P2 Alternative option, each owner or operator of a PFPR
facility hi Subcategory C will make an initial choice of whether the facility will meet zero
discharge or comply with the P2 alternative. This choice can be made on a product
family/process line/process unit basis rather than a facility-wide basis. If the zero discharge
option is chosen, the facility owner/operator will need to do whatever is necessary (e.g., reuse
or recycle the wastewater (either with or without treatment), incinerate the wastewater on site,
or haul it for off-site incineration or underground injection) to ensure zero discharge of PAIs
and priority pollutants in the wastewater.
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Section 9 - Best Practicable Control Technology (BPT)
If the P2 alternative portion of the option is chosen for a particular PAI product
family/process line/process unit, then the owner/operator of the facility must agree to comply
with the P2 practices identified in Table 8 in Appendix A for that PFPR family/line/unit.
This agreement to comply with the P2 practices and any necessary treatment would be
included in the NPDES permit for direct discharging PFPR facilities. In general, PFPR
facilities choosing the P2 alternative need only submit a small portion of the paperwork to a
permitting or control authority (e.g., initial and periodic certification statements).
Stand-Alone PFPR Facilities
EPA is establishing a zero discharge limitation with a compliance alternative
for a P2 allowable discharge for PFPR facilities where no pesticide manufacturing occurs or
where pesticide manufacturing process wastewaters are not commingled with PFPR process
wastewaters. The zero discharge limitation is based on pollution prevention, recycle and reuse
practices and, when necessary, treatment and reuse for those PAIs that are formulated,
packaged, and/or repackaged but are not also manufactured at the facility. The basis also
includes some amount of contract hauling for off-site incineration. EPA believes that,
although the stand-alone PFPR facilities are already achieving zero discharge, in compliance
with the 1978 BPT, the methods they are using may potentially result in cross-media impacts
that the use of the P2 alternative would potentially reduce. Facilities choosing the P2
alternative may have to apply for an NPDES permit if they do not already have a permit.
EPA has not assigned any additional costs to the stand-alone PFPR facilities as
they are also currently achieving zero discharge. However, some facilities may choose to take
advantage of the P2 alternative in order to achieve a decrease in cross-media impacts.
Depending on the current means of achieving zero discharge, a facility's costs may increase or
decrease when switching to the P2 alternative. The costs may increase initially due to the
cost of installing a wastewater treatment system due to the associated capital costs; however,
EPA believes that over the long term, the annual costs for those facilities which select the P2
alternative would be lower. EPA assumes that facilities will make the choice (to continue to
comply with zero discharge or to move to the P2 alternative) based, in significant part, on
economic considerations. Therefore, EPA believes that if the costs associated with the P2
alternative were significantly higher, the facility would not alter their current means of
compliance. Accordingly, EPA has assumed no incremental costs as a result of the addition
of the P2 alternative to BPT for stand-alone PFPR facilities.
PFPR/Manufacturing Facilities
Zero allowance is established for PFPR/Manufacturers for those pesticides that
are formulated, packaged, and/or repackaged and manufactured at the facility. Zero allowance
is based on pollution prevention, recycle and reuse practices, and treatment and discharge
through the manufacturer's wastewater treatment system within the pesticide manufacturing
production-based numeric limitations (i.e., giving no allowance for the PFPEL wastewater or its
production). This is consistent with how the existing 1978 BPT zero discharge requirements
have been implemented by permit writers.
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Section 9 - Best Practicable Control Technology (BPT)
The final PFPR rule will allow PFPR/Manufacturers to discharge PFPR
wastewaters in two specific ways. For those facilities choosing to comply with zero discharge
(as opposed to the P2 alternative), their permits should incorporate the zero allowance
approach for the PFPR portion of their operations for the PAIs that they manufacture. For
those PAIs formulated and not manufactured at the facility, the permit should apply a strict
zero discharge. The reason for this difference, in part, is because their pesticide
manufacturing wastewater treatment system may not consist of the appropriate treatment
technologies for such PAIs or the treatment system may not be designed to treat the additional
volumes and/or concentrations of the "nonmanufactured" PAIs.
However, PFPR/Manufacturers can choose the P2 alternative to zero discharge.
Such facilities would not have to achieve zero discharge or zero allowance of their PFPR
wastewaters. Instead, these facilities would comply with the practices specified hi the P2
alternative and would receive a "P2 discharge allowance" following treatment (see
Appendix A for the definition of P2 allowable discharge). The P2 discharge allowance can be
applied to pesticides that are formulated, packaged, and/or repackaged and manufactured as
well as those that are not manufactured on site.
The treatment system used to treat the combined PFPR and pesticide
manufacturing wastewaters must incorporate treatment that is appropriate for those PAIs
which are not also manufactured on site (i.e., those PAIs for which individual pesticide
manufacturing production-based limitations are not contained in the NPDES permit).
Treatment is deemed appropriate through the use of treatability studies found in literature or
performed by the facility, long-term monitoring data, or Table 10 in Appendix A.
Refilling Establishments (Subcategory E)
The existing BPT regulations do not cover refilling establishments. As
discussed in the proposed regulation (59 FR 17870), the practice of refilling minibulks did not
begin until the late 1980s, after the original BPT regulation was promulgated hi 1978.
Refillers are different from the general packagers and repackagers because of differences in
the raw materials used and the types of operations performed (see Section 4 for detailed
discussion). These types of facilities were not part of the database for the original BPT
regulations and were not considered in the development of those regulations.
In the final regulation, EPA is establishing a BPT limitation for existing
refilling establishments at zero discharge of pollutants in process wastewaters to waters of the
U.S. The zero discharge limitation is based on collection and storage of process wastewaters,
including rinsates from cleaning minibulk containers and then: ancillary equipment, and
wastewaters from secondary containment and loading pads, with the exception of
contaminated storm water. The collected process wastewater would be reused as make-up
water for application to fields in accordance with the product label.
In most cases, refilling establishments hold wastewater until such time as it can
be applied as pesticide on a site compatible with the product label or used as make-up water
9-5
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Section 9 - Best Practicable Control Technology (BPT)
in an application of pesticide chemical to an appropriate site. Of the estimated 1,134 facilities
that would be affected by today's proposal, EPA's questionnaire responses indicate that 98%,
or an estimated 1,101 facilities, already achieve zero discharge, primarily by holding
contaminated wastewater and reusing it as make-up water. Thus, this practice not only
eliminates the discharge of wastewater but also allows the facility to recover the value of the
product in the wastewater. Accordingly, for purposes of setting BPT regulations, EPA
concludes that this regulation represents the average of the best performance at existing
facilities.
EPA recognizes that it is not uncommon for refilling establishments to have
more than one pesticide product on site to be used on different crops. For example, it is
common in the Midwest for a refilling establishment to have bulk Bicep® (atrazine and
metolachlor) that is applied to com early in the season, and also have Freedom® (alachlor and
trifluralin), which is applied to soybeans later hi the growing season. Mixtures of rinsates of
the two products (Bicep® and Freedom®) cannot be used in an application mixture if there is
no crop for which the two pesticides are mutually labelled. In estimating costs, the Agency
has assumed that the containment system, including separate holding tanks, will segregate
pesticide products to avoid spills from becoming cross contaminated. EPA has seen this
segregation in containment systems at refilling establishments that have been designed to
comply with local requirements.
EPA does not expect there to be a significant additional cost associated with
the holding of this water until such time as it can be used as make-up in commercial
application. (The costs associated with the refilling establishments are discussed in Sections
8.8 and 12.2 of this document.) There are estimated to be no existing direct dischargers in
this subcategory.
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Section 10 - Best Conventional Pollutant Control Technology (BCT)
SECTION 10
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY (BCT)
10.1 Introduction
The 1977 Amendments to the Clean Water Act (CWA) 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: biochemical oxygen demand (BOD5),
total suspended solids (TSS), fecal coliform, pH, and any additional pollutants defined by the
Administrator as conventional. On July 30, 1979 (44 FR 44501), the Administrator
designated oil and grease as a conventional pollutant.
The BCT effluent limitations guidelines are not additional guidelines, but
instead, replace guidelines based on the application of the "best available technology
economically achievable" (BAT) for the control of conventional pollutants. BAT effluent
limitations guidelines remain in effect for nonconventional and toxic pollutants. Effluent
limitations based on BCT may not be less stringent than the limitations based on "best
practicable control technology currently available" (BPT). Thus, BPT limitations are a "floor"
below which BCT limitations cannot be established.
In addition to other factors specified in Section 304(b)(4)(B), the CWA requires
that the BCT effluent limitations guidelines be assessed in light of a two-part
"cost-reasonableness" test [see American Paper Institute v. EPA. 660 F 2d 954 (4th Cir.
1981)]. The first test compares the cost for private industry to reduce its discharge of
conventional pollutants with the cost to publicly owned treatment works (POTWs) for similar
levels of reduction in their discharge of these pollutants. The second test examines the
cost-effectiveness of additional industrial treatment beyond BPT. EPA must find that the
limitations are "reasonable" under both tests before establishing them as BCT. If the BCT
technology fails the first test, there is no need to conduct the second test, because the
technology must pass both tests. EPA promulgated a methodology for establishing BCT
effluent limitations guidelines on July 9, 1986 (51 FR 24974).
This section summarizes the final BCT limitations. Specific discussions
regarding their development are included in Section 6 (Pollutant Parameters Selected for
Regulation), Section 7 (Technology Selection and Methods to Achieve the Effluent
Limitations), and Section 8 (Engineering Costs). Implementation of these guidelines is
discussed in Section 14.
10-1
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Section 10 - Best Conventional Pollutant Control Technology (BCT)
10.2 Summary of Final BCT Limitations
10.2.1 Pesticide Formulating, Packaging, and Repackaging (Subcategory C)
EPA is establishing BCT limitations for this subcategory that are equivalent to
the limitations established for BPT. Since BPT establishes a zero discharge limitation with a
compliance alternative for a pollution prevention (P2) allowable discharge, and BCT can be
no less stringent than BPT and no more stringent than BAT, EPA believes an equivalent
technology basis is appropriate for BCT. EPA believes there are no additional costs
associated with these limitations. A discussion of the BPT limitations is presented in
Section 9.
10.2.2
Refilling Establishments (Subcategory E)
EPA is establishing BCT limitations for Subcategory E that are equivalent to
the limitations established for BPT. Since BPT requires zero discharge of process wastewater
pollutants and 98% of the existing refilling establishments already achieve zero discharge,
EPA believes an equivalent technology basis is appropriate for BCT.
10-2
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Section 11 - Best Available Technology Economically Achievable (BAT)
SECTION 11
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT)
11.1 Introduction
The factors considered in establishing the best available technology
economically achievable (BAT) level of control include: the age of process equipment and
facilities, the processes employed, process changes, the engineering aspects of applying
various types of control techniques, the costs of applying the control technology, non-water
quality environmental impacts such as energy requirements, air pollution and solid waste
generation, and such other factors as the Administrator deems appropriate (Section
304(b)(2)(B) of the Act). In general, the BAT technology level represents the best existing
economically achievable performance among plants with shared characteristics. Where
existing wastewater treatment performance is uniformly inadequate, BAT technology may be
transferred from a different subcategory or industrial category. BAT may also include process
changes or internal plant controls which are not common industry practice.
This section summarizes the final BAT limitations. Specific discussions
regarding their development are included in Section 6 (Pollutant Parameters Selected for
Regulation), Section 7 (Technology Selection and Methods to Achieve the Effluent
Limitations), and Section 8 (Engineering Costs). Implementation of these guidelines is
discussed in Section 14.
11.2
11.2.1
Summary of Final BAT Limitations
Pesticide Formulating, Packaging, and Repackaging (Subcategory C)
For this subcategory, EPA has established BAT limitations that are equivalent
to the limitations established for BPT for PFPR/Manufacturers and stand-alone PFPR
facilities.
Under the proposed regulation, existing direct discharging PFPR/Manufacturers
were expected to treat (for reuse) their PFPR wastewaters hi a separate treatment system from
their pesticide manufacturing wastewater treatment systems. EPA estimated the compliance
costs for these facilities by costing them for separate PFPR Universal Treatment Systems
(UTSs). Cost estimates for the UTS are presented in Section 8.
Under the final rule, existing direct discharging Subcategory C facilities will
have a choice of either complying with a zero discharge limitation or a compliance alternative
for a pollution prevention (P2) allowable discharge. However, the rule clarifies that in
meeting the zero discharge limitation, permitting authorities may authorize the commingling
of pesticide manufacturing and PFPR process wastewaters to meet the pertinent BAT
limitations for pesticide manufacturers with a zero allowance for PAIs in PFPR wastewaters.
EPA has revised the cost model to account for changes in the final rule due to updated
11-1
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Section 11 - Best Available Technology Economically Achievable (BAT)
analytical data, changes in scope, and the addition of the P2 alternative. However, EPA
believes that an overestimation of the costs would result if EPA included costs for separate
UTS systems when the facilities' current controls, used for treating PFPR wastewaters (i.e.,
prior to comrningling with pesticide manufacturing wastewater) and/or treating commingled
wastewater (i.e., their pesticide manufacturing treatment systems), already achieve the BAT
limitation of zero discharge or "zero allowance."
Thus, EPA is not including these costs and removals in the total industry
estimate. However, EPA has made a determination of economic achievability even if these
costs would be incurred, and is presenting the costs and pollutant removals associated with the
17 direct discharging PFPR/Manufacturers for informational purposes. When current
treatment in place is not accounted for, the estimated compliance cost for the
PFPR/Manufacturers to comply with BAT is $2.8 million (1995 dollars) and is estimated to
remove greater man 99% of the pollutants. This equals 50,248 Ibs (or 71.6 million Ib-eq.1)
of PAIs. Again, EPA believes this cost is economically achievable.
11.2.2
Refilling Establishments (Subcategory E)
EPA has established BAT limitations for this subcategory that are equivalent to
the limitation established for BPT. Since BPT requires zero discharge of process wastewater
pollutants and 98% of the existing refilling establishments already achieve zero discharge,
EPA believes an equivalent technology basis is appropriate for BAT.
large number of toxic weighted pound equivalents is driven by a large PFPR production value reported
from a single PFPR/Manufacturer using coumaphos with a toxic weighting factor = 5.6 x 103.
11-2
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Section 12 - Pretreatment Standards for Existing Sources (PSES)
SECTION 12
PRETREATMENT STANDARDS FOR EXISTING SOURCES (PSES)
12.1 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
CWA of 1977 indicates that pretreatment standards are to be technology-based and analogous
to the best available technology economically achievable (BAT) for direct dischargers.
This section summarizes the final PSES standards. Specific discussions
regarding their development are included in Section 6 (Pollutant Parameters Selected for
Regulation), Section 7 (Technology Selection and Methods to Achieve the Effluent
Limitations), and Section 8 (Engineering Costs). Implementation of these standards is
discussed in Section 14.
12.2 Summary of Final PSES Standards
12.2.1 Pesticide Formulating, Packaging, and Repackaging (Subcategory C)
Under the final rule, EPA is establishing a zero discharge pretreatment standard
with a P2 alternative which allows a discharge to POTWs. The zero discharge standard is
based on pollution prevention, recycle and reuse practices and, when necessary, treatment
(through the Universal Treatment system) for reuse. The Universal Treatment System (UTS)
is described in detail in Section 7. The basis also includes some amount of contract hauling
for off-site incineration which may be necessary to achieve zero discharge. Compliance with
the P2 alternative is based on performing specific pollution prevention, recycle, reuse, and
water conservation practices (as listed in Table 8 in Appendix A) followed by a P2 allowable
discharge, which requires treatment of some wastewaters prior to discharge to a POTW.
Under the Zero/P2 Alternative option, each owner or operator of a PFPR
facility in Subcategory C will make an initial choice of whether the facility will meet zero
discharge or comply with the P2 alternative. This choice can be made on a product
family/process line/process unit basis rather than a facility-wide basis. If the zero discharge
option is chosen, the facility owner/operator will need to do whatever is necessary (e.g., reuse
or recycle the wastewater, haul it for off-site incineration, or treat the wastewater through the
UTS), to ensure zero discharge.
If the P2 alternative is chosen for a particular PAI product family/process line/
process unit, then the owner/operator of the facility must agree to comply with the P2 recycle,
reuse, and water conservation practices identified in Appendix A, which can be followed by a
P2 allowable discharge. Indirect dischargers are required to treat interior wastewater sources
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Section 12 - Pretreatment Standards for Existing Sources (PSES)
(including drum rinsates), leak/spill cleanup water, and floor wash prior to discharge to a
POTW. In individual cases, the requirement of wastewater pretreatment prior to discharge to
the POTW may be removed by the control authority for floor wash or the final rinse of a
non-reusable triple rinse. This requirement may be removed when the facility has
demonstrated that the levels of PAIs and priority pollutants in such wastewaters are at a level
that is too low to be effectively pretreated at the facility, and those PAIs and priority
pollutants have been shown to neither pass through nor interfere with the operations of the
POTW. Agreements to comply with the P2 practices and any necessary treatment would be
included in the control mechanisms or pretreatment agreements for indirect discharging
facilities.
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). A pollutant is deemed to pass through when
the average percentage removed nationwide by well-operated POTWs (those meeting
secondary treatment requirements) is less than the percentage removed by directly discharging
facilities applying BAT for that pollutant. In the pesticide chemical manufacturing final rule,
phenol, 2-chlorophenol, 2,4-dichlorophenol and 2,4-dimethylphenol were found not to pass
through POTWs (58 FR 50649; September 28 1993). Phenol is a PAI that is exempted from
this final rule under the sanitizer exemption while the remaining three chemicals are priority
pollutants.
Based on comments and the addition of the P2 alternative to the zero discharge
standard for the final rule, EPA has determined it is appropriate to exempt phenol from the
final PFPR effluent guidelines and standards, and to exclude 2-chlorophenol,
2,4-dichlorophenol and 2,4-dimethylphenol from regulation in the final categorical
pretreatment standards (PSES and PSNS) because these three pollutants do not pass through
POTWs.
EPA has estimated the compliance cost for the industry to achieve PSES at
$29.9 million annually (1995 dollars). The current PAI pollutant loading to POTWs is
estimated, at 192,789 pounds with PAI removals achieved by the final regulation estimated at
189,908 pounds. This means that compliance with the final rule would remove almost 99%
of the current pollutant loading. Due to the toxic nature of the majority of PAIs, the
equivalent toxic weighted pollutant removals are 7.6 million pound equivalents .
1The toxic weighted pollutant removals (in pound-equivalents) for the final rule are not directly comparable to
the toxic weighted pollutant removals presented in the proposal or supplemental notice. This is because: (1) the
method used to convert acute toxicity values to chronic value was revised from a 1:100 ratio to a 1:10 ratio and
reduces the toxic weighting factor for many PAIs; (2) the toxic weighting factor for the pyrethrins was revised;
and (3) EPA is using an average non-272 PAI toxic weighting factor based on values for approximately 90 non-
272 PAIs instead of using the production weighted average of the toxic weighting factors for the 272 PAIs.
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12.2.2
Section 12 - Pretreatment Standards for Existing Sources (PSES)
Refilling Establishments (Subcategory E)
EPA is establishing pretreatment standards for existing refilling establishments
at zero discharge of pollutants hi process wastewaters to POTWs. This standard is based on
collection and storage of process wastewaters followed by reuse of the wastewaters as make-
up water for application to fields in accordance with the product label. Based on the PFPR
1988 questionnaire survey, 98% of the existing refilling establishments achieve zero discharge.
Only a small number of refilling establishments are indirect dischargers and
EPA has estimated that they can comply with the final pretreatment standards at nearly zero
cost. EPA has estimated that only 19 of the 1,134 refilling establishments do not achieve zero
discharge and they currently discharge to POTWs. EPA estimates a capital cost of only $500
(i.e., the approximate cost of a minibulk tank to store water for reuse) for each the 19
facilities to meet the zero discharge PSES standard.
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Section 13 - New Source Performance Standards (NSPS) and Pretreatment Standards for New Sources (PSNS)
SECTION 13
NEW SOURCE PERFORMANCE STANDARDS (NSPS) AND PRETREATMENT
STANDARDS FOR NEW SOURCES (PSNS)
13.1
Introduction
New source performance standards (NSPS) under Section 306 of the Clean
Water Act (CWA) 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).
Section 307(c) of the CWA calls for EPA to promulgate pretreatment standards
for new sources (PSNS) at the same time that it promulgates 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, pollution
prevention (P2) practices and equipment, and end-of-pipe treatment technologies, and to use
plant site selection to ensure adequate treatment system installation.
This section summarizes the final NSPS and PSNS standards. Specific
discussions regarding their development are included in Section 6 (Pollutant Parameters
Selected for Regulation), Section 7 (Technology Selection and Methods to Achieve the
Effluent Limitations), and Section 8 (Engineering Costs). Implementation of these standards
is discussed hi Section 14.
13.2
Summary of Final NSPS and PSNS Standards
13.2.1 Pesticide Formulating, Packaging, and Repackaging (Subcategory C)
EPA has set NSPS for PFPR/Manufacturers and stand-alone PFPRs equivalent
to BPT and BAT (i.e., zero discharge with a compliance alternative for a pollution prevention
(P2) allowable discharge). Since EPA found the Zero/P2 Alternative option to be
economically achievable for existing facilities under BPT and BAT on a facility-basis and
since new facilities will be able to choose between zero discharge and the P2 alternative on a
product family/process line/process unit basis, EPA believes that this NSPS standard does not
create a barrier to entry.
EPA is establishing PSNS standards for this subcategory that are equivalent to
the standards established for PSES (i.e., zero discharge with a compliance alternative for a P2
allowable discharge). EPA believes that the standards established for PSNS will not create a
barrier to entry as they are equivalent to PSES, which were found to be economically
achievable.
EPA did not propose to set PSNS (or NSPS) equal to PSES (or BAT).
Although the PSNS Zero/P2 Alternative standard discussed above is a change from the
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Section 13 - New Source Performance Standards (NSPS) and Pretreatment Standards for New Sources (PSNS)
proposed PSNS, it is consistent with the Supplemental Notice (60 FR 30217) and comments
submitted. At proposal, PSES included a partial exemption for exterior wastewater sources
from small sanitizer facilities; however, the proposed PSNS did not include such an
exemption and was found not to create a barrier to entry for new facilities. The partial
sanitizer exemption no longer affects the economic achievability of the standards because, in
response to comments, EPA no longer includes sanitizer chemicals in the scope of the PFPR
effluent guidelines. Based on the addition of the P2 alternative to these effluent guidelines
and standards and the associated estimated reductions hi cross-media impacts, EPA believes
that it is appropriate to give new facilities the opportunity to use the P2 alternative to meet
PSNS.
13.2.2
Refilling Establishments (Subcategory E)
EPA is establishing NSPS standards for this subcategory that are equivalent to
the limitation established for BPT and BAT. Since BPT requires zero discharge of process
wastewater pollutants and 98% of the existing refilling establishments already achieve zero
discharge, EPA believes an equivalent technology basis is appropriate for NSPS and will not
create a barrier to entry.
EPA is establishing PSNS standards for this subcategory that are equivalent to
the limitations established for PSES (i.e., zero discharge). In addition, BPT, BAT, and NSPS
also require zero discharge of process wastewater pollutants, and 98% of the existing refilling
establishments already achieve zero discharge; thus, EPA believes an equivalent technology
basis is appropriate for PSNS and will not create a barrier to entry.
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Section 14 - Regulatory Implementation
SECTION 14
REGULATORY IMPLEMENTATION
14.1
Introduction
The purpose of this section is to provide assistance and direction to permit
writers and control authorities to aid in their implementation of this regulation and its unique
compliance alternative. Sections 14.2 and 14.3 discuss the implementation of the limitations
and standards for Subcategory C and Subcategory E facilities, respectively. Sections 14.4 and
14.5 discuss the upset and bypass provisions and the variances and modifications as they
apply to the PFPR industry. Section 14.6 discusses methods developed for the analysis of
pollutants generated in this industry and that may be used for compliance monitoring and
implementation of the limitation and standards. Section 14.7 lists references.
In addition, EPA is preparing a Pollution Prevention Alternative Guidance
Manual to provide further assistance to the industry and the permitting/control authorities
implementing this rule. (A copy may be obtained by writing to the EPA Office of Water
Resource Center (RC-4100), 401 M Street, SW, Washington, DC, 20460, or calling
(202) 260-7786.)
14.2
Implementation of the Final PFPR Limitations and Standards for
Subcategorv C Facilities
Each facility subject to the final PFPR regulation (referred to as the Zero/P2
Alternative option) will need to make an initial choice of how to comply with the regulation.
They will need to choose to either comply with the zero discharge effluent limitation/
pretreatment standard or choose to agree to conduct the listed pollution prevention (P2)
practices listed hi Table 8 in Appendix A1 of this document. Facilities will also need to
agree to make the practices and the P2 discharge allowance enforceable (see Appendix A for
the definition of P2 allowable discharge). This choice can be made on either a facility-wide
basis or on a process basis (i.e., product family/process line/process unit). For example, a
facility may choose to meet zero discharge for their dry formulation process unit, while
choosing to meet the P2 alternative for their aerosol packaging unit. See Section 7.6.6 for
more discussions of product families. Beyond this initial choice, much of the implementation
of the Zero/P2 Alternative option will differ for direct and indirect dischargers.
The remainder of Section 14.2 discusses the specific implementation of the
final PFPR limitations and standards for direct dischargers (Section 14.2.1) and indirect
dischargers (Section 14.2.2); the paperwork required to comply with the P2 alternative
(Section 14.2.3); and the compliance schedule for Subcategory C facilities subject to the scope
of the final rule (Section 14.2.4).
lThe facility can also use a variation of the listed practices based on modifications listed in Table 8 of the final
rule or those agreed to by the permitting/control authority.
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Section 14 - Regulatory Implementation
14.2.1
Direct Dischargers
For direct dischargers, the Zero/P2 Alternative option will be implemented
through the National Pollutant Discharge Elimination System (NPDES) permitting process.
Each new or existing direct discharging facility will need to make the initial choice between
zero discharge and the P2 alternative at the permitting stage or at the time of permit
modification or renewal, respectively. A facility that does not choose one option for the
facility in its entirety will be required to clearly state hi its NPDES permit the option selected
for each product family, process unit, or process line. When a direct discharger chooses the
P2 alternative for any product family, process unit, or process line, the permitting authority
will include all of the P2 practices and any specified treatment technologies in the facility's
NPDES permit. The P2 practices and treatment technologies included hi such a NPDES
permit will be enforceable under Clean Water Act (CWA) Sections 309 and 505.
The definition of P2 allowable discharge for direct dischargers requires the
appropriate treatment of all PFPR process wastewater prior to discharge. Therefore, permit
writers may want to include hi the permit the method chosen by the facility to demonstrate
that the treatment system: (1) is appropriate for the pesticide active ingredients (PAIs) in
their process wastewaters (that are not also being manufactured); and (2) is properly operated
and maintained. Alternatively, the permit writers can set numerical limitations based on Best
Professional Judgment (BPJ) for any additional PAIs, as necessary. Permit writers may
include an additional allowance above the manufacturing limit for those PAIs that are also
manufactured at the facility.
For those processes where a new or existing direct discharging PFPR/
Manufacturer has chosen to comply with zero discharge, the permit will include: (1) the
pesticide manufacturing limitations (40 CFR Part 455, Subparts A and B) with no additional
allowance for the PFPR wastewaters for those PAIs that are also manufactured; and (2)
limitations set equal to the detection limit of the PAIs expected to be hi the wastewater (or no
PFPR process wastewater flow) for PAIs that are not also manufactured at the facility. The
NPDES permits for new or existing stand-alone direct dischargers that choose to achieve zero
discharge firom specified processes either will include limitations set equal to the detection
limit of the analytical method for the PAIs expected to be hi the wastewater or will allow no
process wastewater flow.
The final regulations do not require facilities to submit all of the necessary
compliance paperwork to the NPDES permit writer, but instead require the facility choosing
the P2 alternative to keep the paperwork on site and available for the permitting authority and
enforcement officials. However, EPA is requiring the submittal of an initial certification
statement at the time of issuance, renewal, or modification of an NPDES permit for direct
dischargers. In addition, EPA is also requiring that a periodic certification statement be
submitted annually to the NPDES permit writer (see Section 14.2.3 for discussion of the
paperwork requirements).
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Section 14 - Regulatory Implementation
14.2.2
Indirect Dischargers
Existing and new PFPR facilities (including PFPR/Manufacturers) that are
indirect dischargers will also need to make an initial choice on a process basis of meeting the
zero discharge pretreatment standard or adopting and implementing the P2 practices and the
treatment technologies (if so specified). The control mechanisms or pretreatment agreements
for facilities that choose to achieve zero discharge from specified processes (or for the entire
facility) will either include pretreatment standards set equal to the detection limit of the
analytical method for the PAIs expected in the wastewater or will allow no process
wastewater flow.
If an indirect discharger chooses the P2 alternative for any or all processes/
lines/product families, the facility will need to notify the control authority of its intention by
submitting an initial certification statement as described in Section 455.41 of the final
regulation. A facility that does not choose the P2 alternative for the facility in its entirety
will be required to include a brief description of each product family, process unit, or process
line and the option selected for each with the initial certification statement. For those
processes for which the P2 alternative was chosen, the facility must include all of the P2
practices (or modifications) and any specified treatment technologies that will be implemented
to meet the requirements of the practices listed in Table 8 in Appendix A. For indirect
dischargers choosing the P2 alternative, pretreatment is required for any interior equipment
cleaning wastewater (including drums), floor wash2, or leak/spill cleanup water that is part of
the P2 allowable discharge. Other wastewater sources can be discharged to a publicly owned
treatment works (POTW) without pretreatment.
The initial certification statement requires a signature by the appropriate
manager in charge of overall operations of the facility to ensure that information provided is
true, accurate, and complete to the best of his or her knowledge. Other required paperwork
can be kept on site. This paperwork may include supporting documentation for any
modifications made to P2 practices, treatment technologies used that are not listed in Table 10
in Appendix A, the method chosen and supporting documentation for demonstrating that the
appropriate treatment is well operated and maintained, and the rationale for choosing the
method of demonstration (see Section 14.2.3). Facilities that make modifications to P2
practices for reasons not listed in Table 8 in Appendix A must submit the modifications to the
control authority for approval.
Once an individual control mechanism (or pretreatment agreement) is in place,
facilities will need to submit a periodic certification statement to the control authority
In individual cases, the requirement of wastewater pretreatment prior to discharge to the POTW may be
removed by the control authority for floor wash or the final rinse of a non-reusable triple rinse when the facility
has demonstrated that the concentrations of PAIs and priority pollutants in such wastewaters are too low to be
effectively pretreated at the facility and have been shown to neither pass through nor interfere with the operations
of me POTW. The control authority should also take into account whether or not the facility has used water
conservation when generating such a non-reusable wastewater.
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Section 14 - Regulatory Implementation
indicating that the P2 alternative is being implemented as in the previous period or that a
modification to the individual control mechanism is needed. The certification statement is to
be submitted to the control authority on the same tune table (i.e., twice per year) as the
reporting required by 40 CFR 403.12(e). The control authority, as part of its approved
pretreatment program, must have the authority to ensure compliance with a pretreatment
standard (40 CFR 403.8(i)(l)(ii)) and to carry out inspections of the indirect dischargers' self-
certifications and other required paperwork (40 CFR 403.8(f)(l)(v)). Additional information
on necessary paperwork is provided in Section 14.2.3.
14.2.3
Necessary Paperwork for the P2 Alternative
As briefly mentioned above, both direct and indirect discharging facilities are
required to keep certain paperwork on site and available for permitting/control authorities and
enforcement officials. [Note: Although EPA is not requiring submittal of all the paperwork
for approval in these national regulations, NPDES programs and control authorities may
choose to require submittal of any of the paperwork for approval.] The paperwork that is
required, to be submitted includes the one-time initial certification statement (see §455.41(a) of
the final rule) and the periodic certification statements (see §455.41(b) of the final rule). The
paperwork that can be kept on site is referred to in this final rule as the "On-site Compliance
Paperwork" (see §455.41(c^). Each of these is described below.
For each PFPR facility, the initial certification statement would include, at a
minimum., a listing of and descriptions of the processes (i.e., product families/process
lines/process units) for which it chooses the P2 alternative and those for which it chooses to
achieve zero discharge; descriptions of me P2 practices (from Table 8 to Part 455 of the
regulation, presented in Appendix A) that are being used and how they are being
implemented; description of any justifications allowing modification to the practices listed on
Table 8 in Appendix A; and a description of the treatment system being used to obtain a P2
allowable discharge (as defined in §455.41). The initial certification statement must be signed
by the responsible corporate officer as defined in 40 CFR 403.12(1) or 40 CFR 122.22.
The periodic certification statement is to be submitted twice per year for
indirect discharging facilities and once per year for direct discharging facilities and should
indicate whether the P2 alternative is being implemented as set forth in the NPDES
permit/control mechanism or that a justification allowing modification of the listed practices
has been implemented resulting hi a change in the P2 practices conducted at the facility. If
the modification needed is not listed in Table 8 in Appendix A, the facility should request a
modification from their permitting/control authority if it has not already done so.
The on-site compliance paperwork should include the information from the
initial and periodic certifications but must also include: (1) the supporting documentation for
any modifications that have been made to the listed P2 practices (including records that
indicate/demonstrate, for example, microbial growth, specific directions for other disposal
from the manufacturer, use of a solvent recovery system, etc.); (2) a written discussion
demonstrating that the treatment system being used contains the appropriate treatment
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Section 14 - Regulatory Implementation
technologies (i.e., listed by PAI in Table 10 to Part 455 of the final regulation (presented in
Appendix A), equivalent system as defined in §455.10(h), or pesticide manufacturing system)
for removing PAIs that are used in production at their facility and could be in their
wastewater; (3) a method for demonstrating that the treatment system is well operated and
maintained; and (4) a discussion of the rationale for choosing the method of demonstration.
For example, a facility may utilize a surrogate method for determining breakthrough of their
carbon adsorption unit. This method could be used instead of performing analytical testing
for all or any of the PAIs that may have been in production at the facility over a specific
period of time. The facility could possibly use records of carbon change out/purchase to
demonstrate that the system is properly operated and maintained and could describe the initial
testing and/or vendor information used to determine the useful life of the activated carbon.
Control authorities, at or any time after entering into an individual control
mechanism, or permitting authorities, at or any time after issuing, reissuing, or modifying the
NPDES permit, could inspect the PFPR facility to see that the listed practices are being used,
that the treatment system is well operated and maintained, and that the -necessary paperwork
provides sufficient justification for any modifications. When a facility needs to modify a
listed P2 practice for which a justification is not listed in the final regulation, the facility must
request the modification from the NPDES permitting authority or the control authority. The
permit writer/control authority is expected to use Best Professional Judgment (BPJ)/Best
Engineering Judgment (BEJ) to approve the modification. As mentioned in Section 14.1,
EPA is preparing a guidance manual to aid permit writers/control authorities as well as PFPR
facilities.
14.2.4
Compliance Dates
EPA has established a three-year deadline for compliance with the PFPR
pretreatment standards for existing sources (PSES). Under the Zero/P2 Alternative option,
facilities will need time to assess which process lines are amenable to the P2 alternative and
which lines will have to comply with zero discharge. This decision will most likely be based
on economics as well as the characteristics of the individual process line. In addition,
facilities will have to determine the treatment necessary for the PAIs expected to be found in
the wastewater at their .facility and they will need time to design and install these systems.
Finally, facilities will need time to institute the practices necessary to support the P2
alternative. Thus, EPA believes that a full three-year compliance period is appropriate.
Existing direct dischargers must comply by the date of issue, reissue, or
modification of the NPDES permit. Facilities must comply with new source standards and
limitations (PSNS and NSPS) when they commence discharging wastewater. [Note: For this
rule, a direct discharger is considered a new source if its construction began following
promulgation of the final rule (40 CFR 122.2), while an indirect discharger is considered a
new source if its construction began after proposal of the pretreatment standards (40 CFR
403.3).]
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Section 14 - Regulatory Implementation
Direct dischargers may be subject to the establishment by the permitting
authority of more stringent effluent limitations based on applicable water quality standards (40
CFR 122.44). In addition, PFPR indirect dischargers remain subject to the pass-through and
interference prohibitions contained in the General Pretreatment Regulations (40 CFR
403.5(a)(l)). Indirect dischargers could also be subject to local limits established by the
control authority receiving their wastewater (40 CFR 403.5(c)).
The Agency emphasizes that, although the CWA is a strict liability statute,
EPA can initiate enforcement proceedings at its discretion. EPA has exercised and intends to
exercise that discretion in a manner that recognizes and promotes good faith compliance.
14.3
Implementation of the Final PFPR Limitations and Standards for
Subcategorv E Facilities
The limitations and standards for existing and new refilling establishments are
set as zero discharge. In addition, many states (with a national regulation under the Federal
Insecticide, Fungicide, and Rodenticide Act (FIFRA) soon to follow) require these facilities to
have secondary containment systems and loading pads for their bulk pesticide and pesticide
dispensing operations. Under these state and eventual national secondary containment
regulations, facilities are collecting process wastewaters that were formerly contaminating soil
and groundwater.
EPA believes that zero discharge can be implemented at refilling establishments
because most of these facilities are not located hi areas where direct or indirect discharge is
feasible, and EPA has documented during site visits and telephone surveys numerous instances
of refilling establishments implementing zero discharge. Typically, these facilities collect
their process wastewaters (including wastewater from interior equipment cleaning of
minibulks, bulk tanks, and related ancillary equipment, and leak/spill cleanup water) and store
them for reuse. These stored rinsates are then used as product make-up water in future
custom application activities. Facilities that do not operate their own custom application
services, or that are located in states where it is prohibited to purchase make-up water for
reuse in applications, have been known to give these rinsates to custom applicators or directly
to farmers. A small number of facilities may also choose some means of off-site disposal,
such as contract hauling to incineration.
14.4
Unset and Bypass Provisions
EPA has examined the question of whether industry limitations and standards
should include provisions authorizing noncompliance with effluent limitations during periods
of "upset" or "bypass". An upset, sometimes called an "excursion," is an unintentional and
temporary noncompliance with technology-based effluent limitations occurring for reasons
beyond the reasonable control of the permittee. EPA believes that, because these exceptional
events (including "Acts of God") do occur, upset provisions are necessary. Because
technology-based limitations can require only what properly designed, maintained, and
operated technology can achieve, it is claimed that liability for such situations is improper.
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Section 14 - Regulatory Implementation
While an upset is an unintentional episode during which effluent limitations are
exceeded, a bypass is an act of intentional noncompliance during which wastewater treatment
facilities are circumvented in emergency situations.
EPA has both upset and bypass provisions in NPDES permits, and has
promulgated NPDES and pretreatment regulations that include upset and bypass permit
provisions (40 CFR 122.41(m), 122.41(n), 40 CFR 403.16, and 403.17). The upset provision
establishes an upset as an affirmative defense to prosecution for violation of technology-based
effluent limitations. The bypass provision authorizes bypassing to prevent loss of life,
personal injury, or severe property damage. Since there are already upset and bypass
provisions in NPDES permits and pretreatment regulations, EPA will let local permit and
control authorities deal with individual upsets or requests for bypass.
14.5
Variances and Modifications
Upon promulgation of these regulations, the effluent limitations for the
appropriate subcategory must be apph'ed in all federal and state NPDES permits issued to
direct dischargers in the PFPR industry. In addition, the pretreatment standards are directly
applicable to indirect dischargers. The few exceptions to these final guidelines and standards
are discussed below.
14.5.1
Fundamentally Different Factors Variances
The only exception to the final BPT limitations is EPA's "fundamentally
different factors (PDF)" variance (40 CFR Part 125, Subpart D). This variance recognizes
factors concerning a particular discharger that are fundamentally different from the factors
considered in this rulemaking. Although this variance clause was set forth in EPA's 1973-
1976 effluent guidelines, it is now included in the NPDES regulations and not the specific
industry regulations. (See 44 FR 32854, 32893, June 7, 1979, for an explanation of the.
"fundamentally different factors" variance.) The procedures to apply for a BPT PDF variance
are set forth at 40 CFR 122.21(m)(l)(I)(A).
Dischargers subject to the BAT limitations in these final regulations may also
apply for an PDF variance, under the provisions of Section 301(n) of the CWA, which
regulates BAT, BCT, and pretreatment FDFs. In addition, BAT limitations for
nonconventional pollutants may be modified under Sections 301 (c) (for economic reasons)
and 301(g) (for water quality reasons) of the CWA. These latter two statutory modifications
are not applicable to "toxic" or conventional pollutants.
Dischargers subject to pretreatment standards for existing sources are also
subject to the FDF variance provision (40 CFR 403.13) and credits for pollutants removed by
POTWs, as discussed hi Section XII.C.2 of the preamble to the final rule. Dischargers
subject to pretreatment standards for new sources (PSNS) are subject only to the removal
credit provision (see Section XII.C.2 of the preamble to the final rule).
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Section 14 - Regulatory Implementation
New sources subject to NSPS are not eligible for EPA's PDF variance or any
statutory or regulatory variances (see E.I. Du Pont v. Train. 430 U.S. 112 (1977)).
14.5.2 Removal Credits
In enacting Section 307(b) of the CWA, Congress recognized that, in certain
instances, POTWs could provide some or all of the treatment of an industrial user's waste
stream that would be required by the pretreatment standard. Consequently, Congress
established a discretionary program for POTWs to grant "removal credits" to their indirect
dischargers. The credit, hi the form of a less stringent pretreatment standard, allows an
increased amount of pollutants to flow from the indirect discharger's facility to the POTW.
Section 307(b) of the CWA establishes a three-part test for obtaining removal
credit authority for a given pollutant. Removal credits may be authorized only in the
following situations: (1) the POTW "removes3 all or any part of such toxic pollutant," (2)
the POTW's ultimate discharge would "not violate that effluent limitation, or standard which
would be apph'cable to that toxic pollutant if it were discharged" directly rattier than through a
POTW, and (3) the POTW's discharge would "not prevent sludge use and disposal by such
[POTW] in accordance with Section [405]...." (Section 307(b)).
EPA has promulgated removal credit regulations in 40 CFR 403.7. The
United States Court of Appeals for the Third Circuit has interpreted the statute to require EPA
to promulgate comprehensive sewage sludge regulations before any removal credits could be
authorized fNRDC v. EPA. 790 F.2d 289, 292 (3rd Cur. 1986) cert, denied. 479 U.S. 1084
(1987)). Congress made this explicit in the Water Quality Act of 1987, which stipulated that
EPA could not authorize any removal credits until it issued the sewage sludge use and
disposal regulations required by Section 405(d)(2)(a)(ii).
Section 405 of the CWA requires EPA to promulgate regulations that establish
standards for sewage sludge when used or disposed of for various purposes. These standards
must include sewage sludge management standards as well as numerical limits for pollutants
that may be present in sewage sludge in concentrations that may adversely affect public health
and the environment. Section 405 requires EPA to develop these standards in two phases, or
"rounds." On November 25, 1992, EPA promulgated the Round One sewage sludge
regulations establishing standards, including numerical pollutant limits, for the use and
disposal of sewage sludge (58 FR 9248). EPA established pollutant limits for ten metals
when sewage sludge is apph'ed to land, for three metals when it is disposed of at surface
disposal sites, and for seven metals and total hydrocarbons (a surrogate for organic pollutant
3In 40 CER 403.7, removal is defined to mean "a reduction in the amount of a pollutant in the POTW's effluent
or alteration of the nature of a pollutant during treatment at the POTW. The reduction or alteration can be
obtained by physical, chemical, or biological means and may be the result of specifically designed POTW
capabilities or may be incidental to the operation of the treatment system. Removal as used [in §403.7] shall not
mean dilution of a pollutant in the POTW."
14-8
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Section 14 - Regulatory Implementation
emissions) when sewage sludge is incinerated. These requirements are codified at 40 CFR
Part 503.
At the same time that EPA promulgated the Round One regulations, the
Agency also amended its pretreatment regulations to stipulate that removal credits would be
available for certain pollutants regulated in the sewage sludge regulations (58 FR 9386). The
amendments to Part 403 provide that removal credits may be made potentially available for
pollutants in the following situations:
1) If a POTW applies its sewage sludge to the land for beneficial uses, disposes
of it on surface disposal sites, or incinerates it, removal credits may be available, depending
on which use or disposal method is selected (so long as the POTW complies with the
requirements in Part 503). When sewage sludge is applied to land, removal credits may be
available for ten metals. When sewage sludge is disposed of on a surface disposal site,
removal credits may be available for three metals. When the sewage sludge is incinerated,
removal credits may be available for seven metals and 57 organic pollutants (40 CFR
403.7(a)(3)(iv)(A)).
2) In addition, when sewage sludge is applied to land, disposed of on a surface
disposal site, or incinerated, removal credits may also be available for additional pollutants as
long as the concentration of the pollutant in sludge does not exceed a concentration level
established in Part 403. Under these circumstances, when sewage sludge is applied to land,
removal credits may be available for two additional metals and 14 organic pollutants. When
the sewage sludge is disposed of on a surface disposal site, removal credits may be available
for seven additional metals and 13 organic pollutants. When the sewage sludge is incinerated,
removal credits may be available for three other metals (40 CFR 403.7(a)(3)(iv)(B)).
3) When a POTW disposes of its sewage sludge in a municipal solid waste
landfill (MSWLF) that meets the criteria of 40 CFR Part 258, removal credits may be
available for any pollutant in the sewage sludge (40 CFR 403.7(a)(3)(iv)(C)).
Thus, given compliance with the requirements of EPA's removal credit
regulations4, and following promulgation of the final pretreatment standards, removal credits
may be authorized for any pollutant subject to pretreatment standards if the applying POTW
disposes of its sewage sludge in a MSWLF that meets the requirements of 40 CFR Part 258.
If the POTW uses or disposes of its sewage sludge by land application, surface disposal, or
incineration, removal credits may be available for the following metal pollutants (depending
on the method of use or disposal): arsenic, cadmium, chromium, copper, lead, mercury,
molybdenum, nickel, selenium, and zinc. Given compliance with Section 403.7, removal
Under Section 403.7, a POTW is authorized to give removal credits only under certain conditions. These
include applying for, and obtaining, approval from the Regional Administrator (or director of a state NPDES
program with an approved pretreatment program), a showing of consistent pollutant removal, and an approved
pretreatment program (40 CFR 403.7(a)(3)(I), (ii), and (iii)).
14-9
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Section 14 - Regulatory Implementation
credits may be available for the following organic pollutants (depending on the method of use
or disposal):
acrylonitrile
aldrin/dieldrin (total)
benzene
benzidine
benzo(a)pyrene
bis(2-chloroethyl)ether
bis(2-ethylhexyl)phthalate
bromodichloromethane
bromoethane
bromoform
carbon tetrachloride
chlordane
chloroform
chloromethane
DDD
DDE
DDT
dibromochloromethane
dibutyl phthalate
1,2-dichloroethane
1,1-dichloroethylene
2,4-dichlorophenol
1,3-dicbloropropene
diethyl phthalate
2,4-dmitrophenol
1,2-diphenylhydrazine
di-n-butyl phtitialate
endosulfan
endrin
ethylbenzene
heptachlor
heptachlor epoxide
hexachlorobutadiene
alphahexachlorocyclohexane
betahexachlorocyclohexane
hexachlorocyclopentadiene
hexachloroethane
hydrogen cyanide
isophorone
lindane
methylene chloride
nitrobenzene
n-nitrosodimethylamine
n-nitrosodi-n-propylamine
pentachlorophenol
phenol
polychlorinated biphenyls
2,3,7,8-tetracWorodibenzo-p-dioxin
1,1,2,2-tetrachloroethane
tetrachloroethylene
toluene
toxaphene
trichloroethylene
1,2,4-trichlorobenzene
1,1,1 -trichloroethane
1,1,2-trichloroethane
2,4,6-trichlorophenol
With regard to the use of removal credit authority for any pollutant subject to
these pretreatment standards, a POTW (once compliance with 40 CFR 403.7 is shown and
removal credit authority is granted) may be able to effectively authorize the waiving of what
otherwise would be required treatment of the PFPR wastewaters by authorizing a removal
credit to the PFPR industrial user to me extent of any pollutants remaining hi its discharge
after all applicable P2 practices have been complied with. However, removal credits could
only be granted to the extent that granting of such credits would not result in pass through or
interference at the POTW as defined in 40 CFR 403.3 and in accordance with the provisions
of Section 403.5, and EPA would expect that the PFPR industrial user would have to continue
to comply with the P2 practices as specified in the P2 alternative even if a removal credit had
been provided.
14-10
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Section 14 - Regulatory Implementation
14.6
Analytical Methods
Section 304(h) of the CWA directs EPA to promulgate guidelines establishing
test methods for the analysis of pollutants. These methods are used to determine the presence
and concentration of pollutants in wastewater, and are used for compliance monitoring, for
filing applications for the NPDES program under 40 CFR 122.21, 122.41, 122.44, and
123.25, and for implementing the pretreatment standards under 40 CFR 403.10 and 403.12.
To date, EPA has promulgated methods for conventional pollutants, toxic pollutants, and for
some nonconventional pollutants. The five conventional pollutants are defined at 40 CFR
401.16. Table I-B at 40 CFR Part 136 lists the analytical methods approved for these
pollutants. The 65 toxic metals and organic pollutants and classes of pollutants are defined at
40 CFR 401.15. From the list of 65 classes of toxic pollutants, EPA identified 126 "priority
pollutants," listed in Appendix C of this document. The list includes nonpesticide organic
pollutants, metal pollutants, cyanide, asbestos, and pesticide pollutants. Currently approved
methods for metals and cyanide are included in the table of approved inorganic test
procedures at 40 CFR 136.3, Table I-B. Table I-C at 40 CFR 136.3 lists approved methods
for measuring nonpesticide organic pollutants, and Table I-D lists approved methods for
measuring the priority pesticide pollutants and for other pesticide pollutants.
EPA believes that the analytical methods for PAIs contained in the promulgated
pesticide manufacturing effluent guidelines and standards (see Methods for the Determination
of Nonconventional Pesticides in Municipal and Industrial Wastewater (1)) will perform as
well on treated PFPR wastewaters as on pesticide manufacturing wastewaters. Many of these
methods have in fact been used on the PFPR sampled wastewaters. Raw wastewater samples
may on occasion require some separation prior to analysis, analogous to the emulsion breaking
pretreatment included in EPA's costed BAT technology. The PAI pollutant data that support
the final PFPR effluent limitations were generated using analytical methods that use the
approved methods or were based on the approved methods under 40 CFR Part 136 or
contained in Methods for the Determination of Nonconventional Pesticides hi Municipal and
Industrial Wastewater (1). For PAIs that have no EPA-approved analytical methods, PFPR
facilities may utilize alternative sampling and analysis methods as specified in 40 CFR 136.4
and 40 CFR 403.12(g)(4). At some future date, EPA may transfer the analytical methods
promulgated under Part 455 to Part 136 as a part of EPA's effort to consolidate analytical
methods and streamline promulgation of new methods.
As discussed in Section 14.2, EPA believes that those facilities achieving zero
discharge will either demonstrate no process wastewater flow or will use the analytical
methods to show that PAI concentrations are below detection limits (or meeting pesticide
manufacturing limitations with no allowance given for PFPR wastewater). Facilities choosing
to demonstrate that they are in compliance with the P2 alternative will use certification
statements, inspections, and demonstrated implementation of the listed P2 practices to assure
compliance with the final rule. However, some facilities, although not required, may use
analytical methods to demonstrate that their treatment systems are "well operated and
maintained," as required by the P2 alternative. In addition, permitting/control authorities can
14-11
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Section 14 - Regulatory Implementation
set numerical limitations using BPJ7BEJ, which may rely on the use of analytical methods for
demonstrating compliance.
14.7
1.
References
U.S. Environmental Protection Agency. Methods for the Determination of
Nonconventional Pesticides in Municipal and Industrial Wastewater. Volumes I
and n, EPA 821-R-93-010, August 31, 1993 (DCNs F7131 and F7132).
5For those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
14-12
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Section 15 - Water Quality Analysis
SECTION 15
WATER QUALITY ANALYSIS
15.1
Introduction
Most of the pesticide active ingredients (PAIs) that fall within the scope of this
rule have at least one toxic effect. For example, 137 of the original 272 PAIs are known to
be highly or moderately toxic to aquatic life, 25 have carcinogenic effects, 149 are known to
have systemic or other health effects, 24 have an established concentration limit under the
Safe Drinking Water Act, and 134 have a high or moderate potential to bioaccumulate in the
environment. (See Potential Fate and Toxicity Categorization of Pollutants Associated with
Pesticide Formulating. Packaging, and Repackaging Wastewater: September 1996 (1).)
Documented human health impacts at pesticide formulating, packaging, and repackaging
(PFPR) facilities include respiratory disease and impaired liver function, primarily through
worker exposure. Because of these potential impacts, EPA has estimated the water quality
benefits expected through compliance with the Zero/Pollution Prevention (P2) Alternative
option. Section 15.2 summarizes documented incidents of soil and groundwater
contamination by PAIs, and Sections 15.3 and 15.4 present estimates of the expected water
quality benefits of controlling wastewater discharges from PFPR facilities. Section 15.5 lists
references.
15.2
Soil and Groundwater Contamination at Refilling Establishments
Numerous incidents of groundwater and soil contamination at refilling
establishments, largely due to spills, are identified in the Office of Pesticide Programs (OPP)
proposed standards for pesticide containers and containment (59 FR 6712; February 11, 1994).
Several examples cited in that proposed rule are summarized below.
Based on the 1991 study Report on Wisconsin Pesticide Mixing and Loading
Site Study (2), an estimated 45 to 75% of the commercial agrichemical facilities in Wisconsin
will require soil remediation and 29 to 63% of these sites potentially exceed the state's
groundwater standards for pesticides. In the report Environmental Cleanup of Facilities and
Agricultural Dealer Sites (3), the Iowa Fertilizer and Chemical Association estimates that 40
to 50% of refilling establishments in Iowa may require groundwater remediation. A 1992
letter from the National Agricultural Retailers Association (formerly NARA, now ARA) stated
that 70 to 80% of the pesticide detections hi groundwater in Kansas could be traced back to
refilling establishments. Pesticide groundwater contamination is also documented at numerous
refilling establishments in Michigan, Minnesota, Illinois, and Utah.
15.3
Water Quality Benefits of Control of Indirect Discharges
The water quality benefits of controlling the indirect discharges from PFPR
facilities were also evaluated by modeling the impact of those discharges on receiving
streams. The effects of POTW wastewater discharges of 139 PAIs were evaluated at
15-1
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Section 15 - Water Quality Analysis
"current" (i.e., 1988) levels and at postcompliance (i.e., following implementation of the
Zero/P2 Alternative option) levels for 85 PFPR facilities that discharge wastewater to 79
POTWs on 77 receiving streams. Water quality models were used to project pollutant in-
stream concentrations based on estimated releases at current and Zero/P2 Alternative option
levels; the in-stream concentrations were then compared to EPA-published water quality
criteria or to documented toxic effect levels.
The in-stream pollutant concentration for one PAI is projected to exceed human
health criteria in two receiving streams at current discharge levels. Both exceedances are
projected to be eliminated under the Zero/P2 Alternative option. The number of pollutants
with receiving streams projected to exceed aquatic life criteria or aquatic toxic effect levels
would be reduced from 21 PAIs in 23 streams at current discharge levels to four PAIs in six
streams following implementation of the Zero/P2 Alternative option.
The potential impacts of these PFPR indirect dischargers were also evaluated hi
terms of inhibition of POTW operation and contamination of sludge. The analysis of POTW
inhibition is based upon engineering and health estimates contained in guidance or guidelines
published by EPA and other sources. At current discharge levels, potential biological
inhibition problems are projected to occur at four POTWs for three PAIs; sludge criteria are
unavailable for PAIs and therefore cannot be evaluated. No potential biological inhibition
problems are projected to occur for the Zero/P2 Alternative option. Although EPA is not
basing its regulatory approach for pretreatment discharge levels upon the finding that some
pollutants interfere with POTWs by impairing their treatment effectiveness, the data indicate
the potential benefits for POTW operation that may result from compliance with the final
regulation.
15.4
Water Quality Benefits of Control of Direct Discharges
In addition, the water quality benefits of controlling the direct discharges from
PFPR facilities were evaluated by modeling the impact of direct wastewater discharges on
receiving stream water quality. However, as described in Section 16.2, EPA's estimates of
costs and current pollutant loadings for direct discharges did not include pollutant removals
for treatment already in place (i.e., pesticide manufacturing treatment systems). Therefore, an
estimate of the water quality impacts resulting from current direct discharges would result in
an overestimation of the current water quality impacts because these facilities do have
treatment in place and are already meeting zero discharge or zero allowance (i.e., no
additional discharge allowance in the pesticide manufacturers' limitations for PFPR
wastewaters). Thus, EPA is presenting only those water quality impacts associated with the
final rule.
Seventeen (17) direct discharging PFPR facilities, which discharge 61 PAIs to
16 receiving streams, were evaluated. Water quality models are used to project pollutant in-
stream concentrations based on estimated releases at post-compliance (e.g., zero/P2
alternative) levels; the in-stream concentrations are then compared to EPA published water
quality criteria or to documented toxic effect levels where EPA water quality criteria are not
15-2
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Section 15 - Water Quality Analysis
available for certain PAIs. The Zero/P2 Alternative option is projected to result in aquatic
life exceedances of three PAIs in two receiving streams. No exceedances of human health
criteria are projected to occur for the Zero/P2 Alternative option.
15.5
1.
2.
3.
References1
U.S. Environmental Protection Agency. Potential Fate and Toxicitv
Categorization of Pollutants Associated with Pesticide Formulating. Packaging.
and Repackaging Wastewater. Revised September 6, 1996 (DCN F7949).
Morrison, P. and S. Kefer. Report on Wisconsin Pesticide Mixing and Loading
Site Study. Wisconsin Department of Agriculture Trade and Consumer
Protection and Wisconsin Department of Natural Resources, 1991.
Frieberg D. Environmental Cleanup of Fertilizer and Agricultural Chemical
Dealer Sites. Iowa Fertilizer and Chemical Association, 1991.
!For those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
15-3
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Section 16 - Non-Water Quality Environmental Impacts
SECTION 16
16.1
NON-WATER QUALITY ENVIRONMENTAL IMPACTS
Introduction
The. elimination or reduction of one form of pollution may create or aggravate
otiier environmental problems. Therefore, Sections 304(b) and 306 of the Clean Water Act
(CWA) call for EPA to consider the non-water quality environmental impacts of effluent
limitations guidelines and standards. Accordingly, EPA has considered the effect of the final
pesticide formulating, packaging, and repackaging (PFPR) regulations on air pollution, solid
waste generation, and energy consumption. This section presents the estimated non-water
quality impacts resulting from the implementation of this final PFPR rule for Subcategory C
facilities; no significant non-water quality impacts are associated with the final rule as it
pertains to Subcategory E facilities.
Section 16.2 summarizes the general impacts of the final PFPR rule on air
pollution, solid waste generation, and energy consumption. Sections 16.3 through 16.5
discuss the individual impacts of the final regulation on each of these areas, respectively.
Section 16.6 lists references.
16.2
Summary of Non-Water Quality Impacts of the Final PFPR Rule
EPA has estimated the non-water quality impacts associated with the
Zero/Pollution Prevention (P2) Alternative option, upon which the final PFPR rule is based.
Under the final rule, existing Subcategory C facilities, including direct dischargers, will have a
choice of either complying with a zero discharge limitation or the P2 alternative (see
Section 2 for a discussion on amending and clarifying BPT). However, for direct discharging
facilities that choose to comply with the zero discharge limitation, the final rule clarifies that
permitting authorities may authorize the commingling of pesticide manufacturing and PFPR
process wastewaters to meet the pertinent BAT limitations for pesticide manufacturers with a
zero allowance for PAIs in PFPR wastewaters. EPA has revised its cost and pollutant
loadings model to account for changes in the final rule due to updated analytical data, changes
in scope, and the addition of the P2 alternative, as discussed in Section 8. However, EPA
believes that an overestimate of the non-water quality impacts would result if EPA included
impacts for separate UTS systems when the facilities' current controls, used for treating PFPR
wastewaters (i.e., prior to commingling with pesticide manufacturing wastewater) and/or
treating commingled wastewater (i.e., their pesticide manufacturing treatment systems),
already achieve the BAT limitation of zero discharge or "zero allowance." Thus, EPA is not
including the non-water quality impacts associated with direct dischargers in the total industry
estimate.
EPA chose the Zero/P2 Alternative option as the basis for this regulation in
part to minimize the cross-media impacts that could occur under a regulation based only on
zero discharge, if facilities chose to comply by disposing of large volumes of non-reusable
16-1
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Section 16 - Non-Wafer Quality Environmental Impacts
wastewaters through off-site incineration. As discussed in previous sections, under the
Zero/P2 Alternative option, a facility will be able to choose between complying with zero
discharge (based on treatment and reuse of wastewaters or based on P2 practices and off-site
incineration of wastewaters), or the P2 alternative on a product family/process line/process
unit basis. However, for the purposes of estimating compliance costs and non-water quality
impacts, EPA has assumed that a facility will choose between these compliance options on a
facility-wide basis and will choose the least expensive option (referred to as the "selected
option"). Therefore, the non-water quality estimates for the Zero/P2 Alternative option
represent those cross-media impacts associated with 69% of the facilities choosing to comply
with the P2 alternative and the rest choosing to comply with zero discharge.
EPA has also evaluated for comparison the costs and non-water quality impacts
associated with a regulation based only on zero discharge, assuming facilities will recycle and
reuse some wastewaters while hauling the remaining wastewaters off site for incineration.
These impacts are referred to as the "zero discharge" option.
Under the P2 alternative, some facilities may be able to avoid having to treat
their wastewater by comprehensively applying source reduction practices to all their
wastewater sources; however, it is more likely that, after implementing recycle and reuse
practices, facilities will need to use some pollution control treatment technologies (e.g., the
UTS) before discharging their wastewaters.
Some cross-media impacts are associated with the on-site treatment of
wastewater that are not associated with off-site incineration of wastewater. These cross-media
impacts include sludge generation, energy consumption, air emissions of volatile priority
pollutants, and emissions of criteria air pollutants1 from the trucks that transport spent
activated carbon for regeneration. However, off-site incineration significantly increases the
cross-media impacts due to air emissions of criteria air pollutants from the trucks that
transport the wastewater to the incinerator and from the incineration of the wastewater itself.
EPA believes that selecting the Zero/P2 Alternative option will minimize the
overall cross-media impacts due to this regulation, as compared to the zero discharge option
originally proposed. In particular, the Zero/P2 Alternative option has a significantly lower
cross-media impact on air emissions of criteria air pollutants than the zero discharge option
while still preventing 98.5% of the pesticide active ingredients (PAIs) from being discharged
to water.
To summarize, after implementation of the final PFPR rule, Subcategory C
facilities in the PFPR industry will generate an estimated 856,000 pounds of UTS sludge and
wastewater per year. An estimated 3,830,000 pounds per year of spent activated carbon will
be generated from the activated carbon adsorption step of the UTS; however, it is assumed
1 Criteria air pollutants include: volatile organic compounds (VOCs), nitrogen oxides (NOX), sulfur dioxide
(SO£, particulate matter (PM), and carbon monoxide (CO). Criteria air pollutants can injure health, harm the
environment, and cause property damage.
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Section 16 - Non-Water Quality Environmental Impacts
that the activated carbon will be sent off site for regeneration and will not become a waste.
The industry will consume an estimated 811,000 kWh/yr of electrical energy to power pumps
and agitators used in the UTS and pumps associated with wastewater storage tanks. An
estimated 63,000,000 pounds of steam per year (at 15 psig, I20°C) will be needed to heat
UTS process vessels, which is the equivalent consumption of approximately 13,600 barrels of
oil.
The implementation of the final PFPR rule would affect the treatment and
handling of an estimated 84,900,000 gallons of wastewater at Subcategory C PFPR facilities.
Using 1988 data, it is estimated that the treatment and handling of these wastewaters resulted
in the air emissions of 381,000 pounds of volatile priority pollutants (baseline, prior to rule
implementation). In comparison, volatile priority pollutant emissions due to the treatment and
handling of these wastewaters after implementation of the final PFPR rule are estimated to be
85,000 pounds per year (an emission reduction of 296,000 Ib/yr).
The following sections present the estimates for air emissions, solid waste
generation, and energy consumption for the final rule. The report Non-Water Quality Impact
Estimates for Subcategorv C Pesticide Formulating. Packaging, and Repackaging (PFPR)
Facilities (1) discusses in greater detail how these impacts were estimated.
16.3
Air Pollution
For the purpose of preparing a cross-media impact analysis, the air pollution
effects.comprise two separate types of air emissions generated as a result of the final rule.
Section 16.3.1 presents criteria air pollutant, emissions and Section 16.3.2 presents volatile
priority pollutant emissions. EPA does not anticipate that there will be any significant losses
of PAIs into the atmosphere under the Zero/P2 Alternative option because most PAIs have
low volatility.
16.3.1
Criteria Air Pollutants
Criteria air pollutants are generated from the transport (i.e., air emissions from
the trucks' exhaust and gasoline) of both wastewater and spent activated carbon as well as
emissions from the incineration of wastewater that is hauled off site for disposal. Table 16-1
presents estimates of criteria air pollutant emissions for the Zero/P2 Alternative option and for
zero discharge. As seen in Table 16-1, the emissions of criteria air pollutants from the
transport of wastewaters and spent activated carbon and from the incineration of the non-
reusable wastewaters under the zero discharge option would create a significant cross-media
impact as compared to the Zero/P2 Alternative option.
16.3.2
Volatile Priority Pollutants
EPA also estimated the reduction of volatile priority pollutants emissions that
would occur under the Zero/P2 Alternative option and under the zero discharge option. EPA
estimates that, in addition to the 192,789 pounds of PAIs that are currently (i.e., prior to
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Section 16 - Non-Water Quality Environmental Impacts
Table 16-1
Criteria Air Pollutant Emissions (Ib/yr)
Emission Source ,
Wastewater Transportation
Zero/P2 Alternative1
Zero Discharge
Wastewater Incineration
Zero/P2 Alternative1
Zero Discharge ,
Spent Activated Carbon
Transportation
Zero/P2 Alternative1
ry
Zero Discharge
Wastewater Treatment?
Zero/P2 Alternative1
Zero Discharge
VOCs
14,720
87,600
5
624
1,692
NA
84,700
52,500
*ox
121,200
720,000
1,838
94,600
13,920
NA
NA
NA
PM
6,800
40,400
10
530
780
NA
NA
NA
CO
175,400
1,044,000
133
6,880
20,200
NA
NA
NA
SOX
NA
2
106
NA
NA
NA
%PA estimates that, under the Zero/P2 Alternative option, 69% of facilities incurring costs will choose the P2
alternative and 31% will choose to comply with zero discharge.
2This zero discharge option does not include on-site wastewater treatment; therefore, no spent activated carbon is
required to be transported for regeneration.
3Air emissions estimates from wastewater treatment include only volatile priority pollutants.
NA - Not applicable.
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Section 16 - Non-Water Quality Environmental Impacts
promulgation of the final regulation) being discharged to water, 381,000 pounds of volatile
priority pollutants are emitted when wastewater is discharged to publicly owned treatment
works (POTWs) or are emitted to the air from the wastewater treatment process at the
POTWs. EPA estimates that, under the Zero/P2 Alternative option, the air emissions from
wastewater reuse, treatment, and discharge to POTWs will be reduced to 85,000 pounds of
volatile priority pollutants. This means that implementing the Zero/P2 Alternative option will
reduce air emissions of volatile priority pollutants from wastewater reuse, treatment, and
discharge by 296,300 pounds annually. In addition, the remaining emissions are localized and
in many cases may be more likely to be captured and treated by the UTS. The loss of
priority pollutants to the atmosphere is likely to occur during reuse of wastewater and
particularly from the emulsion breaking, hydrolysis, and/or chemical oxidation treatment steps
where the application of heat is likely to promote their release.2 It is also possible that some
emissions of priority pollutants could occur during the cleaning of equipment or containers,
particularly if high-pressure cleaning or steam cleaning is used.
Under the zero discharge option, 52,500 pounds of volatile priority pollutants
are expected to be emitted during the recycle and .reuse of wastewaters, although more criteria
air pollutants are emitted as mentioned in Section 16.3.1.
16.4
Solid Waste
The types and amounts of solid waste generated by PFPR facilities are expected
to change after implementation of the final PFPR rule. Facilities that generate solid waste
prior to rule implementation (e.g., through disposal of wastewater) are assumed to continue
generating the same amount of solid waste from those sources. Solid waste impacts presented
in this section reflect only the increase in solid waste expected due to implementation of the
rule. New sources of solid wastes would include sludge generated from emulsion breaking
treatment and spent activated carbon from carbon adsorption treatment.
EPA estimates that, under the Zero/P2 Alternative option, there will be 856,000
pounds of sludge generated from the emulsion breaking and sulfide precipitation treatment
steps of the UTS annually. EPA has assumed that the sludge generated via emulsion breaking
and sulfide precipitation will be hauled to hazardous waste incinerators. In addition to the
sludge generated, treatment of wastewater through the UTS will generate 3,830,000 pounds
annually of spent activated carbon. It is assumed that the activated carbon will be sent off
site for regeneration, which means that it will be reused and will not become a waste. Section
16.3 discusses the estimate of air emissions from transporting the spent activated carbon for
2EPA believes that use of closed vessels in the treatment system will additionally control the release of volatile
priority pollutants to the air and, therefore, has used the costs associated with closed vessels when estimating
costs for the regulation. However, for the analysis of the air pollution emissions estimates for this rule, estimates
on volatile priority pollutant emissions from closed vessels were not available. Therefore, the volatile priority
pollutant emissions estimate assumes the use of open vessels during treatment which may overestimate the
emissions.
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Section 16 - Non-Water Quality Environmental Impacts
regeneration and from the hauling of wastewater/sludge to incineration as well as the air
emissions associated with incineration.
EPA believes the Zero/P2 Alternative option is consistent with the goals
established for EPA's Hazardous Waste Minimization and Combustion Strategy (November
1994). This draft combustion strategy establishes the goal of a strong preference for source
reduction over waste management, thereby reducing the long-term demand for combustion and
other waste management facilities. In addition, the strategy states that combustion does have
an appropriate role and that EPA wants to ensure that combustion facilities (such as
incinerators and boilers and industrial furnaces (BIFs)) are designed in a manner to protect
public health.
16.5
Energy Requirements
The amounts of energy consumed by PFPR facilities are also expected to
change after implementation of the final PFPR rule. EPA does not have available information
on energy use at PFPR facilities prior to rule implementation. Therefore, energy impacts
reflect only the increase in steam and electric use expected due to implementation of the rule.
EPA has estimated the amount of energy that facilities would consume to operate pumps,
agitators, skimmers, and other devices used in the UTS and in the storage of wastewater for
reuse, and the energy required to generate steam that is used in the UTS to accomplish
emulsion breaking and hydrolysis. Steam provides the heat energy to assist with the
separation of emulsified phases and increases the rate at which PAIs hydrolyze.
EPA estimates that the operation of the UTS will consume 811,000 kilowatt
hours per year. This energy is expended by the pumps and agitators used in treatment and
associated with the storage of water until it can be reused. EPA also estimates that about
63 million pounds per year of steam would be required by the UTS. Approximately 13,600
barrels of oil would be required annually to generate this steam. This is, relatively, very
small compared to the 18 million barrels per day that the United States currently consumes.
16.6
1.
References^
Eastern Research Group, Inc. Non-Water Quality Impact Estimates for
Subcategorv C Pesticide Formulating. Packaging, and Repackaging (PFPR)
Facilities. Prepared for U.S. Environmental Protection Agency Office of
Water, September 1996 (F7942).
3For those references included in the administrative record supporting the final PFPR rulemaking, the document
control number (DCN) is included in parentheses at the end of the reference.
16-6
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Section 17 - Glossary of Terms
SECTION 17
GLOSSARY OF TERMS
Administrator: The Administrator of the U.S. Environmental Protection Agency.
Aerosol container (DOT) leak testing wastewaters: Wastewaters from pressurization/leak
testing of pesticide product containers to meet DOT shipping requirements.
Agency: The U.S. Environmental Protection Agency.
Appropriate pollution control technology: The wastewater treatment technology listed on
Table 10 to Part 455 (Appendix A) for a particular PAI(s) including an emulsion breaking
step prior to the listed technology when emulsions are present in the wastewater to be treated.
B.t.: Bacillus thuringiensis, a microorganism pesticide active ingredient that is excluded from
the scope of the final PFPR rule.
BAT: The best available technology economically achievable, as described in Section
304(b)(2) of the Clean Water Act.
[:, The best conventional pollutant control technology, as described in Section 304(b)(4)
of the Clean Water Act.
BEJ: Best engineering judgment.
Bench-scale operation: Laboratory testing of materials, methods, or processes on a small
scale, such as on a laboratory worktable.
Binder: An ingredient added hi order to form films, such as a drying oil or polymeric
substance.
BMP or BMPs: Best management practice(s), as described hi Section 304(e) of the Clean
Water Act.
BOD5: Five-day biochemical oxygen demand. A measure of biochemical decomposition of
organic matter hi a water sample. It is determined by measuring the dissolved oxygen
consumed by microorganisms to oxidize the organic contaminants in a water sample under
standard laboratory conditions of five days and 20°C. BOD5 is not related to the oxygen
requirements hi chemical combustion.
BPJ: Best professional judgment.
BPT: The best practicable control technology currently available, as described hi Section
304(b)(l) of the Clean Water Act
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Section 17 - Glossary of Terms
Bulk product: Formulated product held in inventory prior to packaging into marketable
containers.
CAA: Clean Air Act. The Air Pollution Prevention and Control Act (42 U.S.C. 7401 et.
seq.), as amended, inter alia, by the Clean Air Act Amendments of 1990 (Public Law 101-
549, 104 Stat 2399).
CFR: Code of Federal Regulations, published by the U.S. Government Printing Office. A
codification of the general and permanent rules published in the Federal Register by the
Executive departments and agencies of the federal government. The Code is divided into 50
titles which represent broad areas subject to federal regulation. Each title is divided into
chapters which usually bear the name of the issuing agency, and each chapter is divided into
parts covering specific regulatory areas. Citations of the Code of Federal Regulations include
title, part, and section number (e.g., 40 CFR 1.1 - title 40, part 1, and section 1).
Changeover: Changing from one pesticide product to another pesticide product, to a non-
pesticide product, or to idle equipment condition.
CN: Abbreviation for total cyanide.
CO: Abbreviation for carbon monoxide.
COP: Chemical oxygen demand (COD) - A nonconventional bulk parameter that measures
the total oxygen-consuming capacity of wastewater. This parameter is a measure of materials
in water or wastewater that are biodegradable and materials that are resistant (refractory) to
biodegradation. Refractory compounds slowly exert demand on downstream receiving water
resources. Certain of the compounds measured by this parameter have been found to have
carcinogenic, mutagenic, and similar adverse effects, either singly or in combination. It is
expressed as the amount of oxygen consumed by a chemical oxidant in a specific test.
Combustion device: An individual unit of equipment, including but not limited to, an
incinerator or boiler, used for the thermal oxidation of organic hazardous air pollutant vapors.
Contract hauling: The removal of any waste stream from the plant or facility, excluding
discharges to sewers or surface waters.
Control authority: (1) The POTW if the POTW's submission for its pretreatment program
(§403.3(t)(l)) has been approved in accordance with the requirements of §403.11; or (2) the
approval authority if the submission has not been approved.
Conventional pollutants: Constituents of wastewater as determined in Section 304(a)(4) of
the Clean Water Act and the regulations thereunder (i.e., biochemical oxygen demand
(BOD5), total suspended solids (TSS), oil and grease, fecal coliform, and pH).
CSF: Confidential statement of formula.
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Section 17 - Glossary of Terms
CWA: Clean Water Act. The Federal Water Pollution Control Act Amendments of 1972 (33
U.S.C. 1251 et seq.), as amended, inter alia, by the Clean Water Act of 1977 (Public Law 95-
217) and the Water Quality Act of 1987 (Public Law 100-4).
Device (packaging): Any instrument or conveyance (other than a firearm) which is intended
for trapping, destroying, repelling, or mitigating any pest or any other form of plant or animal
life (other than man and other than bacteria, virus, or other microorganism on or in living
man or other living animals), but not including equipment used for the application of
pesticides when sold separately therefrom.
Direct discharger: The discharge of a pollutant or pollutants directly to a water of the
United States with or without treatment by the discharger.
DOT: Department of Transportation.
Effluent: Wastewater discharges.
EPA: The U.S. Environmental Protection Agency.
Equivalent system: A wastewater treatment system that is demonstrated in literature,
treatability tests, or self-monitoring data to remove a similar level of pesticide active
ingredient or priority pollutants as the applicable appropriate pollution control technology
listed in Table 10 to Part 455 (Appendix A).
FATES: FBFRA and TSCA Enforcement System.
FDA: Food and Drug Administration.
FDF: Fundamentally different factors.
FIFRA: The Federal Insecticide, Fungicide, and Rodenticide Act, as amended (7 U.S.C. 135
etseq.).
Formulation: The process of mixing, blending, or diluting one or more pesticide active
ingredients with one or more other active or inert ingredients, without a chemical reaction that
changes one active ingredient into another active ingredient, to obtain a manufacturing use
product or an end use product.
FR: Federal Register, published by the U.S. Government Printing Office, Washington, D.C.
A publication making available to the public regulations and legal notices issued by federal
agencies. These include Presidential proclamations and Executive Orders and federal agency
documents having general applicability and legal effect, documents required to be published
by act of Congress and other federal agency documents of public interest. Citations of the
Federal Register include volume number and page number (e.g., 55 FR 12345).
17-3
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GMPs: Good Manufacturing Practices.
Section 17 - Glossary of Terms
Generally Recognized as Safe (label given to certain items by the Food and Drug
Administration).
Group 1 mixtures: Any product whose only pesticidal active ingredient(s) is: a common
food/food constituent or nontoxic household item; or is a substance that is generally
recognized as safe (GRAS) by the Food and Drug Administration (21 CFR 170.30, 182, 184,
and 186) in accordance with good manufacturing practices, as defined by 21 CFR Part 182; or
is exempt from FIFRA under 40 CFR Part 152.25.
Group 2 mixtures: Those chemicals listed on Table 9 to Part 455 of the final regulation,
which is included in Appendix A of this document.
Hazardous waste: Any material that meets the Resource Conservation and Recovery Act
definition of "hazardous waste" contained in 40 CFR Part 261.
Incinerator: An enclosed combustion device that is used for destroying organic compounds.
Auxiliary fuel may be used to heat waste gas to combustion temperatures. Any energy
recovery section present is not physically formed into one manufactured or assembled unit
with the combustion section; rather, the energy recovery section is a separate section
following the combustion section and the two are joined by ducts or connections carrying flue
gas.
Indirect discharge: The discharge of a pollutant or pollutants into a publicly owned
treatment works (POTW) with or without pretreatment by the discharger.
Inert ingredient: Any substance (or group of structurally similar substances if designated by
EPA), other than a pesticide active ingredient, which is intentionally included in a pesticide
product.
Inorganic wastewater treatment chemicals: Inorganic chemicals that are commonly used in
wastewater treatment systems to aid in the removal of pollutants through physical/chemical
technologies such as chemical precipitation, flocculation, neutralization, chemical oxidation,
hydrolysis, and/or adsorption.
Interior wastewater sources: Wastewater that is generated from cleaning or rinsing the
interior of pesticide formulating, packaging, or repackaging equipment; or from rinsing the
interior of raw material drums, shipping containers or bulk storage tanks; or cooling water
that comes in direct contact with pesticide active ingredients during the formulating,
packaging, or repackaging process.
Leaks and spills: Leaks and spills to be quantified are those which contain a pesticide active
ingredient(s), or those which are combined prior to disposal with leaks or spills containing an
active ingredient(s).
17-4
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Section 17 - Glossary of Terms
Line: Equipment and interconnecting piping or hoses arranged in a specific sequence to mix,
blend, impregnate, or package, or repackage pesticide products. These products contain one
or more pesticide active ingredients with other materials to impart specific desirable physical
properties for a product or device, or to achieve a desired pesticide active ingredient
concentration for a particular product or device, or to package it into marketable containers.
The line begins with the opening of shipping containers or the transfer of active ingredient(s)
and other materials from a manufacturer or another formulator/packager, or from inventory of
bulk storage. The line ends with the packaging or repackaging of a product into marketable
containers or into tanks for application.
Manufacture: The production of pesticide active ingredient(s) involving a chemical
change(s) in the raw material(s) or intermediate precursors.
Microorganisms: Registered pesticide active ingredients that are biological control agents
listed in 40 CFR 152.20(a)(3) including Eucaryotes (protozoa, algae, fungi), Procaryotes
(bacteria), and Viruses.
Minimum level: The level at which an analytical system gives recognizable signals and an
acceptable calibration point.
New Source: As defined in 40 CFR 122.2, 122.29, and 403.3 (k), a new source is any
building, structure, facility, or installation from which there is or may be a discharge of
pollutants, the construction of which commenced (1) for purposes of compliance with New
Source Performance Standards, after the promulgation of such standards under CWA section
306; or (2) for the purposes of compliance with Pretreatment Standards for New Sources,
after the publication of proposed standards under CWA section 307(c), if such standards are
thereafter promulgated in accordance with that section.
Noncontact cooling water: Water used for cooling in formulating/packaging operations
which does not come into direct contact with any raw material, intermediate product, by-
product, waste product, or finished product. This term is not intended to relate to air
conditioning systems.
Non-water quality environmental impact: An environmental impact of a control or
treatment technology, other than to surface waters.
Noncontinuous or intermittent discharge: Discharge of wastewaters stored for periods of at
least 24 hours and released on a batch basis.
Nonconventional pollutants: Pollutants that are neither conventional pollutants nor toxic
pollutants listed at 40 CFR Section 401, including many pesticide active ingredients.
Nondetect value: A concentration-based measurement reported below the minimum level
that can reliably be measured by the analytical method for the pollutant.
17-5
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Section 17 - Glossary of Terms
NOY: Nitrogen oxides.
NPPES: The National Pollutant Discharge Elimination System, a federal program requiring
industry dischargers, including municipalities, to obtain permits to discharge pollutants to the
nation's water, under Section 402 of the CWA.
NRDC: Natural Resources Defense Council.
NSPS: New source performance standards. This term refers to standards for new sources
under Section 306 of the CWA.
OPCSF: Organic Chemicals, Plastics, and Synthetic Fibers Manufacturing Point Source
Category (40 CFR Part 414).
£2: Pollution prevention.
Packaging: Enclosing or placing a formulated pesticide active ingredient into a marketable
container.
PAI rPesticide Active Ingredient): Any technical grade active ingredient used for
controlling, preventing, destroying, repelling, or mitigating any pest. The PAIs may make up
only a small percentage of the final product which also consists of binders, fillers, diluents,
etc.
Pesticide: A product that is registered under FIFRA and:
(a) In the case of a pesticide other than a plant regulator, defoliant, or
desiccant, an ingredient which is intended to prevent, destroy, repel, or
mitigate any pest;
(b) In the case of a plant regulator, an ingredient which, through
physiological action, will accelerate or retard the rate of growth or rate
of maturation or otherwise alter the behavior of ornamental or crop
plants or the product thereof;
(c) In the case of a defoliant, an ingredient which will cause the leaves or
foliage to drop from a plant;
(d) In the case of a desiccant, an ingredient which will artificially accelerate
the drying of plant tissue.
This definition excludes liquid chemical sterilant products (including any sterilant or
subordinate disinfectant claims on such products) which are used on a critical or semi-critical
device (as defined in Section 201 of the Federal Food, Drug, and Cosmetic Act ("FFDCS")
(21 U.S.C. 321) (see 7 U.S.C. §136 (u), as amended).
17-6
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Section 17 - Glossary of Terms
Pesticide-producing establishment: As defined under FIFRA, any site where a pesticide
product, active ingredient, or device is produced, regardless of whether the site is
independently owned or operated, and regardless of whether the site is domestic and
producing a pesticidal product for export only, or foreign and producing any pesticidal
product for import into the United States.
PFPR/Manufacturers: Pesticide manufacturers that also perform pesticide formulating,
packaging, and/or repackaging at their facilities.
PFPR: Pesticide formulating, packaging, and repackaging operations.
Pilotrscale: The trial operation of processing equipment which is the intermediate stage
between laboratory experimentation and full-scale operation in the development of a new
process or product.
PM: Particulate matter.
Point source category: A category of sources of water pollutants that are included within the
definition of "point source" in Section 502(14) of the CWA.
Pollutant (to water): Chemical constituent, dredged spoil, solid waste, incinerator residue,
filter backwash, sewage, garbage, sewage sludge, munitions, chemical wastes, biological
materials, certain radioactive materials, heat, wrecked or discarded equipment, rock, sand,
cellar dirt, and industrial, municipal, and agricultural waste discharged into water. See CWA
Section 502(6); 40 CFR 122.2.
Pool chemicals: Pesticide products that are intended to disinfect or sanitize, reducing or
mitigating growth or development of microbiological organisms including bacteria, algae,
fungi or viruses in the water of swimming pools, hot tubs, spas or other such areas in the
household and/or institutional environment, as provided in the directions for use on the
product label.
POTW or POTWs (Publicly owned treatment works): A treatment works as defined by
Section 212 of the CWA, which is owned by a state or municipality (as defined by Section
502(4) of the Act). This definition includes any devices and systems used in the storage,
treatment, recycling and reclamation of municipal sewage or industrial wastes of a liquid
nature. It also includes sewers, pipes, and other conveyances only if they convey wastewater
to a POTW Treatment Plant. The .term also means the municipality as defined in Section
502(4) of the CWA, which has jurisdiction over the indirect discharges to and the discharges
from such a treatment works.
PPA: Pollution Prevention Act of 1990 (42 U.S.C. 13101 et seq., Pub.L. 101-508,
November 5, 1990).
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Section 17 - Glossary of Terms
Pretreatment standard: A regulation specifying industrial wastewater effluent quality
required for discharge to a POTW.
Priority pollutants: The toxic pollutants listed in 40 CFR Part 423, Appendix A.
Process: The steps performed on a pesticide active ingredient or group of pesticide active
ingredients, beginning with the opening of shipping containers containing pesticide active
ingredient(s) (or transfer of active ingredient(s) from a manufacturing or another formulating
operation), including the physical mixing of these pesticide active ingredients with each other
or with nonpesticide materials, and concluding with the packaging of a product into
marketable containers.
Process wastewater collection system: A piece of equipment, structure, or transport
mechanism used in conveying or storing a process wastewater stream. Examples of process
wastewater collection system equipment include individual dram systems, wastewater tanks,
surface impoundments, and containers.
PSES: Pretreatment standards for existing sources of indirect discharges, under Section
307(b)oftheCWA.
psig: Pounds per square inch gauge.
PSNS: Pretreatment standards for new sources of indirect discharges, under Section 307(b)
and(c)oftheCWA.
R&D: Research and Development.
RCRA: Resource Conservation and Recovery Act of 1976, as amended (42 U.S.C. 6901, et
seq.).
Reagents: Chemicals used to cause a chemical reaction.
Repackaging: The direct transference of a single pesticide active ingredient or single
formulation from any marketable container to another marketable container, without
intentionally mixing in any inerts, diluents, solvents, or other active ingredients, or other
materials of any sort.
Reuse: The use hi product formulation or cleaning operations of all or part of a waste stream
produced by an operation which would otherwise be disposed of, whether or not the stream is
treated prior to reuse, and whether the reused waste stream is fed to the same operation or to
another operation.
17-8
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Section 17 - Glossary of Terms
Sanitizer products: Pesticide products that are intended to disinfect or sanitize, reducing or
mitigating growth or development of microbiological organisms including bacteria, fungi or
viruses on inanimate surfaces in the household, institutional, and/or commercial environment
and whose labeled directions for use result in the product being discharged to Publicly Owned
Treatment Works (POTWs). This definition shall also include sanitizer solutions as defined
by 21 CFR Part 178.1010 and pool chemicals as defined in this section (455.10(q)). This
definition does not include liquid chemical sterilants (including sporicidals) exempted by
455.40(f) or otherwise, industrial preservatives, and water treatment microbiocides other than
pool chemicals.
SBREFA: Small Business Regulatory Enforcement Fairness Act of 1996 (5 U.S.C. 801).
Septic system: A system which collects and treats wastewater, particularly sanitary sewage.
The system is usually composed of a septic tank which settles and anaerobically degrades
solid waste, and a drainfield which relies on soil to adsorb or filter biological contaminants.
Solid wastes are periodically pumped out of the septic tank and hauled to off-site disposal.
Shipping container rinsate: The water or solvent which is generated by the rinsing of
shipping containers.
SIC: Standard Industrial Classification. A numerical categorization system used by the U.S.
Department of Commerce to denote segments of industry. An SIC code refers to the principal
product, or group of products, produced or distributed, or to services rendered by an operating
establishment. SIC codes are used to group establishments by the primary activity in which
they are engaged.
Solvent: An ingredient added to a formulation in order to dissolve the active ingredient to
form a uniformly dispersed mixture. Also liquids, other than water, used to clean pesticide
formulating and packaging equipment.
Source reduction: The reduction or elimination of waste generation at the source, usually
within a process. Any practice that: 1) reduces the amount of any hazardous substance,
pollutant, or contaminant entering any waste stream or otherwise released into the
environment (including fugitive emissions) prior to recycling, treatment, or disposal; and 2)
reduces the hazards to public health and the environment associated with the release of such
substances, pollutants, or contaminants.
SOX: Sulphur oxides.
Special or nonroutine conditions: Situations which do not normally occur during routine
operations. These may include equipment failure, use of binders, dyes, carriers and other
materials that require additional cleaning time, or larger volumes of solvents and/or water.
SRRP: Source Reduction Review Project.
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Section 17 - Glossary of Terms
Stand-alone PFPR facility: A PFPR facility where either: 1) no pesticide manufacturing
occurs; or 2) where pesticide manufacturing process wastewaters are not commingled with
PFPR process wastewaters. Such facilities may formulate, package, or repackage or
manufacture other nonpesticide chemical products and be considered a "stand-alone" PFPR
facility.
Subcategory C: Pesticide formulating, packaging, and repackaging (PFPR), including
pesticide formulating, packaging, and repackaging occurring at pesticide manufacturing
facilities (PFPR/Manufacturers) and at stand-alone PFPR facilities.
Snbcategorv E: Repackaging of agricultural pesticide products at refilling establishments
(refilling establishments).
Technical Development Document: Development Document for Best Available Technology,
Pretreatment Technology, and New Source Performance Technology for the Pesticide
Formulating, Packaging, and Repackaging Industry (EPA 821-R-96-019).
Technical grade of active ingredient: A material containing an active ingredient: 1) which
contains no inert ingredient, other than one used for purification of the active ingredient and
2) which is produced on a commercial or pilot-plant production scale (whether or not it is
ever held for sale).
Toxic pollutants: The pollutants designated by EPA as toxic in 40 CFR Part 401.15. Also
known as priority pollutants.
TSCA: Toxic Substances Control Act (15 U.S.C. 2613).
TSS: Total suspended solids.
UIC: Underground Injection Control.
UMRA: Unfunded Mandates Reform Act of 1995 (Pub. L. 104-4).
UTS: Universal Treatment System, a treatment system envisioned by EPA to be sized to
handle small volumes of wastewater on a batch basis and would combine the most commonly
used and effective treatment technologies for PAIs (hydrolysis, chemical oxidation, activated
carbon, and sulfide precipitation (for metals)) with one or more pretreatment steps, such as
emulsion breaking, solids settling, and filtration.
VOCs: Volatile organic compounds.
Waters of the United States: The same meaning set forth hi 40 CFR 122.2.
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Section 17 - Glossary of Terms
Wet air pollution or odor pollution control system scrubbers: Any equipment using water
or water mixtures to control emissions of dusts, odors, volatiles, sprays, or other air
pollutants.
Zero/P2 Alternative Option: Regulatory option promulgated by EPA that allows each
Subcategory C facility a choice: to meet a zero discharge limitation or to comply with a
pollution prevention (P2) alternative that authorizes discharge of PAIs and priority pollutants
after various P2 practices are followed and treatment is conducted as needed.
Zero discharge: No discharge of process wastewater pollutants to waters of the United States
or to a POTW.
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Appendix A - Final Regulation
Appendix A
FINAL REGULATION
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follows:
Appendix A - Final Regulation
APPENDIX A
FINAL REGULATION1
For the reasons set forth in the preamble, 40 CFR Part 455 is amended as
PART 455 - PESTICIDE CHEMICALS
1.
The authority citation for part 455 continues to read as follows:
Authority: Sees. 301, 304, 306, 307, and 501, Pub. L. 92-500, 86 Stat, 816,
Pub. L. 95-217, 91 Stat. 156, and Pub. L. 100-4 , 101 Stat. 7 (33 U.S.C. 1311, 1314, 1316,
1317, and 1361).
la.
follows:
§455.10
Section 455.10 is amended by adding paragraphs (g) through (u) to read as
General definitions.
(g) Appropriate pollution control technology means the wastewater
treatment technology listed on Table 10 to Part 455 for a particular PAI(s) including an
emulsion breaking step prior to the listed technology when emulsions are present in the
wastewater to be treated.
(h) Equivalent system means a wastewater treatment system that is
demonstrated in literature, treatability tests or self-monitoring data to remove a similar level
of pesticide active ingredient (PAI) or priority pollutants as the applicable appropriate
pollution control technology listed in Table 10 to Part 455.
(i) Formulation of pesticide products means the process of mixing,
blending or diluting one or more pesticide active ingredients (PAIs) with one or more active
or inert ingredients, without an intended chemical reaction to obtain a manufacturing use
product or an end use product.
0) Group 1 mixtures means any product whose only pesticidal active
ingredient(s) is: a common food/food constituent or non-toxic household item; or is a
substance that is generally recognized as safe (GRAS) by the Food and Drug Administration
(21 CFR 170.30, 182, 184, and 186) in accordance with good manufacturing practices, as
defined by 21 CFR Part 182; or is exempt from FIFRA under 40 CFR part 152.25.
lrThe language in this appendix is taken from the preamble to the final Pesticide Formulating, Packaging, and
Repackaging (PFPR) regulation.
A-l
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Appendix A - Final Regulation
(k) Group 2 mixtures means those chemicals listed on Table 9 to Part 455
of the final regulation.
(1) Inorganic wastewater treatment chemicals means inorganic chemicals
that are commonly used in wastewater treatment systems to aid in the removal of pollutants
through physical/chemical technologies such as chemical precipitation, flocculation,
neutralization, chemical oxidation, hydrolysis and/or adsorption.
(m) Interior wastewater sources means wastewater that is generated from
cleaning or rinsing the interior of pesticide formulating, packaging or repackaging equipment;
or from rinsing the interior of raw material drums, shipping containers or bulk storage tanks;
or cooling water that comes in direct contact with pesticide active ingredients (PAIs) during
the formulating, packaging or repackaging process.
(n) Microorganisms means registered pesticide active ingredients that are
biological control agents listed in 40 CFR 152.20(a)(3) including Eucaryotes (protozoa, algae,
fungi), Procaryotes (bacteria), and Viruses.
(o) Packaging of pesticide products means enclosing or placing a
formulated pesticide product into a marketable container.
(p) PFPR/Manufacturer means a pesticide formulating, packaging and
repackaging facility that also performs pesticide manufacturing on-site and commingles their
PFPR process wastewaters and pesticide manufacturing process wastewaters.
(q) Pool chemicals means pesticide products that are intended to disinfect
or sanitize, reducing or mitigating growth or development of microbiological organisms
including bacteria, algae, fungi or viruses in the water of swimming pools, hot tubs, spas or
other such areas, in the household and/or institutional environment, as provided in the
directions for use on the product label.
(r) ' Refilling establishment means an establishment where the activity of
repackaging pesticide product into refillable containers occurs.
(s) Repackaging of pesticide products means the transfer of a pesticide
formulation (or PAT) from one container to another without a change in composition of the
formulation or the labeling content, for sale or distribution.
(t) Sanitizer products means pesticide products that are intended to
disinfect or sanitize, reducing or mitigating growth or development of microbiological
organisms including bacteria, fungi or viruses on inanimate surfaces in the household,
institutional, and/or commercial environment and whose labeled directions for use result in the
product being discharged to Publicly Owned Treatment Works (POTWs). This definition
shall also include sanitizer solutions as defined by 21 CFR Part 178.1010 and pool chemicals
as defined in this section (455.10(q)). This definition does not include liquid chemical
A-2
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Appendix A - Final Regulation
sterilants (including sporicidals) exempted by §455.40(f) or otherwise, industrial preservatives,
and water treatment microbiocides other than pool chemicals.
(u) Stand-alone PFPR facility means a PFPR facility where either: 1) no
pesticide manufacturing occurs; or 2) where pesticide manufacturing process wastewaters are
not commingled with PFPR process wastewaters. Such facilities may formulate, package or
repackage or manufacture other non-pesticide chemical products and be considered a
"stand-alone" PFPR facility.
Ib. Section 455.11 is revised to read as follows:
§455.11 Compliance date for pretreatment standards for existing sources (PSES)
All discharges subject to pretreatment standards for existing sources (PSES) in
Subparts A and B must comply with the standards no later than September 28, 1993.
2.
Section 455.40 is revised as to read as follows:
Subpart C - Pesticide Formulating, Packaging and Repackaging (PFPR) Subcategory
§455.40 Applicability; description of the pesticide formulating, packaging and
repackaging subcategory.
(a) The provisions of this subpart are applicable to discharges resulting
from all pesticide formulating, packaging and repackaging operations except as provided in
paragraphs (b), (c), (d), (e) and (f) of this section.
(b) The provisions of this subpart do not apply to repackaging of
agricultural pesticides performed at refilling establishments, as described in §455.60.
(c) The provisions of this subpart do not apply to wastewater discharges
from: the operation of employee showers and laundry facilities; the testing of fire protection
equipment; the testing and emergency operation of safety showers and eye washes; storm
water; Department of Transportation (DOT) aerosol leak test bath water from non-continuous
overflow baths (batch baths) where no cans have burst from the time of the last water
change-out; and on-site laboratories from cleaning analytical equipment and glassware and
rinsing the retain sample container (except for the initial rinse of the retain sample container
which is considered a process wastewater source for this subpart).
(d) The provisions of this subpart do not apply to wastewater discharges
from the formulation, packaging and/or repackaging of sanitizer products (including pool
chemicals); microorganisms; inorganic wastewater treatment chemicals; group 1 mixtures and
group 2 mixtures, as defined under §455.10.
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Appendix A - Final Regulation
(e) The provisions of this subpart do not apply to wastewater discharges
from the development of new formulations of pesticide products and the associated efficacy
and field testing at on-site or stand-alone research and development laboratories where the
resulting pesticide product is not produced for sale.
(f) The provisions of this subpart do not apply to wastewziter discharges
from the formulation, packaging and/or repackaging of liquid chemical sterilant products
(including any sterilant or subordinate disinfectant claims on such products) for use on a
critical or semi-critical device, as defined in Section 201 of the Federal Food, Drug and
Cosmetic Act and in Section 2(u) of the Federal Insecticide, Fungicide and Rodenticide Act.
3. New Section 455.41 is added to Subpart C to read as follows:
§455.41 Special definitions
(a) Initial Certification Statement for this subpart means a written
submission to the appropriate permitting authority, e.g., the local Control Authority (the
POTW) or NPDES permit writer, which (1) lists and describes those product families, process
lines and/or process units for which the PFPR facility is implementing the Pollution
Prevention Alternative ("P2 Alternative"); (2) describes the PFPR facility specific practices for
each product family/process line/process unit which are to be practiced as part of the P2
Alternative; (3) describes any justification allowing modification to the practices listed on
Table 8 to Part 455; and (4) lists the treatment system being used to obtain a P2 allowable
discharge (as defined in 455.41). The Initial Certification Statement must be signed by the
responsible corporate officer as defined in 40 CFR 403.12(1) or 40 CFR 122.22.
(b) Periodic Certification Statement for this subpart means a written
submission to the appropriate permitting authority, e.g., the local Control Authority (the
POTW) or NPDES permit writer, which states that the P2 Alternative is being implemented hi
the manner set forth in the local control mechanism (for indirect dischargers) or NPDES
permit (for direct dischargers) or that a justification allowing modification of the practices
listed on Table 8 to Part 455 has been implemented resulting in a change in the pollution
prevention practices conducted at the facility. The Periodic Certification Statement must be
signed by the responsible corporate officer as defined in 40 CFR 403.12(1) or 40 CFR
122.22.
(c) On-site Compliance Paperwork for this subpart means data or
information maintained in the offices of the PFPR facility which supports the initial and
periodic certification statements as follows: (1) lists and describes those product families,
process lines and/or process units for which the facility is implementing the P2 Alternative;
(2) describes the facility specific practices for each product family/process line/process unit
which are to be practiced as part of the P2 Alternative; (3) describes any justification
allowing modification to the practices listed on Table 8 to Part 455; (4) includes a written
discussion demonstrating that the treatment system being used contains the appropriate
pollution control technologies (or equivalent systems/pesticide manufacturing systems) for
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Appendix A - Final Regulation
removing the PAIs which may be found in the wastewater; (5) establishes a method for
demonstrating to the permitting/control authority that the treatment system is well operated
and maintained; and (6) includes a discussion of the rationale for choosing the method of
demonstration.
(d) For Indirect Dischargers:
Pollution prevention (P2) allowable discharge (excluding interior wastewater sources.
leak and spill clean-up water, and floor wash) for this subpart means the quantity
of/concentrations of pollutants in PFPR process wastewaters that remain after a facility has
demonstrated that it is using the specified practices of the Pollution Prevention Alternative as
listed on Table 8 to Part 455.
Pollution prevention (P2) allowable discharge for interior wastewater sources. leak and
spill cleanup water, and floor wash for this subpart means the quantity of/concentrations of
pollutants in PFPR process wastewaters mat remain after a facility has demonstrated that it is
using the specified practices of the Pollution Prevention Alternative as listed on Table 8 to
Part 455 and that have been pretreated using appropriate pollution control technologies, as
defined in 455.10(g), or a pesticide manufacturer's treatment system, or an equivalent system,
used individually, or in any combination to achieve a sufficient level of pollutant reduction.
Pretreatment requirements may be modified or waived by the Control Authority (POTW) to
the extent that removal credits have been granted by the POTW in accordance with 40 CFR
Part 403.7, provided the granting of such credits does not result in pass through or
interference as defined in 40 CFR Part 403.3 and complies with the provisions of 40 CFR
Part 403.5. The facility must demonstrate that the appropriate pollution control technology is
properly maintained and operated.
(e) For Direct Dischargers:
Pollution prevention (P2) allowable discharge for this subpart means the quantity
of/concentrations of pollutants in PFPR process wastewaters that remain after a facility has
demonstrated that it is using the specified practices of the Pollution Prevention Alternative as
listed on Table 8 to Part 455 and that have been treated using appropriate pollution control
technologies, as defined in 455.10(g), or a pesticide manufacturer's treatment system, or an
equivalent system, used individually, or in any combination to achieve a sufficient level of
pollutant reduction. The facility must demonstrate that the appropriate pollution control
technology is properly maintained and operated.
(f) Process wastewater. for this subpart, means all wastewater associated
with pesticide formulating, packaging and repackaging except for sanitary water, non-contact
cooling water and those wastewaters excluded from the applicability of the rule in §455.40.
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4.
§455.42
Section 455.42 is amended to read as follows:
Effluent limitations guidelines representing the degree of effluent
reduction attainable by the application of the best practicable control
technology currently available, (BPT).
Except as provided in §§125.30 through 125.32, any existing point source
subject to this subpart shall achieve the following effluent limitations representing the degree
of effluent reduction attainable by the application of the best practicable control technology
currently available.
(a) Except as provided in paragraph (b) of this section, the following
limitations establish the quantity or quality of pollutants or pollutant properties controlled by
this paragraph which may be discharged from the formulation, packaging or repackaging of
pesticides: There shall be no discharge of process wastewater pollutants to navigable waters.
[Note: For existing PFPR/Manufacturer facilities, as defined in §455.10(p), which are also
subject to the provisions of §§455.22 or 455.32, "zero discharge" means that permitting
authorities shall provide no additional discharge allowance for those pesticide active
ingredients (PAIs) in the pesticide formulating, packaging and repackaging wastewaters when
those PAIs are also manufactured at the same facility.]
(b) Any existing facility subject to §455.42(a) of this subpart may have a
pollution prevention allowable discharge, as defined in §455.41(e), of wastewater pollutants to
navigable waters if the discharger agrees to NPDES permit conditions as follows:
(1) the dischargers will meet the requirements of the Pollution
Prevention Alternative listed on Table 8 to Part 455 (or received a modification by Best
Professional Judgement for modifications not listed on Table 8 of Part 455);
(2) the discharger will notify its NPDES permit writer at the time of
renewal or modification of its permit, of its intent to utilize the Pollution Prevention
Alternative by submitting to the NPDES permit writer an initial certification statement as
described in §455.41(a);
(3) the discharger will submit to its NPDES permitting authority a
periodic certification statement as described in §455.41(b) once each year of operation; and
(4) the discharger will maintain at the office of the facility and make
available for inspection the on-site compliance paperwork as described in §455.41(c).
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5. New §§455.43 through 455.47 are added to subpart C to read as follows:
§455.43 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best conventional pollutant control
technology (BCT).
Except as provided in §§125.30 through 125.32, any existing point source
subject to this subpart must achieve the effluent limitations representing the degree of effluent
reduction attainable by the application of the best conventional pollutant control technology.
(a) Except as provided in paragraph (b) of this section, the BCT limitations
are established as follows: There shall be no discharge of process wastewater pollutants to
navigable waters. [Note: For existing PFPR/Manufacturer facilities, as defined in §455.10(p)3
which are also subject to the provisions of §§455.23, "zero discharge" means that permitting
authorities shall provide no discharge additional discharge allowance for those pesticide active
ingredients (PAIs) in the pesticide formulating, packaging and repackaging wastewaters when
those PAIs are also manufactured at the same facility.]
(b) Any existing facility subject to §455.43(a) of this subpart may have a
pollution prevention allowable discharge, as defined in §455.41(e), of wastewater pollutants to
navigable waters if the discharger agrees to NPDES permit conditions as follows:
(1) the discharger will meet the requirements of the Pollution
Prevention Alternative listed on Table 8 to Part 455 (or received a modification by Best
Professional Judgement for modifications not listed on Table 8 of Part 455);
(2) the discharger will notify its NPDES permit writer at the time of
renewal or modification of its permit, of its intent to utilize the Pollution Prevention
Alternative by submitting to the NPDES permit writer an initial certification statement as
described in §455.41(a);
(3) the discharger will submit to its NPDES permitting authority a
periodic certification statement as described in §455.41 (b) once each year of operation; and
(4) the discharger will maintain at the office of the facility and make
available for inspection the on-site compliance paperwork as described in §455.41(c).
§455.44 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application off the best available control technology
economically achievable (BAT).
Except as provided hi §§125.30 through 125.32, any existing point source
subject to this subpart must achieve the effluent limitations representing the degree of effluent
reduction attainable by the application of the best available technology (BAT).
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Appendix A - Final Regulation
(a) Except as provided in paragraph (b) of this section, the BAT limitations
are established as follows: There shall be no discharge of process wastewater pollutants to
navigable waters. [Note: For existing PFPRyManufacturer facilities, as defined in §455.10(p),
which are also subject to the provisions of §§455.24, "zero discharge" means that permitting
authorities shall provide no additional discharge allowance for those pesticide active
ingredients (PAIs) in the pesticide formulating, packaging and repackaging wastewaters when
those PAIs are also manufactured at the same facility.]
(b) Any existing facility subject to §455.44(a) of this subpart may have a
pollution prevention allowable discharge, as defined in §455.41(e), of wastewater pollutants to
navigable waters if the discharger agrees to NPDES permit conditions as follows:
(1) the discharger will meet the requirements of the Pollution
Prevention Alternative listed on Table 8 to Part 455 (or received a modification by Best
Professional Judgement for modifications not listed on Table 8 of Part 455);
(2) the discharger will notify its NPDES permitting authority at the
time of renewal or modification of its permit, of its intent to utilize the Pollution Prevention
Alternative by submitting to the NPDES permit writer an initial certification statement as
described in §455.41(a);
(3) the discharger will submit to its NPDES permit writer a periodic
certification statement as described in §455.41(b) once each year of operation; and
(4) the discharger will maintain at the office of the facility and make
available for inspection the on-site compliance paperwork as described in §455.41 (c).
§455.45
New Source Performance Standards (NSPS).
(a) Any new source, except as provided in paragraph (b) of this section,
subject to this subpart which discharges process wastewater must meet the following
standards: There shall be no discharge of process wastewater pollutants to navigable waters.
[Note: For new PFPRManufacturer facilities, as defined in §455.10(p), which are also
subject to the provisions of §§455.25, "zero discharge" means that permitting authorities shall
provide no additional discharge allowance for those pesticide active ingredients (PAIs) in the
pesticide formulating, packaging and repackaging wastewaters when those PAIs are also
manufactured at the same facility.]
(b) Any new source subject to §455.45(a) of this subpart may have a
pollution prevention allowable discharge, as defined in §455.41(e), of wastewater pollutants to
navigable waters if the discharger agrees to NPDES permit conditions as follows:
(1) the discharger will meet the requirements of the Pollution
Prevention Alternative listed on Table 8 to Part 455 (or received a modification by Best
Professional Judgement for modifications not listed on Table 8 of Part 455);
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Appendix A - Final Regulation
(2) the discharger will notify its NPDES permit writer at the time of
submitting its application for a permit, of its intent to utilize the Pollution Prevention
Alternative by submitting to the NPDES permit writer an initial certification statement as
described in §455.41(a);
(3) the discharger will submit to its NPDES permitting authority a
periodic certification statement as described in §455.41 (b) once each year of operation; and
(4) the discharger will maintain at the office of the facility and make
available for inspection the on-site compliance paperwork as described in §455.41(c).
§455.46
Pretreatment standards for existing sources (PSES).
(a) Except as provided in 40 CFR 403.7 and 403.13 or in paragraph (b) of
this section, no later than November 6, 1999, any existing source subject to this subpart which
introduces pollutants into a publicly owned treatment works must comply with 40 CFR part
403 and achieve PSES as follows: There shall be no discharge of process wastewater
pollutants.
(b) Except as provided in 40 CFR 403.7 and 403.13, any existing source
subject to §455.46(a) which introduces pollutants into a publicly owned treatment works must
comply with 40 CFR part 403 and may have a pollution prevention allowable discharge of
wastewater pollutants, as defined in §455.41 (d), if the discharger agrees to control mechanism
or pretreatment agreement conditions as follows:
(1) the discharger will meet the requirements of the Pollution
Prevention Alternative listed on Table 8 to Part 455 (or received a modification by Best
Engineering Judgement for modifications not listed on Table 8 to Part 455);
(2) the discharger will notify its local Control Authority at the tune
of renewing or modifying its individual control mechanism or pretreatment agreement of its
intent to utilize the Pollution Prevention Alternative by submitting to the local Control
Authority an initial certification statement as described in §455.41(a);
(3) the discharger will submit to its local Control Authority a
periodic certification statement as described in §455.41(b) during the months of June and
December of each year of operation; and
(4) the discharger will maintain at the offices of the facility and
make available for inspection the on-site compliance paperwork as described in §455.41(c).
(c) Except as provided in 40 CFR 403.7 and 403.13, any existing source
subject to §455.46(b) which introduces pollutants into a publicly owned treatment works must
comply with 40 CFR part 403 and may submit a request to its Control Authority to waive
pretreatment of: (1) floor wash; and/or (2) a non-reusable final rinse of a triple rinse, if the
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Appendix A - Final Regulation
concentrations of pesticide active ingredients and priority pollutants in those wastewater
sources have been demonstrated to be too low to be effectively pretreated at the facility.
Control Authority may waive pretreatment for these two wastewaters only if the existing
source makes the demonstrations and is in compliance with 40 CFR part 403.5.
The
§455.47
Pretreatment Standards for New Sources (PSNS).
(a) Except as provided in 40 CFR 403.7 and 403.13 or in paragraph (b) of
this section, any new source subject to this subpart which introduces pollutants into a publicly
owned treatment works must comply with 40 CFR part 403 and achieve PSNS as follows:
There shall be no discharge of process wastewater pollutants.
(b) Except as provided in 40 CFR 403.7 and 403.13, any new source
subject to §455.47(a) which introduces pollutants into a publicly owned treatment works must
comply with 40 CFR part 403 and may have a pollution prevention allowable discharge of
wastewater pollutants, as defined in §455.41(d), if the discharger agrees to control mechanism
or pretreatment agreement conditions as follows:
(1) the discharger will meet the requirements of the Pollution
Prevention Alternative listed on Table 8 to Part 455 (or received a modification by Best
Engineering Judgement for modifications not listed on Table 8 to Part 455);
(2) the discharger will notify its local Control Authority at the time
of submitting its application for an individual control mechanism or pretreatment agreement of
its intent to utilize the Pollution Prevention Alternative by submitting to the local Control
Authority an initial certification statement as described in §455.41(a);
(3) the discharger will submit to its local Control Authority a
periodic certification statement as described in §455.41(b) during the months of June and
December of each year of operation; and
(4) the discharger will maintain at the offices of the facility and
make available for inspection the on-site compliance paperwork as described in §455.41(c).
(c) Except as provided in 40 CFR 403.7 and 403.13, any new source
subject to §455.47(b) which introduces pollutants into a publicly owned treatment works must
comply with 40 CFR part 403 and may submit a request to its Control Authority to waive
pretreatment of: (1) floor wash; and/or (2) a non-reusable final .rinse of a triple rinse, if the
concentrations of pesticide active ingredients and priority pollutants in those wastewater
sources have been demonstrated to be too low to be effectively pretreated at the facility. The
Control Authority may waive pretreatment for these two wastewaters only if the new source
makes the demonstrations and is in compliance with 40 CFR part 403.5.
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6.
follows:
Appendix A - Final Regulation
A new subpart E consisting of §§455.60 through 455.67 is added to read as
Subpart E - Repackaging of Agricultural Pesticides Performed at Refilling
Establishments
455.60 Applicability; description of the repackaging of agricultural pesticides
performed by refilling establishments subcategory.
455.61 Special Definitions.
455.62 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best practicable pollutant control technology
(BPT).
455.63 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best conventional pollutant control
technology (BCT).
455.64 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best available technology economically
achievable (BAT).
455.65 New source performance standards (NSPS).
455.66 Pretreatment standards for existing sources (PSES).
455.67 Pretreatment standards for new sources (PSNS).
Subpart E - Repackaging of Agricultural Pesticides Performed at Refilling
Establishments
§455.60 Applicability; description of repackaging of agricultural pesticides
performed at refilling establishments subcategory.
(a) The provisions of this subpart are applicable to discharges resulting
from all repackaging of agricultural pesticides performed by refilling establishments, as
defined in §455.10; whose primary business is wholesale or retail sales; and where no
pesticide manufacturing, formulating or packaging occurs, except as provided in paragraphs
(b), (c) and (d) of this section.
(b) The provisions of this subpart do not apply to wastewater discharges
from custom application or custom blending, as defined in 40 CFR §167.3.
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Appendix A - Final Regulation
(c) The provisions of this subpart do not apply to wastewater discharges
from: the operation of employee showers and laundry facilities; the testing of fibre protection
equipment; the testing and emergency operation of safety showers and eye washes; or storm
water.
(d) The provisions of this subpart do not apply to wastewater discharges
from the repackaging of microorganisms or Group 1 Mixtures, as defined under §455.10, or
non-agricultural pesticide products.
§455.61
Special Definitions.
(a) Process wastewater, for this subpart, means all wastewater except for
sanitary water and those wastewaters excluded from the applicability of the rule in §455.60.
§455.62 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best practicable pollutant control
technology (BPT).
Except as provided in 40 CFR 125.30 through 125.32, any existing point source
subject to this subpart must achieve effluent limitations representing the degree of effluent
reduction attainable by the application of the best practicable pollutant control technology:
There shall be no discharge of process wastewater pollutants.
§455.63 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best conventional pollutant control
technology (BCT).
Except as provided in 40 CFR 125.30 through 125.32, any existing point source
subject to this subpart must achieve effluent limitations representing the degree of effluent
reduction attainable by the application of the best conventional pollution control technology:
There shall be no discharge of process wastewater pollutants.
§455.64 Effluent limitations guidelines representing the degree of effluent reduction
attainable by the application of the best available technology economically
achievable (BAT).
Except as provided hi 40 CFR 125.30 through 125.32, any existing point source
subject to this subpart must achieve effluent limitations representing the degree of effluent
reduction attainable by the application of the best available technology economically
achievable: There shall be no discharge of process wastewater pollutants.
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Appendix A - Final Regulation
§455.65
New source performance standards (NSPS).
Any new source subject to this subpart which discharges process wastewater
pollutants must meet the following standards: There shall be no discharge of process
wastewater pollutants.
§455.66
Pretreatment standards for existing sources (PSES).
Except as provided in 40 CFR 403.7 and 403.13, no later than November 6,
1999, any existing source subject to this subpart which introduces pollutants into a publicly
owned treatment works must comply with 40 CFR part 403 and achieve the pretreatment
standards for existing sources as follows: There shall be no discharge of process wastewater
pollutants.
§455.67
Pretreatment standards for new sources (PSNS).
Except as provided in 40 CFR 403.7 and 403.13, any new source subject to this
subpart which introduces pollutants into a publicly owned treatment works must comply with
40 CFR part 403 and achieve the pretreatment standards for existing sources as follows:
There shall be no discharge of process wastewater pollutants.
7. Tables 8, 9, and 10 are added to part 455 to read as follows:
Table 8 to Part 455 - List of Pollution Prevention Alternative Practices
A modification to the list of practices on this table that an individual facility
must comply with to be eligible for the pollution prevention alternative is allowed with
acceptable justification as listed on this table or as approved by the permit writer or control
authority (using BPJ/BEJ) after submittal by the facility of a request for modification. A
modification, for purposes of this table, means mat a facility would no longer have to perform
a listed practice or would need to comply with a modified practice. However, the
modification only applies to the specific practice for which the modification has been justified
and to no other listed practices. Facilities are required to thoroughly discuss all modifications
in the on-site compliance paperwork as described above in the limitations and standards
(§455:41(c)).
1. Must use water conservation practices. These practices may include, but are
not limited to using: spray nozzles or flow reduction devices on hoses, low volume/high
pressure rinsing equipment, floor scrubbing machines, mop(s) and bucket(s), and counter
current staged drum rinsing stations.
[Modification allowed when: rinsing narrow transfer lines or piping where sufficient rinsing
is better achieved by flushing with water.]
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Appendix A - Final Regulation
2.
Must practice good housekeeping:
(a) perform preventative maintenance on all valves and fittings and repair
leaky valves and fittings in a timely manner;
(b) use drip pans under any valves or fittings where hoses or lines are
routinely connected and disconnected, collect for reuse when possible; and
(c) perform quick cleanup of leaks and spills in outdoor bulk storage or
process areas.
3. Must sweep or vacuum dry production areas prior to rinsing with water.
4. Must clean interiors of dry formulation equipment with dry carrier prior to any
water rinse. The carrier material must be stored and reused in future formulation of the same
or compatible product or properly disposed of as solid waste.
5. If operating continuous overflow Department of Transportation (DOT) aerosol
leak test baths —>
Must operate with some recirculatibn.
6.
needed).
If operating air pollution control wet scrubbers —>
Must operate as recirculating scrubbers (periodic blowdown is allowed as
[Modification allowed when: facility demonstrates that they would not be able to meet
Resource Conservation Recovery Act or Clean Air Act (CAA) requirements.]
7. When performing rinsing of raw material drums, storage drums, and/or
shipping containers that contained liquid PAI(s) and/or inert ingredients for the formulation of
water-based products —>
Must reuse the drum/shipping container rinsate DIRECTLY into the
formulation at the time of formulation; or store for use in future formulation of same or
compatible product; or use a staged drum rinsing station (counter current rinsing).
[Modification allowed when: the drum/shipping container holds inert ingredient(s) only and
(1) the facility can demonstrate that, after using water conservation practices, the large
concentration of inert ingredient in the formulation creates more volume than could feasibly
be reused; or (2) the facility can demonstrate that the concentration of the inert in the
formulation is so small that the reuse would cause a formulation to exceed the ranges allowed
in the Confidential Statement of Formula (CSF) (40 CFR 158.155).]
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Appendix A - Final Regulation
8. When performing rinsing of raw material drums, storage drums, and/or
shipping containers that contained liquid PAI(s) and/or inert ingredients for the formulation of
solvent-based products —>
Must reuse the drum/shipping container rinsate DIRECTLY into the
formulation at the time of formulation or store for use in future formulation of same or
compatible product.
[Modification allowed when:
(a) the drum/shipping container holds inert ingredient(s) only and: (1) the
facility can demonstrate that, after using water conservation practices, the large concentration
of inert ingredient in the formulation creates more volume than could feasibly be reused; or
(2) the facility can demonstrate that the concentration of the inert in the formulation is so
small that the reuse would cause a formulation to exceed the ranges allowed in the
Confidential Statement of Formula (CSF)(40 CFR Part 158.155); OR
(b) drums/shipping containers are going to a drum refurbisher/recycler who
will only accept drums rinsed with water.]
9. Must dedicate PFPR production equipment by water-based versus solvent based
products. Dedicated solvent-based or water-based equipment may be used on a non-routine
basis for non-dedicated operations; however the facility may not discharge the solvent/aqueous
changeover rinsate as part of their P2 allowable discharge (i.e., the facility must achieve zero
discharge of those process wastewater pollutants).
[Modification allowed when: facility has installed and is using a solvent recovery system for
the changeover rinsate (can also be used for other solvent recovery).]
10. Must store the rinsate from interior rinsing (does not include drum/shipping
container rinsate) for reuse in future formulation of same or compatible product.
[Modification allowed when:
(a) facility has evidence of biological growth or other product deterioration
over a typical storage period;
(b) facility has space limitations, BUT must still store rinsates for most
frequently produced products;
(c) manufacturer (or formulator contracting for toll formulating) has
directed otherwise (i.e., send back to them or send for off-site disposal);
(d) facility is dropping registration or production of the formulation and
there is no compatible formulation for reuse of the rinsates or facility can provide reasonable
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Appendix A - Final Regulation
explanation of why it does not anticipate formulation of same or compatible formulation
within the next 12 months;
(e) facility only performs packaging of the pesticide product from which
interior rinsate is generated; or
equipment.]
(f) facility has demonstrated that it must use a detergent to clean the
Notes:
For indirect dischargers: After following the practices above, some wastewaters may
require pretreatment prior to discharge to POTWs. See definition of pollution prevention
allowable discharge for indirect dischargers (§455.41(d)).
For direct dischargers: After following the practices above, all wastewaters require
treatment prior to discharge directly to the nation's waters. See definition of pollution
prevention allowable discharge for direct dischargers (§455.41(e)).
Additional information and guidance on implementing these P2 practices as well as
evaluating compliance with these practices will be available in a P2 Guidance Manual for the
PFPR Industry.
Table 9 to Part 455 - List of Group 2 Mixtures
The attached table presents the list of chemicals, called Group 2 mixtures,
excluded from regulation under the final PFPR rule.
Table 10 to Part 455 - List of Appropriate Pollution Control Technologies
This table contains those pollutant control technologies, such as hydrolysis,
chemical oxidation, precipitation and activated carbon adsorption, which have been used for
estimating compliance costs on a PAI specific basis. In general, these treatment technologies
have been determined to be effective in treating pesticide containing wastewaters in literature,
in bench or pilot scale treatability studies or in the Pesticide Manufacturing effluent
guidelines. These are the same technologies that are presented as part of the Universal
Treatment System. However, these technologies are PAI specific and may need to be used in
conjunction with one another to provide treatment for all PAIs used at a facility over a period
of time. In addition, facilities may experience difficulties treating wastewaters that contain
emulsions, therefore, "appropriate" treatment for emulsified wastewaters must include an
emulsion breaking step. For PAIs whose technology is listed as "Pollution Prevention," the
permitting authority/control authority can determine if additional treatment is necessary
through best professional judgement/best engineering judgement, respectively.
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Appendix A - Final Regulation
Table 9 to Part 455 - List of Group 2 mixtures
Shaughaessey Code
Chemical Name
002201
006501
006602
0166012
022003
025001
025003
025004
031801
055601
063501
063502
063503
063506
067003
067205
067207
067302
069152
070801
071004
071501
0726022
0726052
079014
079021
079029
079034
079059
086803
107302
107303
107304
116902
117001
128888
1289342
129029
224600
505200
Sabadilla alkaloids
Aromatic petroleum derivative solvent
Heavy aromatic naphtha
Dry ice
Coal tar
Coal tar neutral oils
Creosote oil (Note: Derived from any source)
Coal tar creosote
Ammonium salts of C8-18 and CIS' fatty acids
BNOA
Kerosene
Mineral oil - includes paraffin oil from 063503
Petroleum distillate, oils, solvent, or hydrocarbons; also p
Mineral spirits
Terpineols ( unspec.)
Pine tar oil
Ester gum
Amines, N-coco alkyltrimethylenedi-, acetates
Amines, coco alkyl, hydrochlorides
Red Squill glycoside
Cube Resins other than rotenone
Ryania speciosa, powdered stems of
Silica gel
Silicon dioxide
Turkey red oil
Potassium salts of fatty acids
Fatty alcohols (52-61% CIO, 39-46% C8, 0-3% C6, 0-3%C12)
Methyl esters of fatty acids (100% C8 - C12)
Fatty alcohols (54.5% CIO, 45.1% C8, 0.4% C6)
Xylene range aromatic solvent
Polyhedral inclusion bodies of Douglas fir tussock moth nucl
Polyhedral inclusion bodies of gypsy moth nucleopolyhedrosis
Polyhedral inclusion bodies of n. sertifer
Gibberellin A4 mixt. with Gibberellin A7
Nosema locustae
Lactofen (ANSI)
Nitrogen, liquid
Bergamot Oil
Diethanolamides of the fatty acids of coconut oil (coded 079
Isoparaffinic hydrocarbons
^haughnessey codes and chemical names are taken directly from the FATES database. Several chemical names
are truncated because the chemical names listed in the FATES database are limited to 60 characters.
n
EPA does not believe this PAI will persist in sanitary streams long enough to reach a POTW.
A-17
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1
PAI Name2
Dicofol • • •
ED0
Dowicil 75 ....
Trindimcfon
"23 6-T S&H or Fenac
9 d ^-T smt\ 2 4 ^-T 9&E
2 4-D (2/J-D S&£)
24-DB S&E
Dichlonm or DCNA .
Busan 90
Sulfallate
MCPA, S&E
Belclcne 310
Chlorprop S&B .
Busan 72 or TCMTB .
Polyphase •
DNOC
CPA, S&E
MCPB S&E
Etridiazolc
PAI Code3
001
002
003
004
005
006
007
008
009
010
Oil
012
013
014
015
016
017
018
019
020
021
022
023
024
025
026
027
028
029
030
031
032
033
034
035
037
038
039
040
041
042
043
044
045
046
047
048
049
Shaughnessy
Code4
10501
51501
42002
82901
29001
12601
17901
109901
44901
55001
84001
82605
*
*
*
80811
36001
31301
8707
15801
84101
100101
19101
*
99901
67703
*
*
60101
80815
21202
35603
67707
101701
100501
28201
107801
86001
101101
*
19202
84701
Structural Group5
DDT
Hydrazide
EDB
s-Triazine
EDB
NR4
Chlorophene
Chlorophene
Phosphate
Carbamate
2,4-D
24-D
2,4-D
2,4-D
s-Triazine
Phenylcrotonate
Aryl Halide
Miscellaneous Organic
Phosphate
Dithiocarbamate
Phosphate
s-Triazine
Acetanilide
2,4-D
Heterocyclic
Miscellaneous Organic
2,4-D
2,4-D
s-Triazine
2,4-D
Heterocyclic
Carbamate
Chlorobenzamide
Carbamate
Chloropropionanilide
Carbamate
Phenol
Triazathione
2,4-D
2,4-D
Carbamate
Heterocyclic
Treatment Technology
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Precipitation . ...
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Chemical Oxidation .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
A-18
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Ethoxyquin
Acephate or Orthene
Acifluorfen
Alachlor
Aldicarb
Allethrin
Ametryn
Amitraz
Atrazine
Bendiocarb
Benomyl '.
BHC
Benzyl Benzoate
Lethane 60
Bifenox
Biphenyl
Bromacil (Lithium Salt)
Bromoxynil
Butachlor
Giv-gard
Cacodylic Acid
Captafol
Cantan
Carbaryl
Carbosulfan
Chloramben '. .
Chlordane
Chloroneb
Chloropicrin
Chlorothalonil
Chloroxuron
Stirofos
Chlorpyrifos Methyl
Chloipyrifos
Mancozeb '.
Bioquin (Copper)
Copper EDTA
Pydrin or Fenvalerate
Cycloheximide
Dalapon
Dienochlor
Demeton
Desmedipham
Amobam
DBCP
Dicamba
Dichlone
Thiophanate Ethyl
PAI Code3
050
052
053
054
055
057
058
059
060
061
062
063
064
065
066
067
068
069
070
071
072
073
074
075
076
077
078
079
080
081
082
083
084
085
086
087
088
089
090
091
092
093
094
095
096
097
098
099
100
Shaughnessy
Code4
55501
103301
114402
90501
98301
*
80801
106201
80803
105201
99101
9501
104301
17002
*
*
101401
*
81301
56801
90601
*
58201
27301
81501
81901
83701
59102
59101
14504
24002
39105
109301
*
27501
104801
*
29601
103401
Structural Group5
Benzoic Acid
Acetanilide
Carbamate .
s-Triazine
Iminamide
Carbamate
Carbamate
Lindane .
Ester
Thiocyanate
Nitrobenzoate
Aryl
Uracil
Benzonitrile
Acetanilide
Phthalimide
Phthalimide
Carbamate
Carbamate
Tricyclic
Aryl Halide
Alkyl Halide
Urea
Phosphate
Phosphorothioate
Phosphorothioate
Organocopper
Pyrethrin .
Alkyl Halide
HCp . . .
Phosphorothioate
EDB
Aryl Halide
Carbamate
Treatment Technology
Hvdrolvsis
A-19
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAIName2
EXD
nppA
MHK" "32 fi
Metasol DGH . .
Hndothsll (Endothall S&E)
Folp€t
Glyphosate (Giyphosate S&E)
Malathion
PAI Code3
101
102
103
104
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
Shaughnessy
Code4
57801
108201
35001
53501
35201
58801
78701
57901
37505
37801
67701
36601
38501
47201
63301
35505
44303
44301
79401
*
41601
113101
58401
41101
100601
28801
41405
206600
53301
34801
35503
81601
*
44801
107201
109401
100201
97401
9001
35506
39504
57701
Structural Group5
DDT
Dithiocarbamate
Phosphorothioate
Urea
Phosphate
Phosphate
Aryl Halide
Phosphonate
Phenol
Phosphorodithioate
Indandione
Aryl Amine
Ester
Isocyanate
Urea
NR4
NR4
Tricyclic
Bicyclic
Tricyclic
'Toluidine
Phosphorodithioate
Phosphorodithioate
Phosphoroamidate
Aryl Halide
Thiocarbamate
Phosphorothioate
Pyrimidine
Phosphorothioate
Dithiocarbamate
Urea
Acetamide
Phthalimide
Phosphoroamidate
Phosphoroamidate .
Tricyclic
Thiocarbamate
s-Triazine
Phosphoroamidothioate
Toluidine
Carbamate
Carbamate
Lindane
Urea
NR4
Phosphorodithioate
Treatment Technology
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Chemical Oxidation .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Chemical Oxidation .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Hydrolysis
Activated Carbon . . .
Chemical Oxidation .
Activated Carbon . . .
Hydrolysis
A-20
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Maneb
Manam
Mefluidide
Methamidophos
Methidathion
Methomyl
Methoprene
Methoxychlor
Methyl Bromide
Monosodium Methyl Arsenate
Nalco D-2303
Metolachlor
Mexacarbate
Metiram
Monuron TCA
Monuron
Napropamide
Deet
Nabam
Naled
Norea
Norflurazon
Naptalam or Neptalam
MGK 264
Benfluralin
Sulfotepp
Aspon
Coumaphos
Fensulfothion
Disulfoton
Fenitrothion
Phosmet
Azinphos Methyl (Guthion)
Oxydemeton Methyl
Organo-Arsenic Pesticides
Organo-Cadmium Pesticides
Organo-Copper Pesticides
Organo-Mercury Pesticides
Organo-Tin Pesticides
o-Dichlorobenzene
Oryzalin
Oxamyl
Oxyfluorfen
Bolstar
Sulprofos Oxon
Santox (EPN)
Fonofos
Propoxur
PAI Code3
151
152
153
154
155
156
157
158
160
161
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
Shaughnessy
Code4
14505
1 14002
101201
100301
90301
*
34001
53201
*
68102
54101
108801
14601
35502
35501
103001
80301
14503
34401
105801
30703
57001
84301
79501
36501
32701
32501
105901
59201
58001
58702
*
*
*
59401
104201
103801
111601
111501
41801
41701
47802
Structural Group5
Dithiocarbamate
Dithiocarbamate
Carbamate .
Ester
DDT
Alkyl Halide
Organoarsenic
Acetanilide
Carbamate
Urea
Urea
Phosphate
Urea
Phthalamide
Bicyclic
Phosphorothioate
Phosphorothioate
Phosphorothioate
Phosphorodithioate
Phosphorodithioate
Phosphorothioate
Organoarsenic
Organocadmium
Organocopper
Organomercury
Organotin
Aryl Halide
Carbamate
Phosphorothioate
Phosphorodithioate
Phosphorodithioate
Carbamate
Treatment Technology
Hydrolysis
A-21
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAIName2
Pf*NR
PRPH nr W^PP SRiKAn 77^
TTM Mrtftvl
Mctesol J26 ....
DBF ....
Silvcx ....
HPrccipitationMS
Bcnsulidc or Betesan
PAI Code3
202
203
204
205
206
207
208
209
210
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
Shaughnessy
Code4
61501
57501
108501
56502
*
109701
98701
64501
57201
97701
18201
*
67501
69183
34803
102901
39002
101301
111401
80804
80805
97601
80808
77702
119301
69004
69001
69002
*
*
58301
71003
74801
35509
*
80807
103901
34804
75003
39003
57101
41301
41401
41402
41403
41404
35604
9801
Structural Group5
Aryl Halide
Phosphorothioate
Benzeneamine
Aryl Halide
Phenol
Sulfonamide
Pyrethrin
Carbamate
Heterocyclic
Phosphorodithioate
Phosphorodithioate
Phosphate
Pyridine
Ester . ;
NR4
Dithiocarbamate
Dithiocarbamate
Dithiocarbamate
Miscellaneous Organic
Phosphorothioate
s-Triazine
s-Triazine
Miscellaneous Organic
s-Triazine
Alkyl Acid
Carbamate i
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Pyrethrin
Phosphorothioate
Miscellaneous Organic
Phosphorotrithioate
Urea
2,4-D
s-Triazine
Heterocyclic
Acetamide
Dithiocarbamate
Miscellaneous Organic
Thiocarbamate
Thiocarbamate . .
Thiocarbamate
Thiocarbamate
Thiocarbamate
Thiosulphonate
Phosphorodithioate
Treatment Technology
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Hydrolysis
Hydrolysis
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Chemical Oxidation .
Chemical Oxidation .
Chemical Oxidation .
-Activated Carbon . . .
Activated Carbon . . .
Chemical Oxidation .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Hydrolysis
Hydrolysis
Hydrolysis
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Chemical Oxidation .
Chemical Oxidation .
Activated Carbon . . .
Chemical Oxidation .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
A-22
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Terbacil
Terbuthylazine
Terbutryn
Dazomet
Thiophanate Methyl
Thiram
Toxaphene
Merphos
Trifliiralin or Treflan
Warfarin
Zinc MBT
Zineb
Ziram
Triallate
Tetramethrin
Chloropropham
Non-272 PAIs
CFC 11
CFC 12
Acrolein
Tetradecyl alcohol
Rosin arnine D acetate
Amitrole . . '
Allyl isothiocyanate
AMS
Calcium sulfate .
Tartar emetic
Diphenylstibene 2-ethylhexanoate . . .
Streptomycin
Oxytetracycline hydrochloride
Streptomycin sescjuisulfate
Antimycin A
Espesol 3A
Arsenic acid
Arsenic acid anhydride
Arsenous acid anhydride
Copper oxychloride
PAI Code3
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
Shaughnessy
Code4
105501
59001
12701
105001
80814
80813
63004
35602
102001
79801
80501
74901
36101
*
51705
14506
34805
78802
69005
69003
18301
13
14
152
701
1001
1509
1510
4201
4213
4401
4901
5501
5602
6201
6202
6306
6308
6310
6313
6314
6321
6601
6801
6802
7001
8001
Structural Group5
Urea
Phosphorothioate
Uracil
Phosphorodithioate
s-Triazine
s-Triazine
Phenol
Heterocyclic
Carbamate
Dithiocarbamate
Bicyclic
Phosphorotrithioate
Toluidine
Coumarin
Organozinc
Dithiocarbamate
Dithiocarbamate .
Thiocarbamate
Pyrethrin
Pyrethrin
Carbamate
Alkyl Halide
Alkyl Halide
Polymer
Alcohol
Heterocyclic
Alcohol
Alcohol
Alkyl Acid
Alkyl Acid
Heterocyclic
Thiocyanate
Inorganic
Inorganic
Inorganic
Aryl
Heterocyclic .... ...
Phthalamide
Heterocyclic
Metallic
Metallic
Metallic
Metallic
Treatment Technology
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Chemical Oxidation .
Hydrolysis
Activated Carbon
Activated Carbon
Hydrolysis . ...
Activated Carbon
Activated Carbon
Precipitation
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon . . .
Hydrolysis
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Pollution Prevention .
Pollution Prevention
Pollution Prevention .
Activated Carbon
Activated Carbon
Precipitation
Precipitation
A-23
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
1
List of Appropriate Pollution Control Technologies (Continued)
PAI Name2
Basic copper HI - zinc sulfate
complex ( Declare copper and .
Benzyl diethyl
((2,6-xylylcarbarnoyl)methyl)
Butoxyethoxy)ethyl thiocyanate ....
2-Naphthol
Boron sodium oxide (B8Na2O13),
tetrahydrate (12280-03-4) ....
Sodium inelaborate (NaBO2)
Boron sodium oxide (B8Na2013)
(12008-41-2)
Boron sodium oxide (B4Na2O7),
pentahydrate (12179-04-3)
Boron sodium oxide (B4Na2O7)
(1330-43-4)
Kcburon (ANSI)
Mcthyltrimethylenedioxy)bis
(4-methyl-l ,3,2-dioxaborinane) .
Oxybis{4>416~trimethyl-
Barban (ANSI)
Chloro-2-propenyl)-3,5,7,triaza-l -azo
Chloromethoxypropylmercuric acetate
Allidochlor
Chromic acid
PAI Code3
Shaughnessy
Code4
8101
8102
8706
8710
9101
9106
9502
9901
10002
10301
11001
11101
11103
11104
11107
11110
11112
11402
11403
11501
11901
12001
12401
12402
12902
13502
1^503
13505
13603
13903
15602
16401
16501
17601
17902
18101
18401
19301
21101
Structural Group5
Metallic
Metallic
Phosphorothioate
Benzole acid
Benzoic acid
NR4
Aryl
Thiocyanate
Phenol
Inorganic
Inorganic
Inorganic
Inorganic . . .
Inorganic
Inorganic
Inorganic
Polymer
Polymer
Alcohol
Polymer
Bicyclic
Metallic
Metallic
Metallic
Metallic
Metallic
Inorganic
Bicyclic
Inorganic
Alkyl Halide
Carbamate ....
Tricyclic .
NR4
Metallic
Acetanilide
Metallic
Treatment Technology
Precipitation
Precipitation
Activated Carbon . . .
Activated Carbon . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Pollution Prevention .
Pollution Prevention .
Pollution Prevention .
Pollution Prevention .
Pollution Prevention .
Pollution Prevention .
Activated Carbon . . .
Activated Carbon . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Precipitation
Precipitation
Precipitation . .
Precipitation
Pollution Prevention .
Activated Carbon . . .
Pollution Prevention .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
PrecipitatioTV
Activated Carbon . . .
Precipitation
A-24
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Chromic oxide .
Cresol (unspec) (Cresylic acid) ....
Cresol
Copper (metallic)
Copper ammonium carbonate
Copper carbonate
Copper hydroxide
Copper chloride hydroxide .
(Cu2CKOH)3)
Copper oxychloride sulfate
Copper sulfate
Copper (from triethanolamine
complex)
Copper as metallic (in the form of
chelates of copper citrat
Copper as elemental from copper -
ethylenediamine complex
Copper sulfate (anhydrous)
Copper(I) oxide
Cuprous thiocyanate
Cyclohexane . . .....
Cyclohexanone
Dichlobenil
Diquat dibromide
Dimethrin (ANSI)
Dicapthon
Ziram, cyclohexylamine complex . . .
Butyl dimethyltrithioperoxycarbamate
Daminozide
Bis(bromoacetoxy)-2-butene
Dazomet, sodium salt
Butonate
Trifluoro-4-nitro-m-cresol (**) =
alpha,alpha,alpha-
Triethanolamine dinoseb
(2-sec-Butyl-4,6-dinitrophenol) .
Sodium 4,6-dinitro-o-cresylate
Dinitrophenol
Alkanol* amine dinoseb
(2-sec-butyl-4,6-dinitrophenol)
*(s
Sodium dinoseb
(2-sec-Butyl-4,6-dinitrophenol) .
Nitrilotriacetic acid, trisodium salt . .
Trisodium(2-hydroxyethyl)ethylene
diaminetriacetate
Ammonium ethylenediaminetetra-
acetate
PAI Code3
Shaughnessy
Code4
21103
22101
22102
22501
22703
22901
23401
23501
23503
24401
24403
24405
24407
24408
25601
25602
25901
25902
27401
32201
34101
34502
34806
34807
35101
35601
35605
35607
35701
36201
37506
37508
37509
37511
37512
39106
39109
39117
Structural Group5
Metallic
Phenol
Phenol
Metallic
Metallic
Metallic
Metallic
Metallic
Metallic
Metallic
Metallic
Metallic
Metallic ...
Metallic
Metallic
Metallic
Aryl
NR4
Dithiocarbamate
Dithiocarbamate . .
AcetaniKde
AlkyI Halide
Heterocyclic
Phenol
Phenol .
Phenol
Phenol
Phenol
Phenol
Acetamide
Treatment Technology
precipitation
Activated Carbon . . .
A-25
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies (Continued)
PAIName2
Pentasodium diethylenetriaminepenta-
EDC
Bis(2-butylenc)tetrahydro-
Glutaial
Monosodium 2,2*-methylenebis
Potassium 2^'-methylenebis
Hexachloroepoxyoctahydro-endo,
cxo-dimethanonaphthalene 85%
Hcptadecenyl-2-(2-hydroxyethyl)-2-i
Hydroxyethyl)-2-a]kyl-2-imidazoline
IDA
Butoxypolypropoxypolyethoxyethanol
Polyethoxypolypropoxyethanol -
Use code no 046904
(polyethoxypolypropoxy ethanol-
iodine complex)
Alkyl-omega-hydroxypoly(oxyethylen
c) - iodine complex *(100%
Lc&d flcct&tc • •
Nickel sulfatc hexahvdrate
PAI Code3
Shaughnessy
Code4
39120
41001
41901
42003
42004
42202
42203
42205
42301
42401
42403
42501
43001
43002
43302
43801
43802
43901
44005
44102
44105
44902
44904
45001
45502
45801
46301
46608
46609
46701
46801
46901
46904
46909
46917
46921
48001
50505
Structural Group5
Acetanilide
Alcohol
Miscellaneous Organic
EDB
Alkyl Halide
Alcohol .
Alcohol
Alcohol
Miscellaneous Organic
Metallic
Metallic
Miscellaneous Organic
Miscellaneous Organic
Polymer •.
Tricyclic
Tricyclic
Tricyclic
Alcohol
Metallic
Miscellaneous Organic
Miscellaneous Organic
Chlorophene
Chlorophene
Tricyclic
Chloropropionanilide
Inorganic
Alcohol
NR4
NR4
Bicyclic
Cyclic ketone
Polymer ...
Polymer
Polymer
Inorganic
Polymer . .
Metallic
Metallic
Treatment Technology
Activated Carbon . . .
Activated Carbon . .
Pollution Prevention .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Precipitation
Precipitation
Pollution Prevention .
Pollution Prevention ,
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Precipitation
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . .
Activated Carbon
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Activated Carbon . . .
Precipitation
Precipitation
A-26
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
P AI Name2
Maleic hydrazide, diethanolamine salt
Maleic hydrazide, potassium salt . . .
Mercuric chloride
Mercurous chloride
Metaldehyde
Methylated naphthalenes
Sodium 2,2'-methylenebis
(4-chIorophenate)
Naphthalene
NAD
NAA (1-Naphthaleneacetic Acid) . . .
Potassium 1-naphthaleneacetate ....
Ammonium 1-naphthaleneacetate . .
Sodium 1-naphthaleneacetate
Ethyl 1-naphthaleneacetate
Nitrophenol
Carbophenothion (ANSI)
Sodium 5-chloro-2-(4-chloro-2-
(3-(334-dichlorophenyl)ureido) .
Monocrotophos
Chlordimeform
Chlordimeform hydrochloride
Thiabendazole hypophosphite ....
Hexachlorobenzene
Butyl paraben
Paraquat dichloride
Chloro-4-phenylphenol
Chloro-2-phenylphenol
Chloro-2-biphenylol, potassium salt .
Chloro-2-phenylphenol
Chloro-2-phenylphenol, potassium
salt
Sodium phenate
Butylphenol, sodium salt
Ammonium 2-phenylphenate
Chloro-2-cyclopentylphenol
Bithionolate sodium
Chloro-3-cresol
Sodium 2,4,5-trichlorophenate
Aluminum phosphide
Phosphorus
Magnesium phosphide
1 -(Alkyl*amino)-3-aminopropane*(Fa
tty acids of coconut oil)
Alkyl* amino)-3-aminopropane
*(53%C12, 19%C14, 8.5%C16,
7%C8
PAI Code3
Shaughnessy
Code4
51502
51503
51704
52001
52201
53001
54002
55005
55801
56001
56002
56003
56004
56007
56008
56301
56702
58102
58802
58901
59701
59702
60102
61001
61205
61601
62206
62208
62209
62210
62211
64002
64115
64116
64202
64203
64206
64217
66501
66502
66504
67301
67305
Structural Group5
Hydrazide
Hydrazide
Metallic *
Metallic
Miscellaneous Organic
Aryl
Chlorophene
Aryl
Benzoic Acid
Benzole Acid
Benzoic Acid
Benzoic Acid
Benzoic Acid
Phenol
Pyridine . .
Phosphorodithioate
Aryl Halide .
Phosphate
Chloropropionanilide
Hydrazide
Phenol
Pyridine
Chlorophene
Chlorophene
Chlorophene
Chlorophene
Phenol
Phenol
Phenol
Chlorophene
Chlorophene
Iminamide
Treatment Technology
Activated Carbon
Activated Carbon . . .
A-27
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAIName2
Alkyl*ammo)-3-aminopropane
benzoate*(fatry acids of coconut
AlkyI* dipropoxyamine *(47% C12,
18% C14, 10% CIS, 9% CIO, 8
Alkyl*amino)-3-ammopropane
hydroxyacetate*(acids of
AlkyI* amino)-3-aminopropane
*(42%C12, 26%C18, 15%C14,
RaiPlfi
Alkyl*amino)-3-aminopropane
diacetate*(fatty acids of coconut
Octadccenyl-1 ,3-propanediamine
AlkyI* amine acetate *(5%C8,
7%C10, 54%C12, 19%C14,
8%C16
Isoval«yl-l,3-indandione, calcium
salt
Alkcnyl* dimethyl ethyl ammonium
bromide *(90%C18', 10%C16')
Alkyl*-N-ethyl morpholinium ethyl
sulfate *(92%C18 8%C16)
AlkyI* isoquinolinium bromide
*(50% C12, 30% C14, 17%
C16 3
AlkyI* methyl isoquinolinium
chloride *(55%C14, 12%C12,
17%C
Cctyl trimethyl ammonium bromide .
Dodecyl dimethyl benzyl ammonium
AlkyI* dimethyl ethylbenzyl
ammonium cyclohexylsulfamate
*(S
Alkyl*-N-ethyl morpholinium ethyl
ciilfatf *tfifi,%C1 K 95%P16
AlkyI* trimethyl ammonium bromide
*(95%C14 5%C16)
Bcnzyl((dode<^lcarbarnoyl)methyl)di
AlkyI* dimethyl ethyl ammonium
bromide *f85% C16. 15% C181
PAI Code3
Shaughnessy
Code4
67307
67308
67309
67310
67313
67316
67329
67704
67705
67706
68103
68302
68303
68304
69102
69113
69115
69116
69117
69118
69127
69135
69147
69153
69159
69160
69186
Structural Group5
Iminamide
Iminamide
Iminamide
Iminamide
Acetamide
Indandione
Indandione
Indandione
Thiocyanate
Inorganic
Inorganic
Metallic
NR4
Heterocyclic
Quinolin
Quinolin
NR4
Pyridine
NR4
NR4
Heterocyclic
NR4
NR4
Pyridine
NR4
Treatment Technology
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Pollution Prevention .
Pollution Prevention .
Precipitation
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon ....
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
A-28
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Cetyl-N-ethylmorpholinium ethyl
sulfate
Use code no. 069102 (Alkenyl*
Dimethyl Ethyl Ammonium
Nitrapyrin (ANSI)
Pyrazon (ANSI)
Capsaicin (in oleoresin of capsicum) .
Silver
Silver chloride
Silver thiuronium acrylate co-polymer
Sodium chlorate
Sodium cyanide
Cryolite
Sodium fluosilicate
Potassium tctrathionate . . .
Sodium nitrate
Benzenesulfonamide, N-chloro-,
Salicylic acid
Ethoxyethyl p-methoxycinnamate . . .
Niclosamide
Tribromsalan
Dibromosalicylanilide
Sulfur
Sulfuryl fluoride
Tetrachloroethylene
Ethoxylated isooctylphenol
Laurie diethanolamide
Dioctvl sodium sulfosuccinate
PAI Code3
,
Shaughnessy
Code4
69187
69198
69201
69203
69205
69601
70701
71502
72501
72506
72701
73301
74001
74002
75101
75202
75301
75306
75701
75903
76103
76104
76204
76501
76602
76604
76702
76901
76902
77401
77402
77404
77405
77406
77501
77901
77904
78003
78201
78501
79004
79018
79025
79027
Structural Group5
Heterocyclic
NR4
Pyridine
Pyridine
Pyridine
Heterocyclic
Phenol
Tricyclic
Inorganic
Inorganic
Polymer
Inorganic
Inorganic
Inorganic
Inorganic
Inorganic
Inorganic
Inorganic
Inorganic . .
Inorganic
Inorganic
Inorganic
Sulfbnamide
Benzoic Acid
Aryl
Polymer
Tricyclic . .
Tricyclic
Chlorobenzamide . . .
Chlorobenzamide
Chlorobenzamide
Chlorobenzamide
Chlorobenzamide
Inorganic
Sulfanilamide
Inorganic . .
EDB
Phenol
Acetanilide
NR4
Thiosulfonate
Treatment Technology
Activated Carbon
Activated Carbon . .
Activated Carbon
Pollution Prevention
Pollution Prevention .
Pollution Prevention
Pollution Prevention
Pollution Prevention
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Pollution Prevention .
Activated Carbon
Activated Carbon . . .
A-29
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Use code no. 069179 (alkyl*mono-
AlkyI* diethanolamide *(70% C12,
30% C14)
Tctradccyl formate
Polyoxyethylene sorbitol
Sodium trichloroacetate
Hexahydro-1 ,3i5-tris{2-hydroxyethyl)-
2-{Hydroxymethyl)-2-nitro-
Chloro-l-(2^-dichlorophenyl)vinyl)
Hydroxy-2-{lH)-pyridinethione,
Ornadine TBAO
Zinc phosphide (Zn3P2)
Azscosterol HC1
Use code no. 039502 (gentian violet)
Methyl 2-benzimidazolecarbamate
phosphate ......
Ethcohon
PAI Code3
Shaughnessy
Code4
79036
79045
79069
79075
79094
79099
80101
80103
80401
80402
81001
81002
83301
83902
84201
84501
84901
87801
88002
88004
88005
88301
88502
88601
89002
89101
90101
90201
90202
97001
97003
97005
97301
98101
98401
98501
98601
98801
98901
99102
99801
Structural Group5
Miscellaneous Organic
Miscellaneous Organic
AlkyI Acid
Polymer
Polymer
Acetanilide
Inorganic
Inorganic
Benzoic Acid
Phenol
AlkyI Halide
AlkyI Halide
s-Triazine
Alcohol
Phosphate
Miscellaneous Organic
Phosphorothioate
Metallic
Metallic
Pyridine
Pyridine
Metallic
Metallic
Metallic
Metallic
Metallic
Carbamate
Heterocyclic
Heterocyclic
Benzeneamine
2,4-D
Toluamide
Tricyclic
NR4
Inorganic
Metallic
Aryl Halide
Heterocyclic
Carbamate
Phosphate
Treatment Technology
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Pollution Prevention .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Precipitation
Precipitation
Activated Carbon . . .
Activated Carbon . . .
Precipitation
Precipitation
Precipitation
Precipitation
Precipitation
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Pollution Prevention .
Precipitation
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
A-30
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Pentanethiol
Nitrobutyl)morpholine
Ethyl-2-nitrotrimethylene)
dimorpholine
Tolyl diiodomethyl sulfone
Isobutyric acid
Dibromo-3-nitrilopropionamide ....
Polyethoxylated oleylamine
Dinitramine (ANSI)
Phenylethyl propionate
Eugenol :
Tticosene
Tricosene
Sodium M'.S'-trichloro^'-
(2,4,5-trichlorophenoxy)
methanes
Hexahydro-1 ,3,5-tris
(2-hydroxypropyl)-s-triazine . . .
Methazole
Difenzoquat methyl sulfate
Butralin
Fosamine ammonium
Asulam
Sodium asulam
Hydroxymethoxymethyl-l-aza-3,7-dio
xabicyclo(3.3.0)octane
Hydroxymethyl-l-aza-3,7-dioxabicycl
o(3.3.0)octane '.
Hydroxypoly(methyleneoxy)* methyl-
l-aza-3,7-dioxabicyclo(3.3 ....
Chloro-2-methyl-3(2H)-isothiazolone
Methyl-3(2H)-isothiazolone
Trimethoxysilyl)propyl dimethyl
octadecyl ammonium chloride . .
Kinoprene
Triforine (ANSI)
Pirimiphos-methyl (ANSI)
Thiobencarb
Ancymidol (ANSI)
Oxadiazon (ANSI)
Mepiquat chloride
Fluvalinate
Chloro-N-(hydroxymethyl)acetamide .
Dikegulac sodium
Iprodione (ANSI)
Phenylmethyl)-9-(tetrahydro-2H-
pyran-2-yl)-9H-purin-6-amine . .
Prodiamine
PAI Code3
Shaughnessy
Code4 .
100701
100801
100802
101002
101502
101801
101901
102301
102601
102701
103201
103202
104101
105601
106001
106401
106501
106701
106901
106902
107001
107002
107003
107103
107104
107401
107502
107901
108102
108401
108601
109001
109101
109302
109501
109601
109801
110001
110201
Structural Group5
Heterocyclic
Heterocyclic
Thiosulfonate
Alkyl Acid
Acetamide
Acetamide
Nitrobenzoate
Phenol
2,4-D
s-Triazine .
Carbamate
Carbamate
Bicyclic . .
Bicyclic . .
NR4 ... .
Ester
Hydrazide
Phosphorothioate
Hydrazide
NR4
Acetamide .
Tricyclic
Benzeneamine
Treatment Technology
Activated Carbon . . .
A-31
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAIName2
FtfmfiimMfltp /'AN'sH
Aldoxycarb (ANSI)
Bromo-I -(bromomethyl)-
Poly(iminoimidocarbonyliminoimidoc
Pmrrv»thaKn fANSH
Flnn'Honr /"AN9Tt
Thiodicarb (ANSI)
Hydroxyphcnyl)oxoacetohydroximic
Triclopyr (ANSI)
Clopyralid (ANSI)
Flucythrinatc (ANSI)
Hydramethylnon (ANSI)
Clcthodim
PAI Code3
•
Shaughnessy
Code4
110301
110302
110401
110601
110801
110902
111001
111801
111901
. 112001
112701
112802
112900
113201
113501
113601
113701
114101
114102
114301
114501
114801
114802
114901
115001
115501
115502
116001
116002
116004
116501
116801
116901
117401
117403
118301
118401
118601
118901
120001
120002
120301
120401
120901
121001
121011
Structural Group5
Benzeneamine
Hydrazide
Heterocyclio
Bicyclic
Carbamate
Aryl Halide
Isocyanate
Polymer
Aryl Halide
Coumarin
Aryl Halide
Aryl Halide
Benzeneamine
Phosphoroamidothioate
Phthalamide
Ester
Ester
Heterocyclic
Thiocarbamate
Heterocyclic
Heterocyclic
Phenol
Carbamate
Hydrazide
Hydrazide
Pyridine
Pyridine
Pyridine
Ester
Toluidine
Pyrimidine
Pyridine
Pyridine
Pyrethrin
Iminimide
s-Triazine
Heterocyclic
Miscellaneous Organic
Miscellaneous Organic
Urea
Hydrazide
Tricyclic
Cyclic Ketone
Heterocyclic
Treatment Technology
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon ... •
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
A-32
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Tridecen-1-yl acetate
Propiconazole
Abamectin (ANSI)
Fluazifop-R-butyl
Fosetyl-Al
Methanol, (((2-(dihydro-5-methyl-
3(2H)-oxazolyl)-l-methyl)et .
Clomazone
Paclobutrazol . . . ,
Flurprimidol
Sulfosate
Fenoxaprop-ethyl
Bensulfuron-rnethyl
Imazapyr isopropylamine salt .....
Sodium salt of 1-carboxymethyl-
3 5 7-triaza-l-azoniatricyclo . . .
Linalool
Thifensulfuron methyl
Myclobutanil (ANSI)
Zinc boiate (3ZnO, 2B03, 3.5H2O;
mw 434 66)
Cyhalothrin
Potassium cresvlate
PAI Code3
Shaughnessy
Code4
121301
121501
121701
121901
121902
122001
122010
122101
122301
122302
122804
122805
122809
123001
123301
123702
123802
123901
124601
124801
125301
125401
125501
125601
125701
125851
126901
127201
127901
128501
128701
128711
128820
128821
128825
128829
128832
128838
128840
128842
128845
128848
128857
128859
128867
128870
Structural Group5
Pyrethrin
Tricyclic
Ester
Ester
s-Triazine
Aryl Halide
Cyclic Ketone
Cyclic Ketone
Tricyclic
Pyridine
Pyridine
Nitrobenzoate ....
Phosphate ..............
Heterocyclic
Nitrobenzoate
Aryl Halide
Alcohol
Bicyclic ........ .
Carbamate
Aryl Halide . .
Aryl Halide
Hydrazide
Heterocyclic
Phosphorothioate ...
Hydrazide . .
Pyrethrin
Phosphorothioate
Heterocyclic
Phthalimide
Pyrimidine
Hydrazide ...
Pyrethrin .
Hydrazide
s-Triazine
Alcohol
Pyrimidine ....
Pyrimidine ,
s-Triazine
Metallic
Pyrethrin
Phenol
Treatment Technology
Activated Carbon
Activated Carbon
Activated Carbon . .
Activated Carbon
Activated Carbon . . .
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon
Activated Carbon
Activated Carbon . . .
Activated Carbon
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon
Activated Carbon
Activated Carbon .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon
Activated Carbon . .
Activated Carbon
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon .
Activated Carbon . . .
Activated Carbon
Activated Carbon
Activated Carbon . . .
Precipitation
Activated Carbon . . .
Activated Carbon . . .
A-33
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAIName2
DDOL
TTntratna7n1<* fAtJ^H
Dithiopyr (ANSI)
Bcnzenemethanaminium, N-(2-((2,6-
Alkyl* bis(2-hydroxyethyl)
ammonium acetate *(as in fatty
Alkenyl* dimethyl ammonium acetate
*f7"M&P1R' ?'?% Plfi'1
Amines, N-coco alkyltrimethylenedi-,
Dialkyl* dimethyl ammonium
Alkyl* bis(2-hydroxyethyl) amine
acetate *(65% CIS 30% C16
Dodecyl bis(hydroxyethyl)dioctyl
Dodecyl bis{2-hydroxyethyl) octyl
Didecyl-N-methyl-3-{trimethoxysilyl)
nrooanaminium chloride
PAI Code3
Shaughnessy
Code4
128879
128887
128897
128901
128906
128907
128908
128910
128911
128912
128920
128922
128923
128930
128961
128966
128969
128973
128976
128980
128991
128992
128994
129008
129015
129019
129023
129028
129030
129042
129045
129092
169103
169104
169109
169111
169125
169154
169155
169160
Structural Group5
Toliiidine
s-Triazine
Pyrethrin
Pyrimidine
Ester
Ester
Alcohol
Alcohol
Alcohol
Pyrethrin
Chloropropionanilide
Pyrimidine
Polymer
Urea
Miscellaneous Organic
Urea
Urea
s-Triazine
Miscellaneous Organic
Polymer
Sulfonamide
Pyridine
Pyrimidine
Metallic
Alkyl Acid
Pyrimidine
Alcohol
Miscellaneous Organic
Aryl Halide
NR4
Tricyclic
NR4
NR4
Iminamide
NR4
Acetamide
NR4
NR4
NR4
Treatment Technology
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Precipitation
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
Activated Carbon . . .
A-34
-------
Appendix A - Final Regulation
Table 10 to Part 455 -
List of Appropriate Pollution Control Technologies1 (Continued)
PAI Name2
Cholecalciferol
Use code no. 202901 (Vitamin D3) .
Alkyl* N,N-bis(2-hydroxyethyl)amine
*(100% C8-C18)
Bromo-2-nitropropane-l,3-diol
Use code no. 114601 (cyclohexyl-4,5-
dichloro-4-isothioazolin-3-one) .
Diethatyl ethyl
Hydroprene (ANSI)
Zinc sulfate monohydrate
PAI Code3
Shaughnessy
Code4
202901
208700
210900
216400
229300
279500
486300
527200
597501
Structural Group5
Bicyclic
Bicyclic . .
NR4
Alcohol
Heterocyclic
Toluidine
Metallic
Treatment Technology
'The 272 Pesticide Active Ingredients (PAIs) are listed first, by PAI code, followed by the non-272 PAIs from the 1988 FIFRA and TSCA
Enforcement System (FATES) Database, which are listed in Shaughnessy code order. PAIs that were exempted or reserved from the PFPR
effluent guidelines are not listed in the table.
2The non-272 PAI names are taken directly from the 1988 FATES database. Several of the PAI names are truncated because the PAI names
listed in the FATES database are limited to 60 characters.
3The non-272 PAIs do not have PAI codes.
4A11 Shaughnessy codes are taken from the 1988 FATES database. Some of the 272 PAIs are not listed in the 1988 FATES database;
therefore, no Shaughnessy codes are listed for these PAIs.
Structural groups are based on an analysis of the chemical structures of each PAI.
6EPA has also received data indicating that acid hydrolysis may also be effective in treating this PAI.
*This PAI code represents a category or group of PAIs; therefore, it has multiple Shaughnessy codes.
A-35
-------
-------
Appendix B - Pesticide Product Codes and Definitions
Appendix B
PESTICIDE PRODUCT CODES AND DEFINITIONS
-------
-------
Appendix B - Pesticide Product Codes and Definitions
Table B-l
Pesticide Type Codes
Code
01
02
03
04
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
39
40
41
Definitions
Chemosterilant
Poison, Multidose
Poison, Single Dose
Repellent
Tuberculocide .
Sterilizer
Sporicide
Disinfectant/Bacteriocide/Germicide
Sanitizer
Bacteriostat
Virucide
Water Purifier Bacteriacidal
Water Purifier Bacteriastatic
Microbiocide/Microbiostat
Fungicide/Fungistat
Fungicide and Nematicide
Fungicide
Nematicide
Viracide
Microbiocide/Microbiostat
Bacteriocide/Bacteriostat
Biological Agent
Herbicide Unspecified
Algaecide
B-l
-------
Appendix B - Pesticide Product Codes and Definitions
Table B-l (Continued)
Code
42
43
45
46
47
48
49
50
51
53
54
55
56
57
58
59
\ ; BefinitioBS
Defoliant
Desiccant
Antifouling
Herbicide Terrestrial
Herbicide Aquatic
Slimacides
Biological Agents
Insecticide and Miticide
Miticide
Mollusicide, Tadpole, Shrimp
Repellant or Feeding Depressant
Antifouling
Chemosterilant
Pheromone, Insect Growth Regulator, Attractant
Mechanical
Biological Agents
B-2
-------
Appendix B - Pesticide Product Codes and Definitions
Table B-2
Pesticide Formulation Codes
Code
01
02
03
04
05
06
07
08
09
10
12
13
14
Definitions
Technical Chemical: Raw chemical ingredients as manufactured with no
additives; usually 90% or greater active ingredient; ordinarily for
formulating use only, but sometimes used directly as a ULV spray.
Formulation Intermediate: Technical chemical to which something has
been added, e.g., a stabilizer; for formulating use only.
Dust: Active ingredient mixed with a powdered dry inert substance such as
talc or clay; applied dry. Abbreviation: 'D'.
Grandular: Vermiculite, attaclay, ground walnut shells, or other similar
coarse particles impregnated with an active ingredient. Abbreviation: 'G'.
Pelletted/Tabletted: Active ingredient mixed with binders, fillers, and/or
other inerts and formed into a pellet, tablet, or cake; also includes capsules
(encapsulated material) which contain active ingredient alone or with inerts.
Wettable Powder: Use as a suspension mixed in water. Abbreviation:
'WP' or 'W.
Wettable Powder/Dust: Can be used either as a wettable powder in liquid
suspension or dry as a dust.
Crystalline: An essentially pure chemical in solid form, such as copper
sulfate (for water treatments) and paradichlorobenzene (moth crystals).
Microencapsulated: Time-release formulation.
Impregnated Materials: May be either a useful article or material
impregnated with a pesticide (e.g., no-pest-strip, towellettes, weed-killing
bars, roach tape).
Emulsifiable Concentrate: Always diluted for use; diluent is a liquid with
polar characteristics opposite that of solvent in formulation; usually contains
emulsifiers such as glycols, sulfonates, etc. Abbreviation: 'EC' or 'E'.
Invert Emulsion: Emulsion consisting of water droplets surrounded by oil
(a common emulsion consists of oil droplets surrounded by water); this code
should be used only when formulation is stated as an invert emulsion or
invert emulsifiable; invert emulsions will not be encountered frequently.
Flowable Concentrate: A suspension of solid or semi-solid active
ingredient in a liquid; always diluted for use; also called flowable solid.
B-3
-------
Appendix B - Pesticide Product Codes and Definitions
Table B-2 (Continued)
Code
15
16
17
18
19
20
•• • j
; * \ , Definitions
Soluble Concentrate: Always diluted for use, forming a true solution;
diluent is a solvent with the same polar characteristics as that of the
materials in the formulation.
Solution-Ready to Use: Used without dilution; may be a liquid, lotion, or
paste. Abbreviation: 'S'.
Active Ingredient Other
Pressurized Gas: Active ingredients are gaseous at room temperature and
atmospheric pressure; packaged under pressure in a tank, or spray can; self-
pressurized; sometimes called liquified gases.
Pressurized Liquid: Active ingredients are solid or liquid at room
temperature and atmospheric pressure; packaged under pressure with
appropriate solvents and propellents in a tank or spray can; released for use
as an aerosol or liquid spray.
Pressurized Dust: Active ingredient is a finely powdered solid or is mixed
with a finely powdered inert such as talc, suspended in a volatile liquid
under pressure in a tank or spray can; released for use as a dry powder
spray.
B-4
-------
Appendix C - Priority Pollutant List
Appendix C
PRIORITY POLLUTANT LIST
-------
-------
APPENDIX C
PRIORITY POLLUTANT LIST
Appendix C - Priority Pollutant List
1,1-Dichloroethane
1,1-Dichloroethylene
1,1,1 -Trichloroethane
1,1 ^-Trichloroethane
1,1,2,2-Tetrachloroethane
1,2-Dichlorobenzene
1,2-Dichloroethane
1,2-Dichloropropane
1 ,2-Diphenylhydrazine
1,2-Trans-dichloroethylene
1 ,2,4-Trichlorobenzene
1,3-Dichlorobenzene
1,3-Dichloropropylene
1,4-Dichlorobenzene
2-Chloroethyl vinyl ether (mixed)
2-Chloronaphthalene
2-Chlorophenol
2-Nitrophenol
2,3,7,8-Tetrachlorodibenzo-p-dioxin
2,4-Dichlorophenol
2,4-Dimethylphenol
•2,4-Dinitrophenol
2,4-Dinitrotoluene
2,4,6-Trichlorophenol
2,6-Dinitrotoluene
3,3 '-Dichlorobenzidine
3,4-Benzo fluoranthene
Cbenzo(b)fluoranthene)
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
4-Nitrophenol
4,4'-DDD
-------
-------
Appendix D - Transfer of Treatability Data
Appendix D
TRANSFER OF TREATABILITY DATA
-------
-------
Appendix D - Transfer of Treatabilify Data
TABLE OF CONTENTS
Page
Appendix D - TRANSFER OF TREATABILITY DATA
D.I Introduction D_l
D.2 Hydrolysis D_l
D.2.1 Hydrolysis Treatability Data Transfer Using Rate
Estimation Techniques D-2
D.2.2 PAI-Specific Hydrolysis Data Extrapolated to a
pH of 12 and 60°C D-6
D.3 Activated Carbon Adsorption D-8
D.4 References D-24
D-i
-------
Appendix D - Transfer of Treatability Data
D-l
D-2
D-3
D-4
D-5
LIST OF TABLES
Page
pKa Values of Hydrolysis Products for Select PAIs D-4
Physical Property Data for PAIs D-13
Data Used to Generate PAI 90th Percentile Lowest Saturation
Loading Graph D-16
Carbamate Fruendlich Isotherm Data D-20
Carbamate Group D-22
D-ii
-------
Appendix D - Transfer of Treatability Data
LIST OF FIGURES
D-l
D-2
D-3
D-4
Page
Plot of In K2 vs. 1/T for Atrazine at a pH of 14 D-9
Plot of In A vs. pH for Atrazine D-10
90th Percentile Lowest Freundlich Isotherm for Pesticide Active
Ingredients D-17
Carbamate Minimimi Adsorption Isotherm D-21
D-iii
-------
-------
Appendix D - Transfer of Treatability Data
APPENDIX D
TRANSFER OF TREATABILITY DATA
D.I
Introduction
This appendix discusses methodologies for transferring hydrolysis and activated
carbon adsorption treatability data from pesticide active ingredients (PAIs) with data to those
PAIs lacking data. A PAI is deemed to require transfer of treatability data if it has no
treatability data indicating effective treatment. Treatability data were not transferred for
chemical oxidation.
The transfer of hydrolysis and activated carbon treatability data are performed
for the 272 PAIs considered for regulation in the pesticide manufacturers' effluent limitations
guidelines and standards (the 272 PAIs) (58 FR 50638). The transfer of hydrolysis and
activated carbon treatability data for the 272 PAIs is described in the Final Pesticides
Formulators. Packagers, and Repackagers Treatabilitv Database Report (1). Activated carbon
adsorption treatability data transfers are also performed for additional PAIs within the scope
of the PFPR final rule (the non-272 PAIs). However, due to the large number of non-272
PAIs and the limited number of PAIs to which hydrolysis data are transferrable, transfer of
hydrolysis treatability data was not performed for the non-272 PAIs. The transfer of
treatability data to non-272 PAIs is described in the Pesticide Formulators. Packagers, and
Repackagers Treatabilitv Database Report Addendum (2). Detailed below are the
methodologies for treatability data transfer and examples that illustrate the treatability data
transfer methodology. Sections D.2 and D.3 discuss treatability data transfers for hydrolysis
and activated carbon adsorption, respectively.
D.2
Hydrolysis
Hydrolysis is an aqueous chemical reaction in which a molecule is broken into
two or more organic molecules. As a PAI wastewater treatment technology, hydrolysis
typically takes place at elevated pH and temperature. At these conditions, the hydrolysis
reaction consists of displacing a functional group on a molecule with a hydroxyl group (OH").
For example, the hydrolysis of organophosphate PAIs ((RO)2-P(O)-(OX)), where P is
phosphorus, O is oxygen, R is an alkyl group (usually a methyl or ethyl group), and X is any
organic radical, typically involves the base-promoted formation of a weak organic acid
(H-OX) and a dialkyl phosphate ((RO)2-P(O)-OH).
Two types of data gaps exist within the hydrolysis treatability data. First, there
are many PAIs for which no treatability data, hydrolysis or otherwise, exist. For some of
these PAIs, hydrolysis data may be transferred from structurally similar PAIs with hydrolysis
treatability data, based on hydrolysis rate estimation techniques (3). However, these
techniques are limited in applicability to only a few types of structures. Second, half-life data
(the common measurement unit of the hydrolysis reaction rate for a particular constituent) are
available for 31 PAIs at conditions other than those considered optimum for wastewater
D-l
-------
Appendix D - Transfer of Treatability Data
treatment (in the case of the Universal Treatment System (UTS) described in Section 7.4, the
conditions are a pH of 12 and a temperature of 60°C). Data transfers may be conducted for
these PAIs by extrapolating PAI data measured at conditions other than a pH of 12 and 60°C
to these conditions using kinetically derived relationships, provided that sufficient data are
available to calculate the pH and temperature dependency of the hydrolysis rate constant.
D.2.1
Hydrolysis Treatability Data Transfer Using Rate Estimation Techniques
Data Transfer Method
Hydrolysis treatability data, as summarized in the Final Treatability Database
Report (1), indicate that one or more PAIs hi the following structural groups are amenable to
hydrolysis: carbamate, DTT, heterocyclic, lindane, phosphate, phosphorothioate,
phosphorodithioate, phosphorotrithioate, pyrethrin, and symmetrical triazine. However, there
are some PAIs in these structural groups that lack treatability data. These PAIs may, to some
extent, be amenable to hydrolysis. In addition, PAIs containing one of the following reactive
functional groups may tend to hydrolyze readily: alkyl halide, ester, phosphate,
thiophosphate, carbamate, epoxide, and nitrile. The PAIs containing these reactive functional
groups but lacking treatability data are in the following structural groups: alkyl halide,
chloropropionanilide, dithiocarbamate, ester, phosphoroamidothioate, phthalamide, and
amobam (which is from the miscellaneous structural group).
All of the PAIs within the following structural groups are considered amenable
to hydrolysis based on the available treatability data and an analysis of the chemical structure
of the PAIs: alkyl halide, carbamate, chloropropionanilide, DDT, dithiocarbamate, ester,
heterocyclic, lindane, phosphate, phosphoroamidothioate, phosphorodithioate,
phosphorothioate, phosphorotrithioate, phthalamide, pyrethrin, and symmetrical triazine.
However, actual transfers of hydrolysis data are limited to those structural groups for which
hydrolysis rate estimation techniques are available. Hydrolysis estimation techniques are
available only for the carbamate, phosphorothioate, phosphate, and phosphorodithioate
structural groups. The transfer of treatability data within these structural groups is discussed
below.
Hydrolysis Data Transfers
Half-life data can be transferred within the carbamate, phosphate,
phosphorothioate, and phosphorodithioate structural groups, based on an analysis of the
dissociation constant (pKa value) of the hydrolysis leaving group, typically a weak organic
D-2
-------
Appendix D - Transfer of Treatability Data
acid. For example, the hydrolysis of generic organophosphate PAIs or PAI groups follows
the reaction:
(R0)2 - P(0) - OX + OH' (+ H20) -» (R0)2 - P(O) - OH + (H) - OX
where the (H) - OX will most likely dissociate in alkaline solution.
For carbamate and organophosphorus compounds, the rate of hydrolysis is
expected to increase as the acid strength of H-OX increases, as measured by the negative log
of the H-OX dissociation constant, pKa (3). As a result, the rate of hydrolysis increases for
organophosphate PAIs with H-OX complexes that have decreasing pKa values. Using pKa
values tabulated in reference texts and pKa estimation techniques, relative rates of hydrolysis
may be estimated for PAIs based on the half-lives and pKa values of structurally similar
PAIs.
For some PAIs, the degradation product that is not the leaving group may
affect the rate of hydrolysis. For example, under alkaline hydrolysis conditions, the methyl
derivative of a PAI hydrolyzes faster than the ethyl derivative, for constant X. For example,
the half-life of methyl parathion is 6 minutes shorter than ethyl parathion at a pH of 12 and
60°C. There is no hydrolysis rate estimation method available to account for the effect of the
structure of the degradation product that is not the leaving group. However, this effect is not
expected to cause a significant change in the predicted hydrolysis half-life. Therefore, the
hydrolysis treatability data transfer methodology assumes that the degradation product that is
not the leaving group does not affect the hydrolysis reaction rate.
Table D-l lists the PAIs in the carbamate structural group, for which hydrolysis
treatability data transfers have been performed. The table identifies the PAI structural group,
whether treatability data are available, pKa value of the hydrolysis leaving group, and source
of the leaving group pKa value. The table is sorted by pKa value. A "yes" in the
"Hydrolysis Treatability Data" column indicates that data are available showing effective
treatment of the PAI by hydrolysis. Hydrolysis treatability data are listed in the Final
Treatability Database Report (1). A blank in the "Hydrolysis Treatability Data" column
indicates that data are not available showing effective hydrolysis of the PAI. "Not Available"
is listed in the pKa value column if the pKa value of the leaving group is not available in the
identified literature, and cannot be calculated with available pKa value estimation techniques.
"SD" is listed in the pKa value column if the leaving group cannot be identified for the PAI
because the structure of the PAI is significantly different from other PAIs within the structural
group, or transfer of hydrolysis data is inappropriate due to dissimilarities in structure between
the PAI and other PAIs witihin the structural group. The numbers listed hi the "Source"
column correspond to the references listed at the end of this appendix. pKa values '
determined by estimation methods are designated as "Taft" or "Hammett" according to the
method used for estimating the pKa value. An example of the transfer of hydrolysis
treatability data for the structural group listed in Table D-l is described below.
D-3
-------
Appendix D - Transfer of Treatability Data
Table D-l
pKa Values of Hydrolysis Products for Select PAIs
PAI
Code
166
201
038
013
048
040
061
146
075
272
145
228
095
100
260
062
209
076
156
055
077
195
042
, ,si'v ^
£AXKame\
Mexacarbate
Propoxur
Landrin-1
Landrin-2
Aminocarb
Methiocarb
Bendiocarb
Karabutilate
Carbaryl
Cbloropropham
Propham
Previcur N
Desmedipham
Thiophanate Ethyl
Thiophanate
Methyl
Benomyl
Phenmedipham
Carbofuran.
Methomyl
Aldicarb
Carbosulfan
Oxamyl
Polyphase
Structural
s / '" <3roup
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate ,
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Hydrolysis
Treatability j
Data1
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Hydrolysis
Product pKa
Value
12.04
10.87
10.72
10.72
10.63
10.36
10.33
9.89
9.34
-1.58
-1.58
-1.58
-1.65
-1.65
-1.65
-2.00
-2.00
NA
NA
NA
NA
NA
NA
Source*
Hammett (3)
Hammett (3)
Hammett (3)
Hammett (3)
Hammett (3)
Hammett (3)
Hammett (3)
Hammett (3)
(4)
Taft (3)
Taft (3)
Taft (3)
Taft (3)
Taft (3)
Taft (3)
Taft (3)
Taft (3)
D-4
-------
Appendix D - Transfer of Treatability Data
Table D-l (Continued)
'%$AI
Code
153
170
PAI Name i
Mefluidide
Napropamide
Structural
. Group
Carbamate
Carbamate
Hydrolysis
TjeeajaWlify
Data1
Hydrolysis
Product pKa
Value
SD
SD
s
Source2
!A "Yes" indicates that data are available indicating a hydrolysis half-life of less than 12 hours at a pH of 12 and
60°C.
2Numbers in parentheses indicate the source of the data as listed in the references at the end of this appendix.
NA - pKa of hydrolysis products is not available in the literature and is not calculable using available estimation
techniques.
SD - Transfer of hydrolysis data based on structural analysis is not considered appropriate because the structure
of the PAI is significantly different from other PAIs in the structural group.
D-5
-------
Appendix D - Transfer of Treatability Data
EPA treatability study half-life data are available for seven carbamate PAIs:
carbofuran, carbaryl, aminocarb, methomyl, methiocarb, chlorpropharh, and propham, and,
therefore, these PAIs were not considered as recipients of data transfers. The highest leaving
group pKa value for carbamate PAIs with EPA treatability study half-life data is 10.63
(aminocarb, with a half-life of <30 minutes). A hydrolysis half-life of <30 minutes is
transferred to bendiocarb, karabutylate, previcur N, desmedipham, thiophanate ethyl,
tbiophanate methyl, benomyl, and phenmedipham, because these PAIs are all carbamate PAIs
without treatability data that have expected leaving group pKa values less than that of
aminocarb. The expected leaving group pKa values for mexacarbate, propoxur, landrin-1, and
landrin-2 are greater than 10.63; therefore, hydrolysis half-life data are not transferred to these
PAIs. Hydrolysis treatability data are not transferred to aldicarb, carbosulfan, polyphase, and
oxamyl because the pKa values of their leaving groups cannot be identified. Hydrolysis
treatability data are not transferred to napropamide and mefluidide, because the chemical
structure of these PAIs is significantly different from other carbamates.
D.2.2
PAI-Specific Hydrolysis Data Extrapolated to a pH of 12 and 60°C
Data Extrapolation Method
For several PAIs, hydrolysis data are available, but at conditions other than a
pH of 12 and 60°C. Hydrolysis treatability data obtained at ambient and acidic conditions, as
well as slightly alkaline conditions, may be extrapolated to heated and strongly alkaline
conditions (5). The extrapolation methodology requires half-life data measured at several
temperatures for the same pH.
Given the hydrolysis reaction (using a generic organophosphate PAI or PAI
group as an example):
(RO)2 - P(O) - OX + OH
The rate of reaction would be:
(R0)2 - P(O) - OH + HOX
r =
dt
= k2[PAI][OH-]
where:
PAI
k2
(R0)2 - P(0) - OX
Second-order rate constant.
D-6
-------
Appendix D - Transfer of Treatability Data
Arrhenius' equation may be used to model kinetic rate constants at varying
temperatures. The second order rate constant k2 would therefore be:
where:
T
R
Ea
A
k2 = Ae'
Temperature (°K)
1.987 cal/mole-°K
Activation energy (cal/mol)
Constant (1/mol-min)
Second order rate constant (1/mole-min).
As the pH increases, the hydroxyl ion concentration becomes much larger than
the PAI concentration, which results in a pseudo first order rate equation. The rate of
reaction becomes:
r .
Integrating:
The half-life equation is therefore:
PAI
PAI
O
= exp(-k1t)
t
1/2 -
_ ln(2)
where:
tyz = Half-life hi minutes
kj = Pseudo first order rate constant (min^).
The pseudo first order rate constant is related to the second order rate constant
by the following equation:
kj = k2 x 10-P°H
D-7
-------
Appendix D - Transfer of Treatability Data
where:
pOH = -log[OIT] = 14 - pH.
The hydrolysis half-life at elevated pH and temperature can therefore be
extrapolated from half-life data measured at other pHs and/or temperatures, using the
following methodology. First, it is necessary to define the values of the constants A and Ea/R
in Arrhenius' equation at the pH at which the available hydrolysis data were measured.
Plotting hi k2 versus 1/T yields a slope equal to the activation energy coefficient (-Ea/R) and
an intercept equal to hi A. Data collected and analyzed in the administrative record
supporting the 1978 BPT rule indicate that lines plotted for half-life data measured at different
pHs are approximately parallel (5). The parallel lines indicate that the activation energy
coefficient is nearly constant with respect to pH. Since the rate constant varies with pH, hi A
will also vary with pH. Plotting hi A versus pH, based on half-life data measured at different
pHs, should yield a straight line. This plot may then be used to determine the hi A value for
the PAI at the desired pH, and the activation energy coefficient can then be figured hi, along
with the desired temperature, in order to calculate the second-order rate constant. The pOH is
then factored in order to calculate the pseudo-first order rate constant, which hi turn yields the
half-life at the heated and alkaline conditions. This approach appears to be technically valid
for PAIs with adequate hydrolysis rate data measured at different pHs and temperatures.
Most PAIs requiring this type of data transfer, however, have only limited data.
Example Hydrolysis Data Extrapolation
PAIs for which a half-life at-a pH of 12 and 60°C can be estimated are
identified based on the availability of hydrolysis half-life data for each PAI. An example
estimation of the half-life for atrazine is described below. A detailed discussion of all of the
half-life estimations conducted for the 272 PAIs can be found hi the Final Treatability
Database Report (1).
Hydrolysis half-life data are available for atrazine at pH values of 12, 12.9, and
14 at 25°C, at a pH of 16 at 80°C, and at a pH of 14 at 100°C. (A pH greater than 14 may
be achieved in saturated NaOH solutions or with the use of organic solvents (6).) Figure D-l
shows the temperature dependence of the atrazine hydrolysis rate, and is based on the
hydrolysis data at a pH of 14 at temperatures of 25°C and 100°C. Figure D-2 shows the pH
dependance of the atrazine hydrolysis rate, based on all available hydrolysis half-life data for
atrazine. The hydrolysis half-life of atrazine at a pH of 12 at 60°C is estimated to be 731
minutes.
D.3
Activated Carbon Adsorption
Activated carbon adsorption is a treatment technology that removes certain
organic constituents from wastewater. The term "activated carbon" refers to carbon materials,
such as coal or wood, that are processed through dehydration, carbonization, and oxidation to
yield a material that has a high capacity for adsorption due to large surface .area and a high
D-8
-------
Appendix D - Transfer of Treatabffity Data
Figure D-l. Plot of In K2 vs. 1/T for Atrazine at a pH of 14
(6-0)
Ink2= (-3910K1/T) + 7.156
lnk2(pH14)
0.0026 0.0028 0.0030 0.0032 0.0034
1/T (Deg. K)
D-9
-------
Appendix D - Transfer of Treatability Data
Figure D-2. Plot of In A vs. pH for Atrazinc
14-
13-
12-
11-
10-
9-
8-
lnA= (-0.800)(pH) + 21.351
D D
n
In A
11 12 13 14 15 16 17
pH
D-10
-------
Appendix D - Transfer of Treatability Data
number of internal pores. The activated carbon removes organic constituents from wastewater
by physical and chemical forces which bind the constituents to the carbon surface. The
treatability studies summarized in Section 7.4 indicate that activated carbon is capable of
removing a wide range of PAIs from wastewater. These treatability studies also demonstrate
that, in general, organic constituents consisting of certain common physical properties (e.g.,
low water solubility and relatively high molecular weights) and certain common chemical
structures (e.g., aromatic functional groups) are amenable to activated carbon adsorption.
Carbon saturation loading data (the measure of the amount of organic
compounds that can be adsorbed onto a unit amount of activated carbon), overall pollutant
loadings, and pollutant concentrations in a facility's wastewater stream, are important
parameters in designing an activated carbon adsorption treatment system. The saturation
loading achievable by a carbon adsorption treatment system varies with the concentration of
the compounds being adsorbed, the wastewater pH and temperature, and the presence of other
adsorbable compounds. As a result, precise carbon saturation loadings are specific to a
facility's individual wastewater stream. Approximate carbon saturation loadings, however,
may be estimated for a facility's wastewater stream by using treatability study data and
estimates of the pollutant concentrations in facility wastewaters. Activated carbon treatability
studies present data in the form of carbon adsorption isotherms. These isotherms are
graphical representations of the variability of the carbon saturation loading in equilibrium with
varying concentrations of the target compound being adsorbed at a constant temperature.
Thus, a carbon adsorption isotherm may be used to identify the carbon saturation loadings
over a range of target compound concentrations.
The Langmuir and Freundlich equations are the two most commonly
encountered equations that describe carbon adsorption isotherms (7). However, the Langmuir
equation, which has a simple theoretical basis, often does not provide a good fit to isotherms
for adsorption systems (8). The empirical Freundlich equation typically provides a better fit
for adsorption from liquids (8). The Freundlich equation is also widely used and has been
found to describe adequately the adsorption process in dilute solution (9). Therefore, EPA
has determined Freundlich isotherms for all PAIs identified as amenable to activated carbon
adsorption.
The Freundlich equation has the form:
— = KCJ
M f
where:
M
Amount of adsorbate (PAI) adsorbed per unit weight of
adsorbent (carbon) (g/g)
D-ll
-------
K
n
Appendix D - Transfer of Treatability Data
Equilibrium concentration of adsorbate (PAI) in solution after
adsorption (mg/L)
Empirical constant characteristic of the adsorbate-adsorbent
system (g/g)
Empirical constant characteristic of the adsorbate-adsorbent
system (unitless).
When X/M is plotted vs. Cf on logarithmic paper, K is the X/M intercept of the isotherm plot
at Cf = 1 and 1/n is the slope of the isotherm.
This section discusses the methodology used to estimate carbon saturation
loadings for PAIs for which activated carbon treatability data are not available. This
methodology consists of two steps: identifying PAIs likely to be amenable to carbon
adsorption, and determining Freundlich isotherm parameters for the amenable PAIs based on
data transfers from PAIs for which data are available.
The identification of PAIs likely to be amenable to carbon adsorption is based
on an analysis of each PAI's chemical structure and physical properties. The following types
of compounds are readily adsorbed onto carbon: aromatics (9); high molecular weight (in the
case of PAIs, this includes PAIs with greater than four carbon atoms) compounds (10), and
compounds with low water solubility (10). The effectiveness of activated carbon adsorption
tends to increase as the PAI's molecular weight increases and the PAI's water solubility
decreases. Table D-2 lists the water solubility and molecular weight for each 272 PAI in the
carbamate structural group. Table D-2 also identifies the PAIs containing aromatic functional
groups. This information, combined with structural similarities to PAIs for which activated
carbon treatability data exist, is used to determine whether each PAI is likely to be amenable
to carbon adsorption. The following method is used to identify PAIs amenable to activated
carbon adsorption:
1. ' If a saturation loading is available for a PAI, then that PAI is amenable
to carbon adsorption.
2. If no saturation loading data are available for a PAI, men the PAI's
structure is analyzed to determine if it falls into one of the structural
categories amenable to activated carbon. If it does, then the PAI is
considered to be amenable to activated carbon adsorption.
Experimental data identifying the Freundlich isotherm parameters K and 1/n are
not available for all PAIs amenable to activated carbon adsorption. The PFPR treatability
database contains data from a variety of sources and of varying quality. Only data from
EPA-sponsored, bench-scale treatability studies are used hi transfers of K and 1/n values to
D-12
-------
Appendix D - Transfer of Treatability Data
Table D-2
Physical Property Data for PAIs
PAX
Code
013
038
040
042
048
055
061
062
075
076
077
095
100
145
146
153
156
166
170
195
201
209
228
FAIJfanae
Landrin-2
Landrin-1
Methiocarb
Polyphase
Aminocarb
Aldicarb
Bendiocarb
Benomyl
Carbaryl
Carbofuran
Carbosulfan
Desmedipham
Thiophanate Ethyl
Propham
Karabutilate
Mefluidide
Methomyl
Mexacarbate
Napropamide
Oxamyl
Propoxur
Phenmedipham
Previcur N
Structural
Group
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Carbamate
Water Solubility1
(mg/L)
NA
NA
Insoluble (11)
NA
Slightly soluble (11)
6,000 (11)
40(11)
Insoluble (11)
120(11)
700 (11)
0.3 (12)
NA
NA
250 (13)
NA
180(11)
58,000 (12)
lOOppm(ll)
NA
280 (11)
2,000 (13)
5(12)
>500 (12)
Aromatic?
Yes
Yes
Yes
No
Yes
No
• Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
No
Yes
Yes
No
Molecular
Weigh*
193
193
225
194
208
190
223
290 .
201
221
380
300
370
179
279
310
162
222
271
219
209
300
225
D-13
-------
Table D-2 (Continued)
Appendix D - Transfer of Treatability Data
PAI
Code
260
272
FAIS&me *
Thiophanate
Methyl
Chloropropham
, Structaral
^ Group
Carbamate
Carbamate
Water Solubility1
(Wgflb) ' i
Slightly soluble (12)
Slightly soluble (11)
Aromatic?
Yes
Yes
Molecular :
Weight
342
214
Numbers in parentheses indicate the source of the data as listed in the references at the end of this appendix.
NA - Data not available.
D-14
-------
Appendix D - Transfer of Treatability Data
ensure that only the data subjected to the rigorous EPA QA/QC procedures are transferred.
The following hierarchy is used to identify K and 1/n values for each PAI:
1. Where K and 1/n values are available for a PAI from an EPA-sponsored,
bench-scale treatability study, or other treatability data, then those K and
1/n values describe the isotherm for that PAI.
2. If K and 1/n values are not available for a PAI that is amenable to
activated carbon, and K and 1/n values are available from an
EPA-sponsored, bench-scale treatability study for only one other PAI in
the same structural group, then those K and 1/n values are transferred to
the PAI without K and 1/n values.
3. If K and 1/n values are not available for a PAI that is amenable to
activated carbon, and K and 1/n values are available from
EPA-sponsored, bench-scale treatability studies for more than one PAI
in the same structural group, then K and 1/n values for a minimum
Freundlich isotherm for the structural group are transferred to the PAI.
The minimum Freundlich isotherm is generated by plotting the lowest
saturation loading for all PAIs with experimentally determined K and 1/n
values within the structural group over a range of concentrations from
0.0001 mg/L to 1,000 mg/L. An isotherm fitted to the plotted points is
the minimum Freundlich isotherm for the structural group.
4. If K and 1/n values are not available for a PAI that is amenable to
activated carbon treatment, and K and 1/n values are not available for
any PAIs within the same structural group, then K and 1/n values from
the 90th percentile lowest Freundlich isotherm for all PAIs are
transferred to the PAI. The 90th percentile lowest Freundlich isotherm
is generated by plotting the 90th percentile lowest saturation loading for
all PAIs with experimentally determined K and 1/n values from
EPA-sponsored, bench-scale treatability studies over a range of
concentrations from 0.0001 mg/L to 1,000 mg/L. An isotherm fitted to
the plotted points is the 90th percentile lowest Freundlich isotherm.
This 90th percentile isotherm represents a conservatively low estimate of
saturation loadings at various concentrations while discounting outlier
values. Table D-3 lists the data used to construct the 90th percentile
minimum isotherm. Figure D-3 presents the 90th percentile minimum
isotherm.
D-15
-------
Appendix D - Transfer of Treatability Data
Table D-3
Data Used to Generate PAI 90th Percentile Lowest Saturation Loading
Graph
£AI
Code
005
005
129
129
256
239
239
239
•^
s ^.
PAIJSTame
1,3-Dichloropropene
1,3-Dichloropropene
DCPA
DCPA
Terbuthylazine
Simazine
Simazine
Simazine
" Structural
Group
EDB
EDB
Aryl Halide
Aiyl Halide
s-Triazine
s-Triazine
s-Triazine
s-Triazine
3EC
(g® ;
2.35E-02
2.35E-02
2.82E-03
2.82E-03
7.89E-03
7.97E-03
7.97E-03
7.97E-03
Ita
{unitless)
0.69
0.69
0.27
0.27
0.13
0.17
0.17
0.17
Concentration i
(mg/L) :
0.0001
0.001
0.01
0.1
1
10
100
1,000
Saturation
Loading
&$
4.08E-05
2.00E-04
8.13E-04
1.51E-03
7.89E-03
1.18E-02
1.74E-02
2.58E-0.2
D-16
-------
Appendix D - Transfer of Treatability Data
Figure D-3. 90th Percentile Lowest Freundlich Isotherm for Pesticide Active Ingredients
(2V
(4)-
y m 0.399x - 5.693
(10)-
(12)
(10) (5)
O ln(X/M)
10
ln(c)
D-17
-------
Appendix D - Transfer of Treatability Data
5. An analysis of the chemical structure and properties of some PAIs
indicated that, although the PAI is amenable to activated carbon
treatment, it is not as amenable as other PAIs within the same structural
group. For example, a PAI may be more water soluble than other PAIs
within the same structural group. The PAI that is more water soluble
may be less amenable to activated carbon treatment. If K and 1/n values
are available for a PAI that is amenable to activated carbon treatment,
and K and 1/n values are available for other PAIs within the same
structural group, but analysis of chemical structures and properties
indicates that the PAI without K and 1/n values is not as amenable to
activated carbon treatment, then the K and 1/n values, of the 90th
percentile lowest Freundlich isotherm are transferred to the PAI. This
ensures that conservatively low K and 1/n values are transferred, and K
and 1/n values are not transferred from PAIs that are more amenable to
activated carbon treatment to PAIs that are less amenable to activated
carbon treatment.
Activated carbon adsorption treatability data transfers were attempted for all
PAIs. The remainder of this section discusses the activated carbon treatability data transfers
for an example structural group, carbamates. Because the transfer of treatability data to 272
PAIs was conducted separately from the transfer of treatability data to non-2,72 PAIs, the
example below describes the transfer of treatability data to the 272 PAIs in the carbamate
structural group first, followed by a discussion of the treatability data transfer to the non-272
PAIs in the carbamate structural group.
272 Carbamate PAIs
EPA saturation loading data are available for carbofuran and propoxur. EPA
sampling data indicate that carbaryl is amenable to treatment by activated carbon adsorption.
Saturation loading data are available from other sources for benomyl, carbaryl, methomyl, and
propoxur. In addition, data exist indicating that chloropropham is amenable to carbon
adsorption. Landrin-1, landrin-2, methiocarb, aminocarb, bendiocarb, carbosulfan,
desmedipham, thiophorate ethyl, propham, karabutilate, mefluidide, mexacarbate,
napropamide, phenmedipham, thiophanate methyl, and chloropropham are all structurally
similar (high molecular weight aromatic esters). As a result, these PAIs should be amenable
to carbon adsorption. Aldicarb, previcur N, polyphase, and oxamyl are high, molecular weight
compounds, and therefore should be amenable to activated carbon adsorption treatment.
Experimentally determined K and 1/n values are available for carbofuran and
propoxur from EPA-sponsored, bench-scale treatability studies and for benomyl, carbaryl, and
methomyl from other data sources. A minimum Freundlich isotherm constructed for the
carbamate structural group has a K value of 0.064 and a 1/n value of 0.311. The carbamate
minimum Freundlich isotherm K and 1/n values are transferred to landrin-1, landrin-2,
methiocarb, aminocarb, bendiocarb, carbosulfan, desmedipham, thiophorate ethyl, propham,
karabutilate, mefluidide, mexacarbate, napropamide, phenmedipham, thiophamate methyl, and
D-18
-------
Appendix D - Transfer of Treatability Data
chloropropham. Table D-4 lists the data used to generate the carbamate minimum adsorption
isotherm. Figure D-4 shows the plot of the carbamate minimum adsorption isotherm.
Although aldicarb, oxamyl, polyphase, and previcur N should be amenable to
activated carbon adsorption treatment, these PAIs are not aromatic, and may be less amenable
to activated carbon adsorption treatment than other members of the carbamate structural
group. Therefore, K and 1/n values from the 90th percentile lowest Freundlich isotherm (K =
0.0034, 1/n = 0.399) are transferred to aldicarb, oxamyl, polyphase, and previcuruN.
Non-272 Carbamate PAIs
The non-272 PAIs in this structural group are separated into two categories
based on aromaticity. Asulam, barban, EEEBC, fenoxycarb, methyl 2-benzimidazole-
carbamate phosphate, and sodium asulam are all aromatic, high molecular weight compounds.
Alcoxycarb, dimetilan, and fosamine ammonium are nonaromatic high molecular weight
compounds. All non-272 PAIs in the carbamate structural group should be amenable to
activated carbon adsorption treatment.
Physical property data and Freundlich isotherm parameters for the 272 and
non-272 carbamate PAIs are listed in Table D-5. Experimentally determined K and 1/n values
are available for five 272 PAIs in the carbamate structural group: benomyl, carbaryl,
carbofuran, methomyl, and propoxur. Experimentally determined K and 1/n values are
available for carbofuran and propoxur from EPA-sponsored bench-scale treatability studies
and for benomyl, carbaryl, and methomyl from other data sources. A minimum Freundlich
isotherm constructed for the carbamate structural group is based on the Freundlich isotherm
parameters of carbofuran and propoxur (K = 0.064, 1/n = 0.31). The carbamate minimum
Freundlich isotherm K and 1/n values are transferred to barban, fenoxycarb, and methyl
2-benzimidazolecarbamate phosphate, because these PAIs are high molecular weight aromatic
compounds, like carbofuran and propoxur, and have lower water solubilities than carbofuran
and propoxur.
Although asulam and sodium asulam are high molecular weight aromatic
compounds, the K and 1/n values from the 90th percentile lowest Freundlich isotherm are
transferred to these PAIs because they are more water soluble than carbofuran and propoxur.
Although aldoxycarb, dimetilan, EEEBC, and fosamine ammonium should be amenable to
activated carbon adsorption treatment, these PAIs are either not aromatic or do not have water
solubility data available, and may be less amenable to activated carbon adsorption treatment
than other members of the carbamate structural group. Therefore, K and 1/n values from the
90th percentile lowest Freundlich isotherm (K = 0.0034,1/n = 0.399) are transferred to
aldoxycarb, dimetilan, EEEBC, and fosamine ammonium.
D-19
-------
Appendix D - Transfer of Treatability Data
Table D-4
Carbamate Fruendlich Isotherm Data
PAX
Code
76
201
201
201
201
201
201
201
PAIName
Carbofuran
Propoxur
Propoxur
Propoxur
Propoxur
Propoxur
Propoxur
Propoxur
-r K
!^ <3&&
0.0818
0.0644
0.0644
0.0644
0.0644
0.0644
0.0644
0.0644
1/tt
(unitless)
0.34
0.31
0.31
0.31
0.31
0.31
0.31
0.31
Concentration
(mgflL)
0.0001
0.001
0.01
0.1
1
10
100
1,000
Saturation Loading
-&$
3.57E-03
7.57E-03
1.54E-02
3.15E-02
6.44E-02
1.31E-01
.2.68E-01
5.48E-01
D-20
-------
Appendix D - Transfer of Treatability Data
Figure D-4. Carbamate Minimum Adsorption Isotherm
-1-
-4-
-5-
y = 0.3 llx-2.746
ln(x/m)
ln(c)
D-21
-------
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-------
Appendix D - Transfer of Treatability Data
D.4
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
References
Radian Corporation. Final Pesticides Formulators. Packagers, and Repackagers
Treatabilitv Database Report. Prepared for U.S. Environmental Protection
Agency, Office of Water, Washington, D.C., March 1994 (DCN F7185).
Radian Corporation. Pesticide Formulators. Packagers, and Repackagers
Treatabilitv Database Report Addendum. Prepared for U.S. Environmental
Protection Agency, Office of Water, Washington, D.C., September 1995 (DCN
F7700).
Lyman, W.J., et. al. Handbook of Chemical Property Estimation Methods.
Mc-Graw Hill Book Company, 1981.
Weast, R.C., editor. CRC Handbook of Chemistry and Physics. 60th Edition.
CRC Press, Inc., Boca Raton, Florida, 1980.
Environmental Science and Engineering, Inc. Hydrolysis Report. Gainesville,
FL, September 27, 1977.
Dickerson, R.E. et. al., Chemical Principles. Third Edition. The
Benjamin/Chimmings Publishing Company, Inc., Menlo Park, CA, 1979.
Tchobanaglous, G. and E.D. Schroeder. Water Quality. Addison-Wesley
Publishing Company, Inc., Reading, MA, 1985.
McCabe, W.L., et. al. Unit Operations of Chemical Engineering, Fourth
Edition. McGraw-Hill Book Company, New York, NY, 1985.
U.S. Environmental Protection Agency. Carbon Adsorption Isotherms for
Toxic Organics. Municipal Environmental Research Laboratory,
EPA-600/8-80-023, Cincinnati, Ohio, April 1980 (DCN F5786).
U.S. Environmental Protection Agency. Final Development Document for
Effluent Limitations Guidelines and Standards for the Organic Chemicals,
Plastics, and Synthetic Fibers Point Source Category. Volume I.
EPA 440/1-87/009, Washington, D.C., October, 1987, p. VH-121.
Badavari, S., et. al., editors. The Merck Index. Eleventh Edition. Merck
Publishing Co., Inc., Rahway, NJ, 1989.
Hall, F.R., et. al., editors. Farm Chemicals Handbook '92. Mepter Publishing
Company, Willoughby, OH, 1992.
D-24
-------
13.
. Appendix D - Transfer of Treatability Data
U.S. Environmental Protection Agency, "Office of Drinking Water Health
Advisories. Drinking Water Health Advisory: Pesticides. Lewis Publishers,
Inc., Chelsea, MI, 1989.
D-25
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