DEVELOPMENT DOCUMENT
FOR
EFFLUENT LIMITATIONS GUIDELINES
NEW SOURCE PERFORMANCE STANDARDS
AND
PRETREATMENT STANDARDS
FOR THE
ORGANIC CHEMICALS
AND THE
PLASTICS AND SYNTHETIC FIBERS
POINT SOURCE CATEGORY
Volume I
Lee M. Thomas
Administrator
Lawrence J. Jensen
Assistant Administrator for Water
William A. Whittington
Director
Office of Water Regulations and Standards
Devereaux Barnes, Director
Industrial Technology Division
Marvin B. Rubin
Chief, Chemicals Industry Branch
Elwood H. Forsht
Senior Project Officer
Frank H. Hund
Hugh E. Wise
Janet K. Goodwin
Wendy D. Smith
Project Team
October 1987
Industrial Technology Division
Office of Water Regulations and Standards
U.S. Environmental Protection Agency
Washington, D.C. 20460
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ABSTRACT
This document describes the technical development of the U.S.
Environmental Protection Agency's promulgated effluent limitations guidelines
and standards that control the discharge of pollutants into navigable waters
and publicly owned treatment works (POTWs) by existing and new sources in the
organic chemicals, plastics, and synthetic fibers point source category. The
regulation establishes effluent limitations guidelines attainable by the
application of the "best practicable control technology currently available"
(BPT) and the "best available technology economically achievable" (BAT),
Pretreatment standards applicable to existing and new discharges to POTWs
(PSES and PSNS, respectively), and new source performance standards (NSPS)
attainable by the application of the "best available demonstrated control
technology." The regulation was promulgated under the authority of Sections
301, 304, 306, 307, 308, 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).
It was also promulgated in response to the Settlement Agreement in Natural
Resources Defense Council, Inc. v. Trian, 8 ERC 2120 (D.D.C. 1976), modified,
12 ERC 1833 (D.D.C.).
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TABLE OF CONTENTS
VOLUME I
I. INTRODUCTION
A. LEGAL AUTHORITY 1-1
1. Best Practicable Control Technology Currently
Available (BPT) 1-2
2. Best Available Technology Economically
AchieVable (BAT) 1-3
3. Best Conventional Pollutant Control
Technology (BCT) 1-3
4. New Source Performance Standards (NSPS). . ...... . . 1-4
5. Pretreatment Standards for Existing
Sources (PSES) 1-4
6. Pretreatment Standards for New Sources (PSNS). . . . 1-4
B. HISTORY OF OCPSF RULEMAKING EFFORTS 1-5
II. SUMMARY AND CONCLUSIONS
A. OVERVIEW OF THE INDUSTRY H-l
B.. ..-.CONCLUSIONS 11-^5
1. Applicability of the Promulgated Regulation. .... II-5
2. BPT II-6
3. BCT II-8
4. BAT II-8
5. NSPS :.'..... 11-11
6. PSES '". 11-16
7. PSNS H-17
III. INDUSTRY DESCRIPTION
A. INTRODUCTION III-l
B. DEFINITION OF THE INDUSTRY III-3
1. Standard Industrial Classification System. ..... III-3
2. Scope of the Final Regulation. . III-3
3. Raw Materials and Product Processes 111-20
4. Geographic Distribution 111-32
5. Plant Age 111-32
6. Plant Size 111-35
7. Mode of Discharge. 111-41
C. DATA BASE DESCRIPTION. ....... 111-41
1. 1983 Section 308 Questionnaire Data Base 111-41
2. Daily Data Base Development 111-46
3. BAT Data Base 111-47
111
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TABLE OF CONTENTS (Continued)
IV. SUBCATEGORIZATION
A. INTRODUCTION IV-1
B. BACKGROUND „ IV_2
1. March 21, 1983, Proposal IV-2
2. July 17, 1985, Federal Register NOA .... IV-3
3. December 8, 1986, Federal Register ,• • • IV-5
C. FINAL ADOPTED BPT AND BAT SUBCATEGORIZATION
METHODOLOGY AND RATIONALE IV-9
1. Performance and Treatment System Shifts. ...... IV-12
2. Flow and Total Production Adjustment Factors .... IV-13
b. FINAL ADOPTED BAT SUBCATEGORIZATION APPROACH ...... IV-16
E. SUBCATEGORIZATION FACTORS. ...-..• IV-18
1. Introduction IV-18
2. Manufacturing Product/Process IV-19
3. Raw Materials IV-22
4. Facility Size .....'..... IV-24
5. Geographical Location IV-24
6. Age of Facility and Equipment IV-26
7. Wastewater Characteristics and Treatability IV-28
V. WATER USE AND WASTEWATER CHARACTERIZATION
A. WATER USE AND SOURCES OF WASTEWATER V-l
B. WATER USE BY MODE OF DISCHARGE V-3
C. WATER USE BY SUBCATEGORY . '' V-3
i
D. WATER REUSE AND RECYCLE. V-23
1. Water Conservation and Reuse Technologies V-23
2. Current Levels of Reuse and Recycle V-24
E. WASTEWATER CHARACTERIZATION V-29
1. Conventional Pollutants V-29
2. Occurrence and Prediction of Priority Pollutants . . V-49
iv
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TABLE OF CONTENTS (Continued)
F. RAW WASTE¥ATER CHARACTERIZATION DATA .... ! . . ;. . . V-89
1. General . . .". . .' '. V-89
2. Raw tfastewater Data Collection Studies . . . . ;. . i V-90
3. Screening Phase I i . V-90
4. Screening Phase II . . . . . . . . • -..;'• • • • • . • , V-94
5. Verification Program . . . .... . . • . ... ... '• .••' ' • V-94
6. EPA/CMA Five-Plant Sampling .Program. . .... . ., . V-101
7. 12-Plant Long-Term Sampling Program -.".'• V-103
, G. WASTEWATER DATA SUMMARY. . . '. '..". V . ,."".".'," • ..".,". X'.,...;,." ' V-105
1. Organic Toxic Pollutants . ... . . . . ...... . . . -. V-105
2. Toxic Pollutant Metals . . ., . ...,..,.-.;.;. V-112
VI. SELECTION OF POLLUTANT PARAMETERS , ,
A. INTRODUCTION .... .^ . ..;.' ...;.;_/ VI-1
B. CONVENTIONAL POLLUTANT PARAMETERS. .... , •«,..> • • /. VI-2
1. Five-Day Biochemical Oxygen Demand (BOD5). . . . . . ,. VI-2
2. Total Suspended Solids (TSS) . . . .. ... ... . ,.• . _ VI-3
3. PH ...,..'... '<..,,..;.;;'.<• . : VI-4
4. Oil and Grease .(O&G) .... ... .. . . . v. . . !,v ... . ,;-, VI-5
C. NONCONVENTIONAL POLLUTANTiPARAMETERS . . . .'. . . . '. . VI-6
1. Chemical Oxygen Demand (COD) . '.'". . . . . . . . . . VI-6
2. Total Organic Carbon (TOC) •. . ... . -•-. . . .. .;;, •: ;- r Vf-6
D. TOXIC POLLUTANT PARAMETERS . ... , . .. . .• . •..• . --,..., • • , .v?-7
E. SELECTION CRITERIA . . , • > ;.„ >;•*.}•;•••? \\ V,I-9
1. Conventional Pollutants. . . . . »,.,•; .. -•;. %;.>;...>-; >;.,« V*;' VI-9
2. Nonconventional Pollutants .... .' . . . . . .' . . VI-10
3. Toxic Pollutants . .. . . ..... ,.. •• •-.•--.;-..:..- ..i, . , VI-10
REFERENCES . '." .: . ..... . . . . . ... VI-44
- V.,;-:--'-"-.; --'I.-- ,; .; v.vif. ^' ^ ,'i- -
VII. CONTROL AND TREATMENT TECHNOLOGIES
A. INTRODUCTION ... ..... ....;... Y •.;. ., .. ",, "••.- .'-. -,--. . VII-1
B. BEST MANAGEMENT PRACTICES VII-4
1. In-Plant Source Controls VII-4
2. Operation and Maintenance (O&M) Practices VII-9
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TABLE OF CONTENTS (Continued)
C. IN-PLANT TREATMENT TECHNOLOGIES VII-11
1. Introduction VII-11
2. Chemical Oxidation (Cyanide Destruction) VII-13
3. Chemical Precipitation VII-18
4. Chemical Reduction (Chromium Reduction) .• VII-27
5. Gas Stripping (Air and Steam). VII-29
6. Solvent Extraction '. . VII-36
7. Ion Exchange . ........ VII-39
8. Carbon Adsorption VII-40
9. Distillation ..." 1 .'.... VII-42
10. Reverse Osmosis „ VII-44
11. Ultrafiltration. VII-46
12. Resin Adsorption . VII-48
13. In-Plant Biological Treatment. . VII-48
D. END-OF-PIPE TREATMENT TECHNOLOGIES VII-49
1. Introduction . VII-49
2. Primary Treatment Technologies ........... VII-51
3. Secondary Treatment Technologies ..... VII-61
4. Polishing and Tertiary Treatment Technologies. . . . VII-105
E. TOTAL TREATMENT SYSTEM PERFORMANCE ........... VII-125
1. Introduction VII-125
2. BPT Treatment System VII-127
3. Nonbiological Treatment Systems VII-127
4. BAT Treatment System . VII-137
F. WASTEWATER DISPOSAL VII-138
1. Introduction . VII-138
2. Deep Well Injection VII-138
3. Off-Site Treatment/Contract Hauling. . . VII-147
4. Incineration *...'...... VII-148
5. Evaporation. . VII-149
6. Surface Impoundment VII-149
7. Land Application VII-150
G. SLUDGE TREATMENT AND DISPOSAL VII-150
H. LIMITATIONS DEVELOPMENT VII-153
1. BPT Effluent Limitations VII-153
2. BAT Effluent Limitations .... VII-183
3. BAT and PSES Metals and Cyanide Limitations .VII-219
4. BAT Zinc Limitations for Plants Manufacturing
Rayon by the Viscose Process and Acrylic
Fibers by the Zinc Chloride/Solvent Process. . . . VII-227
VI
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TABLE OF CONTENTS. (Continued)
Page
5. PSES Effluent Limitations. .. . .... . ... , . .. ... . VII-228
REFERENCES VII-230
'": ; ; VOLUME II
VIII. ENGINEERING COSTS AND NON-WATER QUALITY ASPECTS
A. INTRODUCTION ,,., . VIII-1
1. BPT Costing Methodology VIII-2
2. BAT Costing Methodology VIII-7
3. PSES Costing Methodology VIII-24
4. Other Factors. .................. VIII-26
B. BPT TECHNOLOGIES ; * . . VIII-40
1. Activated Sludge ,...,.• VIII-40
2. Biological Treatment Upgrades VIII-56
3. Chemically Assisted Clarification VIII-67
4. Filtration Systems .. . . .• . . .... . . ... . VIII-77
5. Polishing Ponds. .................. VIII-78
6. Algae Control. . . VIII-84
C. BAT AND PSES TECHNOLOGIES. . VIII-95
1. Steam Stripping. . . . . VIII-95
2. Activated Carbon Systems ......,,. VIII-119
; 3. Coagulation/.Flocculation/Clarification System. . . VIII-139
4. Cyanide Destruction . , VIII-180
5. In-Plant Biological Treatment. .......... . VIII-187
D. ADDITIONAL COSTS ... ....... ...... VIII-197
1. Contract Hauling- . VIII-197
2., Monitoring Costs VIII-198
3. Sludge Disposal and Incineration . . . . . . . . . VIII-203
4. RCRA Baseline Costs, ....... , , . VIII-222
E. WASTEWATER AND AIR EMISSION LOADINGS ... VIII-236
1. BPT Conventional Pollutant Wastewater Loadings . . VIII-236
• - 2. BAT and PSES Toxic\Pollutant Wastewater •
Loadings . . . VIII-236
,- . 3. BAT and PSES Toxic1 Pollutant Air Emission . . '
'' Loadings . . . .'...<.., .... . • . . . :. . . •".' . VIII-270
VII
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TABLE OF CONTENTS (Continued)
IX. EFFLUENT QUALITY ATTAINABLE THROUGH THE APPLICATION OF
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
A. INTRODUCTION ix_l
1. Regulated Pollutants . ., IX-2
2. BPT Subcategorization IX-2
B. TECHNOLOGY SELECTION IX-2
C. BPT EFFLUENT LIMITATIONS GUIDELINES IX-5
D. COST AND EFFLUENT REDUCTION BENEFITS . . . IX-9
E. IMPLEMENTATION OF THE BPT EFFLUENT LIMITATIONS
GUIDELINES IX-9
F. NON-WATER QUALITY ENVIRONMENTAL IMPACTS IX-12
1. Air Pollution. . . ^ . . . . . . . . . . . . . . . . IX-12
2. Solid Waste . IX-13
3. Energy Requirement IX-13
X. EFFLUENT QUALITY ATTAINABLE THROUGH THE APPLICATION OF
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
A. INTRODUCTION . . ., X-l
B. BAT SUBCATEGORIZATION X-l
C. TECHNOLOGY SELECTION . X-2
1. Option I ......... ....... X-3
2. Option II X-3
3. Option III X-4
D. POLLUTANT SELECTION X-4
E. BAT EFFLUENT LIMITATIONS GUIDELINES X-10
1. Volatiles Limits X-ll
2. Cyanide Limitations x-11
3. Metals Limitations X-12
4. Other Organic Pollutants X-28
F. COST AND EFFLUENT REDUCTION BENEFITS IMPLEMENTATION
OF THE BAT EFFLUENT. . X-31
Vlll
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G.
TABLE OF JCONTENTS (Continued)
LIMITATIONS GUIDELINES ... . . . . . ."".. . • • • • • •' X-31
1. NPDES Permit Limitations „ . ...... X-31
2. NPDES Monitoring Requirements. ~. . X-32
H. NON-WATER QUALITY ENVIRONMENTAL IMPACTS: . . . ... . . . X-36
1. Air Pollution • X-37
2. Solid Waste . . , X-37
3. Energy Requirements X-37
XI. EFFLUENT QUALITY ATTAINABLE THROUGH THE APPLICATION OF
NEW SOURCE PERFORMANCE STANDARDS (NSPS)<
A. INTRODUCTION . . ..'..' . • • • • • • ; • •• • XI-1
B. POLLUTANT AND TECHNOLOGY SELECTION . ..... XI-1
XII. EFFLUENT QUALITY ATTAINABLE THROUGH THE PRETREATMENT
STANDARDS FOR EXISTING SOURCES AND PRETREATMENT
STANDARDS FOR NEW SOURCES
A. INTRODUCTION • XII-1
B. POLLUTANT SELECTION. ... .:.'. ...... ...;.... XII-1
C. TECHNOLOGY SELECTION .............. ... . XII-2
D. PSES AND PSNS XII-3
E. COST AND EFFLUENT REDUCTION BENEFITS . . ..... . . . XII-6
F. NON-WATER QUALITY ENVIRONMENTAL IMPACTS. ........ XII-6
1. Air Pollution '.' . .. . . . . ,,.;-•.. .. • XII-7
2. Solid Waste. .' . ?. ._ ... • • ...... • •'•.-• -• . • • • • XII-7
3. Energy Requirements. ..'..-, XII-7
XIII. BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY' ..'.i ... . . XIII-1
XIV. ACKNOWLEDGEMENTS • XIV-1
XV. GLOSSARY '. XV-1
APPENDIX III-A: PRODUCT LISTINGS BY INDUSTRIAL'SEGMENT . ..."." • • III-A1
APPENDIX IV-A: RATIONALE FOR THE FORM OF THE>BPT BOD5 :
REGRESSION MODEL IV-A1
ix
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TABLE OF CONTENTS (Continued)
APPENDIX VI-A:
APPENDIX VII-A:
APPENDIX VII-B:
APPENDIX VII-C:
APPENDIX VII-D:
APPENDIX VII-E:
APPENDIX VII-F:.
APPENDIX VII-G:
APPENDIX VIII-A:
APPENDIX VIII-B:
APPENDIX VIII-C:
APPENDIX VIII-D:
APPENDIX VIII-E:
LIST OF THE 126 PRIORITY POLLUTANTS
BPT LONG-TERM AVERAGE BOD- AND TSS PLANT-
SPECIFIC TARGETS. . .
RAW WASTEWATER AND TREATED EFFLUENT BOD , TSS,
COD, AND TOC DATA BEFORE AND AFTER ADJUSTMENT
BY PLANT-SPECIFIC DILUTION FACTORS.
LISTING OF 69 BPT DAILY DATA PLANTS INCLUDED
AND EXCLUDED FROM BPT VARIABILITY
FACTOR CALCULATIONS .....
BPT STATISTICAL METHODOLOGY ...
DISTRIBUTIONAL HYPOTHESIS TESTING
BAT STATISTICAL METHODOLOGY . . .
EVALUATION OF THE VALIDITY OF USING FORM 2C
DATA TO CHARACTERIZE PROCESS AND FINAL
EFFLUENT WASTEUATER JUNE 17, 1985 . . . .
METHODOLOGY FOR CALCULATING BPT TARGETS AND
IMPUTING MISSING ACTUAL BODE AND TSS
EFFLUENT VALUES ... . . . . . . .
BPT, BAT, AND PSES COMPLIANCE COST ESTIMATES
AND TECHNOLOGY BASIS
BPT PLANT-BY-PLANT BOD. AND TSS LOADINGS.
BAT AND PSES PLANT-BY-PLANT TOXIC POLLUTANT
WASTEWATER LOADINGS ....
BAT .AND PSES PLANT-BY-PLANT AIR EMISSION
LOADINGS
Page
VI-A1
VII-A1
VII-B1
VII-C1
VII-D1
VII-E1
VII-F1
VII-G1
VIII-A1
VIII-B1
VIII-C1
VIII-D1
VIII-E1
x
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LIST OF FIGURES
VOLUME I
Figure
III-l
IV-1
IV-2
IV-3
IV-4
IV-5
IV-6
IV-7
V-I
V-2
V-3
V-4
V-5
V-6
V-7
V-8
V-9
V-10
V-ll
V-12
V-13
Relationships Among the SIC Codes Related to the
Production of Organic dhemicals, Plastics, and
Synthetic Fibers
Distribution of Plants by Product and BOD5
(Thermoplastics) .... . . . ......
Distribution of Plants by Product and BOD5
(thermosets) . . . ....... . . ....*..••
Distribution of Plants by Product and BOD5 (Rayon) . . .
Distribution of Plants by Product and BOD5 (Fibers). . .
Distribution of Plants by Product and BODg
(Commodity) • • v • ,« •*•*•** * •'
Distribution of Plants by Product and BOD5 (Bulk). . . .
Distribution of Plants by Product and BOD5 (Specialty) .
Primary Feedstock Sources . . . . . . .
Coal Tar Refining. . . . ,. . . .... ...... ....
Ethylene ... .....
Propylene . . . . . . . • • • • ... • • .... • . . •
Butanes/Butenes. . . . . . .'•*..;'..'; . . . , . . . i '• >
Aromatics . .. . • • . « «.• «, « •
Plastics and Fibers •
Plastics and Fibers
Nitroaromatics, Nitrophenols, Benzidines, Phenols,
Nitrosamines ................
Chlorophenols , Chloroaromatics, Haloaryl Ethers, PCBs. .
Chlorinated C2s, C4, Chloroalkyl Ethers
Chlorinated C3s, Chloroalkyl Ethers, Acrolein,
Arrvloni trile. Isoohorone '. . . .
rage
III-6
IV-30
IV-31
IV-32
IV-33
IV-34
IV-35
IV-36
V-57
V-58
V-59
V-6Q
V^-61
V-62
V-63
V-64
V-65
V-66
V-67
V-68
V-69
xi
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LIST OF FIGURES (Continued)
Figure
V-14
V-15
V-16
VII-1
VII-2
VIII-1
VIII-2
VIII-3
VIII-4
VIII-5
VIII-6
VIII-7
VIII-8
VIII-9
VIII-10
VIII-11
VIII-12
Halogenated Methanes . .
Priority Pollutant (PRIPOL) Profile of the
OCPSF Industry . .
A Chemical Process
Solubility of Metal Hydroxides and Sulfides as a
Function of pH
Plot of Average TSS Effluent Versus BOD Effluent
for Plants With Biological Only Treatment With
> = 95% BOD5 Removal or BOD5 Effluent < = 40 mg/1. . .. . .
VOLUME II
Annualized Capital Cost Versus Additional
BOD Removal
Annualized Unit Capital Cost Curve Versus Additional
BOD5 Removal
Total Capital Cost Curve Versus Flow for Chemically
Assisted Clarification Systems
Annual O&M Cost Curve Versus Flow for Chemically
Assisted Clarification Systems
Land Requirements Curve Versus Flow for Chemically
Assisted Clarification Systems
Total Capital Cost Curve Versus Flow for Multi-
media Filter Systems
Annual O&M Cost Curve Versus Flow for Multi-media
• Filter Systems
Land Requirements Curve Versus Flow for Multi-
media Filter Systems
Total Capital Cost Curve Versus Flow for Polishing
Pond Systems
Annual O&M Cost Curve Versus Flow for Polishing
Pond Systems
Land Requirements Curve Versus Flow for Polishing
Pond Systems
Annual O&M Cost Curve Versus Flow for Algae
Control in Polishing Ponds Systems
Page
V-70
V-73
V-75
VII-20
VII-167
VIII-64
VIII-65
VIII^72
VIII-73
VIII-74
VIII-81
VIII-82
VIII-83
VIII-86
VIII-87
VIII-88
VIII-91
xii
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LIST OF FIGURES (Continued)
Figure
VIII-13 Capital Cost Curve Versus Flow for Benzene at
Effluent Concentration of 0.01 mg/1. . . . • VII.I~>11
VIII-14 Capital Cost Curve Versus Flow for Benzene at
Effluent Concentration of 1.0 rag/1 VIII-112
VIII-15 Capital Cost Curve Versus, Flow for Hexachloro-
benzene at Effluent Concentration of 0.01 mg/1 . . • • VIII-113
VIII-16 Capital Cost Curve Versus Flow for Hexachloro-
benzene of Effluent-Concentration of 1.0 mg/1;'"." . . !; ' VIIT-114
VIII-17 Annual O&M Cost Curve Versus Flow for Benzene
and Hexachlorobenzene. VIII-llo
VIII-18 Total Capital Cost Curve Versus Flow for Large BAT
In-Plant Control Carbon Treatment Systems;
Medium Carbon Adsorption Capacity. .......... VIII-143
VIII-19 Total Capital Cost Curve Versus Flow for Large PSES
'<••«'.' In-Plant Control Carbon Treatment Systems;
Medium Carbon Adsorption Capacity. . . ' ' .V
VIII-20 Annual O&M Cost Curve Versus Flow for Large BAT
In-Plant Control Carbon Treatment Systems;
Medium Carbon Adsorption Capacity. . . . . . . • • • • VIII-1
VIII-21 Annual O&M Cost Curve Versus Flow for Large PSES .-...•>
In-Plant Control Carbon Treatment Systems;
Medium Carbon Adsorption Capacity. ... . . . . . . • VIII-146
VIII-22 Total Capita! Cost Curve Versus Flow for Large BAT -
'•', " In-Plant Control Carbon Treatment Systems;
Low Carbon Adsorption Capacity VIII-147
....-., . :. . , ' .-.,:"• , <:<•. • '••;••'';" -1 '. . •-.•' ' * '
VIII-23 Total Capital Cost Curve Versus Flow for Large PSES
In-Plant Control Carbon Treatment Systems;
Low Carbon Adsorption Capacity . . ... . ; .- . . % . ; VIII-T48
VIII-24 Annual O&M Cost Curve Versus Flow for Large BAT ....,„
In-Plant Control Carbon Treatment Systems; •
Low Carbon Adsorption Capacity .......... •'* .' VIII-149
VIII-25 Annual O&M Cost Curve Versus Flow for Large PSES
In-Plant Control Carbon Treatment Systems;
Low Carbon Adsorption Capacity , • • VIII-150
VIII-26 Total Capital Cost Curves Versus Flow for Large
End-of-Pipe Carbon Treatment Systems (On-site ,
Carbon Regeneration Systems) . . . . . • ...» . • • VIH-151
XI11
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LIST OF FIGURES (Continued)
Figure
VIII-27 Annual O&M Cost Curves Versus Flow for Large
End.-of-Pipe Carbon Treatment Systems (On-site
Carbon Regeneration Systems) VIII-152
VIII-28 Total Capital Cost Curve Versus Flow for Small
In-Plant and End-of-Pipe Carbon Treatment
Systems (Low, Medium, High Carbon Adsorption
Capacities) _ VIII-157
VIII-29 Annual O&M Cost Curve Versus Flow for Small BAT
In-Plant Control Carbon Treatment Systems;
Medium Carbon Adsorption Capacity VIII-158
VIII-30 Annual O&M Cost Curve Versus Flow for Small PSES
In-Plant Control Carbon Treatment Systems;
Medium Carbon Adsorption Capacity VIII-159
VIII-31 Annual O&M Cost Curve Versus Flow for Small BAT
In-Plant Control Carbon Treatment Systems;
Low Carbon Adsorption Capacity VIII-160
VIII-32 Annual O&M Cost Curve Versus Flow for Small PSES
In-Plant Control Carbon Treatment Systems;
Low Carbon Adsorption Capacity VITi-161
VIII-33 Annual O&M Cost Curves Versus Flow for Small
End-of-Pipe Carbon Treatment Systems VIII-162
VIII-34 Land Requirements Curve Versus Flow for Activated
Carbon Treatment Systems VIII-163
VIII-35 Total Capital Cost Curve Versus Flow for
Coagulation/Flocculation/Clarification Systems VIII-166
VIII-36 Land Requirements Curve Versus Flow for
Coagulation/Flocculation/Clarification Systems VIII-168
VIII-37 Annual O&M Cost Curve Versus Flow for
Coagulation/Flocculation/Clarification Systems VIII-169
VIII-38 Comparison of Actual Systems Capital Cost and EPA's
Estimates for Coagulation/Flocculation/
Clarification VIII-17T
VIII-39 Total Capital Cost Curve Versus Flow for Sulfide
Precipitation Systems VIII-177
VIII-40 Annual O&M Cost Curve Versus Flow for Sulfide
Precipitation Systems VIII-178
xiv
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LIST OF FIGURES (Continued)
Figure
VIII-41
VIII-42
VIII-43
VIII-44
VIII-45
VIII-46
VII 1-47
VIII-48
VIII-49
, , .
VIII-50
VIII-51
VIII-52
VIII-53
VIII-54
VIII-55
VIII-56
VIII-57
Total Capital Cost Curve Versus Flow for Cyanide
Destruction Systems
Annual O&M Cost Curve Versus Flow for Cyanide
Destruction Systems . . ... . . . . • • -
Total Capital Cost Curve Versus Flow for Small
In-Plant Biological Treatment Systems
Total Capital Cost Curve Versus Flow for Large
In-Plant Biological Treatment Systems
Annual O&M Cost Curve Versus Flow for Small
In-Plant Biological Treatment Systems . . . . . .......
Annual O&M Cost Curve Versus Flow for Large
In-Plant Biological Treatment Systems .........
Land Requirements Curve Versus Flow for Small
In-Plant Biological Treatment Systems
Land Requirements Curve Versus Flow for Large
In-Plant Biological Treatment Systems . . . ... .....
Total Capital Cost Curve Versus Flow for Belt
Filter Press Systems., . . ... ... « «. • • -• - • •
Land Requirements Curve Versus Flow for Belt
Filter Press Systems. . . . .•-.•.-.••
Annual O&M Cost Curve Versus. Flow for Belt
Filter Press Systems., .- . . . ....
Total Capital. Cost Curve Versus Flow for
Fluidized Bed Incineration Systems. . .. . . < . . •
Annual O&M Cost Curve Versus Flow for.
Fluidized Bed Incineration, Systems. ........
Overview of Methodology for Identification of
OCPSF Plants Requiring RCRA Baseline Costing* ... ..
Raw Waste Load Calculation Logic Flow
BPT, BAT, and Current Waste Load Calculation
Logic Flow
PSES Waste Load Calculation ..
rage
, , VIII-185
, . VIII-186
VIII-190
, . VIII-191
VIII-192
VIII-193
VIII-195
VIII-196
" • , >
. . VIII-209
.,
. . VIII-210
VIII-212
VIII-217
VIII-219
VIII-223
VIII-261
VIII-268
, . VIII-269
XV
-------
LIST OF TABLES
VOLUME I
Table
II-l BPT Effluent Limitations and NSPS by
Subcategory (mg/1) I]:_9
II-2 BAT Effluent Limitations and NSPS for the End-of-.
Pipe Biological Treatment Subcategory 11-12
II-3 BAT Effluent Limitations and NSPS for the Non-End-
of-Pipe Biological Treatment Subcategory 11-14
II-4 Pretreatment Standards for Existing and New Sources
(PSES and PSNS) H-1Q
III-l SIC 2865: Cyclic (Coal Tar),- Crudes, and Cyclic
Intermediates, Dyes, and Organic Pigments
(Lakes and Toners) 111-10
III-2 SIC 2869: Industrial Organic Chemicals, Not
Elsewhere Classified . 111-12
III-3 SIC 2821: Plastic Materials, Synthetic Resins,
and Nonvulcanizable Elastomers 111-15
III-4 SIC 2823: Cellulosic Man-Made Fibers 111-16
III-5 SIC 2824: Synthetic Organic Fibers, Except
Cellulosic 111-17
III-6 OCPSF Chemical Products Also Listed as SIC 29110582
Products 111-18
III-7 OCPSF Chemical Products Also Listed as SIC 29116324
Products 111-19
III-8 Major Generalized Chemical Reactions and Processes
of the Organic Chemicals, Plastics, and
Synthetic Fibers Industry 111-29
III-9 Plant Distribution by State 111-33
111-10 Distribution of Plants by age of Oldest OCPSF
Process Still Operating as of 1984 111-34
III-ll Plant Distribution by Number of Employees 111-36
111-12 Plant Distribution by Number of Product/Processes
and Product/Product Groups for Primary Producers
That are Also "Direct and/or Indirect Dischargers . . . 111-37
xvi
-------
LIST OF TABLES (Continued)
Table
111-13 Distribution of 1982 Plant Production Quantity by
OCPSF SIC Group. ........ ......... . • .'
111-14 Distribution of 1982 Plant Sales Value by OCPSF
SIC Group ...... ..........•••••••
111-15 Mode of Discharge ..... • • ..... • • ...... 111-42
111-16 Data Base Designation. ...... .. ^ ........ 111-49
IV-1 BAT Effluent Estimated Long-Term Average Concentration
Comparison Between Plastics and Organics Plants
and Pure BPT Subcategory Plants .......... • . IV-4U
V-l Total OCPSF Plant Process Wastewater Flow
Characteristics by Type of Discharge ......... v-4
V-2 Total OCPSF Plant Nonprocess Wastewater Flow
Characteristics by Type of Discharge ......... V-5
V-3 Process Wastewater Flow for Primary OCPSF Producers by
Subcategory and Disposal Method. ... ........ v '
V-4 Process Wastewater Flow During 1980 for Secondary
OCPSF Producers by Subcategory and Disposal Method . . V-«
V-5 Process Wastewater Flow for Primary and Secondary
OCPSF Producers That are Zero/Alternative
Dischargers ................. •*'.**.*'
V-6 Non-Process Wastewater Flow During 1980 for Secondary
OCPSF Producers and Zero/Alternative Dischargers
by Subcategory and Disposal Method .......... "-1U
V-7 Total OCPSF Non-Process Wastewater Flow in 1980 for
Primary Producers by Subcategory and Disposal
Method , ..... .................. V~li
V-8 Non-Process Cooling Water Flow for Primary OCPSF
Producers by Subcategory and Disposal Method ..... v-i*.
V-9 OCPSF Miscellaneous Non-Cooling Non-Process
Wastewater Flow for Primary Producers by Sub-
category and Disposal Method . ..... .......
V-10 Process Wastewater Flow for Primary OCPSF Producers
by Subcategory and Disposal Method .......... v
xvii
-------
LIST OF TABLES (Continued)
V-12
V-13
V-14
V-15
V-16
V-17
V-18
V-19
V-20
V-21
V-22
V-23
V-24
Process Wastewater Flow During 1980 for Secondary
OCPSF Producers by Subcategory and Disposal Method . . V-15
Process Wastewater Flow for Primary and Secondary
OCPSF Producers That are Zero/Alternative
Dischargers V-16
Non-Process Wastewater Flow During 1980 for Secondary
OCPSF Producers and Zero/Alternative Dischargers
by Subcategory and Disposal Method V-17
Total OCPSF Non-Process Wastewater Flow in 1980 for
Primary Producers by Subcategory and Disposal
Method V-18
Non-Process Cooling Water Flow for Primary OCPSF
Producers by Subcategory and Disposal Method V-19
OCPSF Miscellaneous Non-Cooling Non-Process Waste-
water Flow for Primary Producers by Subcategory
and Disposal Method ?..... V-20
Water Conservation and Reuse Technologies . v-25
Water Reciirculated and Reused by Use for the OCPSF
Industries 1978 Census Data (a) v_2y
Summary of OCPSF Process and Nonprocess Wastewater
Recycle Flow for Primary Producers Excluding
Zero Dischargers ?..... V-28
Summary Statistics of Raw Wastewater BOD Concen-
trations by Subcategory Group and Disposal Methods
Producer = Primary V 32
Summary Statistics of Raw Wastewater BOD Concen-
trations by Subcategory Group and Disposal Method
Producer = Secondary ^ v_33
Summary Statistics of Raw Wastewater COD Concen-
trations by Subcategory Group and Disposal Method
Producer = Primary ...... v-34
Summary Statistics of Raw Wastewater COD Concen-
trations by Subcategory Group and Disposal Method
Producer = Secondary • .^ v_35
Summary Statistics of Raw Wastewater TOC Concen-
trations by Subcategory Group and Disposal Method
Producer = Primary ; v_36
xviii
-------
LIST OF TABLES (Continued)
Table
V-25 Summary Statistics of Raw Wastewater TOG Concen-
trations by Subcategory Group and Disposal Method
Producer = Secondary • • • •. • • V-37
V-26 Summary Statistics of Raw Wastewater TSS Concen-
trations by Subcategory Group and Disposal Method
Producer = Primary V-38
V-27 Summary Statistics of Raw Wastewater TSS Concen-
trations by Subcategory Group and Disposal Method
Producer = Secondary . . • -.' -•. - •• • v ' V-39
V-28 Summary Statistics of ,Raw Wastewater BOD Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Primary ...... V-41
V-29 Summary Statistics of Raw Wastewater BOD Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Secondary ..... V-42
V-30 Summary Statistics of Raw Wastewater COD Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Primary . . . . . . V-43
V-31 Summary Statistics of Raw Wastewater COD Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Secondary . . • • • v~44
V-32 Summary Statistics of.Raw Wastewater TOG Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Primary . . . • • • v-45
V-33 Summary Statistics of Raw Wastewater TOG Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Secondary V-46
V-34 Summary Statistics of Raw Wastewater TSS Concen- .
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer .= Primary . . . . v v-47
V-35 Summary Statistics of Raw Wastewater TSS Concen-
trations by Subcategory Group and Disposal Method
(with 95% and 70% Rule) Producer = Secondary ... . . V-48
V-36 Generic Procceses Used to Manufacture Organic
Chemical Products. , V-52
V-37 Major Plastics and Synthetic Fibers Products by
Generic Process. ... . . • • • • •, • • • V-54
xix
-------
LIST OF TABLES (Continued)
Table
V-38
V-39
V-40
V-41
V-42
V-43
V-44
V-45
V-46
V-47
V-48
V-49
V-50
VI-1
VI-2
VI-3
Page
Critical Precursor/Generic Process Combinations
That Generate Priority Pollutants. . . V-72
Organic Chemicals Effluents with Significant
Concentrations (>0.5 ppm) of Priority Pollutants . . . V-77
Plastics/Synthetic Fibers Effluents with Significant
Concentrations (>0.5 ppm) of Priority Pollutants . . . V-81
Priority Pollutants in Effluents of Precursor-
Generic Process Combination V-84
Overview of Wastewater Sampling Programs Included
in BAT Raw Waste Stream Data Base. . V-91
Phase II Screening - Product/Process and Other
Waste Streams Sampled at Each Plant V-95
Selection Criteria for Testing Priority Pollutants
in Verification Samples. . . . V-100
Number of Sampling Days for 12-Plant Long-Term
Sampling Program V-104
Summary Statistics for Influent Concentrations for
All OCPSF Plants V-106
Summary Statistics for Influent Concentrations for
Organics-Only OCPSF Plants V-108
Summary Statistics for Influent Concentrations for
Plastics-Only OCPSF Plants V-109
Summary Statistics for Influent Concentrations for
Organics and Plastics OCPSF Plants . . V-110
Summary of Priority Pollutant Metal-Product/
Process-Plant Validation . . . . : V-115
Twenty-six Toxic Pollutants Proposed for Exclusion . . . VI-8
Frequency of Occurrence and Concentration Ranges
for Selected Priority Pollutants in Untreated
Wastewater t VI-12
..Toxic Pollutants Excluded from Regulation for BAT
Subcategories One and Two Under Paragraph 8(a)(iii)
of the Settlement Agreement Because they Were... . ,
VI-16
xx
-------
LIST OF TABLES (Continued)
Table
Page
VI-4 Wastewater Loading for Eight Toxic Pollutants .
Being Considered for Paragraph Eight Exclusion ..,.'. . VI-19
VI-5 Four Toxic Pollutants Reserved from Regulation Under
BAT for Subcategory One. • • • • • • VI-21
VI-6 Eight Toxic Pollutants Reserved from Regulation
Under BAT for Subcategory Two. .... . . . VI-21
VI-7 Final PSES Pass-Through Analysis Results (Non-
End-of-Pipe Biological Subcategory Data) VI-23
VI-8 Final PSES Pass-Through Analysis Results (End-of-
Pipe Biological Subcategory Data). .......... VI-25
VI-9 Volatile and Semivolatile Toxic Pollutants
Targeted for Control Due to Air Stripping, ...... VI-29
VI-10 Estimated POTW Removal Data from Pilot- or Bench-.
scale Studies for Selected Toxic Pollutants, ...... VI-35
VI-11 Forty-seven Toxic Pollutants Determined to Interfere
With, Inhibit, or Pass-Through POTWs, and Regulated
Under PSES and PSNS Based on Table VII-7 VI-39
VI-12 Six Toxic Pollutants Determined not to ,interfere
With, Inhibit, or Pass-Through POTWs, and Excluded
from Regulation Under PSES and PSNS. .......... VI-40
VI-13 Six Toxic Pollutants That Do Not Volatilize
Extensively and Do Not Have POTW Percent
Removal Data VI-40
VI-14 Results of PSES Analysis to Determine if Toxic
Pollutant Removals were "...Sufficiently Controlled
by Existing Technologies..." . VI-41
VI-15 Three Toxic Pollutants Excluded from PSES and PSNS
Regulation Under Paragraph 8(a)(iii) of the Settle-
ment Agreement because they were "... Sufficiently.
Controlled by Existing Technologies..." VI-42
VI-16 Three Pollutants Reserved from Regulation,Under
PSES and PSNS Due to Lack of POTW Percent.
Removal Data . : VI-42
VII-1 Frequency of In-Plant Treatment Technologies in the
OCPSF Industry Listed by Mode of Discharge and
Type of Questionnaire Response VII-12
xxi
-------
LIST OF TABLES (Continued)
Table
VII-2
VII-3
VII-4
VII-5
VII-6
VII-7
VII-8
VII-9
VII-10
VII-11
VII-12
VII-13
VII-14
VII-15
VII-16
VII-17
VII-18
Oxidation of Cyanide Wastes With Ozone
Performance Data for Total Cyanide Oxidation
Using Chlorination
Comparison of OCPSF and Metal Finishing Raw Waste
Metals and Cyanide Concentrations
Raw Waste and Treated Effluent Zinc Concentrations
from Rayon and Acrylic Fibers Manufacturing. ....
Henry's Law Constant (Hi) Groupings
Steam Stripping Performance Data
Steam Stripping and Activated Carbon Performance
Data ...
Daily Activated Carbon Performance Data for
Nitrobenzene, Nitrophenols, and 4,6-Dinitro-
0-Cresol Plant No. 2680T .
Typical Ion Exchange Performance Data . . . . . .
Carbon Adsorption Performance Data from Plant
No. 2680T
Performance Data from Hydroxide Precipitation and
Hydroxide Precipitation Plus Filtration for
Metal Finishing Facilities .
Ultrafiltration Performance Data for Metals in
Laundry Wastewater-OPA Locka, Florida
Performance Data Basis for In-Plant Biological
Systems
Frequency of Primary Treatment Technologies in the
OCPSF Industry
Frequency of Secondary Treatment Technologies in
the OCPSF Industry
Frequency of Polishing/Tertiary Treatment
Technologies in the OCPSF Industry
Activated Sludge Performance Data for BOD
and TSS 5
Po IT A
rage
VII 15
VII-16
VII-25
VII 28
VII-33
VII-35
VII-37
VII-38
VII-41
VII-43
VII-45
} .
VII-47
VII-50
VII-52
VII-53
VII-54
VII-65
XXll
-------
LIST OF TABLES (Continued)
Table
VII-19
VII-20
VII-21
VII-22
VII-23
VII-24
VII-25
VII-26
VII-27
VM-28
VII-2.9
VII-30
VII-31
• j.
VII-32
"\
VII-33
: •;.,
VII-34
VII-35
Lagoon Performance Data for BOD5 and TSS
Attached Growth Treatment Systems Performance
Data for BOD5 and TSS :
Typical Design Parameters for Secondary Clarifiers
Treating Domestic Wastewater.
Monthly BOD5 Removal Efficiency .
Monthly BOD Efficiency by Region Subset I
(Northern— WV, IA, IL, IN, RI).
Monthly BOD Efficiency by Region Subset II
(Southern— GA, LA, SC, TX). .... . . ,
Monthly BOD Efficiency by Region Subset III
(Middle-Latitude— VA, NC) . . .
Average Effluent BOD by Month . . . . . . . . . . . . .
Average Effluent TSS by Month . . . . . . . . . . . . •
Monthly Effluent BOD5 by Region Subset I
(Northern— WV, IL, RI, IA, IN).
Monthly Effluent BOD5 by Region Subset H!
(Southern— TX, GA, LA, SC)
Monthly Effluent BOD. by; Region Subset III
(Middle-Latitude-,-VA, NC)
Monthly Effluent TSS by Region Subset I
(Northern— WV, IL, RI, IA, IN). . . . .... . . . .
Monthly Effluent TSS by Region Subset II
(Southern — TX, GA, LA, SC)
Monthly Effluent TSS by Region Subset III
(Middle-Latitude— VA, NC)
Monthly Data for Plant #2394. • • • •' • • • • • > • '« • '
Matrix of . 18 Plants With Polishing Ponds Used
as Basis for BPT Option II Limitations
Page
VII-69
VII-72
VII-74
VII-84
VII-85
VII-86
VII-87
VII-91
VII-92
VII-94
VII-95
VII-96
VII-97
VII-98
VII-99
VII-103
VII-106
VII-36 Option III OCPSF Plants With Biological Treatment
Plus Filtration Technology That Pass the BPT
'•}••'" Editing Criteria ,. . .
VII-109
xxiii
-------
LIST OF TABLES (Continued)
VII-37 Summary of Chemically Assisted Clarification
Technology Performance Data . . .......... '. VII-114
VII-38 Final Effluent Quality of a Chemically Assisted
Clarification System Treating Bleached
Kraft Wastewater .................. • e VII-116
VII-39 Classes of Organic Compounds Adsorbed on Carbon .... VII-121
VII-40 Summary of Carbon Adsorption Capacities ..... ... VII-122
VII-41 End-of-Pipe Carbon Adsorption Performance Data
from Plant No. 3033 .................. VII-126
VII-42 Treatment Technologies for Direct Nonbiological
Plants. • •*'• ..... ....... . ........ VII-128
VII-43 Performance of OCPSF Nonbiological Wastewater
Treatment Systems .............. .... VII-135
VII-44 BOD5 and TSS Reductions by Clarification at
Selected Pulp, Paper, and Paperboard Mills ...... VII-136
VII-45 List of Regulated Toxic Pollutants and the
Technology Basis for BAT Subcategory One and
Two Effluent Limitations ............... VII-139
VII-46 Summary of the Long-Term Weighted Average Effluent
Concentrations for the Final BAT Toxic Pollutant
Data Base for BAT Subcategory One .... ...... VII-142
VII-46 Summary of the Long-Term Weighted Average Effluent
Concentrations for the Final BAT Toxic Pollutant
Data Base for BAT Subcategory Two .......... VII-144
VII-48 Frequency of Waste Stream Final Discharge and
Disposal Techniques ...... ........... VII-146
VII-49 Frequency of Sludge Handling, Treatment, and
Disposal Techniques ................ . VII-151
VII-50 Contaminated and Uncontaminated Miscellaneous
"Nonprocess" Wastewaters Reported in the 1983
Section 308 Questionnaire ........... ... VII-155
VII-51 Summary Statistics for Determination of BPT BOD
Editing Criteria by Groups .......... 5. VII-163
VII-52 Rationale for Exclusion of Daily Data Plants
from Data Base ................... ; VII-173
xxiv
-------
LIST OF TABLES (Continued)
Table
VII-53
VII-54
VII-55
VII-56
VII-57
:'-•' '
VII-58
VII-59
VII-60
VII-61
VII-62
VII-63
VII-64
VII-65
VII-66
VII-67
BPT Subcategory Long-Term Averages (LTAs)
for BOD5
BPT Subcategory Long-Term Averages (LTAs)
for TSS
Overall Average Versus Production-Proportion-
Weighted Variability Factors
BOD Variability Factors for Biological Only
Systems (Effluent BOD < 40 mg/1 or BOD5
Percent Removal > 95%).: . . . ..... » . . . . . •
TSS Variability Factors for Biological Only
Systems (Effluent BOD5 < 40 mg/1 or BOD ;
Percent Removal > 95% and TSS < 100 mg/1) •'•; . . .
Priority Pollutant (PRIPOL) Data Sources for the
Final ;OCPSF Rule. . . . .... ... ..... .
Data Retained from Data Sets 3 and 4 Following
BAT Toxic Pollutant Editing Criteria. ........
Explanation of BAT Toxic Pollutant Data Base
Performance Edits . . . .......
. '
Plant and Pollutant Data Retained in BAT Organic
Toxic Pollutant Data Base > for BAT Subcategory
One Limitations
Plant and Pollutant Data Retained in BAT Organic
Toxic Pollutant 'Data Base for BAT Subcategory
Two Limitations .... i ........ . . .. • • • •
Treatment Technologies for Plants in the Final BAT
Toxic Pollutant Data Base . • ...
BAT Toxic Pollutant Median of Estimated Long-Term
Averages for BAT Subcategory One and Two. . '. . . ." .
Priority Pollutants by Chemical Groups
Individual Toxic Pollutants Variability Factors
for BAT Subcategory One ......... .
Individual Toxic Pollutants Variability Factors
for BAT Subcategory Two . .' • • •
Page
VII-176
VII-176
VII-178.
. VII-179
VII-181
VII-184
. . '
VII-188
,
VII-189
1 1
VII-191
VII-199
VII-202
VII-208
VII-212
VII-220
VII-223
XXV
-------
Table
VII-68
LIST OF TABLES (Continued)
BAT Subcategory One and Two Long-Term Averages and
Variability Factors for Metals and Total Cyanide.
VII-226
VII-69 BAT Zinc Long-Term Averages and Variability Factors
for Rayon (Viscose Process) and Acrylic (Zinc
Chloride/Solvent Process) Fibers Plants VIII-229
VOLUME II
VIII-1 BPT Costing Rules ........ VIII-3
VIII-2 Generic Chemical Processes . VIII-8
VIII-3 "Trigger" Values Used as BAT Option II In-Plant
Costing Targets for Plants With End-of-Pipe
Biological Treatment In-Place . . . . . . . . . . . . VIII-10
VIII-4 BAT Long-Term Medians Used as Costing Targets for
Plants Without Biological Treatment In-Place. .... VIII-12
VIII-5 Pollutants to be Controlled Using In-Plant
Biological Treatment VIII-14
VIII-6 High Strippability Priority Pollutants Costed
Steam Stripping for BAT Option IIA and PSES IVA ... VIII-16
VIII-7 Medium Strippability Priority Pollutants Costed
for Steam Stripping for BAT Option IIA and
PSES Option IVA VIII-17
VIII-8 Medium Adsorpability Priority Costed for Activated
Carbon for BAT Option IIA and PSES Option IVA .... VIII-18
VIII-9 Low Adsorpability Priority Pollutants Costed for
Activated Carbon for BAT Option IIA and PSES
Option IVA VIII-19
VIII-10 High Strippability Priority Pollutants Costed for
Steam Stripping for BAT Option IIB and PSES
Option IIB VIII-20
VIII-11 Medium Strippability Priority Pollutants Costed r
for Steam Stripping for BAT Option IIB and
PSES Option IVB; VIII-21
VIII-12 Medium Adsorpability Priority Pollutants Costed [
for Activated Carbon for BAT Option IIB and
PSES Option IVB ...... VIII-22
xxvi
_
-------
LIST OF TABLES (Continued)
Table
VIII-13 Low Adsorpability Priority Pollutants Costed
for Steam Stripping for BAT Option IIB and
PSES Option IVB. ........ VIII-23
VIII-14 Overall Averages of the Average Ratio Values
(Process to Total Flow). . . . . . . ... . . . . . . VIII-25
VIII-15 Regulated Pollutants and LTMs for PSES Option IV ... VIII-27
VIII-16 Temperatures and Temperature Cost Factors Used
to Calculate Activated Sludge Cost and to
Adjust Biological Treatment Upgrade Costs. . . . . . VIII-30
VIII-17 Land Cost for Suburban Areas ... VIII-33
VIII-18 Summary of Land Cost in the United States. VIII-37
VIII-19 Activated Sludge Default and Replacement Data
for Unit Cost Items Used in Costing Exercise
CAPDET Model (1979) VIII-42
VIII-20 Activated Sludge K-Values and MLVSS Values
from 308 Questionnaires VIII-43
VIII-21 Activated Sludge Table of Reported 308
Questionnaire Data VIII-45
VIII-22 Activated Sludge Table of Reported Capital Cost
Per Gallon and O&M Cost per 1,000 Gallon VIII-46
VIII-23 Activated Sludge Comparison of CAPDET and
Reported Capital and O&M Costs (1982 Dollars). ... VIII-48
VIII-24 Activated Sludge Comparison of Reported and
CAPDET Detention Times (Td). ..... VIII-49
VIII-25 Activated Sludge Comparison of Reported and
and CAPDET O&M Costs (1982 Dollars) . VIII-50
VIII-26 Activated Sludge Comparison of Operation and
Maintenance Man-Hours. ... . . . . . . VIII-52
VIII-27 Activated Sludge Table of Reported Operating
and Maintenance Labor Rates (1982 Dollars) . . . . . VIII-54
=*• ' ' ' "
VIII-28 Activated Sludge Revised Land Requirements ...... VIII-55
VIII-29 Capital and Annual Costs of Biological
v Treatment Modifications for Activated Sludge
System Upgrades. . . VIII-58
.xxvai
-------
LIST OF TABLES (Continued)
Table
VIII-30 Product Mix of the Five Facilities Used in the
Development of the Capital Cost Curve for
Activated Sludge System Upgrades VIII-59
VIII-31 Current Influent and Effluent BOD5 Concen-
trations at the Five Facilities Used in the
Development of Capital Cost Curves for
Activated Sludge System Upgrades .... VIII-62
VIII-32 Project Capital and Operation and Maintenance (O&M)
Costs Associated with Activated Sludge
System Upgrades VIII-66
VTII-33 Summary of Chemically Assisted Clarification
Specifications VIII-68
VTII-34 Itemized Capital Costs for Chemically Assisted
Clarifiers VIII-69
VIII-35 Itemized Annual Operating Costs for Chemically
Assisted Clarifiers VTII-71
VIII-36 Benchmark Comparison VIII-75
VIII-37 Sumnfary of Filtration System Specifications VIII-79
VIII-38 Summary of Capital and O&M Costs for Filtration
Systems 1982 Dollars (March) VIII-80
VIII-39 Summary of Capital and O&M Costs for Polishing
Ponds VIII-85
VIII-40 Annual Operating Cost for Algae Control in
Polishing Ponds (1982 Dollars) VIII-90
i
VIII-41 Ten Treatment Systems With Polishing Ponds
In-Place (At Nine Plants) That Were Costed
Only for Copper Sulfate Addition ..... VTII-92
VIII-42 Summary of Capital and O&M Costs for Polymer
Addition Systems for Upgrading Secondary
Clarifiers VIII-93
VIII-43 Summary of Polymer Addition Costs for Six
Treatment Systems Selected for Secondary
Clarifier Upgrades VIII-94
xxviii
-------
LIST OF TABLES (Continued)
Table
VIII-44 Comparison of Predicted and Reported Capital
and O&M Costs for Steam Stripping
VIII-45 Priority Pollutants Divided Into Groups
According to Henry's Constant Values
VIII-46 Reported Steam Stripping Average Influent and
Effluent BAT from the 1983 Supplemental
Questionnaire
VIII-47 Steam Stripping Design Parameters for High
Henry's Law Constant Pollutants
VIII-48 Steam Stripping Design Parameters for Medium
Henry's Law Constant Pollutants. . . . . . . .
VIII-49 Steam Stripping Design Parameters for Low
Henry's Law Constant Pollutants
VIII-50 Steam Stripping Results for Removal of
Benzene (1982 Dollars) . . . . .... . . . .
VIII-51 Steam Stripping Results for Removal of
Hexachlorobenzene (1982 Dollars)
VIII-52 Equations for Determining Computerized Cost
Curves from Steam Stripping Results
(1982 Dollars)
VIII-53 Steam Stripping ($$) Overhead Disposal Cost
Estimates . . . . .
VIII-54 Steam Stripping Upgrade Costs
VIIB-55 Adjustments to CAPDET Default Data and Results
for Activated Carbon Systems ....
VIIIr56 Influent/Effluent Levels of Total Organic
*-• - Priority Pollutants of Biological Treatment
Systems for Typical Organic Chemical Plants. .
VIII-57 Summary of In-Plant Carbon Adsorption Capacities
- (Ibs of Pollutants Adsorbed/lb Carbon) ....
VIII-58 Carbon Usage Rate for Priority Pollutants
(In-Plant BAT Treatment) (Ibs of Pollutants
- Adsorbed/lb Carbon). .
VIII-59 Summary of In-Plant Carbon Adsorption Capacities
(Ibs of Pollutants Adsor,bed/lb Carbon) ....
VIII-96
VIII-99
VIII-100
VIII-102
VIII-104
VIII-106
VIII-108
VIII-109
VIII-110
VIII-117
VIII-120
VIII-122
VIII-125
VIII-127
VIII-130
VIII-131
XXIX
-------
LIST OF TABLES (Continued)
Table
VIII-60 Carbon Usage Rate for Priority Pollutants
(In-Plant PSES Treatment) (Ibs of Pollutants
Adsorbed/lb Carbon)
VIII-61 Summary of Carbon Adsorption Capacities (End-
of-Pipe) (Ibs of Pollutants Adsorbed/lb
Carbon)
VIII-62 Carbon Usage Rate for Priority Pollutants
(End-of-Pipe Treatment) (Ibs of Pollutants
Adsorbed/lb Carbon)
VIII-63 Granular Activated Carbon Equipment Cost Basis
In-Plant Carbon Treatment System Low Carbon
Adsorption Capacity
VIII-64 Granular Activated Carbon Equipment Cost Basis
In-Plant Carbon Treatment System Low Carbon
Adsorption Capacity
VIII-65 Granular Activated Carbon Equipment Cost Basis
(Erd-of-Pipe Treatment)
VIII-66 Total Capital and O&M Costs for Large In-Plant
Medium Carbon Adsorption Treatment Systems
(1982 Dollars)
VIII-67 Total Capital and O&M Costs for Large In-Plant
Low Carbon Adsorption Treatment Systems
(1982 Dollars)
VIII-68 Cost Estimate for Large End-of-Pipe Carbon
Treatment Systems (1982 Dollars)
VIII-69 Itemized Capital Cost for Small In-Plant and
End-of-Pipe Carbon Treatment Systems
(1982 Dollars)
VIII-70 Itemized O&M Cost for Small In-Plant Medium
Carbon Treatment Systems (1982 Dollars). . .
VIII-71 Itemized O&M Cost for Small In-Plant Low
Carbon Treatment Systems (1982 Dollars). . .
VIII-72 Itemized O&M Cost for Small End-of-Pipe
Carbon Treatment Systems (1982 Dollars). . .
VIII-73 Itemized Capital Costs for Coagulation/
Flocculation/Clarification Systems
VIII-133
VIII-134
VIII-135
VIII-136
VIII-137
VIII-138
VIII-140
VIII-141
VIII-142
VIII-153
VIII-154
VIII-155
VIII-156
VIII-165
xxx
-------
LIST OF TABLES (Continued)
Table
VIII-74
VIII-75
VIII-76
VIII-77
VIII-78
VIII-79
VIII-80
VIII-81
VIII-82
VIII-83
VIII-84
VIII-85
VIII-86
VIII-87
VIII-88
VIII-89
VIII-90
Itemized Annual Operating Costs for Coagulation/
Flocculation/Clarification Systems
Benchmark Comparison for Coagulation/
Flocculation/Clarification Systems .
Itemized Capital Costs for Sulfide Precipitation
Systems • • •
Annual Operating Costs for Sulfide Precipitation
Systems.
A Comparison of Annual Operating Cost for Lime
Precipitation Systems and Sulfide Precipitation
Systems
Chemical Precipitation Upgrade Costs •
Design Specifications for Cyanide Destruction
System . •
Total Capital and O&M Cost for Cyanide
Destruction Systems. . .
Comparison of Technology Costs for PSES Plants ....
Total Capital and O&M Cost for the In-Plant
Biological Treatment Control Systems
In-Plant Biological Treatment Land Requirements. . . .
Monitoring Frequencies .....
Number of Parameters and Fractions to be Analyzed. . .
Comparison of Annual Monitoring Cost (1982
Dollars) for Organic and Plastics Facilities
Using Analysis Methods 624/625 or 1624/1625
With Either a More Stringent or Less Stringent
Monitoring Frequency
Summary of Design Specifications for Belt Filter
Press Systems.
Itemized Capital Costs for Belt Filter Press
Systems
Itemized Annual Operating Cost for Belt Filter
Press Svstems
Page
VIII-170
VIII-171
VIII-175
VIII-176
VIII-179
VIII-181
VIII-183
VIII-184
VIII-188
VIII-189
VIII-194
VIII-200
VIII-201
VIII-204
VIII-207
VIII-208
VIII-211
xxxi
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LIST OF TABLES (Continued)
Table . D
Page
VIII-91 Summary of Fluidized Bed Incinerator System
Design Specifications VIII-214
VIII-92 Itemized Capital Costs for Fluidized Bed
Incinerator Systems „ VIII-215
VIII-93 Itemized Annual Operating Cost for Fluidized
Bed Incineration Systems VIII-218
VIII-94 Capital and O&M Costs for the Belt Filter Press
and Fluidized Bed Incineration Systems VIII-220
VIII-95 Annualized Cost for Sludge Handling Systems VIII-221
VIII-96 Parameters Used to Design and Cost Liners and
Monitoring VIII-226
VIII-97 Liner and Monitoring Well Equipment and
Installation Costs for Selected OCPSF Facilities . . VIII-228
VIII-98 Summary of Liner, Monitoring, and Administrative
RCRA Baseline Costs VIII-232
VIII-99 Summary of BPT, BAT, and PSES Compliance Costs
For Final Regulatory Options (1982 Dollars) VIII-233
VIII-100 Plants With No Cost VIII-234
VIII-101 Major Products by Process of the Organic
Chemicals Industry VIII-239
VIII-102 Major Products by Process of the Plastics/
Synthetic Fibers Industry VIII-247
VIII-103 Generic Chemical Processes VIII-250
VIII-104 Overview of Wastewater Studies Included in Raw
Wastewater Toxic Pollutant Loadings Calculations . . VIII-251
VIII-105 Phase II Screening - Product/Process and Other
Waste Streams Sampled at Each Plant VIII-255
VIII-106 BPT, BAT Option II, BAT Option III, and PSES
Toxic Pollutant Concentrations Used in Loadings. . . VIII-263
VIII-107 BAT Wastewater Toxic Pollutant Loadings VIII-271
VIII-108 PSES Wastewater Toxic Pollutant Loadings VIII-273
XXX11
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LIST OF TABLES (Continued)
Table
VIII-109
VIII-110
VIII-111
VIII-112
IX-1
IX-2
X-l
X-2
X-3
X-4
X-5
XII-1
Priority Pollutants Considered for Estimating
a Portion of the OCPSF Industry Air Emissions
from Wastewater Treatment Systems for 32
Selected VOCs
Volatilization from Pre-Biological Unit Operations
for Selected VOCs
BAT Toxic Pollutants Air Emission Loadings
(Ibs/year) • •
PSES Toxic Pollutant Air Emission Loadings
(Ibs/year)
BPT Effluent Limitations and NSPS by Subcategory
(mg/1)
Derivation of BPT Limitations for a Hypothetical
Plant •
BAT Effluent Limitations and NSPS for the End-of-
Pipe Biological Treatment Subcategory •
BAT Effluent Limitations and NSPS for the Non-
End-of-Pipe Biological Treatment Subcategory
Cyanide-Bearing Waste Streams (by product/
process) • • • •
Noncomplexed Metal-Bearing Waste Streams for
Chromium, Copper, Lead, Nickel, and Zinc
(by product/process) . ... . . • • • • •
Complexed Metal Bearing Waste Streams for
Chromium, Copper, Lead, Nickel, and Zinc
(by product/process) • •
Pretreatment Standards for Existing and New
Sources (PSES and PSNS). . . . . . • • • •
VIII-277
VIII-281
VIII-284
VIII-285
IX-8
IX-11
X-6
X-8
X-13
X-15
X-26
XII-4
xxxiii
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SECTION I
INTRODUCTION
This document describes the technical development of the U.S.
Environmental Protection Agency's ,(EPA's) promulgated effluent limitations
guidelines and standards that limit the discharge of pollutants into navigable
waters and publicly owned treatment wbrks (POTWs) by existing and new sources
in the organic chemicals, plastics, and synthetic fibers (OCPSF) point source
category. The regulation establishes effluent limitations guidelines
attainable by the application of the "best practicable control technology
currently available" (BPT) and the "best available technology economically
achievable" (BAT), pretreatment standards applicable to existing and new
discharges to POTWs (PSES and PSNS, respectively), and new source performance
standards (NSPS) attainable by the application of the "best available
demonstrated technology."
A. LEGAL AUTHORITY
This regulation was promulgated under the authority of Sections 301, 304,
306, 307, 308, 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) also
referred to as "the Act" or "CWA." It was also promulgated in response to the
Settlement Agreement in Natural Resources Defense Council, Inc. v. Train,
8 ERG 2120 (D.D.C. 1976), modified, 12 ERC 1833 (D.D.C. 1979), modified by
Orders dated October 26, 1982; August 2, 1983; January 6, 1984; July 5, 1984;
January 7, 1985; April 24, 1986; and January 8, 1987.
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 was required to issue effluent limitations guidelines, pretreat-
ment standards, and NSPS for industrial dischargers.
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In addition to these regulations for designated industrial categories,
EPA was required to promulgate effluent limitations guidelines and standards
applicable to all discharges of toxic pollutants. The Act included a time-
table for issuing these standards. However, EPA was unable to meet many of
the deadlines and, as a result, in 1976, it was sued by several environmental
groups. In settling this lawsuit, EPA and the plaintiffs executed a "Settle-
ment Agreement" that was approved by the Court. This agreement required EPA
to develop a program and adhere to a schedule for controlling 65 "priority"
toxic pollutants and classes of pollutants. In carrying out this program, EPA
was required to promulgate BAT effluent limitations guidelines, pretreatment
standards, and NSPS for a variety of major industries, including the OCPSF
industry.
Many of the basic elements of the Settlement Agreement were incorporated
into the Clean Water Act of 1977. Like the Agreement, the Act stressed con-
trol of toxic pollutants, including the 65 priority toxic pollutants and
classes of pollutants.
Under the Act, the EPA is required to establish several different kinds
of effluent limitations guidelines and standards. These are summarized
briefly below.
1. Best Practicable Control Technology Currently Available (BPT)
BPT effluent limitations guidelines are generally based on the average of
the best existing performance by plants of various sizes, ages, and unit pro-
cesses within the category or subcategory for control of familiar (e.g., con-
ventional) pollutants, such as BOD5, TSS, and pH.
In establishing BPT effluent limitations guidelines, EPA considers the
total cost in relation to the effluent reduction benefits, age of equipment
and facilities involved, processes employed, process changes required,
engineering aspects of the control technologies, and nonwater quality
environmental impacts (including energy requirements). The Agency balances
the category-wide or subcategory-wide cost of applying the technology against
the effluent reduction benefits.
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2. Best Available Technology Economically Achievable (BAT)
BAT effluent limitations guidelines, in general, represent the best
existing performance in the category or subcategory. The Act establishes BAT
as the principal national means of controlling the direct discharge of toxic
and nonconventional pollutants to navigable waters.
In establishing BAT, the Agency considers the age of equipment and facil-
ities involved, processes employed, engineering aspects of the control
technologies, process changes, cost of achieving such effluent reduction, and
nonwater quality environmental impacts.
3. Best Conventional Pollutant Control Technology (BCT)
The 1977 Amendments to the Clean Water Act added Section 301(b)(2)(E),
establishing "best conventional pollutant control technology" (BCT) for the
discharge of conventional pollutants from existing industrial point sources.
Section 304(a)(4) designated the following as conventional pollutants: BODg,
TSS, fecal coliform, pH, and any additional pollutants defined by the Admin-
istrator as conventional. The Administrator designated oil and grease a con-
ventional 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 the BCT effluent limitations guidelines be
assessed in light of a two part "cost-reasonableness" test [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 costs to 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 limitations
are "reasonable" under both tests before establishing them as BCT. In no case
may BCT be less stringent than BPT.
EPA has promulgated a methodology for establishing BCT effluent limita-
tions guidelines (51 FR 24974, July 8, 1986).
1-3
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4. New Source Performance Standards (NSPS)
NSPS are based on the performance of the best available demonstrated
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 best available demonstrated control technology for
all pollutants (i.e., toxic, conventional, and nonconventional).
5. 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
POTWs. The Clean Water Act requires pretreatment standards for pollutants
that pass through POTWs or interfere with either the POTW's treatment process
or chosen sludge disposal method. The legislative history of the 1977 Act
indicates that pretreatment standards are to be technology-based and analogous
to the BAT effluent limitations guidelines for removal of toxic pollutants.
For the purpose of determining whether to promulgate national category-wide
PSES and PSNS, EPA generally determines that there is pass through of pollu-
tants, and thus a need for categorical standards if the nationwide average
percentage of pollutants 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 serve as the framework for
categorical pretreatment standards, are found at 40 CFR Part 403. (Those
regulations contain a definition of pass through that addresses localized
rather that national instances of pass through and does not use the percent
removal comparison test described above (52 FR 1586, January 14, 1987).)
6- Pretreatment Standards for New Sources (PSNS)
Like PSES, PSNS are designed to prevent the discharge of pollutants that
pass through, interfere with, or are otherwise incompatible with the operation
of a POTW. PSNS are to be issued at the same time as NSPS. New indirect
dischargers, like new direct dischargers, have the opportunity to incorporate
in their plant the best available demonstrated technologies. The Agency con-
siders the same factors in promulgating PSNS as it considers in promulgating
NSPS.
1-4
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B. HISTORY OF OCPSF RULEMAKING EFFORTS
EPA originally promulgated effluent limitations guidelines and standards
for the organic chemicals manufacturing industry in two phases. Phase I,
covering 40 product/processes (a product that is manufactured by the use of a
particular process — some products may be produced by any of several proces-
ses), was promulgated on April 25!, 1974 (39 FR 14676). Phase II, covering 27
additional product/processes, was promulgated on January 5, 1976 (41 FR 902).
The Agency also promulgated effluent limitations guidelines and standards for
the plastics and synthetic fibers industry in two phases. Phase I, covering
13 product/processes, was promulgated on April 5, 1974 (39 FR 12502). Phase
II, covering eight additional product/processes, was promulgated on January
23, 1975 (40 FR 3716).
These regulations were challenged, and on February 10, 1976, the Court in
Union Carbide v. Train, 541 F.2d 1171 (4th Cir. 1976), remanded the Phase I
organic chemicals regulation. EPA also withdrew the Phase II organic chem-
icals regulation on April 1, 1976 (41 FR 13936). However, pursuant to an
agreement with the industry petitioners, the regulations for butadiene manu-
facture were left in place. The .Court also remanded the Phase I plastics and
synthetic fibers regulations in FMC Corp. v. Train, 539 F.2d 973 (4th Cir.
1976) and in response EPA withdrew both the Phase I and II plastics and
synthetic fibers regulations on August 4, 1976 (41 FR 32587) except for the pH
limitations, which had not been addressed in the lawsuit. Consequently, only
the regulations covering butadiene manufacture for the organic chemicals
industry and the pH regulations for the plastics and synthetic fibers industry
have been in effect to date. These regulations were superseded by the regula-
tions described in this report.
In the absence of promulgated, effective effluent limitations guidelines
and standards, OCPSF direct dischargers have been issued National Pollutant
Discharge Elimination System (NPDES) permits on a case-by-case basis using
best professional judgment (BPJ), as provided in Section 402(a)(l) of the CWA.
'•'••'•• •' Subsequent to the withdrawal/suspension of the national regulations cited
above, studies and data-gathering were initiated in order to provide a basis
1-5
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for issuing effluent limitations guidelines and standards for this industry.
These efforts provided a basis for the March 21, 1983 proposal (48 FR 11828);
the July 17, 1985 (50 FR 29071), October 11, 1985 (50 FR 41528), and December
8, 1986 (51 FR 44082) post-proposal notices of availability of information;
and the final regulation.
This report presents a summary of the data collected by the Agency since
1976, the data submitted by the OCPSF industry in response to the Federal
Register notices cited above, and the analyses used to support the promulgated
regulations. Section II presents a summary of the findings and conclusions
developed in this document as well as the promulgated regulations. Sections
III through VIII present the technical data and the supporting analyses used
as the basis for the promulgated regulations, and Sections IX through XIII
include the rationale and derivation of the national effluent limitations and
standards. Detailed data displays and analyses are included in the
appendices.
1-6
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SECTION II
SUMMARY AND CONCLUSIONS
A. OVERVIEW OF THE INDUSTRY
The organic chemicals, plastics, and synthetic fibers (OCPSF) industry is
large and diverse, and many plants in the industry are highly complex. The
industry includes approximately 750 facilities whose principal or primary
production activities are covered under the OCPSF regulations. There are
approximately 250 other plants that are secondary producers of OCPSF products
(i.e., OCPSF production is ancillary to their primary production activities).
Thus, the total number of plants to be regulated totally or in part by the
OCPSF industry regulation is approximately 1,000. Secondary OCPSF plants may
be part of the other chemical producing industries such as the petroleum
refining, inorganic chemicals, pharmaceuticals, and pesticides industries as
well as the chemical formulation industries such as the adhesives and
sealants, paint and ink, and the plastics molding and forming industries.
Although over 25,000 different organic chemicals, plastics, and synthetic
fibers are manufactured, less than half of these products are produced in
excess of 1,000 pounds per year.
Some plants produce chemicals in large volumes while others produce only
small volumes of "specialty" chemicals. Large volume production tends to
utilize continuous processes. Continuous processes are generally more effi-
cient than batch processes in minimizing water use and optimizing the consump-
tion of raw materials.
Different products are made by varying the raw materials, the chemical
reaction conditions, and the chemical engineering unit processes. The
products being manufactured at a single large chemical plant can vary on a
weekly or even daily basis. Thus, a single plant may simultaneously produce
many different products using a variety of continuous and batch operations,
and the product mix may change on a weekly or daily basis. /
II-l
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A total of 940 facilities (based on 1982 production) are included in the
technical and economic studies used as a basis for this regulation. Approxi-
mately 76 percent of these facilities are primary OCPSF manufacturers (over
50 percent of their total plant production involves OCPSF products), and
approximately 24 percent of the facilities are secondary OCPSF manufacturers
that produce mainly other types of products. An estimated 32 percent of the
plants are direct dischargers; about 42 percent discharge indirectly to
publicly owned treatment works (POTWS); and the remaining facilities
(26 percent) are either zero or alternative dischargers, or their discharge
status is unknown. The estimated average daily process wastewater discharge
per plant is 1.31 millions of gallons per day (MGD) for direct dischargers and
0.25 HGD for indirect dischargers. The non-discharging plants use dry
processes, reuse their wastewater, or dispose of their wastewater by deep well
injection, incineration, contract hauling, or by means of evaporation and
percolation ponds.
As a result of the wide variety and complexity of raw materials and
processes used and of products manufactured in the OCPSF industry, an excep-
tionally wide variety of pollutants are found in the wastewaters of this
industry. This includes conventional pollutants (pH, BOD5, TSS, and oil and
grease); an unusually wide variety of toxic priority pollutants (both metals
and organic compounds); and a large number of nonconventional pollutants.
Many of the toxic and nonconventional pollutants are organic compounds
produced by the industry for sale. Others are created by the industry as
by-products of their production operations. This study focused on the
conventional pollutants and on the 126 priority pollutants.
To control the wide variety of pollutants discharged by the OCPSF
industry, OCPSF plants use a broad range of in-plant controls, process
modifications, and end-of-pipe treatment techniques. Most plants have
implemented programs that combine elements of both in-plant control and
end-of-pipe wastewater treatment. The configuration of controls and
technologies differs from plant to plant, corresponding to the differing mixes
of products manufactured by different facilities. In general, direct
dischargers treat their wastes more extensively than indirect dischargers.
II-2
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The predominant end-of-pipe control technology for direct dischargers in
the OCPSF industry is biological treatment. The chief forms of biological
treatment are activated sludge and aerated lagoons. Other systems, such as
extended aeration and trickling filters, are also used, but less extensively.
All of these systems reduce biochemical oxygen demand (BOD5) and total
suspended solids (TSS) loadings, and in many instances, incidentally remove
toxic and nonconventional pollutants. Biological systems biodegrade some of
the organic pollutants, remove bio-refractory prganics and metals by sorption
into the sludge, and strip some volatile organic compounds (VOCs) into the
air. Well-designed biological treatment systems generally incorporate
secondary clarification unit operations to ensure adequate control of solids.
Other end-of-pipe treatment technologies used in the OCPSF industry
include neutralization, equalization, polishing ponds, filtration, and carbon
adsorption. While most direct dischargers use these physical/chemical
technologies in conjunction with end-of-pipe biological treatment, at least
71 direct dischargers use only physical/chemical treatment.
In-plant control measures employed at OCPSF plants include water
reduction and reuse techniques, chemical substitution, and process changes.
Techniques to reduce water use includ.e the elimination of water use where
practicable, and the reuse and recycling of certain streams, such as reactor
and floor washwater, surface runoff, scrubber effluent, and vacuum seal
discharges. Chemical substitution is utilized to replace process chemicals
possessing highly toxic or refractory properties with others that are less
toxic or more amenable to .treatment. Process changes include various measures
that reduce water use, waste discharges, and/or waste loadings while improving
process efficiency. Replacement of barometric condensers with surface
condensers, replacement of steam jet ejectors with vacuum pumps, recovery of
product or by-product by steam stripping, distillation, solvent extraction or
recycle, oil-water separation, and carbon adsorption, and the addition of
spill control systems are examples of process changes that have been
successfully employed in the OCPSF industry to reduce pollutant loadings while
improving process efficiencies.
II-3
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Another type of control widely used in the OCPSF industry is physical/
chemical in-plant control. This treatment technology is generally used
selectively on certain process wastewaters to recover products or process
solvents, to reduce loadings that may impair the operation of the biological
system, or to remove certain pollutants that are not treated sufficiently by
the biological system. In-plant technologies widely used in the OCPSF
industry include sedimentation/clarification, coagulation, flocculation,
equalization, neutralization, oil-water separation, steam stripping, distil-
lation, and dissolved air flotation.
Some OCPSF plants also use physical/chemical treatment after biological
treatment. Such treatment is usually intended to reduce solids loadings that
are discharged from biological treatment systems. The most common post-
biological treatment unit operations are polishing ponds and multimedia,
•filtration. These unit operations are sometimes used in lieu of secondary
clarification or to improve upon substandard biological treatment systems. A
few plants also use activated carbon after biological treatment as a final
"polishing" step.
At approximately 9 percent of the direct discharging plants surveyed,
either no treatment is provided or no treatment beyond equalization and/or
neutralization is provided. At another 19 percent, only physical/chemical
treatment is provided. The remaining 72 percent utilize biological treatment.
Approximately 41 percent of biologically treated effluents are further treated
by polishing ponds, filtration, or other forms of physical/chemical control.
At approximately 39 percent of the indirect discharging plants surveyed,
either no treatment is provided or no treatment beyond equalization and/or
neutralization is provided. At another 47 percent, some physical/chemical
treatment is provided. The remaining 14 percent utilize biological treatment.
Approximately 22 percent of biologically treated effluents are further treated
by polishing ponds, filtration, or other forms of physical/chemical control.
Economic data provided in response to questionnaires completed pursuant
to Section 308 of the CTA indicate that OCPSF production in 1982 totaled 185
billion pounds and that the quantity shipped was 151 billion pounds. The
II-4
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corresponding value of shipments equaled $59 billion, while employment in the
industry totaled 187,000 in 1982. In that same, year a total of 455 firms
operated the 940 facilities referenced above.
B. CONCLUSIONS
1. Applicability of the Promulgated Regulation
The OCPSF regulation applies to process vastewater discharges from
existing and new organic chemicals, plastics, and synthetic fibers (OCPSF)
manufacturing facilities. OCPSF process wastewater discharges are defined as
discharges from all establishments or portions of establishments that manufac-
ture products or product groups listed in the applicability sections of the
promulgated regulation (see Appendix III-A of this report), and are included
within the following U.S. Department of Commerce, Bureau of the Census,
Standard Industrial Classification (SIC) major groups:
• SIC 2865 - Cyclic Crudes and Intermediates, Dyes, and Organic Pigments
• SIC 2869 - Industrial Organic Chemicals, not Elsewhere Classified
• SIC 2821 - Plastic Materials, Synthetic Resins, and Nonvulcanizable
Elastomers
• SIC 2823 - Cellulosic Man-Made Fibers
• SIC 2824 - Synthetic Organic Fibers, Except Cellulosic.
The regulations apply to plastics molding and forming processes only when
plastic resin manufacturers mold or form (e.g., extrude and pelletize) crude
intermediate plastic material for shipment off-site. This regulation also
applies to the extrusion of fibers. Plastic molding and forming processes
other than those described above are regulated by the plastics molding and
forming effluent guidelines and standards found in 40 CFR Part 463.
The regulations also apply to wastewater discharges from OCPSF research
andidevelopment, pilot plant, technical service, and laboratory bench-scale
operations if such operations are conducted in conjunction with and related to
existing OCPSF manufacturing activities at the plant;site. ;
II-5
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The regulations do not apply to discharges resulting from the manufacture
of OCPSF products if the products are included in the following SIC subgroups,
and have in the past been reported by the establishment under these subgroups
and not under the OCPSF SIC groups listed above:
• SIC 2843085 - Bulk Surface Active Agents
• SIC 28914 - Synthetic Resin and Rubber Adhesives
• Chemicals and Chemical Preparations, not Elsewhere Classified
- SIC 2899568 - sizes, all types
- SIC 2899597 - other industrial chemical specialties, including
fluxes, plastic wood preparations, and embalming fluids
• SIC 2911058 - Aromatic Hydrocarbons Manufactured from Purchased
Refinery Products
• SIC 2911632 - Aliphatic Hydrocarbons Manufactured from Purchased
Refinery Products.
The regulations are not applicable to any discharges for which a
different set of previously promulgated effluent limitations guidelines and
standards in 40 CFR Parts 405 through 699 apply, unless the facility reports
OCPSF production under SIC codes 2865, 2869, or 2821, and the facility's OCPSF
wastewater is treated in a separate treatment system or discharged separately
to a POTW. They also do not apply to any process wastewater discharges from
the manufacture of organic chemical compounds solely by extraction from plant
and animal raw materials or by fermentation processes.
2. BPT
The technology basis for the promulgated effluent limitations for each
BPT subcategory consists of biological treatment, which usually involves
either activated sludge or aerated lagoons, followed by clarification (and
preceded by appropriate process controls and in-plant treatment to ensure that
the biological system may be operated optimally). Many of the direct dis-
charge facilities have installed this level of treatment.
II-6
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The Agency designated seven subcategory classifications for the OCPSF
category to be used for establishing BPT limitations. These subcategory
classifications are 1) rayon fibers .(viscose process only); 2) other fibers
(SIC 2823, .except rayon, and 2824);' 3) thermoplastics (SIC 28213); 4 thermo-
sets (SIC 28214); 5) commodity organic chemicals (SIC 2865 and 2869); 6) bulk
organic chemicals (SIC 2865 and 2869); and 7) specialty organic chemicals
(SIC 2865 and 2869). The specific products and product groups within each
subcategory are listed in Appendix III-A.
While some plants may have production that falls entirely within one of
the seven subcategory classifications, most plants have production that is
divided among two or more subcategories. In applying the subcategory
limitations set forth in the regulation, the permit writer will use what is
essentially a building-block approach that takes into consideration applicable
subcategory characteristics based upon the proportion of production quantities
within each subcategory at the plant. Production characteristics are
reflected explicitly in the plant's limitations through the use of this
approach.
The long-term median effluent BOD5 concentrations were calculated for
each subcategory through the use of a mathematical equation that estimates
effluent BOD5 as a function of the proportion of the production of each
subcategory at each facility. The coefficients of this equation were
estimated from reported plant data using standard statistical regression
methods. Plants were selected for developing BPT BOD5 limitations only if
they achieved at least 95 percent removal for BOD5 or a long-term average
effluent BOD5 concentration at or below 40 mg/1. The long-term median
effluent TSS concentrations were calculated for each subcategory through the
use of a mathematical equation that estimates effluent TSS as a function of
effluent BOD5. The coefficients of this equation were also estimated from
reported plant data using standard statistical regression methods. Plants
were selected for developing BPT TSS limitations if they passed the BOD5 edit
and also achieved a long-term average effluent TSS concentration at or below
100 mg/1. This statistical analysis is described in detail in Sections IV and
VII.
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"Maximum for monthly average" and "maximum for any one day" effluent
, limitations were determined by multiplying long-term median effluent concen-
trations by appropriate variability factors that were calculated through
statistical analysis of long-term BOD5 and TSS daily data. This statistical
analysis is described in detail in Section VII.
The BPT subcategory BOD5 and TSS effluent limitations are presented in
Table II-l; pH, also a regulated parameter, must remain within the range of
6.0 to 9.0 at all times. EPA has determined that the BPT effluent limitations
shall apply to all' direct discharge point sources.
3. BCT
The Agency did not promulgate BCT effluent limitations as part of this
regulation. BCT is reserved until a future BCT analysis is completed.
4. BAT ,
The Agency promulgated BAT limitations for two subcategories. These
subcategories are largely determined by conventional pollutant raw waste
characteristics. The end-of-pipe biological treatment subcategory (BAT Sub-
category One) includes plants that have or will install biological treatment
to comply with BPT limits. The non-end-of-pipe biological treatment sub-
category (BAT Subcategory Two) includes plants that either generate such low
levels of BOD5 that they do not need to utilize biological treatment, or that
choose to use physical/chemical treatment to comply with the BPT limitations.
The Agency has concluded that, within each subcategory, all plants can treat
priority pollutants to the levels established for that subcategory.
Different limits are being established for these two subcategories.
Biological treatment is an integral part of the model BAT treatment technology
for the end-of-pipe biological treatment subcategory; it achieves incremental
removals of some priority pollutants beyond the removals achieved by in-plant
treatment without end-of-pipe biological treatment. In addition, the Agency
is establishing two different limitations for zinc. One is based on data
collected from rayon manufacturers and acrylic fibers manufacturers using the
zinc chloride/solvent process. This limitation applies only to those plants
II.-8
-------
TABLE XI-1.
BPT EFFLUENT LIMITATIONS AND NSPS BY SUBCATEGORY (rag/1)
Subcategory
Rayon Fibers
Other Fibers
Thermoplastic Resins
Thermosetting Resins
Commodity Organic Chemicals
Bulk Organic Chemicals
Specialty Organic Chemicals
Effluent Limitations1
Maximum for
Monthly Average
BOD5 TSS
24
18
24
61
30
34
45
40
36
40
67
46
49
57
Maximum
Any One
BOD5
64
48
64
;163
80
92
120
for
Pay
TSS
130
115
130
216
149
159
183
xpH, also a regulated parameter, shall remain within the range of 6.0 to 9>0,
at all times.
2Product and product group listings for each subcategory are contained in
Appendix III-A.
II-9
-------
that use the viscose process to manufacture rayon and the zinc chloride/
solvent process to manufacture acrylic fibers. The other zinc limitation is
based on the performance of chemical precipitation technology used in the
metal finishing point source category, and applies to all plants other than
those described above.
The concentration-based BAT effluent limitations hinge on the performance
of the end-of-pipe treatment component (biological treatment for the end-6f-
pipe biological treatment subcategory and physical/chemical treatment for the
non-end-of-pipe biological treatment subcategory) plus in-plant control
technologies that remove priority pollutants prior to discharge to the
end-of-pipe treatment system.
The in-plant technologies include steam stripping to remove selected
volatile and semivolatile priority pollutants, such as toluene, benzene,
carbon tetrachloride, and the dichlorobenzenes; activated carbon for selected
base/neutral priority pollutants, such as 4-nitrophenol and 4,6-dinitro-
o-cresolj hydroxide precipitation for metals; alkaline chlorination for
cyanidej and in-plant biological treatment for selected acid and base/neutral
priority pollutants, such as phenol, the phthalate esters, and the polynuclear
aromatics.
The limits are based on priority pollutant data from both OCPSF and other
industry plants with well-designed and well-operated BAT model treatment
technologies in place. The organic priority pollutant limits are derived from
selected data within the Agency's verification study, cooperative EPA/CMA
study, the 12-Plant Study, and the industry-supplied data base. Except as
noted above, the cyanide and metal priority pollutant limits are derived from
the metal finishing industry data base. The organic priority pollutant limits
apply at the end-of-pipe process wastewater discharge point. There are no
in-plant limitations established for volatile organic priority pollutants.
However, the cyanide and metal limitations apply only to the process waste-
water flow from cyanide-bearing and metal-bearing waste streams. Compliance
for cyanide and metals could be monitored in the plant or, after accounting
for dilution by noncyanide- and nonmetal-bearing process wastewater and
nonprocess wastewater, at the outfall.
11-10
-------
Derivation of the limitations is detailed in Section VII. "Maximum for
Monthly Average" and "Maximum for Any One Day" limitations have been
calculated for each regulated pollutant. Effluent limitations have been
established for 63 pollutants for the end-of-pipe biological treatment
subcategory and 59 pollutants for the non-end-of-pipe biological treatment
subcategory; these limitations are listed in Tables II-2 and II-3,
respectively.
In the final rule, EPA has decided that each discharger in a subcategory
will be subject to the effluent limitations for all pollutants regulated for
that subcategory. Once a pollutant is regulated in the OCPSF regulation, it
must also be limited in the NPDES permit issued to direct dischargers (see
Sections 301 and 304 of the Act; see also 40 CFR Part 122.44(a)). EPA
recognizes .that, guidance on appropriate monitoring requirements for OCPSF ,
plants would be useful, particularly to assure that monitoring will not be
needlessly required for pollutants that are not likely to be discharged at a
plant. EPA intends to publish guidance on OCPSF monitoring in the near
future. This guidance wi;ll address the issues of compliance monitoring in
general, of initially determining which pollutants should be subject only to
infrequent monitoring based on a conclusion that they are unlikely to be
discharged, and of determining the appropriate flow upon which to derive
mass-based permit requirements.
,, ,EPA has determined that this technology basis is the best available
technology economically achievable ,for all plants except for a subset,of small
facilities. For plants whose annual OCPSF production is less than,or equal to
5 million pounds, EPA has concluded that the BAT effluent limitations are not
economically achievable. For these plants, EPA has set BAT equal to BPT.
5. . NSPS : . -.. .• . ' • . , • • ••..-. ; •- • v .''•.•:""•"••
'EPA promulgated new source performance standards (NSPS) on the basis of
the::best available demonstrated technology. NSPS are established for convert
tional pollutants (BOD5, TSS, and pH) on the basis of BPT model treatment
technology; Priority pollutant limits are based on BAT model treatment
technology.
11-11
-------
TABLE II-2.
BAT EFFLUENT LIMITATIONS AND NSPS FOR THE
END-OF-PIPE BIOLOGICAL TREATMENT SUBCATEGORY
Pollutant
Number
1
3
4
6
7
8
9
10
11
12
13
14
16
23
24
25
26
27
29
30
31
32
33
34
35
36
38
39
42
44
45
52
55
56
57
58
59
60
65
66
68
70
Pollutant Name
Acenaphthene
Acrylonitrile
Benzene
Carbon Tetrachloride
Chlorobenzene
1,2, 4-Trichlorobenzene
Hexachlorobenzene
1 , 2-Dichloroethane
1,1,1-Trichloroethane
Hexachloroe thane
1-1-Dichloroethane
1,1, 2-Trichloroethane
Chloroe thane
Chloroform
2-Chlorophenol
1 , 2-Di chlorobenzene
1 , 3-rDichlorobenzene
1 , 4-Dichlorobenzene
1 , 1-Dichloroethylene
1, 2-Trans-dichloroethylene
2,4-Dichlorophenol
1 , 2-Dichloropropane
1 , 3-Dichloropropene
2 , 4-Dimethylphenol
2,4-Dinitrotoluene
2 , 6-Dini tro toluene
Ethylbenzene
Fluoranthene
Bis(2-Chloroisopropyl)ether
Methylene Chloride
Methyl Chloride
Hexachlorobutadiene
Naphthalene
Nitrobenzene
2-Ni trophenol
4-Nitrophenol
2 , 4-Dini trophenol
4, 6-Dini tro-o-cresol
Phenol
Bis(2-ethylhexyl)phthalate
Di-n-butyl phthalate
Diethyl phthalate
BAT Effluent
Maximum for
Any One Day
59
242
136
38
28
140
28
211
54
54
59
54
268
46
98
163
44
28
25
54
112
230
44
36
285
641
108
68
757
89
190
49
59
68
69
124
123
277
26
279
57
203
Limitations and NSPS1
Maximum for
Monthly Average
22
96
37
18
15
68
15 .
68
21
21
22
'21
104
21
31
77
31
15
16
21
39
153
29
18
113
255
32
25
301
40
86
20
22
27
41
72
71
78
15
103
27
81
11-12
-------
TABLE II.-2.
BAT EFFLUENT LIMITATIONS AND NSPS FOR THE
END-OF-PIPE BIOLOGICAL TREATMENT SUBCATEGORY (Continued)
BAT Effluent Limitations and NSPS1
Pollutant
Number
71
72
73
74
75
76
77
78
80
81
84
85
86
87
88
119
120
121
122
124
128
Pollutant Name
Dimethyl phthalate
Benzo(a)anthracene
Benzo(a)pyrene
3,4-Benzofluoranthene
Benzo(k) f luoranthene
Chrysene
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride
Total Chromium
Total Copper
Total Cyanide
Total Lead
Total Nickel
Total Zinc2'4
Maximum for
Any One Day
47
59
61
61
59
59
59
59
59 .
59
67
56
80
54
268
2,770 ,
3,380
1,200
690
3,980
2,610
Maximum for
Monthly Average
19
22
,23
23
: 22
22
22
22
22
22
25
22
26
21
104
1,110
1,450
420
320
1,690
1,050
All units are micrograms per liter.
2Metals limitations apply only to noncomplexed metal-bearing waste streams,
including those listed in Table X-4. Discharges of chromium, copper, lead,
nickel, and zinc from "complexed metal-bearing process wastewater," listed in
Table X-5, are not subject to these limitations.
3Cyanide limitations apply only to cyanide-bearing waste streams, including
those listed in Table X-3.
4Total zinc limitations and standards for rayon fiber manufacture by the
viscose process and acrylic fiber manufacture by the zinc chloride/solvent
process are 6,796 ug/1 and 3,325 ug/1 for Maximum for Any One Day and Maximum
for Monthly Average, respectively.
11-13
-------
TABLE II-3.
BAT EFFLUENT LIMITATIONS AND NSPS FOR THE
NON-END-OF-PIPE BIOLOGICAL TREATMENT SUBCATEGORY
Pollutant
Number
1
3
4
6
7
8
9
10
11
12
13
14
16
23
25
26
27
29
30
32
33
34
38
39
42
44
45
52
55
56
57
58
59
60
65
66
68
70
Pollutant Name
Acenaphthene
Acrylonitrile
Benzene
Carbon Tetrachloride
Chlorobenzene
1,2, 4-Tri chlorobenzene
Hexachlorobenzene
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Hexachloroethane
1-1-Dichloroethane
1,1, 2-Trichloroethane
Chloroethane
Chloroform
1 , 2-Dichlorobenzene
1 , 3-Di chlorobenzene
1,4-Dichlorobenzene
1, 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
1 , 2-Dichloropropane
1 , 3-Dichloropropene
2,4-Dimethylpheriol
Ethylbenzene
Fluoranthene
Bis (2-Chloroisopropyl) ether
Methylene Chloride
Methyl Chloride
Hexachlorobutadiene
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2 , 4-Dini trophenol
4 , 6-Dini tro-o-cresol
Phenol
Bis(2-ethylhexyl)phthalate
Di-n-butyl phthalate
Diethyl phthalate
BAT Effluent
Maximum for
Any One Day
, 47
232
134
380
380
794
794
574
59
794 .
59
127
295
325
794
380
380
60
66
794
794
47
380
54
794
170
295
380
47
6,402
231
576
4,291
277
47
258
43
113
Limitations and NSPS1
Maximum for
Monthly Average
19
94
57
142
142
196
196
180
22
196
22
32
110
111
196
142
J-*ri*
142
J.*T£>
22
25
196
196
19
142
22
196
36
110
142
19
i
2.237
£* p £, J /
65
\J *J
162
1,207
78
/ \J
19 ";
•*• *f
95 ;
20
£j\J
46
11-14
-------
TABLE II-3.
BAT EFFLUENT LIMITATIONS AND NSPS FOR THE
NON-END-OF-PIPE BIOLOGICAL TREATMENT SUBCATEGORY (Continued)
BAT Effluent Limitations and NSPS1
Pollutant
Number
- 71
72
73
74
75
76
77
78
80
81
84
85
86
87
88
119
120
121
122
124
128
Pollutant Name
Dimethyl phthalate
Benzo(a)anthracene
Benzo(a)pyrene
3 , 4-Benzof luoranthene
, Benzo(k)f luoranthene
Chrysene
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride2
Total Chromium
Total Copper
Total Cyanide
Total Lead
Total Nickel^
Total Zinc2'
Maximum
Any One
47
47
48
48
47
47
47
47
47
47
48
164
74
69
172
2,770
3,380
1,200:
690
3,980
2,610
for Maximum for
Day Monthly Average
19
19
20
20
19
19
19
19
19
19
; 20
IT ri
52
28
' 26
97
1,110
1,450
420
320
1,690
1,050
units are micrograms per,liter. ,
2Metals limitations apply only to nbncomplexed metal-bearing waste streams,
including those listed in Table X-4. Discharges of chromium, copper, lead,
nickel, and zinc from "complexed metal-bearing process wastewater," listed in
Table X-5, are not subject to these limitations. , .
3Cyanide limitations apply only to cyanide-bearing waste streams, including
those listed in Table X-3. . , ,
4Total zinc limitations and standards for rayon fiber manufacture by the ;
viscose process and acrylic fiber manufacture by the zinc,chloride/solvent
process are 6,796 ug/1 and 3,325; ug/1 for Maximum for Any One Day and Maximum
for Monthly Average, respectively. :
11-15
-------
The Agency issued conventional pollutant new source standards for the
same seven subcategories for which BPT limits were established. These
standards are equivalent to the limits established for BPT shown in
Table II-l. Priority pollutant new source standards are applied to new sources
according to the same subcategorization scheme applicable under BAT. The set
of 63 standards listed in Table II-2 for the end-of-pipe biological treatment
subcategory will apply to new sources that use biological treatment in order1
to comply with BOD5 and TSS limitations. The standards in the subcategory for
sources that do not use end-of-pipe biological treatment apply to new sources
that will either generate such low levels of BOD5 that they do not need to use
end-of-pipe biological treatment, or that choose to use physical/chemical
treatment to comply with the BOD5 standard. These facilities will have to
meet the 59 priority pollutant standards listed in Table II-3, which are based
on the application of in-plant control technologies with or without end-of-
pipe physical/chemical treatment.
EPA has determined that NSPS will not cause a barrier to entry for new
source OCPSF plants.
6. PSES ,
Pretreatment standards for existing sources applicable to indirect
dischargers are generally analogous to BAT limitations applicable to direct
dischargers. The Agency promulgated PSES for 47 priority pollutants which
were determined to pass through POTWs. The standards apply to all existing
indirect discharging OCPSF plants. EPA determines which pollutants to
regulate in PSES on the basis of whether or not they pass through, cause an
upset, or otherwise.interfere with operation of a POTU (including interference
with sludge practices). A detailed discussion of the pass-through analysis is
presented in Section VI.
Indirect dischargers generate wastewater with the same pollutant
characteristics as the direct discharge plants; therefore, the same tech-
nologies that were discussed for BAT are appropriate for application at PSES.
The Agency established PSES for all indirect dischargers on the same
technology basis as the BAT non-end-o'f-pipe biological treatment subcategory.
' 11-16
-------
Therefore, the pretreatment standards for existing sources>-shown in Table
II-4, are equivalent to the BAT limitations for the non-end-of-pipe biological
treatment subcategory for the pollutants deemed to pass through,
EPA is not including end-of^pipe biological treatment in the final PSES
model technology in part, because, as a matter of treatment thepry, biological
pretreatment may be largely redundant to the biological treatment provided by
the POTV. ,, . .;--, ,.....,--,.
Although EPA has rejected the option pf adding end-of-pipe biological
treatment, EPA sometimes uses biological treatment as part of its model
technology for the in-plant treatment of certain semivolatile pollutants such
as phenol, the phthalate esters, and the polynuclear aromatics. Specifically,
for such pollutants, EPA has in some cases used in-plant biological treatment
systems as an alternative to in-plant activated carbon adsorption for these
organic pollutants. Thus, EPA actually has used biological treatment.as part
of PSES model treatment technology where appropriate.
7. PSNS
Like PSES and BAT, PSNS is generally analogous to NSPS. However, as for
PSES, EPA is not establishing PSNS limits for conventional pollutants or
including end-of-pipe biological treatment in its PSNS model treatment tech-
nology, for the same reasons discussed above with respect to PSES. The Agency
promulgated PSNS on the same technology basis as PSES, and issued standards
for the 47 priority pollutants in Table II-4 that have been determined to pass
through or otherwise interfere with the operation of POT¥s. The Agency has
determined that PSNS will not cause a barrier to entry for new source OCPSF
plants.
11-17
-------
TABLE II-4.
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES (PSES AND PSNS)
Pollutant
Number
1
4
6
7
8
9
10
11
12
13
14
16
23
25
26
27
29
30
32
33
34
38
39
44
45
52
55
56
57
58
60
65
66
68
70
71
78
80
81
84
85
86
87
Pretreatment Standards1
Pollutant Name
Acenaphthene
Benzene
Carbon Tetrachloride
Chlorobenzene
1,2, 4-Trichlorobenzene
Hexachlorobenzene
1 , 2-Dichloroethane
1 , 1 , 1-Trichloroethane
Hexachloroethane
1-1-Dichloroe thane
1,1, 2-Tri chloroe thane
Chloroethane
Chloroform
1 , 2-Dichlorobenzene
1 , 3-Di chlorobenzene
1,4-Dichlorobenzene
1, 1-Di chloroe thy lene
1,2-Trans-dichloroethylene
1 , 2-Dichloropropane
1 , 3-Dichloropropene
2 , 4-Dimethylphenol
Ethylbenzene
Fluoranthene
Methylene Chloride
Methyl Chloride
Hexachlorobutadiene
Naphthalene
Ni.trobenzene
2-Nitrophenol
4-Nitrophenol
4,6-Dinitro-o-cresol
Phenol
Bis(2-ethylhexyl)phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Anthracene
Fluorene
Phenanthrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Maximum for
Any One Day
47
134
380
380
794
794
574
59
794
59
127
295
325
794
380
380
60
66
794
794
47
380
54
170
295
380
47
6,402
231
576
Til
47
258
43
113
47
47
47
47
48
164
74
69
Maximum for
Monthly Average
19
57
142
142
196
196
180
22
196
22
32
110
111
196
142
142
22
25
196
196
19
142
22
36
110
142
19
2,237
65
162
78
19
95
20
46
19
19
19
19
20
52
28
26
11-18
-------
TABLE II-4.
PRETREATMENT STANDARDS FOR:EXISTING AND NEW SOURCES (PSES AND PSNS)
(Continued)
Pollutant
Number
88
121
122
128
Pollutant Name
Vinyl Chloride
Total Cyanide
Total Lead
Total Zinc '
Pre treatment
Maximum for
Any One Day
172
1,200
690
2,610
Standards
Maximum for
Monthly Average
97
420
320
1,050
units are micrograms per liter.
2Cyanide limitations apply only to cyanide-bearing waste streams, including
those listed in Table X-3.
3Metals limitations apply only to noncomplexed metal-bearing waste streams,
including those listed in Table X-4. Discharges of lead and zinc from
"complexed metal-bearing process wastewater," listed in Table X-5, are not
subject to these limitations.
4Total zinc limitations and standards for rayon fiber manufacture by the
viscose process and acrylic fiber manufacture by the zinc chloride/solvent
process are 6,796 ug/1 and 3,325 ug/1 for Maximum for Any One Day and Maximum
for Monthly Average, respectively.
11-19
-------
-------
SECTION III
INDUSTRY DESCRIPTION
A. INTRODUCTION
The organic chemicals industry began modestly in the middle of the 19th
century. The production of coke, used both as a fuel and reductant in blast
furnaces for steel production, generated coal tar as a by-product. These tars
were initially regarded as wastes. However, with the synthesis of the first
coal tar dye by Perkin in 1856, chemists and engineers began to recover the
waste tar and use it to manufacture additional products.
The organic chemicals industry began with the isolation and commercial
production of aromatic hydrocarbons (e.g., benzene and toluene and phenolics
from coal tar). As more organic compounds possessing valuable properties were
identified, commercial production methods for these compounds became desir-
able. The early products of the chemical industry were dyes, explosives, and
Pharmaceuticals.
The economic incentive to recover and use by-products was a driving force
behind the growing synthetic chemicals industry. For example, the manufacture
of chlorinated aromatics was prompted by: 1) the availability of large
quantities of chlorine formed as a by-product from caustic soda production
(already a commodity chemical), 2) the availability of benzene derived from
coal tar, and 3) the discovery that compounds could serve as intermediates for
the production of other valuable derivatives, such as phenol and picric acid.
Specialty products such as surfactants, pesticides, and aerosol propellants
were developed later to satisfy particular commercial needs.
The plastics and synthetic fibers industry began later as an outgrowth of
the organic chemicals industry. The first commercial polymers, rayon and
bakelite, were produced in the early 1900's from feedstocks manufactured by
the organic chemicals industry. In the last several decades, the development
of a variety of plastic and synthetic fiber products and the diversity of
III-l
-------
markets and applications of these products have made the plastic and synthetic
fibers industry the largest (measured by volume) consumer of organic
chemicals.
i
Chemicals derived from coal were the principal feedstocks of the early
industry, although ethanol, derived from fermentation, was the source of some
aliphatic compounds. Changing the source of industry feedstocks to less ex-
pensive petroleum derivatives lowered prices and opened new markets for
organic chemicals, plastics, and synthetic fibers during the 1920's and
1930's. By World War II, the modern organic chemicals and plastics and syn-
thetic fiber industries based on petro-chemicals were firmly established in
the United States.
Today, the organic chemicals, plastics and synthetic fibers (OCPSF)
industry includes production facilities of two distinct types: those whose
primary function is chemical synthesis, and those that recover organic chemi-
cals as by-products from unrelated manufacturing operations such as coke
plants (steel production) and pulp mills (paper production). The majority of
the plants in this industry are plants that process chemical precursors (raw
materials) into a wide variety of products for virtually every industrial and
consumer market.
Approximately 90 percent (by weight) of the precursors, the primary
feedstocks for all of the industry's thousands of products, are derived from
petroleum and natural gas. The remaining 10 percent is supplied by plants
that recover organic chemicals from coal tar condensates generated by coke
production.
There are numerous ways to describe the OCPSF industry; however, tradi-
tional profiles such as number of product lines or volume of product sales
mask the industry's complexity and diversity. The industry is even more
difficult to describe in terms that make distinctions among plants according
to wastewater characteristics. Subsequent parts of this section discuss the
OCPSF industry from several different perspectives, including product line,
product sales, geographic distribution, facility size, facility age, and
wastewater treatment and disposal methods as practiced by the industry. OCPSF
III-2
-------
wastewater treatment practices are summarized in Section II and described in
detail in Section VII of this document. The subcategorization of plants
within the OCPSF industry by process chemistry, raw and treated wastewater
characteristics, and other plant-specific factors, is discussed in Section IV.
B. DEFINITION OF THE INDUSTRY
A single definition of the OCPSF industry is difficult to derive because
of the complexity and diversity of the products and the manufacturing proces-
ses used in the industry. However, some traditional profiles can provide
general descriptions of the industry, and these are discussed briefly in the
following subsections:
• Standard Industrial Classification (SIC) system
• Scope of the final regulation
• Raw materials and product, processes
• Geographic location
• Age of plant
• Size of plant
• Mode of discharge.
1. Standard Industrial Classification System
Standard Industrial Classification (SIC) codes, established by the U.S.
Department of Commerce, are classifications of commercial and industrial es-
tablishments by type of activity in which they are engaged. The primary pur-
pose of the SIC code is to classify the manufacturing industries for the col-
lection of economic data. For this reason, the product descriptions in SIC
codes are arbitrary, often technically ambiguous, and in some cases inaccur-
ately representative of the products that are purported to be classified. SIC
codes also list archaic products that are no longer relevant to the OCPSF
industry. In some industries the SIC Code(s) match the activities covered by
the issuance of effluent guidelines and standards regulations. For the OCPSF
industry, product descriptions under the following SIC codes are nominal at
best:
2865 Cyclic (Coal Tar) Crudes, and Cyclic Intermediates, Dyes, and
Organic Pigments (Lakes and Toners)
III-3
-------
2869
2821
2823
2824
Industrial Organic Chemicals, Not Elsewhere Classified
Plastics Materials, Synthetic Resins, and Nonvulcanizable
Elastomers
Cellulosic Man-Made Fibers
Synthetic Organic Fibers, Except Cellulosic.
In addition, as a result of 1976 litigation and agreement, the organic chemi-
cals manufacturing, and the plastics and synthetic materials manufacturing
industries (since combined into the industry category addressed by this devel-
opment document) was defined to include all facilities manufacturing products
that could be construed to fall within these specific SIC codes. The U.S.
Environmental Protection Agency (EPA) considered two of these SIC codes: SIC
2865, cyclic (coal tar) crudes, and cyclic intermediates, dyes, and organic
pigments (lakes and toners); and SIC 2869, industrial organic chemicals, not
elsewhere classified, to be applicable to the organic chemicals manufacturing
industry.
The products that the SIC Manual includes in the industrial organic chem-
ical industry (SIC 286) are natural products such as gum and wood chemicals
(SIC 2861), aromatic and other organic chemicals from the processing of coal
tar and petroleum (SIC 2865), and aliphatic or acyclic organic chemicals (SIC
2869).
These chemicals are the raw materials for deriving products such as plas-
tics, rubbers, fibers, protective coatings, and detergents, but have few
direct consumer uses. Gum and wood chemicals (SIC 2861) are regulated under a
separate consent decree industrial category, gum and wood chemicals manufac-
turing (40 CFR 454).
The plastics and synthetic materials manufacturing category as defined by
the 1976 agreement, comprises SIC 282, plastic materials and synthetic resins,
synthetic rubber, and synthetic and other manmade fibers, except glass. SIC
282 includes the following SIC codes:
2821
Plastics Materials, Synthetic Resins, and Nonvulcanizable
Elastomers
III-4
-------
2822 Synthetic Rubber (Vulcanizable Elastomers)
2823 Cellulosic Man-Made Fibers
2824 Synthetic Organic Fibers, Except Cellulosic.
Of these codes, SIC 2822 is covered specifically in the 1976 agreement by
another industrial category, rubber manufacturing (40 CFR 428). Similarly,
miscellaneous plastic products (SIC 3079), which is related to the plastics
industry, is covered by the specific industrial category, plastics molding and
forming (40 CFR 463). EPA considers a plant that merely processes a polymeric
material for any end use other than as a fiber to be in SIC 3079. In con-
trast, if the plant manufactures that polymeric material from monomeric raw
materials, then that portion of its production is in SIC 2821.
The relationship of all the industries listed in the SIC Manual as being
related to production of organic chemicals, plastics, or synthetic fibers is
shown in Figure III-l.
a. Additional SIC Codes Could Be Considered as Part of the OCPSF
Industry
A review of SIC product code data supplied by OCPSF industry facilities
in the 1983 Section 308 Questionnaire identified 11 SIC product categories
that are classified under SIC codes different from those in the Settlement
Agreement discussed above that could be considered as part of the OCPSF
industry because they include the manufacture of OCPSF products or utilize
OCPSF process chemistry. These additional SIC code product categories are
also shown in Figure III-l and listed below.
SIC Code
2891400
2891423
2891433
2891453
Description
Synthetic Resin (and Rubber)
Adhesives
Phenolics and Modified Phenolics
Adhesives
Urea and Modified Urea Adhesives
Acrylic Adhesives
III-5
-------
Petrochemical Inter-Industry Relationship
Feedstock Industries
Petrochemical Industries
Petrochemical-Dependent
Chemical Industries
2821
Plastic
Materials
2822
Synthetic
Rubbers
2824
Synthetic
Fibers
2843
Surfactants
3079
Misc. Plastics
Products
1311
Crude .
Petroleum
and Natural Gas
r-»> 1321 -*.
Natural
Gas Liquids
—*-2911— *•
Petroleum
Refining
r-+~ 2865 — ft*
Cyclics and 1
Aromatics 1
— »- 2869 Jft.
Acyclics and
Aliphatics
^
^
*
^
Nitrogenous j __
Fertilizers *
Carbon """
Black
2823 Cellulosic Fibers
2831 Biologicals
2833 Medicinals and Botanicals
2834 Pharmaceuticals
2841 Detergents
2842 Polishes
2844 Toiletries ,
2851 Paints
2879 Pesticides
2891 Adhesives
2874 Phosphatic Fertilizers
2875 Mixed Fertilizers
2892 Explosives
2893 Printing Inks
Source: U.S. Department of Commerce, 1981. " 1981 U.S. Industrial Outlook."
Bureau of Industrial Econo'mics, Washington, D.C.
Figure 111-1.
Relationships Among the SIC Codes Related to the Production
of Organic Chemicals, Plastics, and Synthetic Fibers
m-6
-------
2843085
2899568
2899597
2899598
2911058
2911632
3079000
Bulk Surface Active Agents
Sizes, All Types
Other Industrial Chemical Specialties,
Including Fluxes, Plastic Wood Prep-
arations and Embalming Chemicals
Other Industrial Chemical Specialties,
Including Fluxes and Plastic Wood
Preparations
Aromatics", Made from Purchased
Refinery Products
Liquified Refinery Gases (Including
Other Aliphatics), Made from Purchased
Refinery Products
Miscellaneous Plastics Products (Including
Only Cellophane Manufacture From the
Viscose Process)
b. Primary, Secondary, and Tertiary SIC Codes
SIC codes, established by the U.S. Department of Commerce, are classifi-
cations of commercial and industrial establishments by type of activity in
which they are engaged. The SIC code system is commonly employed for collec-
tion and organization of data (e.g., gross production, sales, number of em-
ployees, and geographic location) for U.S. industries. An establishment is
an economic unit that produces goods or services (e.g., a chemical plant, a
mine, a factory, or a store). The establishment is a single physical loca-
tion and is typically engaged in a single or dominant type of economic activ-
ity for which an industry code is applicable.
Where a single physical location encompasses two or more distinct and
separate economic activities for which different industrial classification
codes seem applicable (e.g., a steel plant that produces organic chemicals as
a result of its coking operations), such activities are treated as separate
establishments under separate SIC codes, provided that: 1) no one industry
description in the SIC includes such combined activities; 2) the employment in
each such economic activity is significant; 3) such activities are not
ordinarily associated with one another at common physical locations; and
III-7
-------
4) reports can be prepared on the number of employees, their wages and
salaries, and other establishment type data. A single plant may include more
than one establishment and more than one SIC code.
A plant is assigned a primary SIC code corresponding to its primary
activity, which is the activity producing its primary product or group of
products. The primary product is the product having the highest total annual
shipment value. The secondary products of a plant are all products other
than the primary products. Frequently in the chemical industry a plant may
produce large amounts of a low-cost chemical, but be assigned another SIC code
because of lower-volume production of a high-priced specialty chemical. Many
plants are also assigned secondary, tertiary, or lower order SIC codes corres-
ponding to plant activities beyond their primary activities. The inclusion
of plants with a secondary or lower order SIC code produces a list of plants
manufacturing a given class of industrial products, but also includes plants
that produce only minor (or in some cases insignificant) amounts of thpse
products. While the latter plants are part of an industry economically, their
inclusion may distort the description of the industry's wastewater production
and treatment, unless the wastewaters can be segregated by SIC codes.
c- Products of Various SIC Categories
Important classes of chemicals of the organic chemicals industry within
SIC 2865 include: 1) derivatives of benzene, toluene, naphthalene, anthra-
cene, pyridine, carbazole, and other cyclic chemical products; 2) synthetic
organic dyes; 3) synthetic organic pigments; and 4) cyclic (coal tar) crudes,
such as light oils and light oil products; coal tar acids; and products of
medium and heavy oil such as creosote oil, naphthalene, anthracene and their
high homologues, and tar.
Important classes of chemicals of the organic chemicals industry within
SIC 2869 include: 1) non-cyclic organic chemicals such as acetic, chloroi-
acetic, adipic, formic, oxalic acids and their metallic salts, chloral, for-
maldehyde, and methylamine; 2) solvents such as amyl, butyl, and ethyl alco-
hols; methanol; amyl, butyl, and ethyl acetates; ethyl ether, ethylene glycol
ether, and diethylene glycol ether; acetone, carbon disulfide, and chlorinated
III-8
-------
solvents such as carbon tetrachloride, tetrachloroethene, 'and trichloroethene;
3) polyhydric alcohols such as ethylene glycol, sorbitol, pentaerythritol, and
synthetic glycerin? 4) synthetic perfume and flavoring materials such as
coumarin, methyl salicylate, saccharin, citral, citronellal, synthetic
geraniol, ionone, terpineol, and synthetic vanillin; 5) rubber processing
chemicals such as accelerators and antioxidants, both cyclic and acyclic; 6)
plasticizers, both cyclic and acyclic, such as esters of phosphoric acid,
phthalic anhydride, adipic acid, lauric acid, oleic acid, sebacic acid, and —
stearic acid; 7) synthetic tanning agents such as sulfonic acid condensates;
and 8) esters, amines, etc. of polyhydric alcohols and fatty and other acids.
Tables III-l and 111^2 list specific products of SIC 2865 and SIC 2869,
respectively.
important products produced by the plastics and synthetic fibers industry
within SIC 2821 include: cellulose acetate, phenolic, and other tar acid
resins; urea and melamine resins; vinyl acetate resins; polyethylene resins;
polypropylene resins; rosin modified resins; coumarone-indene resins;
petroleum resins; polyamide resins, silicones, polyisobutylenes, polyesters,
polycarbonate resins, acetal resins, fluorohydrocarbon resins. Table III-3
lists important products of SIC 2821:.
Important cellulosic man-made fibers (SIC 2823) include: cellulose
acetate, cellulose triacetate and rayon, triacetate fibers. Important non-
cellulosic synthetic organic fibers (SIC 2824) include: acrylic, modacrylic,
fluorocarbon, nylon, olefin, polyester, and polyvinyl. Tables III-4 and -111-5
list 'specific products of SIC 2823 and SIC 2824, respectively.
Certain products of SIC groups other than 2865, 2969, 2821, 2823, and
2824 are identical to OCPSF industry products. Benzene, toluene, and mixed
xylenes manufactured from purchased refinery products in SIC 29110582 (in
contrast to benzene, toluene, and mixed xylenes manufactured in refineries—
SIC 2,9110558) are manufactured with the same reaction chemistry and unit
operations as OCPSF products (see Table III-6). Similar considerations apply
to aliphatic hydrocarbons manufactured from purchased refinery products—
SIC .29116324 (see Table III-7).
III-9
-------
TABLE III-l.
SIC 2865: CYCLIC (COAL TAR), CRUDES, AND CYCLIC INTERMEDIATES,
DYES, AND ORGANIC PIGMENTS (LAKES AND TONERS)
Acid dyes, synthetic
Acids, coal tar: derived from coal tar
distillation
Alkylated diphenylamines, mixed
Alkylated phenol, mixed
Arainoanthraquinone
Aminoazobenzene
Arainoazotoluene
Arainophenol
Aniline
Aniline oil
Anthracene
Anthraquinone dyes
Azine dyes
Azo dyes
Azobenzene
Azoic dyes
Benzaldehyde
Benzene hexachloride (BHC)
Benzene, product of coal tar
distillation
Benzoic acid
Benzol, product of coal, tar distillation
Biological stains
Chemical indicators
Chlorobenzene
Chloronaphthalene
Chlorophenol
Chlorotoluene
Coal tar crudes, derived from coal
tar distillation
Coal tar distillates
Coal tar intermediates
Color lakes and toners
Color pigments, organic: except animal
black and bone black
Colors, dry: lakes, toners, or full
strength organic colors
Colors, extended (color lakes)
Cosmetic dyes, synthetic
Creosote oil, product of coal tar
distillation
Cresols, product of coal tar
distillation
Cresylic acid, product of coal tar
distillation
Cyclic crudes, coal tar: product of
coal tar distillation
Hydroquinone
Isocyanates
Lake red C toners
Leather dyes and stains, synthetic
Lithol rubine lakes and toners
Maleic anhydride
Methyl violet toners
Naphtha, solvent: product of coal
tar distillation
Naphthalene chips and flakes
Naphthalene, product of coal tar
distillation
Naphthol, alpha and beta
Nitro dyes
Nitroaniline
Nitrobenzene
Nitrophenol
Nitroso dyes
Oil, aniline
Oils: light, medium, and heavy—pro-
duct of coal tar distillation
Organic pigments (lakes and toners)
Orthodichlorobenzene
Paint pigments, organic
Peacock blue lake
Pentachlorophenol
Persian orange lake
Phenol
Phloxine toners
Phosphomolybdic acid lakes and toners
Phosphotungstic acid lakes and toners
Phthalic anhydride
Phthalocyanine toners
Pigment scarlet lake
Pitch, product of coal tar
distillation
Pulp colors, organic
Quinoline dyes
Resorcinol
Scarlet 2 R lake
Stains for leather
Stilbene dyes
Styrene
Styrene monomer
Tar, product of coal tar distillation
Toluene, product of coal tar
distillation
111-10
-------
, • TABLE .1.11-1.
SIC 2865: CYCLIC (COAL TAR), CRUDES, AND CYCLIC INTERMEDIATES,
DYES, AND ORGANIC PIGMENTS (LAKES AND TONERS)
(Continued)
Cyclic intermediates
Cyclohexane
Diphenylamine
Drug dyes, synthetic
Dye (cyclic) intermediates
Dyes, food: synthetic
Dyes, synthetic organic
Eosine toners
Ethylbenzene
Toluidines
Toluol, product of coal tar distilla-
tion
Vat dyes, synthetic
Xylene, product of coal.tar distilla-
tion
Xylol, product of coal tar distilla-
tion
Source: OMB 1972. Standard Industrial Classification Manual 1972.
Statistical Policy Division, Washington, D.C.
III-ll
-------
SIC 2869:
TABLE III-2.
INDUSTRIAL ORGANIC CHEMICALS, NOT ELSEWHERE
CLASSIFIED
Accelerators, rubber processing:
cyclic and acyclic
Acetaldehyde
Acetates, except natural acetate of
lime
Acetic acid, synthetic
Acetic anhydride
Acetin
Acetone, synthetic
Acid esters, amines, etc.
Acids, organic
Acrolein
Acrylonitrile
Adipic acid
Adipic acid esters
Adiponitrile
Alcohol, aromatic
Alcohol, fatty: powdered
Alcohol, methyl: synthetic
(methanol)
Alcohols, industrial: denatured
(nonbeverage)
Algin products
Amyl acetate and alcohol
Antioxidants, rubber processing:
cyclic and acyclic
Bromochlorome thane
Butadiene, from alcohol
Butyl acetate, alcohol, and
proprionate
Butyl ester solution of 2, 4-D
Calcium oxalate
Camphor, synthetic
Carbon bisulfide (disulfide)
Carbon tetrachloride
Casing fluids, for curing fruits,
spices, tobacco, etc.
Cellulose acetate, unplasticized
Chemical warfare gases
Chloral
Chlorinated solvents
Chloroacetic acid and metallic
salts
Chloroform
Chloropicrin
Citral
Citrates
Citric acid
Citronellal
Coumarin
Cream of tartar
Cyclopropane
DDT, technical
Decahydronaphthalene
Dichlorodifluoromethane
Diethylcyclohexane (mixed isomers)
Diethylene glycol ether
Dimethyl divinyl acetylene
(di-isopropenyl acetylene)
Dimethylhydrazine, unsymmetrical
Embalming fluids
Enzymes
Esters of phosphoric, adipic,
lauric, oleic, sebacic, and
stearic acids
Esters of phthalic anhydride
Ethanol, industrial
Ether
Ethyl acetate, synthetic
Ethyl alcohol, industrial
(non-beverage)
Ethyl butyrate
Ethyl cellulose, unplasticized
Ethyl chloride
Ethyl ether
Ethyl formate
Ethyl nitrite
Ethyl perhydrophenanthrene
Ethylene
Ethylene glycol
Ethylene glycol ether
Ethylene glycol, inhibited
Ethylene oxide
Fatty acid esters, amines, etc.
Ferric ammonium oxalate
Flavors and flavoring materials,
synthetic \
Fluorinated hydrocarbon gases ;
Formaldehyde (formalin)
Formic acid and metallic salts ;
Freon
Fuel propellants, solid: organic .
Fuels, high energy: organic ;
Geraniol, synthetic
Glycerin, except from fats
(synthetic) ,
Grain alcohol, industrial
(non-beverage)
111-12
-------
TABLE III-2.
SIC 2869: INDUSTRIAL ORGANIC CHEMICALS, NOT ELSEWHERE
•CLASSIFIED (Continued)
Hexamethylenediamine
Hexamethylenetetramine
High purity grade chemicals,
organic: refined from technical
grades
Hydraulic fluids, synthetic base
Hydrazine
Industrial organic cycle compounds
lonone
Isopropyl alcohol
Ketone, methyl ethyl
Ketone, methyl isobutyl
Laboratory chemicals, organic
Laurie acid esters
Lime citrate
Malononitrile, technical grade
Metallic salts of acyclic organic
chemicals
Metallic stearate
Methanol, synthetic (methyl
alcohol)
Methyl chloride
Methyl perhydrofluorine
Methyl salicylate
Methylamine
Methylene chloride
Monochlorodifluoromethane
Monomethylparaminophenol sulfate
Monosodium glutamate
Mustard gas
Napthalene sulfonic acid
condensates
Naphthenic acid soaps .
Normal hexyl decalin
Nuclear fuels, organic
Oleic acid esters
Organic acid esters
Organic chemicals, acyclic
Oxalates
Oxalic acid and metallic salts
Pentaerythritol
Perchloroethylene
Perfume materials, synthetic
Phosgene
Phthalates * •.
Plasticizers, organic: cyclic and
acyclic
Polyhydric alcohol esters, amines,
etc.
Polyhydric alcohols
Potassiium bitartrate
Propellants for missiles, solid:
organic
Propylene
Propylene glycol
Quinuclidinol ester of benzylic
acid
Reagent grade chemicals, organic:
refined from technical grades
Rocket engine fuel, organic
Rubber processing chemicals,
organic: accelerators and
antioxidants
Saccharin
Sebacic acid
Silicones
Soaps, naphthenic acid
Sodium acetate
Sodium alginate
Sodium benzoate
Sodium glutamate
Sodium pentachlorophenate
Sodium sulfoxalate formaldehyde
Solvents, organic
Sorbitol
Staaric acid salts
Sulfonated naphthalene
Tackifiers, organic
Tannic acid
Tanning agents, synthetic organic
Tartaric acid and metallic salts
Tartrates
Tear gas
Terpineol
Tert-butylated bis
(p-phenoxyphenyl) ether fluid
Tetrachloroethylene
Tetraethyl lead
Thioglycolic acid, for permanent.
wave lotions
Trichloroethylene
Trichloroethylene stabilized,
degreasing
Trichlorophenoxyacetic acid
Trichlorotrifluoroethane
tetrachlorodi fluoroethane
isopropyl alcohol
Tricresyl phosphate
111-13
-------
TABLE III-2.
SIC 2869: INDUSTRIAL ORGANIC CHEMICALS, NOT ELSEWHERE
CLASSIFIED (Continued)
Tridecyl alcohol
Trimethyltrithiophosphite (rocket
propellants)
Triphenyl phosphate
Vanillin,' synthetic
Vinyl acetate
Source: OMB 1972. Standard Industrial Classification Manual 1972.
Statistical Policy Division, Washington, D.C.
111-14
-------
TABLE III-3.
SIC 2821: PLASTIC MATERIALS, SYNTHETIC RESINS,
AND NONVULCANIZABLE ELASTOMERS
Acetal resins
Acetate, cellulose (plastics)
Acrylic resins
Acrylonitrile-butadiene-styrene resins
Alcohol resins, polyvinyl
Alkyd resins
Allyl resins
Butadiene copolymers, containing less
than 50% butadiene
Carbohydrate plastics
Casein plastics
Cellulose nitrate resins
Cellulose propionate (plastics)
Coal tar resins
Condensation plastics
Coumarone-indene resins
Cresol-furfural resins
Cresol resins
Dicyandiamine resins
Diisocyanate resins
Elastomers, nonvulcanizable (plastics)
Epichlorohydrin bisphenol
Epichlorohydrin diphenol
Epoxy resins
Ester gum
Ethyl cellulose plastics
Ethylene-vinyl acetate resins
Fluorohydrocarbon resins
Ion exchange resins
lonomer resins
Isobutylene polymers
Lignin plastics
Melamine resins
Methyl acrylate resins
Methyl cellulose plastics
Methyl methacrylate resins
Molding compounds, plastics
Nitrocellulose plastics (pyroxylin)
Nylon resins
Petroleum polymer resins
Phenol-furfural resins
Phenolic resins
Phenoxy resins
Phthalic alkyd resins
Phthalic anhydride resins
Polyacrylonitrile resins
Polyamide resins
Polycarbonate resins
Polyesters
Polyethylene resins
Polyhexamethylenediamine adipamide
resins
Polyisobutylenes
Polymerization plastics, except
fibers
Polypropylene resins
Polystyrene resins
Polyurethane resins
Polyvinyl chloride resins
Polyvinyl halide resins
Polyvinyl resins
Protein plastics
Pyroxylin
Resins, phenolic
Resins, synthetic: coal tar and
non-coal tar
Rosin modified resins
Silicone fluid solution (fluid for
sonar transducers)
Silicone resins
Soybean plastics
Styrene resins
Styrene-acrylonitrile resins
Tar acid resins
Urea resins
Vinyl resins
Source: OMB 1972. Standard Industrial Classification Manual 1972.
Statistical Policy Division, Washington, D.C.
111-15
-------
TABLE III-4.
SIC 2823: CELLULOSIC MAN-MADE FIBERS
Acetate fibers
Cellulose acetate monofilament, yarn,
staple, or tow
Cellulose fibers, man-made
Cigarette tow, cellulosic fiber
Cuprammonium fibers
Fibers, cellulose man-made
Fibers, rayon
Horsehair, artifical: rayon
Nitrocellulose fibers
Rayon primary products: fibers,
straw, strips, and yarn
Rayon yarn, made in chemical
plants (primary products)
Regenerated cellulose fibers
Triacetate fibers
Viscose fibers, bands, strips,
and yarn
Yarn, cellulosic: made in chemical
plants (primary products)
Source: OMB, 1972. Standard Industrial Classification Manual 1972.
Statistical Policy Division, Washington, D.C.
111-16
-------
TABLE III-5
SIC 2824: SYNTHETIC ORGANIC FIBERS, EXCEPT CELLULOSIC
Acrylic fibers
Acrylonitrile fibers
Anidex fibers
Casein fibers
Elastomeric fibers
Fibers, man-made: except cellulosic
Fluorocarbon fibers
Horsehair, artificial: nylon
Linear esters fibers
Modacrylic fibers
Nylon fibers and bristles
Olefin fibers
Organic fibers, synthetic: except
cellulosic
Polyester fibers
Polyvinyl ester fibers
Polyvinylidene chloride fibers
Protein fibers
Saran fibers
Soybean fibers (man-made textile
materials)
Vinyl fibers
Vinylidene chloride fibers
Yarn, organic man-made fiber
except cellulosic
Zein fibers
Source: OMB 1972. Standard Industrial Classification Manual 1972.
Statistical Policy Division, Washington, D.C.
111-17
-------
TABLE III-6.
OCPSF CHEMICAL PRODUCTS ALSO LISTED AS SIC 29110582 PRODUCTS
Benzene
Cresylic acid
Cyclopentane
Naphthalene
Naphthenic Acid
Toluene
Xylenes, Mixed
C9 Aromatics
Sources 1982 Census of Manufacturers and Census of Mineral Industries.
Numerical List of Manufactured and Mineral Products. U.S. Department
of Commerce, Bureau of the Census, 1982.
111-18
-------
TABLE III-7.
OCPSF CHEMICAL PRODUCTS ALSO LISTED AS SIC 29116324 PRODUCTS
C2 Hydrocarbons
Acetylene
Ethane
Ethylene
C3 Hydrocarbons
Propane
Propylene
C4 Hydrocarbons
Butadiene and butylene fractions
1,3-Butadieae, grade for rubber
n-Butane
Butanes, mixed
1-Butene
2-Butene
1-Butane and 2-butene, mixed
Hydrocarbons, C4, fraction
Hydrocarbons, C4, mixtures
Isobutane (2-Methylpropane)
Isobutylene (2-Methylpropene)
C4 Hydrocarbons, all other
amylenes
Dibutanized aromatic concentrate
C5 Hydrocarbon, mixtures
Isopentane (2-Methylbutane)
Isoprene (2-Methyl-l,3-bu£adiene)
n-Pentane
1-Pentene
Pentenes, mixed
Piperylene (1,3-Pentadiene)
C5 Hydrocarbons, all other
C6 Hydrocarbons
Diisopropane
Hexane
Hexanes, mixed
Hydrocarbons, C5-C6, mixtures
Hydrocarbons, C5-C7, mixtures
Isohexane
Methylcyclopentadiene
Neohexane (2,2-Dimethylbutane)
C6 Hydrocarbons, C6, all other
n-Heptane
Heptenes, mixed
Isoheptanes
C7 Hydrocarbons
C8 Hydrocarbons
Diisobutylene (Diisobutene)
n-Octane
Octenes, mixed
2,2,4-Trimethylpentane (Isooctane)
C8 Hydrocarbons, all other
C9 and above Hydrocarbons
Dodecene
Eicosane
Nonene (Tripropylene)
Alpha olefins
Alpha olefins, C6-C10
Alpha olefins, Cll and higher
n-Paraffins
n-Paraffins, C6-C9
n-Paraffins, C9-C15
n-Paraffins, C10-C14
n-Paraffins, C10-C16
n-Paraffins, C12-C18
n-Paraffins, C15-C17
n-Paraffins, other
Hydrocarbons, C5-C9, mixtures
Polybutene
Hydrocarbon derivatives
n-Butyl mercaptan (1-Butanethiol)
sec-Butyl mercaptan (2-Butanethiol)
tert-Butyl mercaptan (2-Methyl-
2-propanethiol)
Di-tert-butyl disulfide
Diethyl sulfide (Ethyl sulfide)
Dimethyl sulfide
Ethyl mercaptan (Ethanethiol)
Ethylthioethanol
n-Hexyl mercaptan (1-Hexanethiol)
Isopropyl mercaptan (2-Propanethiol)
Methyl ethyl sulfide
Methyl mercaptan (Methanethiol)
tert-Octyl mercaptan (2,4,4-Trimethyl-
2-pentanethiol)
Octyl mercaptans
Thiophane (Tetrahydrothiophene)
Hydrocarbon derivatives: all other
hydrocarbon derivatives
Hydrocarbons, C9 and above, all other,
including mixtures
Source: 1982 Census of Manufacturers and Census of Mineral Industries.
Numerical List of Manufactured and Mineral Products. U.S. Department
of Commerce, Bureau of the Census, 1982.
111-19
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2. Scope of the Final Regulation
The promulgated regulation establishes effluent limitations guidelines
and standards for existing and new organic chemicals, plastics, and synthetic
•fibers manufacturing facilities (BPT, BAT, NSPS, PSES, and PSNS). The final
regulations apply to process wastewater discharges from these facilities.
For the purposes of this regulation, OCPSF process wastewater discharges
are defined as discharges from all .establishments or portions of establish-
ments that manufacture the products or product groups listed in the applica-
bility sections of the regulation and also in Appendix III-A of this document,
and are included within the following U.S. Department of Commerce Bureau of
the Census SIC major groups:
• SIC 2865 - Cyclic Crudes and Intermediates, Dyes, and Organic Pigments
• SIC 2869 - Industrial Organic .Chemicals, Not Elsewhere Classified
• SIC 2821 - Plastic Materials, Synthetic Resins, and Nonvulcanizable
Elastomers
• SIC 2823 - Cellulosic Man-Made Fibers
• SIC 2824 - Synthetic Organic Fibers, Except Cellulosic.
The OCPSF regulation does not apply to process wastewater discharges from
the manufacture of organic chemical compounds solely by extraction from plant
and animal raw materials or by fermentation processes. Thus, ethanol derived
from natural sources (SIC 28095112) is not considered to be an OCPSF industry
product; however, ethanol produced synthetically (hydration of ethene) is an
OCPSF industry product.
The OCPSF regulation covers all OCPSF products or processes whether or
not they are located at facilities where the OCPSF covered operations are a
minor portion of and ancillary to the primary production activities or a major
portion of the activities.
The OCPSF regulation does not apply to discharges from OCPSF product/
process operations that are covered by the provisions of other categorical
111-20
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industry effluent limitations 'guidelines and standards if the wastewater is
treated in combination with the non-OCPSF industrial category regulated waste-
water. (Some products or product groups'are manufactured by different pro-
cesses and some processes with slight operating condition variations give dif-
ferent products; EPA uses the term "product/process" to define all different
variations within this category of the same basic process to manufacture dif-
ferent products as well as to manufacture the same product using different
processes.) However, the OCPSF regulation applies to the product/processes
covered by this regulation if the .facility'reports OCPSF products under SIC
codes 2865, 2869, or 2821, and its OCPSF wastewaters are treated in a separate
treatment system at the facility or discharged separately to a publicly owned
treatment works (POTW).
For example, some vertically integrated petroleum refineries and pnarma-
ceutical manufacturers discharge wastewaters from the production of synthetic
organic chemical products that are specifically regulated under the petrochem-
ical and integrated subcategories of the petroleum refining point source cate-
gory (40 CFR Part 419, Subparts C and E) or the chemical synthesis products
subcategory of the Pharmaceuticals manufacturing point source category (40 CFR
Part 439, Subpart C). Thus, the principles discussed in the preceding para-
graph apply as follows: the process wastewater discharges by petroleum refin-
eries and pharmaceutical manufacturers from production of organic chemical
products specifically covered by 40 CFR Part 419 Subparts C and E and Part 439
Subpart C, respectively, that are treated in combination with other petroleum
refinery or pharmaceutical manufacturing wastewater, respectively, are not
subject to regulation no matter what SIC they use to report their products.
However, if the wastewaters from their OCPSF production is separately dis-
charged to a POT¥ or treated in a separate treatment system, and they report
their products (from these processes) under SIC codes 2865, 2869, or 2821,
then these manufacturing operations are subject to regulation under the OCPSF
regulation, regardless of whether the OCPSF products are covered by 40 CFR
Part 419, Subparts C and E and Part 439, Subpart C.
_,.-,---,,. , . '•'-•,.'., - -1' -..•>, '-<•-
The promulgated OCPSF category regulation applies to plastics molding and
forming processes when plastic resin manufacturers mold or form (e.g., extrude
and pelletize) crude intermediate plastic material for shipment off-site.
111-21
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This regulation also applies to the extrusion of fibers. Plastics molding and
forming processes other than those described above are regulated by the plas-
tics molding and forming effluent guidelines and standards (40 CFR Part 463).
Public comments requested guidance relating to the coverage of OCPSF
research and development facilities. Stand-alone OCPSF research and develop-
ment, pilot-plant, technical service, and laboratory bench-scale operations
are not covered by the OCPSF regulation. However, wastewater from such opera-
tions conducted in conjunction with and related to existing OCPSF manufactur-
ing operations at OCPSF facilities is covered by the OCPSF regulation because
these operations would most likely generate wastewater with characteristics
similar to the commercial manufacturing facility. Research and development,
pilot-plant, technical service, and laboratory operations that are unrelated
to existing OCPSF plant operations, even though conducted on-site, are not
covered by the OCPSF regulation because they may generate wastewater with
characteristics dissimilar to that from the commercial OCPSF manufacturing
facility.
Finally, as described in the following paragraphs, this regulation does
not cover certain production that has historically been reported to the Bureau
of Census under a non-OCPSF SIC subgroup heading, even if such production
could be reported under one of the five SIC code groups covered by the final
regulation.
The Settlement Agreement required the Agency to establish regulations for
the organic chemicals manufacturing SIC codes 2864 and 2869 and for the plas-
tics and synthetic materials manufacturing SIC Code 282. SIC 282 includes the
three codes covered by this regulation, 2821, 2823, and 2824, as well as SIC
2822, synthetic rubber (vulcanizable elastomers), which is covered specific-
ally in the Settlement Agreement by another industrial category, rubber manu-
facturing (40 CFR 428). The Agency therefore directed its data collection
efforts to those facilities that report manufacturing activities under SIC
codes 2821, 2823, 2824, 2865, and 2869. Based on an assessment of this infor-
mation and the integrated nature of the synthetic OCPSF industry, the Agency,
also defined the applicability of the OCPSF regulation by listing the specific
products and product groups that provide the technical basis for the regula-
tion (see Appendix II1-A).
111-22
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Since many of these products may be reported under more than one SIC code
even though they are often manufactured with the same reaction chemistry or
unit operations, the Agency proposed to extend the applicability of the OCPSF
regulation (50 PR 29068; July 17, 1985 or 51 PR.44082; December 8,, 1986) to
include OCPSF production reported under the following SIC subgroups:
• SIC 2911058 - aromatic hydrpcarbons manufactured from purchased
refinery products
• SIC 2911632 - aliphatic hydrocarbons manufactured from purchased
refinery products
• SIC 28914 - synthetic resin and rubber adhesives (including only those
synthetic resins listed under both SIC 28914 and SIC 2821 that are
polymerized for use or sale, by adhesive manufacturers)
• Chemicals and chemical preparations, not elsewhere classified:
- SIC 2899568 - sizes, all types
- SIC 2899597 - other industrial chemical specialties,^including
fluxes, plastic wood preparations, and embalming fluids
• SIC 2843085 - bulk surface active agents
• SIC 3079 - miscellaneous plastics products (including only cellophane
manufacture from the viscose process).
However, for the reasons discussed below, the Agency has decided not to extend
the applicability of the OCPSF regulation to discharges from establishments
that manufacture OCPSF products and have, in the past, reported such produc-
tion under these non-OCPSF SIC subgroups.
As noted earlier, the SIC codes are classifications of commercial and
industrial establishments by type of activity in which they are engaged. The
predominant purpose of the SIC code is to classify the manufacturing indus-
tries for the collection of economic data. The product descriptions in SIC
codes are often technically ambiguous and also list products that are no
longer produced in commercial quantities. For this reason, the Agency pro-
posed to define the applicability of the OCPSF regulation in terms Of both SIC
codes and specific products and product groups (50 FR 29073, July 17/ 1985).
Many chemical products.may appear under more than one SIC code depending on
111-23
-------
the manufacturing raw material sources, use in the next stiage of the manufac-
turing process, or type of sale or end use. For example, phenolic, urea, and
acrylic resin manufacture may be reported under SIC 28914, synthetic resin
adhesives, as well as under SIC 2821, plastics materials and resins. Benzene,
toluene, and xylene manufacture may be reported under SIC 2911, petroleum
refining, or under SIC 2911058, aromatics, made from purchased refinery pro-
ducts, as well as SIC 2865, cyclic crudes and intermediates. Likewise, alkyl-
benzene sulfonic acids and salts manufacture may be reported under SIC
2843085, bulk surface active agents, which include all amphoteric, anionic,
cationic, and nonionic bulk surface active agents excluding surface active
agents produced or purchased and sold as active incredients in formulated
products, as well as SIC 286, industrial'organic chemicals.
Many commenters stated that the Agency's OCPSF technical and economic
studies do not contain sufficient information to extend coverage to all
facilities reporting OCPSF manufacturing under all of the above SIC subgroups.
The Agency agrees in part with these commenters. The OCPSF technical, cost,
and economic impact, data-gathering efforts focused only on those primary and
secondary manufacturers that report OCPSF manufacturing activities under SIC
codes 2821, 2823, -2824, 2865, and 2869. Specific efforts were not directed
toward gathering technical and financial data from facilities that report
OCPSF manufacturing under SIC subgroups 2911058, 2911632, 28914, 2843085,
2899568, 2899597, and 3079. As a result, EPA lacks cost and economic informa-
tion from a significant number of plants that report OCPSF manufacturing
activities to the Bureau of the Census under these latter SIC subgroups. Con-
sequently, the applicability section of the final regulation (§414.11) clari-
fies that the OCPSF regulation does not apply to a plant's OCPSF production
that has been reported by the plant in the past under SIC groups 2911058,
2911632, 28914, 2843085, 2899568, 2899597, and 3079.
Approximately 140 of the 940 OCPSF plants that provide the technical
basis for the final regulation reported parts of their OCPSF production under
SIC codes 2911058, 2911632, 28914, 2843085, 2899568, and 2899597, as well as
SIC codes 2821, 2823, 2824,,2865, and 2869. As a result of the definition of
applicability, a smaller portion of plant production than was reported as
OCPSF production for these plants is covered by the final regulation.
111-24
-------
The Agency does note, however, that theOCPSF,manufacturing processes are
essentially identical regardless of how manufacturing facilities may report
OCPSF production to the Bureau of the Census. Therefore, the OCPSF technical
.data base and effluent limitations and standards provide permit issuing
authorities with technical guidance for establishing "Best Professional Judg-
ment" (BPJ) permits for OGPSF production activities to which this regulation
does not apply.
Some of the nbn-OCPSF SIC subgroups were the subject of prior EPA deci-
sions not to establish national regulations for priority pollutants under the
terms of Paragraph 8 of the Settlement Agreement. Such action was taken for
adhesive and sealant manufacturing (SIC 2891), as well as plastics molding and
forming (SIC 3079), paint and ink formulation and printing (which industries
were within SIC 2851, 2893, 2711, ,2721, 2731 and 10 other SIC 27 groups) and
soap and detergent manufacturing (SIC 2841). However, it should be noted that
in specific instances where a plant in these categories has OCPSF production
activities, toxic pollutants may be present in the discharge in amounts that
warrant BPJ regulatory control. Moreover, the adhesives and sealants, plas-
tics molding and forming, and paint and ink formulation and printing Paragraph
8 exclusions do not include process wastewatier from the secondary manufacture
of synthetic resins. Similarly, the soaps and detergents Paragraph 8 exclu-
sion does not include process wastewater from the manufacture of surface
active agents (SIC 2843). In these cases, and even in cases where priority
pollutants from OCPSF production covered by other categorical standards (e.g.,
petroleum refining and Pharmaceuticals) have been excluded from those regula-
tions under the terms of Paragraph 8 of the Settlement Agreement, BPJ priority
pollutant regulation for individual plants having OCPSF production may be
appropriate.
3. Raw Materials and Product Processes
a. Raw Materials
Synthetic organic chemicals are derivatives of naturally occurring mater-
ials (petroleum, natural gas, and coal) that have undergone at least one chem-
ical reaction. Given the large number of potential starting materials and
111-25
-------
chemical reactions available to the industry, many thousands of organic chemi-
cals are produced by a potentially large number of basic processes having many
variations. Similar considerations also apply to the plastics and synthetic
fibers industry, although both the number of starting materials and processes
are more limited. Both organic chemicals and plastics are commercially pro-
duced from six major raw material classifications: methane, ethane, propene,
butanes/butenes, and higher aliphatic and aromatic compounds. This list can
be expanded to eight by further defining the aromatic compounds to include
benzene, toluene, and xylene. These raw materials are derived from natural
gas and petroleum, although a small portion of the aromatic compounds is
derived from coal.
Using these eight basic raw materials (feedstocks) derived from the
petroleum refining industry, process technologies used by the OCPSF industry
lead to the formation of a wide variety of products and intermediates, many of
which are produced from more than one basic raw material either as a primary
reaction product or as a co-product. Furthermore, the reaction product of one
process is frequently used as the raw material for a subsequent process. The
primary products of the organic chemicals industry, for example, are the raw
materials of the plastics and synthetic fibers industry. Furthermore, the
reaction products of one process at a plant are frequently the reactants for
other processes at the same plant, leading to the categorization of a chemical
as a product in one process and a reactant in another. This ambiguity con-
tinues until the manufacture of the ultimate end product, normally at the
fabrication or consumer stage. Many products/intermediates can be made from
more than one raw material. Frequently, there are alternate processes by
which a product can be made from the same basic raw material.
A second characteristic of the OCPSF industry that adds to the complexity
of the industry is the high degree of integration in manufacturing units.
Most plants in this industry use several of the eight basic raw materials '
derived from petroleum or natural gas- to produce a single product.
In addition, many plants do not use the eight basic raw materials, but
rather use products produced at other plants as their raw materials. Rela-
tively few manufacturing facilities are single product/process plants unless
111-26
-------
the final product is near the fabrication or consumer product stage. Any
attempt to define or subcategorize the industry on the basis of the 8 raw
materials would require the establishment of over 256 definitions or subcate-
gories. Schematic diagrams illustrating some of these relationships are shown
in Section V of this document (see Figures V-l to V-16).
b. Process Chemistry
Chemical and plastics manufacturing plants share an important character-
istic: chemical processes never convert 100 percent o£ the feedstocks to the
desired products, since the chemical reactions/processes never proceed to
total completion.
Moreover, because there is generally a variety of reaction pathways
available to reactants, undesirable by-products are often generated. This
produces a mixture of unreacted raw materials, products, and by-products that
must be separated and recovered by operations that generate residues with
little or no commercial value. These losses appear in process wastewater, in
air emissions, or directly as chemical wastes. The specific chemicals that
appear as losses are determined by the feedstock and the process chemistry
imposed upon it. The different combinations of products and production
processes distinguish the wastewater characteristics of one plant from those
of another.
Manufacture of a chemical product necessarily consists of three steps:
1) combination of reactants under suitable conditions to yield the desired
product; 2) separation of the product from the reaction matrix (e.g., by-
products, co-products, reaction solvents); and 3) final purification and/or
disposal of the wastewaters. Pollutants arise from the first step as a
result of alternate reaction pathways; separation of reactants and products
from a reaction mixture is imperfect and both raw materials and products are
typically found in process wastewaters.
Although there is strong economic incentive to recover both raw materials
and products, there is little incentive to recover the myriad of by-products
formed as the result of alternate reaction pathways. An extremely wide
111-27
-------
variety of compounds can form within a given process. Typically, chemical
species do not react via a single reaction pathway; depending on the nature of
the reactive intermediate, there is a variety of pathways that lead to a
series of reaction products. Often, and certainly the case for reactions of
industrial significance, one pathway may be greatly favored over all others,
but never to total exclusion. The direction of reactions in a process
sequence is controlled through careful adjustment and maintenance of condi-
tions in the reaction vessel. The physical condition of species present
(liquid, solid, or gaseous phase), conditions of temperature and pressure, the
presence of solvents and catalysts, and the configuration of process equipment
dictate the kinetic pathway by which a particular reaction will proceed.
Therefore, despite the differences between individual chemical production
plants, all transform one chemical to another by chemical reactions and physi-
cal processes. Although each transformation represents at least one chemical
reaction, production of most of the industry's products can be described by
one or more of the 41 major generalized chemical reactions/processes listed in
Table III-8. Subjecting the basic feedstocks to sequences of these 41 generic
processes produces most commercial organic chemicals and plastics.
Pollutant formation is dependent upon both the raw material and process
chemistry, and broad generalizations regarding raw wastewater loads based
solely on process chemistry are difficult at best. Additionally, OCPSF manu-
facturing processes typically employ unique combinations of the major generic
processes shown in Table III-8 to produce organic chemicals, plastics, and
synthetic fibers that tend to blur any distinctions possible.
c. Product/Processes
Each chemical product may be made by one or more combinations of raw
feedstock and generic process sequences. Specification of the sequence of
product synthesis by identification of the product and the generic process by
which it is produced is called a "product/process." There are, however,
thousands of product/processes within the OCPSF industries. Data gathered on
the nature and quantity of pollutants associated with the manufacture of
specific products within the organic chemicals and plastic/synthetic fibers
111-28
-------
TABLE III-8.
MAJOR GENERALIZED CHEMICAL REACTIONS AND PROCESSES
OF THE ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS INDUSTRY
Acid cleavage
Alkoxylation
Alkylation
Amination
Ammonolysis
Ammoxidation
Carbonylation
Chlorohydrination
Condensation
Cracking
Crystallization/Distillation
Cyanation/Hydrocyanation
Dehydration
Dehydrogena t i on
Denydrohalogenati on
Distillation
Electrohydrodimerization
Epoxidation
Esterification
Etherification
Extractive distillation
Extraction
Fiber production
Halogenation
Hydration
Hydroacetylation
Hydrodealkylat ion
Hydrogenation
Hydrohalogenat ion
Hydrolysis
Isomerizatio.n
Neutralization
Nitration
Oxidation
Oxyhalogena t i on
Oxymation
Peroxidation
Phosgenation
Polymerization
Pyrolysis
Sulfonation
111-29
-------
industries have been indexed for 176 product/processes.
cussed in Section V of this document.
These data are dis-
Organic chemical plants vary greatly as to the number of products manu-
factured and processes employed, and may be either vertically or horizontally
integrated. One representative plant, which is both vertically and horizon-
tally integrated, may produce a total of 45 high-volume products with an
additional 300 lower-volume products. In contrast, a specialty chemicals
plant may produce a total of 1,000 different products with 70 to 100 of these
being produced on any given day.
On the other hand, specialty chemicals may involve several chemical
reactions and require a more detailed description. For example, preparation
of toluene diisocyanate involves three synthesis steps — nitration, hydro-
genation, and phosgenation. This example, in fact, is relatively simple;
manufacture of other specialty chemicals is more complex. Thus, as individual
chemicals become further removed from the feedstock of the industry, more
processes are required to produce them.
In contrast to organic chemicals, plastics and synthetic fibers are
polymeric products. Their manufacture directly utilizes only a small subset
of either the chemicals manufactured or processes used within the OCPSF indus-
try. Such products are manufactured by polymerization processes in which
organic chemicals (monomers) react to form macromolecules or polymers, com-
posed of thousands of monomer units. Reaction conditions are designed to
drive the polymerization as far to completion as practical and to recover
unreacted monomer.
Unless a solvent is used in the polymerization, by-products of polymeric
product manufacturers are usually restricted to the monomer(s) or to oliomers
(a polymer consisting of only a few monomer units). Because the mild reaction
conditions generate few by-products, there is economic incentive to recover
the monomer(s) and oliomers for recycle; the principal yield loss is typically
scrap polymer. Thus, smaller amounts of fewer organic chemical co-products
(pollutants) are generated by the production of polymeric plastics and syn-
thetic fibers than are generated by the manufacture of the monomers and other
organic chemicals.
111-30
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For the purposes of characterizing the OCPSF industry in this section,
the manufacturing facilities are assigned to one of the following three groups
based on SIC codes reported in the 1983 Section 308 Questionnaire.
Plant Group
Organics Plants
Plastics Plants
Organics and Plastics
Plants (Mixed)
Associated SIC Codes Reported
2865, 2869
2821, 2823, 2824
One or more from each of
the two groups above
d. Industry Structure by Product/Process
A portion of the branched product structure of the OCPSF industry is
illustrated in Figures V-l to V-16 of Section V, which include key OCPSF pro-
ducts and organic priority pollutants. The total product line of the industry
is considerably more complex, but Figures V-l to V-16 illustrate the ability
of the organic chemicals industry to produce a product by different synthesis
routes. For each of the products that are produced in excess of 1,000 pounds
per year (approximately 1,500 to 2,500 products), there is an average of two
synthetic routes. The more than 20,000 compounds that are produced in smaller
quantities by the industry tend to be more complex molecules that can be syn-
.thesized by multiple routes. Because many products are often produced by more
than one manufacturer, using the same or different synthetic routes, few
plants have exactly the same product/process combinations as other plants.
An important characteristic of the OCPSF industry is the degree of verti-
cal integration among manufacturing units at individual plants.. Since a
majority of the basic raw materials is derived from petroleum or natural gas,
many of the commodity organic chemical manufacturing plants are either part of
or contiguous to petroleum refineries; most of these plants have .the flexi-
bility to produce a wide variety of products.
Relatively few organic chemical manufacturing facilities.are single
product/process plants, unless the final product is near the fabrication or
consumer product stage.
111-31
-------
Additionally, many process units are integrated in such a way that pro-
duction levels of related products can be varied as desired over wide ranges.
There can be a wide variation in the size (production capacity) of the manu-
facturing complex, as well as diversity of product/processes. In addition to
variations based on the design capacity and design product mix, economic and
market conditions of both the products and raw materials can greatly influence
the production rate and the processes that are employed even on a relatively
short-term basis.
4. Geographic Distribution
Plant distribution by state is presented in Table III-9. Most organic
chemical plants are located in coastal regions or on waterways near either
sources of raw materials (especially petrochemicals) or transportation
centers. Plastics and synthetic fibers plants are generally located near
organic chemicals plants to minimize costs of monomer feedstock transporta-
tion. However, a significant number of plastics plants are situated near
product markets (i.e., large population centers) to minimize costs of trans-
porting the products to market.
5. Plant Age
The ages of plants within the OCPSF industry are difficult to define,
since the plants are generally made up of more than one process unit, each
designed to produce different products. As the industry introduces new pro-
ducts and product demand grows, process units are added to a plant. It is not
clear which process should be chosen to define plant age. Typically, the
oldest process in current operation is used to define plant age. Information
concerning plant age was requested in the 1983 "308" Questionnaire.
Respondents were asked to report the year plant operation began and the
year the oldest OCPSF process line still operating went into operation. Table
111-10 presents the plant distribution of the age of the oldest OCPSF process
line still operating. Table 111-10 indicates that a few plants are currently
operating processes that are over 100 years old. However, over two-thirds of
the plants began operating the oldest process within the past 35 years. In
addition, the startup of new plants has been declining since the early 1970's.
111-32
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TABLE III-9.
PLANT DISTRIBUTION BY STATE
State*
AL
AR
CA
CO
CT
DE
FL
GA
TA
IL
IN
KS
KY
LA
MA
MD
MI
MN
MO
MS
MT
NC
NE
NH
NJ
NY
OH
OK
OR
PA
PR
RI
SC
TN
TX
UT
VA
WA
WI
WV
Total
Organ! cs
Plants
14
4
19
2
6
5
2
7
2
16
7
3
7
27
4
4
9
1
8
4
_
13
1
2
70
23
27
_
1
22
_
4
17
8
57
2
7
3
4
13
425
Plastics
Plants
4
2 ;
40 ,
1
8 ,
2 '
6
9
4
24
3
_
9
12
13
5
8 :
1
6
5
_
18 !
—
2
23
15 •
30
2
5
13
1
2
12
6
20;
— . -
15
4
5
3
338
Organ! cs and
Plastics Plants
5
2
4
-
2
2
3
2
.
15
2
1
5
8
3
1
4
1
1
3
1
10
1 ' ; -" " "
-
16
5
12
'
4
8
1
3
8
4
29
.-......-
2
1
3
6
177
Total
23
8
63
3
16
9
11
18
6
55
12
4
21
47
20
10
21
3
15
12
1
41
1
4
109
43
69
2
10
43
2
9
37
18
106
... 2 •
24
8
12
22
940
*0nly states that contain at least one facility are listed.
Source: EPA CWA Section 308 Survey, October 1983.
111-33
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TABLE 111-10.
DISTRIBUTION OF PLANTS BY AGE OF OLDEST
OCPSF PROCESS STILL OPERATING AS OF 1984
Plant Age
1-5
6-10
11-15
16-20
21-25
26-30
31-35
36-40
41-50
51-60
61-70
71-80
81-90
91-100
101-120
>120
Data not
Available
Total
Organ! cs
Plants
24
37
40
55
44
50
42
24
30
23
28
16
3
3
5
-
1
425
Plastics
Plants
14
29
41
54
46
41
24
17
23
19
16
4
5
1
1
-
3
338
Organics and
Plastics Plants
2
2
20
17
19
28
20
21
16
8
10
5
4
3
1*
1
177
Total
40
68
101
126
109
119
86
62
69
50
54
25
12
7
6
1*
5
940
*Note: The one plant whose age is >120 is 137 years old.
Source: EPA CffA Section 308 Survey, 1983.
111-34
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This major decline in startup of combined organics and plastics plants in
the past 10 years may indicate a trend toward construction of plants that
produce fewer products or many specialty products geared toward specific mar-
kets, since the combined plants tend to be the larger, multi-product, verti-
cally integrated plants.
6. Plant Size
Although plant size may be defined in many ways, including number of
employees, number of product/processes, plant capacity, production volume, and
sales volume, none of these factors alone is sufficient to define plant size;
each is discussed in this subsection.
t,
a. Number of Employees
Perhaps the most obvious definition of plant size would be the number of
workers employed. However, continuous process plants producing high-volume
commodity chemicals typically employ fewer workers per unit of production than
do plants producing specialty (relatively low-volume) chemicals. Table III-ll
presents the plant distribution by the average number of employees engaged in
OCPSF operations during 1982. These data were obtained from the 1983 Section
308 Questionnaire.
b. Number of Product/Processes
Plant size may also be expressed in terms of the number of product/
processes that are operated at a plant. Analysis of the number of product/
processes for 546 primary producers in the edited 1983 Section 308 Question-
naire data base is presented in Table 111-12. The table generally includes
only direct and indirect discharge facilities whose total plant production is
greater than 50 percent OCPSF products. Detailed product/process information
was not collected from zero discharge or secondary OCPSF. manufacturing
facilities.
The data presented in Table 111-12 may understate the number of distinct
product/processes because plants were requested to group certain products that
were listed in the questionnaire instructions or that individually constituted
less than 1 percent of the total plant production. For example, many dye
111-35
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TABLE III-ll.
PLANT DISTRIBUTION BY NUMBER OF EMPLOYEES
Number of
Employees
1-105
11-20
21-30
31-40
41-50
51-100
101-200
201-500
501-1000
1001-2000
2001-5000
>5000
Data not
Available
Total
Organ! cs
Plants
70
55
41
39
34
64
53
36
7
5
—
-
11
425
Plastics
Plants
73
58
32
26
23
45
27
23
9
9
7
-
6
338
Organics and
Plastics Plants
19
16
11
10
4
21
14
30
19
17
8
*1
7
177
Total
162
i±\J £r
129
•L £* s
94
x^
75
/ -*•
61
\J -L
no
JL.+J\J
94
^*T
RQ
o y
OK
*J-^
Tl
J a.
15
*1
24
940
*Note: The only plasnt with >5,000 employees hasd 11,262 employees,
Source: EPA OTA Section 308 Survey, 1983.
111-36
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TABLE 111-12.
PLANT DISTRIBUTION BY NUMBER OF PRODUCT/PROCESSES AND
PRODUCT GROUPS FOR PRIMARY PRODUCERS THAT ARE ALSO
DIRECT AND/OR INDIRECT DISCHARGERS*
Number of
Product/Processes
1
2
3
4
5
6
7
8
9
10
11-12
13-15
16-20
21-30
31-40
41-50
Total
Organics
Plants
41
23
30
24
15
34
18
11
6
16
12
9
4
7
_
-
250
Plastics
Plants
72
30
27
17
8
10
6
2
2
_
1
-
-
-
-
175
Organics and
Plastics Plants
5
15
16
13
11
13
-
3
5
13
6
7
12
1
1 (50)
121
Total
113
58
72
57
36
55
37
13
11
21
26
15
11
19
1
1
546
*Table consists of plants that completed Part B of the 1983 Section 308
Questionnaire.
111-37
-------
plants reported individual dye products, while others reported types of dyes
such as Azo- or Vat-dyes as one product. A review of Table 111-12 shows that:
plastics plants tend to have fewer product/processes with 88 percent reporting
5 or fewer; organics plants have a wider range of number of product/processes
with 87 percent reporting 10 or fewer; and that plants manufacturing both
organics and plastics, although fewer in number, tend to have more product/
processes with 88 percent reporting 20 or fewer.
c. Plant Capacity and Production Volume
For the purposes of this report, plant size cannot be sufficiently de-
fined based on design capacity due to the often broad differences between a
plant's design capacity or rate and its average production rate per year.
Plants continuously producing high-volume chemicals (generally employing
relatively few workers), may be physically smaller than plants producing
lower-volume specialty chemicals by batch processes. Table 111-13 presents
the distribution of plant OCPSF production and total production for the year
1982 with plants sorted by their primary SIC code. The rates given are total
(all products) production for the plant, not just the product SIC group under
which they are listed. All data are from the 1983 Section 308 Questionnaire.
Additional production information is available in the Economic Impact Analysis
Report. Even though the table includes 38 plants that have been determined to
be non-scope facilities, the general trends reflected in the table should
apply to the final list of 940 scope facilities.
d. Plant Sales Volume
Sales volume alone is not necessarily an accurate indicator of plant
size. High-volume commodity chemicals are typically less expensive than
specialty chemicals. However, sales volume or production volume in terms 6f
dollars is very useful in describing plant size in economic terms. This
definition of size has been used in the economic analysis for this OCPSF rule.
Table 111-14 presents the distribution of plants by OCPSF total 1982 sales
value with plants sorted by their major SIC code. These 1983 Section 308 "
Questionnaire data are presented in the same format as production volumes
above. Additional sales data are available in the Economic Impact Analysis
Report. Like Table 111-13, Table 111-14 includes 38 facilities that have been
determined to be non-scope facilities.
111-38
-------
TABLE 111-13.
DISTRIBUTION OF 1982 PLANT PRODUCTION QUANTITY BY OCPSF SIC GROUP
No SIC
No. of
Plants
OCPSF Production
(Million Ibs.)
No data
0-.2
.2-1
1-2
2-10
10-20
20--100
100 Plus
All
Total Production
(Million Ibs.)
No .data
0-.2
.2-1
1-2
2-10 ,
10-20
20-100
100 Plus
All " '
39
-
-
-
-
-
-
-
39
12
2
2
1
12
5
3
2
39
2821
No. of
Plants
3
10
22
18
67
60
120
83
383
3
6
12
12
40
50
151
109
383
2823 2824
No. of No. of
Plants Plants
2
-
. -_ . ' 1
-
1 6
2
1 12
4 '18
.6 41
2
-
_ i
. • -
1 6
2
1 11
4 19
6 41
2865
No. of
Plants
6
17
5
25
10
14
34
111
3
14'
7
23
11
14
39
111
2869
No. of
Plants
3
29
22
19
75
37
109
104
398
3
22
12
11
65
33
107
145
398
All
No. of
Plants
47
45
62
42
174
109
256
243
9781
20
33
41
31
147
101
287
318
9781
All
Percent
4.8
4.6
6.3
4.3
17.8
11.1
26.2
24.8
100.0
2.0
3.4
4.2
3.2
15.0
10.3
29.3
32.5
100.0
1Includes 38 plants that have been determined to be lion-scope facilities.
Source: OCPSF Economic Impact Analysis.
111-39
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TABLE 111-14.
DISTRIBUTION OF 1982 PLANT SALES VALUE BY OCPSF SIC GROUP
No SIC
No. of
Plants
OCPSF Production
(Million $)
No data 39
0-1
1-5
5-10
10-50
50-100
100-500
500 Plus
All 39
Total Sales
Value (Million $)
No data 13
0-1 2
1-5 9
5-10 3
10-50 9
50-100 2
100-500 1
500 Plus
All 39
2821
No. of
Plants
11
34
76
61
128
33
38
r*
" 2
383
5
15
32
56
157
58
50
10
383
2823 2824 2865
No. of No. of No. of
Plants Plants Plants
2
-
2
1 3
1 8
5
4 20
_ -^
6 41 ,
2
-
1
1 3
1 9
5
4 20
1
6 41
-
5
23
11
45
10
17
-
Ill
-
5
15
13
47
13
18
-
Ill
2869
No. of
Plants
8
39
56
47
132
43
57
16
398
6
26
45
33
143
46
82
17
398
All
No. of
Plants
60
78
157
123
314
91
136
19
9781
26.
48
102
109
366
124
175
28
9781
All
Percent
6.1
8.0
16.1
• 12.6
32.1
9.3
13.9
1.9
100.0
2.6
4.9
10.4
11.1
37.4
12.7
17.9
2.9
100.0
Includes 38 plants that have been determined to
Source: OCPSF Economic Impact Analysis.
be non-scope facilities.
111-40
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7. Mode of Discharge
There are three basic discharge modes utilized by the industry: direct,
indirect, and zero or alternative disposal/discharge. Direct dischargers are
plants that produce a contaminated process wastewater, treated or untreated,
that is discharged directly into a surface water. Plants that produce only
noneontact cooling water and/or sanitary sewage effluents (non-process waste-
water) are not considered to be direct dischargers of OCPSF process wastewater
for purposes of this report. Indirect dischargers are plants that .route their
OCPSF process wastewater effluents to POTWs. Zero or alternative disposal/
dischargers are plants that discharge no OCPSF process wastewater to surface '
streams or to POTWs. For the purposes of this report, these include plants
that generate no process wastewaters, plants that recycle all contaminated
waters, and plants that use some kind of alternative disposal technology
(e.g., deep well injection, incineration, contractor • removal, etc).
The discharge of process wastewaters into the system of an adjoining
manufacturing facility or to* a treatment system not owned by a government
entity is not considered indirect discharge, but is termed off-site treatment
and is considered an alternative disposal method. Table 111-15 shows the
plant distribution based on mode of discharge. The table also shows the
distribution between primary producers (i.e., plants 'whose OCPSF production
exceeds 50 percent of the plant total) and secondary producers.
Fifteen plants discharge treated and/or untreated wastewater both di-
rectly and indirectly. In general, these plants discharge high-strength or
"difficult to treat" wastewater to POTWs and direct discharge more easily
treated low-strength wastewater.
* ' ;
C. DATA BASE DESCRIPTION
%r •' •
~1. 1983 Section 308 Questionnaire Data Base
"•In the preamble to the March 21, 1983 proposed regulation, the Agency
recognized the need to gather additional data to ensure that the final regula--
tion is based upon information that represents the entire industry and to
assess wastewater treatment installed since 1977. Therefore, the Agency
111-41-
-------
TABLE 111-15.
MODE OF DISCHARGE
Direct
Primary Producers
Organics Plants 96
Plastics Plants 72
Organics & Plastics
Plants 70
Total Primary
Producers 238
Secondary Producers
and/or Zero Dischargers
Organics Plants 30
Plastics Plants 13
Organics & Plastics
Plants 8
Total Secondary
Producers/Zero
Dischargers 51
Total All Plants 289
Indirect
146
96
45
287
48
41
17
106
393
Direct and
Indirect
5
2
5
12
1
1
1
3
15
Zero Unknown
3
5
1
9
92 4
104 4
29 1
225 9
234 9
Total
250
175
121
546
175
163
56
393
940,
Source: EPA OTA Section 308 Survey, 1983.
111-42
-------
conducted an extensive data-gathering program to improve the coverage of all
types of OCPSF manufacturers. A comprehensive Clean Water Act Section 308
Questionnaire was developed and distributed in 1983. The mailing list was
compiled from the following references that identify manufacturers of OCPSF
products:
• Economic Information Service
• SRI Directory of Chemical Manufacturers
• Dun and Bradstreet Middle Market Directory
• Moody's Industrial Manual
« Standard and Poor's Index
• Thomas Register
• Red Book of Plastics Manufacturers
• 1976 and 1977 308 Questionnaire Data Bases
• Plastics Manufacturers Telephone Survey of 301 Plants.
In October 1983, the Agency sent a General Questionnaire to 2,840 facili-
ties and corporate headquarters to obtain information regarding individual
plant characteristics, wastewater treatment efficiency, and the statutory
factors expected to vary from plant to plant. The General Questionnnaire
consisted of three parts: Part I (General Profile), Part II (Detailed Produc-
tion Information), and Part III (Wastewater Treatment Technology, Disposal
Techniques, and Analytical Data Summaries).
Some plants that received the Section 308 Questionnaire had OCPSF
operations that were a minor portion of their principal production activities
and related wastewater streams. The data collected from these facilities
allow the Agency to characterize properly the impacts of ancillary (secondary)
OCPSF production. Generally, if a plant's 1982 OCPSF production was less than
50 percent of the total facility production (secondary manufacturer), then
only Part I of the questionnaire was completed.
Part I identified the plant, determined whether the plant conducted
activities relevant to the survey, and solicited general data (plant age,
ownership, operating status, permit numbers, etc.). General OCPSF and non-
OCPSF production and flow information was collected for all plant manufactur-
ing activities. This part also requested economic information, including data
111-43
-------
on shipments and sales by product groups, as well as data on plant employment
and capital expenditures.
Part I determined whether a respondent needed to complete Parts II and
III (i.e., whether the plant is a primary or secondary producer of OCPSF pro-
ducts, whether the plant discharges wastewater, and for secondary producers,
whether the plant segregates OCPSF process wastewaters). For those plants
returning only the General Profile, Part I identified the amounts of process
wastewater generated, in-place wastewater treatment technologies, wastewater
characteristics, and disposal techniques.
Part II requested detailed 1980 production information for 249 specific
OCPSF products, 99 specific OCPSF product groups, and OCPSF products that
constituted more than 1 percent of total plant production. Less detailed
information was requested for the facility's remaining OCPSF and non-OCPSF
production. Part II also requested information on the use or known presence
of the priority pollutants for each OCPSF product/process or product group.
Part III requested detailed information on plant wastewater sources and flows,
technology installed, treatment system performance, and disposal techniques.
Responses to economic and sales items in Part I pertained to calendar
year 1982, which were readily available, since the plants were required to
submit detailed 1982 information to the Bureau of the Census. This reduced
the paperwork burden for responding plants.
The remainder of the Section 308 Questionnaire, however, requested data
for 1980, a more representative production year. The Agency believed that
treatment performance in 1982 would be unrepresentative of treatment during
more typical production periods. This is because decreased production nori
mally results in decreased wastewater generation. With lower volumes of
wastewater being treated, plants in the industry might be achieving levels'of
effluent quality that they could not attain during periods of higher produc-
tion. The year 1980 was selected in consultation with industry as representa-
tive of operations during more normal production periods, but recent enough to
identify most new treatment installed by the industry since 1977. The indus-
try representatives did not assert that significant new treatment had been
installed since 1980.
111-44
-------
The Section 308 Questionnaires were designed to be encoded into a
computer data base directly from the questionnaires. To ensure that the ques-
tionnaires were filled out completely and correctly a copy of each question-
naire was reviewed by engineers. Due to the diversity and complexity of the
OCPSF industry, a number of problems were encountered in reviewing the ques-
tionnaires. Some of the problems encountered included incorrect units of
measure, incomplete responses, misinterpretation of data requested, conflict-
ing data, for different questions, pooling of data for separate questions, ,and
unusual circumstances at the plant.
Solutions to these problem included recalculation of the data, followup
contacts for clarification, or in some cases rejection of the data. Some of
these, problems may be explained in part by the fact that some companies simply
did not keep records of the information that was requested by the question-
naire, and consequently could not respond fully on all items of interest.
The data were encoded onto computer .tapes from the corrected copies of
the.questionnaires. Each questionnaire was double entered by separate indi-
viduals to help eliminate keypunch errors. The data were then sorted into
separate computer files for each question.
- The data in each question-file were then verified by various means.
Verification methods included but were not limited to: visual inspection of
the file printout, checks for missing data, checks for conflicting data, and
checks for unusually high or low values. In addition, many of the engineering
analyses required a more detailed review of the data, plus the execution of
the analyses often exposed faulty data through erroneous results or the in-
ability of a program to run. Wherever suspect data were identified, .they were
referred to the review engineers who then took appropriate action to resolve .
the problem. The economic study assessments also determined that some plants
that responded as a scope facility should be considered non-scope. A separate
data file called the Master Analysis File has been created, from the 308
Questionnaire data. This data file contains only data that are useful in, the
engineering analyses and are used for that purpose.
i 111-45
-------
The Section 308 Questionnaires were mailed in October 1983. In February
1984, Section 308 followup letters were sent to 914 nonrespondents. A total
of 940 questionnaire responses provide the basis for the final technical and
.economic studies. A total of 1,574 responses were from facilities that were
determined to be outside of the scope of the final regulations (e.g., sales
offices, warehouses, chemical formulators, non-scope production, etc.); 166
were returned by the Post Office; and 160 did not respond. A followup
telephone survey of 52 randomly selected nonrespondents concluded that over 90
percent of the nonrespondents were not manufacturers of OCPSF products.
In addition, a Supplemental Questionnaire was sent to 84 facilities known
to have installed selected wastewater treatment unit operations. Detailed
design and cost information was requested for four major treatment components
commonly used to treat OCPSF wastewaters (i.e., biological treatment, steam
stripping, solvent extraction, and granular activated carbon) and summary
design and cost information for other wastewater and sludge treatment compon-
ents. The questionnaires also collected available treatment system perform-
ance data for in-plant wastewater control or treatment unit operations, in-
fluent to the main wastewater treatment system, intermediate waste stream
sampling locations, and final effluent from the main wastewater treatment
system. Unlike the General Questionnaire, it asked for individual daily data
rather than summary data. After a followup effort 64 plants responded with
useful data and information.
2. Daily Data Base Development
One of the major purposes of this study is the development of long-term
daily pollutant data. These data are required to derive variability factors
that characterize wastewater treatment performance and provide the basis for
derivation of proposed effluent limitations guidelines and standards. Hun-
dreds of thousands of data points have been collected, analyzed, and entered
into the computer.
The first effort at gathering daily data involved the BPT and BAT mail-
ings in 1976 and 1977. These questionnaires asked each plant for backup
information to support the long-term pollutant values reported. Many plants
111-46
-------
submitted influent and effluent daily observations convering the time period
of interest in the BPT questionnaire (January 1, 1976 to September 30, 1976).
Additionally, there were other conventional and nonconventional pollutant
daily data in the files from the period of verification sampling. Some plants
also submitted additional data with their public comments for the 1983 pro-
posed requlations. Additional data were collected through the supplemental
1983 Section 308 Supplemental Questionnaires.
3. BAT Data Base
The BAT Data Base contains long- and short-term priority pollutant data
used in the development of effluent limits. The data base consists primarily
of end-of-pipe wastewater treatment system influent and effluent data, but
also includes other types of samples. These other samples, include individual
process streams* intermediate samples within the end-of-pipe system, and in-
fluent and effluent samples of individual treatment units, especially those
under consideration as BAT technology.
Data sources include both EPA sampling programs and data supplied by
OCPSF plants. In all cases, the analytical data have been considered accept-
able for limitations development only if the QA/QC procedures were documented
and in the case 'of organic pollutants the analyses were confirmed by GC/MS or
known to be present based on process chemistry. The major sources of data are
listed below:
• EPA Screening Sampling Program (1977 to 1979)
• EPA Verification Sampling Program (1978 to 1980)
• EPA/CMA Five-Plant Study (1980 to 1981)
• EPA 12-Plant Sampling Program (1983 to 1984)
• Plant Submissions Accompanying Comments to the March 1983 Proposed
Regulations
• Plant Submissions Accompanying Comments to the July and October 1985
and December 1986 Notices of New Information
• Supplemental Sections to the 1983 Section 308 Questionnaire.
111-47
-------
The data base designations used throughout this report are listed in
Table 111-16. The four EPA sampling programs are discussed in greater detail
in Sections V and VII of this report.
±JL±-4
-------
TABLE 111-16.
DATA BASE DESIGNATION
Data Base File Name
Description
308 Data Base
Data base containing all data
extracted from 1983 Section 308
Questionnaires
Master Analysis File (MAF)
Contains data excerpted from the
1983 Section 308 Data Base
(includes conventional pollutant
parameter long-term average data)
Daily Data Base
Contains long-term conventional
pollutant effluent daily data from
69 plants
BAT Data Base
Contains long- and short-term
treatment system influent and
effluent daily data for priority
pollutants
Master Process File (MPF)
Contains priority pollutant raw
wastewater characterization data
for 176 OCPSF product/processes
111-49
-------
-------
SECTION IV
SUBCATEGORIZATION
A. INTRODUCTION
Sections 304(b)(l)(B) and 304(b)(4)(B) of the Clean Water Act (CWA) re-
quire the U.S. Environmental Protection Agency (EPA) to assess certain factors
in establishing effluent limitations guidelines based on the best practicable
control technology (BPT) and best available technology economically achievable
(BAT). These factors include the age of equipment and facilities involved;
the manufacturing process employed; the engineering aspects of the application
of recommended control technologies,.including process changes and in-plant
controls; nonwater quality environmental impacts, including energy require-
ments; and such other factors as deemed appropriate by the Administrator.
To accommodate these factors, it may be necessary to divide a major
industry into a number of subcategories of plants sharing some common charac-
teristics. This allows the establishment of uniform national effluent limita-
tions guidelines and standards, while at the same time accounting for the
particular characteristics of different groups of facilities.
The factors considered for technical significance in the subcategoriza-
tion of the Organic Chemicals and Plastics and Synthetics Fibers (OCPSP) point
source categories include:
• Manufacturing product/processes
« Raw materials
• Wastewater characteristics
• Facility size
• Geographical location
• Age of facility and equipment
• Treatability
• Nonwater quality environmental impacts
• Energy requirements.
IV-1
-------
The impacts of these factors have been evaluated to determine if sub-
categorization is necessary or feasible. These evaluations, which are dis-
cussed in detail in the following sections, result in the following final
subcategories:
o BPT: Rayon, other fibers, thermoplastic resins, thermosetting resins,
commodity organics, bulk organics, and specialty organics
o BAT: Subcategory One (end-of-pipe biological treatment) and Subcate-
gory Two (non-end-of-pipe biological treatment).
B. BACKGROUND
In the March 21, 1983, Federal Register, EPA proposed a subcategorization
approach for regulation of the OCPSF industry. A Notice of Availability (NOA)
appeared in the July 17, 1985, Federal Register, which addressed a number of
concerns raised by industry relating to the March 1983 proposal. Another NOA
appeared in the December 8, 1986, Federal Register, which presented an altern-
ative subcategorization approach. This section discusses the subcategoriza-
tion methodologies for the proposal and the two NOAs and presents the concerns
and issues raised during the public comment periods for each.
1. March 21, 1983 Proposal
The March 21, 1983, proposal established four subcategories (Plastics
Only, Oxidation, Type I, and Other Discharges) for BPT effluent limitations,
which were based on generic chemical reactions such as oxidation, peroxida-
tion, acid cleavage, and esterfication and whether a plant produced plastics
or organics. This approach was found to be too cumbersome to implement be-
cause the process information necessary to place a plant in a subcategory was
not readily available. Also, a major problem raised by both industry and
regulatory agencies in public comments on the proposal was that a plant could
shift from one subcategory to another simply by changing a single product/
process.
The March 21, 1983, proposal also established two subcategories (Plastics
Only and Not Plastics Only) for BAT effluent limitations. The rationale for
this two-subcategory approach was that plants in the Plastics Only subcategory
tended to have fewer toxic pollutants present and less significant levels than
IV-2
-------
the remaining discharges, all of which result from the manufacture of at least
some organic chemicals which were contained in the Not Plastics,Only subcat-
egory. The Agency also announced its intention to establish a separate BAT
subcategory with different zinc limitations for those plants manufacturing
rayon and utilizing the viscose process.
After reviewing public comments and evaluating its proposed subcategori-
zation methodology, the Agency decided to revise its approach and developed
another subcategorization approach, which was published for public comment in
the July 17, 1985, Federal Register NOA. This revised methodology is dis-
cussed in the following section.
2. July 17, 1985, Federal Register NOA /
The July 17, 1985, Federal Register NOA sought to correct some of the
difficulties described above by categorizing plants according to the products
accounting for most of their production. Under this .subcategorization strat-
egy, every plant was to be put into a single categoric grouping. The subeate-
gories in this approach were as follows! , ,
1. Thermoplastics Only (SIC 28213) , .
2. Thermosets (SIC 28214 plus Organics)
3. Rayon (Viscose)
4. Other Fibers (SIC 2824 and 2823 plus Organics)
5. Thermoplastics and Organics (SIC 28213 and 2865 or 2869)
6. Commodity Organics
7. Bulk Organics ,
8.1 Specialty Organics. ,
These eight subcategories were defined as follows:
• Subcategories 1 and 3 were defined as facilities that produced at
least 95 percent thermoplastics and rayon, respectively.
• Subcategories 2 and 4 were for facilities whose production was at
least 95 percent of the subcategory heading or facilities whose combi-
nation of organic chemicals and the subcategory heading represented at
least 95 percent of the plant production.
IV-3
-------
• Subcategory 5 represented plants with a production that was at least
95 percent thermoplastic and organic products with neither product
group representing 95 percent production. This group was interpreted
to be vertically integrated plants producing organics, which were then
used primarily for the production of thermoplastics.
• Subcategories 6 through 8 identified the relatively pure organics
plants that had a production that was at least 95 percent organics.
Organics production was further subdivided according to volume.
- Commodity: Those chemicals produced nationally in amounts greater
than or equal to 1 billion pounds per year.
- Bulk: Those chemicals produced nationally in amounts less than 1
billion but more than 40 million pounds per year.
- Specialty: Those chemicals produced nationally in amounts less
than or equal to 40 million pounds per year.
Plants were assigned to these categories based on their mix of produc-
tion; plants having at least 75 percent commodity or specialty were assigned
to these respective subcategories. Remaining plants were assigned to the bulk
subcategory. Thus, a plant might be assigned to the bulk subcategory, but it
could also manufacture both commodity and specialty chemicals.
The July 17, 1985, Federal Register NOA also announced the Agency's in-
tentions to establish a single set of BAT effluent limitations that would be
applicable to all OCPSF facilities rather than the two subcategory approach
presented in the March 21, 1983, proposal. The rationale for this "one BAT
subcategory" approach was that the available data for BAT show that plants in
differing BPT subcategories can achieve similar low toxic pollutant effluent
concentrations by installing the best available treatment components. The
Agency also again announced its intention to establish a separate BAT subcate-
gory with different zinc limitations for those plants manufacturing rayon and
utilizing the viscose process.
While the subcategories developed for the July 17, 1985, Federal Register
NOA were more useful than those established for the March 21, 1983, proposal,
the revised subcategorization approach was still criticized by OCPSF trade
associations and companies for the reasons summarized below.
IV-4
-------
a. Multiple Subcategory Plants
A significant number of the plants cannot be classified according to the
July 17, 1985, Federal Register NOA subcategorization approach for the follow-
ing reasons:
• No single subcategory accounts for the majority of the production at a
number of plants.
• No allowance was made in the thermoplastics and organics subcategory
for variations in the types of organic products produced. From analy-
sis of the data, plants with high specialty volume can be expected to
have higher BOD5 effluent concentrations when compared to plants with
high commodity production.
• Plants could change their subcategory classifications by making small
changes in the proportion of products produced.
b. Low Flow/High Flow Plants
In the March 21, 1983, Proposal, the Agency incorporated a low flow/high
flow cutoff in one of its proposed subcategories, because flow was found to be
a statistically significant subcategorization factor. This adjustment was not
made in the July 17, 1985, Federal Register NOA because flow was not found to
be a statistically.significant factor for the revised subcategorization
approach. However, the Agency received numerous public comments requesting
that consideration be given to plants that conserve water and are low water,
users.
All the above considerations led the Agency to modify the July 17, 1985,
subcategorization approach to accommodate these issues while trying to pre-
serve a workable subcategorization and guideline structure.
3. December 8, 1986, Federal Register
The Agency again revised its subcategorization methodology and presented
it in the December 8, 1986, Federal Register NOA. Initially, a regulatory
approach that would have created plant specific long-term averages based on a
flow proportioning of individual product subcategory long-term averages was
attempted. This would have eliminated a number of difficulties associated
with multiple subcategory plants and was consistent with current permit writ-
ing "building block" practices.
IV-5
-------
Production/flow information had been requested from industry in the 1983
308 Questionnaire Survey in'anticipation of implementing such an approach.
Unfortunately, much of the production/flow information (when supplied) was
either- estimated or grouped with other product/process flows and was con-
sidered too inaccurate or nebulous for subcategorization purposes. However,
since relatively accurate production volume information by product/process or
product groups was available, a regulatory approach that proportions the vari-
ous subcategory long-term averages for each plant based on the reported pro-
portion of production by product group was developed. This revised subcate-
gorization approach incorporated essentially the same product-based subcate-
gories as presented in the July 17, 1985, Federal Register NOA:
1. Thermoplastics (SIC 28213)
2. Thermosets (SIC 28214)
3. Rayon (Viscose Process)
4. Other Fibers (SIC 2823 and 2824)
5. Commodity Organics (SIC 2865 and 2869)
6. Bulk Organics (SIC 2865 and 2869)
7. Specialty Organics (SIC 2865 and 2869).
While the prior subcategorization approaches incorporated subcategories that
included both a major production group and other secondary production, these
seven subcategories represented only single production groups, while plants
that have production that falls into more than one production group, were
handled by a regression model that emulates the production proportioning used
by permit writers. This regression model was as follows:
ln(BODA) = a + Z wij-Tj + B- [ln(flowi )] + D-15.^ +
where li^BODj), w , ln(flow ), and 15 are plant-specific data
available in the data base (for plant i), and the parameters a, T ,
and D are values, estimated from the data base using standard j
statistical regression methods. Definitions of the terms in this
regression equation (and also used in subsequent equations) are as
follows :
ln(BODi) = natural logarithm (In) of the 1980 annual arithmetic average
BOD effluent in mg/1, which has been adjusted for dilution
with uncontaminated miscellaneous wastewaters (as described
in Section VII), for plant i.
IV-6
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) = ln(total flow (MGD)), corrected for non-process waste
streams) for plant i, with associated coefficient B.
15. = indicator variable for plant i
= 1, if plant i meets 95 percent BODg removal or at most 50
mg/1 BOD5 effluent editing criteria (95/50), for plants with
biological treatment and polishing ponds,
=0, otherwise
w = proportion of OGPSF 1980 production from plant i from sub-
13 category j
e. = statistical error term associated with plant i
The seven subcategories, represented by the subscript j, are as follows:
j=l: Thermoplastics
j=2: Thermosets
j=3: Rayon .
j=4: Other Fibers ,
j=5: Commodity Organics
j=6: Bulk Organics
j=7: Specialty Organics.
The coefficients T. and D are related to the intercept of this equation
(denoted by "a"). The T.. coefficients are subcategorical deviations from the.
7
overall intercept "a.
The restriction E T.=0 is placed on the regression
3=1 D
equation, as discussed in Appendix IV-A, to allow for estimation of these
values by standard multiple regression methods. The coefficient D represents
the difference between the intercept of this equation (based on .all.full-
response, direct discharge OCPSF plants that have at least biological treat-
ment in place and have provided BOD5 effluent, subcategorical production, and
flow data) and the intercept based on the subset of these plants that have
biological treatment and polishing ponds and meet the 95/50 editing criteria
used by EPA at the time of the 1986 NOA.
IV-7
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In addition to its production proportioning approach, the Agency also
included a flow adjustment factor in its regression model in an attempt to
respond to public comments criticizing its elimination in the July 17, 1985,
subcategorization approach. When included in the regression model and tested
statistically, the flow adjustment coefficient, B, was found to be statistic-
ally significant in explaining plant-to-plant variation of reported average
BOD5 effluent.
A regression model relating effluent TSS to effluent BOD5 was also devel-
oped to calculate estimated TSS effluent long-term averages for individual
plants, as follows:
= a
b- [ln(BOD. )]
where:
ln(TSS..) = ln(1980 annual arithmetic average TSS effluent in mg/1,
which has been adjusted for dilution with uncontaminated
miscellaneous wastewaters, as described in Section VII),
for plant i
e.. = statistical error term associated with plant i.
The data base used to determine these long-term averages included all
full-response, direct discharge OCPSF plants with biological treatment and
polishing ponds that met the 95/50 editing criteria for BOD5 described pre-
viously and that had TSS effluent concentrations of at most 100 mg/1. The
variables ln(BOD±) [defined previously] and ln(TSS.) are plant-specific data
available in this data base, and the intercept and slope parameters a and b,
respectively, are values estimated from the data base using standard statis-
tical regression methods.
The December 8, 1986, Federal Register NOA retained the "one BAT subcate-
gory" approach along with the separate subcategory and different zinc limita-
tions for rayon manufacturers utilizing the viscose process.
While the revised subcategorization approach was yet another improvement
on previous subcategorizations, a number of major issues were raised during
the public comment period for the December 8, 1986, Federal Register NOA,
which are detailed below.
IV-8
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a. Flow Adjustment Factor
Many comments were received which stated that the flow adjustment factor
was not the equitable flow correction that the Agency intended, since it util-
ized total wastewater flow in its adjustment that would penalize high-
production facilities with high flows and plants with certain product/
processes that typically utilize and discharge large volumes of wastewater
(e.g., rayon and fibers plants). Commenters suggested that the flow adjust-
ment factor be changed to account for production volume at each facility;
i.e., use a gallon of wastewater/pound production adjustment factor.
A related issue raised by commenters also concerned the flow adjustment
factor: a flow adjustment coefficient based on the use of all OCPSF plants
with biological treatment, regardless of effluent BOD5,.. causes a small group.
of plants exhibiting high effluent BOD5 and low wastewater flow to dispropor-
tionately influence the estimated long-term averages for other plants, based
on the regression model. The commenters stated that if approximately 16
plants with effluent BOD5 values greater than 200 mg/1 were removed from the
regression, the flow adjustment coefficient, B, was no longer significant.
b. Total Production
Commenters stated that a total production factor should be included in
the regression model even though production was evaluated in the December 8,
1986, subcategorization approach and was found not to be significant.
C.
FINAL ADOPTED BPT AND BAT SUBCATEGORIZATION METHODOLOGY AND RATIONALE
Based on an assessment of the comments on the subcategorization method-
ology presented in the December 8, 1986, Federal Register NOA, the Agency
revised its regression model and the methodology for using the model to estab-
lish effluent BOD5 long-term averages. The final revised regression model is
as follows:
ln(BOD.) = a + I w •T, + B-I4 + C-Ib. + e.
IV-9
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Ib
where:
1^ « performance indicator variable for plant i
J"A if ?lant i meets the 95 Percent BOD removal or at most
40 mg/1 BOD5 effluent editing criteria (the final BODC perform-
ance editing criteria) 5
= 0, otherwise
treatment indicator variable for plant i
1, if plant i has only biological treatment
0, if plant i has treatment in addition to biological treatment
e.,^ = statistical error term associated with plant i.
The other terms have been defined previously.
The values for a, T^ , B and C are regression coefficients that are esti-
mated from the 157 full-response, direct discharge OCPSF plants that have at
least biological treatment in place and provided BOD5 effluent and subcategor-
ical production data.
Procedures used to estimate the model coefficients and the estimates are
presented in Appendix IV-A, Exhibit 1. The data base employed to obtain the
estimates is presented in Appendix IV-A, Exhibit 8.
This regression model differs from the model presented in the December 8,
1986, Federal Register NOA in several major respects:
• BPT_Treatment System: The revised regression model is designed to
estimate BOD effluent long-term averages for biological treatment
only (the selected BPT regulatory option) rather than for biological
treatment and polishing ponds (see Section IX for rationale of options
selection) .
^formance Edit: The indicator variable 15. in the December 8,
subcategorization specified at least 95 percent BODC removal or
at most 50 mg/1 BOD5 in the treated .was tewater (95/50), while the
otT/n/ reSression model has indicator variable 14. , which specifies
95/40 (see Section VII for discussion on change of performance editing
rules). • e
198
IV-10
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Performance and Treatment System Shifts: The regression model pre-
sented in the December 8, 1986 Federal Register NOA included a single-
parameter to account for differences in the logarithm of BOD, due to
treatment systems other than biological treatment and polishing ponds
and less than adequate performance: (defined as 95/50). The revised
regression model includes separate parameters to accourit for differ-
ences: one parameter to distinguish between BPT treatment systems
(now biological only) and other treatment systems; ancT another para-
meter to account for performance (now defined as 95/40). Discussion
of these changes in parameters is included in this section.
Adjustment for OCPSF flow: The model published in the December 8,
1986, subcategorization included an OCPSF flow adjustment, but the
current model includes no such adjustment for flow. Discussion of
this change is included in this section.
• Individual Plant Versus Subcategory Long-Term Averages! Q
subcategorization methodology published in the December 8, 1986, NOA
yielded individual plant-specific long-term averages, the revised
subcategorization methodology yields pure subcategory BOD and TSS
effluent long-term averages that will be applied by the NPDES permit
writers.
The procedures used to calculate the pure subcategory long-term averages are
presented in Appendix IV-A. (See Section VII for discussion of rationale for
choosing between pure subcategory and individual plant-specific long-term
averages . )
'The Agency retained the same methodology presented in the December 8,
1986, Federal Register NOA for calculating TSS effluent long-term averages. A
discussion of the relationship of TSS to BOD5 effluent concentrations is pre-
sented in Section VII, along with a discussion of the final TSS performance
criterion. The regression model for estimating TSS effluent long-term
averages is as follows: . ;
a •
b-[ln(BOD.)]
ei
The coefficients a and b are estimated from the 61 OCPSF plants that have
only biological treatment in place, meet the 95/40 editing criteria for BOD5
described previously, and have TSS effluent concentrations of at most
100 mg/1.
IV-11
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Estimates of the TSS-model coefficients are given in Appendix IV-A,
Exhibit 2. The data base employed to generate the estimates is presented in
.Appendix IV-A, Exhibit 8.
The following sections discuss the rationale behind some of the changes
made to the subcategorization methodology.
1- Performance and Treatment System Shifts
One change in the form of the BOD5 long-term average model is a revision
of the indicator functions. The regression model published in the December 8,
1986, Federal Register NOA had a single shift indicator. This indicator was
the sole explanatory variable to account for adjusted differences in average
treatment performance between biological plants having polishing ponds and
satisfying the proposed 95/50 performance criterion and all other plants.
If this kind of single indicator function was applied to the revised BPT
treatment and performance standards of biological only and 95/40, then this
single shift indicator would account for adjusted differences between biologi-
cal only, 95/40 plants and all other plants. The set of all other facilities
can be divided into three distinct subsets; plants with treatment other than
biological only which satisfy the performance criterion; plants with treatment
other than biological only which do not satisfy the performance criterion? and
plants with only biological treatment which do not satisfy the performance
criterion. Clearly, plants with more than biological treatment are expected
to perform at least as well as biological-only facilities, and biological-only
plants that fail to satisfy the 95/40 edit will perform below the BPT "average
of the best" performance. A single shift indicator alone, similar to that
included in the regression model published in the December 8, 1986, NOA,
cannot separately account for the adjusted differences due to treatment'and
performance between the biological-only, 95/40 plants and all other plants.
In an effort to reformulate the revised BOD5 long-term average model to better
reflect the separate effects of the treatment and performance characteristics
of the data base, EPA redefined the single indicator shift in the form of two
indicator variables for the model: one indicator accounts for adjusted dif-
ferences between biological only treatment and treatment other than biological
IV-12
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only, and the other indicator accounts for adjusted differences between plants
meeting the 95/40 performance criteria and those that do not.
2. Flow and Total Production Adjustment Factors
The regression model published in the December 8, 1986, Federal Register
NOA contained a flow adjustment term in the form of the natural logarithm of
the plant OCPSF flow in MGD. EPA included this term in an effort to account
for plants that practice water conservation. The regression coefficient for
that term was negative, which resulted in a decreasing BOD5 long-term average
concentration for increasing flow. Although this result is reasonable and may
account for water conservation, it could impose unreasonably low limitations
on plants with a high proportion of fibers production that already achieve low
effluent BOD5 levels (i.e., 12 mg/1). Industry commenters claimed that flow
rate alone cannot distinguish between plants that practice water conservation
and those plants that use excessive amounts of water. Certain product/pro-
cesses (e.g., rayon manufacture) must use large amounts of water in relation
to other plants and are then unjustly penalized with lower limits. Further-
more, commenters stated the inclusion of the flow adjustment term does not
reflect total production, which should be incorporated into the subcategorical
regression model. According to the commenters, increased production should
result in larger flows and higher BOD5 concentrations, which is contrary,to
the results obtained from the regression model EPA published in the December
8, 1986, NOAi An examination of these issues is summarized below.
EPA reexamined the inclusion of the flow adjustment factor. Based on
that examination, EPA agrees that flow rate alone does not indicate whether a
plant practices water conservation. Moreover, the 1986 published model, in
EPA's assessment, did result in excessively low BOD5 long-term average con-
centrations for some plants with large flows.
Commenters further argued that the statistical significance of the flow
adjustment factor for the regression model presented in the December 8, 1986,
NOA was due entirely to a small number of plants with small flows and large
BOD effluents. EPA's examination of the data base revealed that facilities
IV-13
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with relatively high BOD, and low flows are mostly facilities that have bio-
logical treatment but failed the 95/40 performance criteria. To formalize
this analysis, EPA considered models in the context of the data base used for
determining BOD5 effluent long-term averages to explore the effects of these
plants on flow adjustments. In particular, the model
/
ln(BOD±) = a + Z w^-T., + F- [ln(flow. )] + e±
was examined separately for the following four subsets of the data base:
(1) Biological only and 95/40
(2) Biological only and not 95/40
(3) Not biological only and 95/40
(4) Not biological only and not 95/40
These four mutually exclusive subsets partition completely the 153 full-
response, direct discharger OCPSF plants that have at least biological treat-
ment in place and provided BOD5 effluent, flow, and subcategorical production
data. The computer analysis for these regression models and plots of ln(BOD
effluent) versus In(flow) are presented in Appendix IV-A, Exhibit 3. Note *
that the set of plants in (1) above has information regarding all subcate-
gories. Rayon plants are not present in the set of plants in subsets (2),
(3), and (4), however, and the term corresponding to rayon has been excluded
from the model for these sets of plants. Also, fibers plants are not present
in the set of plants in subset (4), and the term corresponding to fibers has
also been excluded from the model when examining the set of plants in (4).
These models were examined for the significance of the coefficient F, corres-
ponding to the natural logarithm of flow.
Based on this analysis, the Agency agrees with the commenters that the
significance of the flow adjustment term in the December model is largely
influenced by the poorly performing plants (plants that do not meet the 95/40
BPT performance edit) with only biological treatment. Because this pattern is
exhibited only by a subset of plants that are not well-designed and operated,
IV-14
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the Agency concludes that this pattern should not be reflected in the esti-
mation of long-term BODg averages as a construct of the model. Therefore, EPA
has deleted the flow adjustment factor from the model.
EPA has also examined the inclusion of a production adjustment factor
using the following model:
7
ln(BOD..) = a + E w.^Tj + G-[ln(prod. )] + e..
where:
ln(prod.) = In (OCPSF 1980 total production) from plant i, in
1 millions of pounds per year, with associated
coefficient G.
As described in the analysis of flow, this model was examined separately
for the four subsets of the 157 full-response, direct discharge OCPSF plants
that have at least biological treatment in place and provided BOD5 effluent
and subcategorical production data. The computer analysis for these regres-
sion models and plots of In(BOD) are presented in Appendix IV-A, Exhibit 4.
These models were examined for the coefficient of G, corresponding to the
natural logarithm of production. The same pattern emerges with this factor as
was present when the natural logarithm of flow was examined; namely, the sig-
nificance of this term is largely due to the poorly performing plants with
biological only treatment (plants that do not meet the 95/40 BPT performance
edit). Consequently, EPA has decided not to add a production adjustment
factor to the model.
Commenters have asserted that increased production should result in
higher BOD effluent concentrations. As seen by the regressions involving
total production, the data do not support a positive association between BOD5
effluent concentration and total production (higher BOD5 effluent concentra-
tions associated with.higher production levels), after adjustment for propor-
tion of production in a subcategory.
IV-15
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EPA has also considered the effect of flow per unit of production, using
the following model, applied separately to the 4 subsets of 153 full-response,
direct discharge OCPSF plants that have at least biological treatment in place
and provided BOD5 effluent, flow, and subcategorical production data (4 of the
157 full-response plants did not report flow):
ln(BOD.) =
a +
w.
. + H- [ln(365*flowi/prodi)] +
where?
= annual total flow (MGD), corrected for non-process
waste streams, for plant i, divided by OCPSF 1980
production (in millions of pounds per year), for
plant i.
The units for ln(365*f low, /prod,) are gallons/pound-the significance of
the coefficient H, associated with this quantity, was examined. Results simi-
lar to those found for flow and production were observed, in the sense that
this flow per unit production variable is only marginally significant for
plants with biological only treatment that do not meet the 95/40 BPT perform-
ance edit (see Appendix iy-A, Exhibit 5). The Agency concluded that a flow
per unit production adjustment factor was not appropriate for the same reasons
described for flow and production; that is, the model should not reflect a
pattern exhibited only by a subset of plants that are not well-designed and
operated.
D. FINAL ADOPTED BAT SUBCATEGORIZATION APPROACH
Based on comments received during public comment periods for the proposal
and the NOAs, the Agency noted that a certain subset of OCPSF plants existed
that either generate such low raw waste BOD5 levels that they do not require
end-of-pipe biological treatment or choose to use physical/chemical treatment
alone to comply with BPT effluent limitations. The Agency has decided to
establish two BAT subcategories that are largely determined by raw waste BOD
characteristics, as follows": 5
• Subcategory One - all plants that have or will install biological
treatment to comply with BAT effluent limitations.
IV-16
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. Subcategory Two - all plants which, based on raw waste characteris-
tics, will not utilize biological treatment to comply with BPT
effluent limitations.
In addition, the Agency is also establishing a different BAT effluent
limitation for zinc, including manufacturers of rayon by the viscose process
and plants manufacturing acrylic fibers utilizing the zinc chloride/solvent
process.
BAT effluent limitations for, Subcategory One will be based on the per-
formance of biological treatment and in-plant controls. Biological treatment
is an integral part of this subcategory's model BAT treatment technology; it
achieves incremental removals of some toxic pollutants beyond the removals
achieved by in-plant treatment without end-of-pipe biological treatment. BAT
effluent limitations for Subcategory Two will be based on the performance of
only in-plant treatment technologies such as steam stripping, activated
carbon, chemical precipitation, cyanide destruction, and in-plant biological
treatment of selected waste streams. The Agency has concluded that, within
each Subcategory, all plants can treat priority pollutants to the levels
established. (The Agency determined that further BPT subcategorization for
plants without end-of-pipe biological treatment is unnecessary. As described
in the Section VII assessment of mmbiological end-of-pipe treatment systems,
the Agency concluded that plants that do not need biological treatment to
comply with the BPT BOD5 limitations can meet the TSS limitations with physi-
cal/chemical controls alone. As also shown, some plants achieve sufficient
control of BOD5 through the use of •, only physical/chemical treatment unit
operations.)
The Agency also received comments (supported by submitted data) during
public comment periods stating that plants manufacturing acrylic fibers by the
zinc chloride/solvent process produced raw waste and treated effuent levels of
zinc similar to those levels produced by rayon manufacturers utilizing the
viscose process. After examining these data, the Agency agreed with the
commenters that it was appropriate to include these plants along with rayon
manufacturers. Based on this decision, the Agency is establishing two dif-
ferent limitations for the pollutant zinc. One is based on data collected
IV-17
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from rayon manufacturers and acrylic fibers manufacturers using the zinc
chloride/solvent process. This limitation applies only to those plants that
use the viscose process to manufacture rayon and the zinc chloride/solvent
process to manufacture acrylic fibers. The other zinc limitation is based on
the performance of chemical precipitation technology used in the metal fin-
ishing point source category, and applies to all plants other than described
above.
E. SUBCATEGORIZATION FACTORS
1. Introduction
All nine factors listed in the beginning of this section were examined
for technical significance in the development of the proposed subcategoriza-
tion scheme. However, in general, the proposed subcategorization reflected
primarily differences in waste characteristics, since many of the other eight
factors, while considered, could not be examined in appropriate technical and
statistical depth due to the intricacies of the plants in this industry.
Therefore, variations in waste characteristics were utilized to evaluate the
impact of the other eight factors on subcategorization. For example, the
ideal data base for evaluating the need for subcategorization and the develop-
ment of individual subcategories would include raw wastewater and final efflu-
ent pollutant data for facilities which segregate and treat each process raw
waste stream separately. In this manner, each factor could be evaluated
independently. However, the available information consists of historical data
collected by individual companies, primarily for the purpose of monitoring the
performance of end-of-pipe wastewater treatment technology and compliance with
NPDES permit limitations.' The OCPSF industry is primarily composed of multi-
product/process, integrated facilities. Wastewaters generated from each
product/process are typically collected in combined plant sewer systems and
treated in one main treatment facility.
Therefore, each plant's overall raw wastewater characteristics are
affected by all of the production processes occurring at the site at one time.
The effects of each production operation on the raw wastewater characteristics
cannot be isolated accurately from all of the other site-specific factors.
Therefore, a combination of both technical and statistical methodologies had
IV-18
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to be used to evaluate the significance of each of the subcategorization fac-
tors. The methodologies and analyses necessarily are limited to indicating
trends rather than yielding definitive quantitative significance of the fac-
tors considered.
In the methodology that was employed, the results of the technical analy-
sis were compared to the results of the statistical efforts to determine the
usefulness of each factor as a basis for subcategorization. The combined
technical/statistical evaluations of the nine factors are presented below.
2. Manufacturing Product/Processes
Comments have been received that state that the choice of the final seven
subcategories based on production is arbitrary, since the Agency did not per-
form a statistical analysis to group plants in optimal subcategories. Product
groups are based on both the marketing structure of the industry and technical
factors affecting the generation of contaminants.
By choosing subcategories based on SIC codes, the marketing character-
istics by which the industry is organized are emphasized; facilities can be
easily classified since the SIC codes are readily available to the plant.
Furthermore, from a technical point of view, based on engineering judgment and
analysis of the data supplied by the industry, most of these subcategories
represent different waste streams.
The purpose of subcategorization is the division of the OCPSF industry
into smaller groups that account for the particular common characteristics of
different facilities. The OCPSF industry (as defined by EPA) is recognized to
comprise several product groups:
• Organic Chemicals (SIC 2865/2869)
• Plastic Materials and Synthetic Resins (SIC 2821)
• Cellulosic Manmade Fibers (SIC 2823)
• Synthetic Organic Fibers (SIC 2824).
IV-19
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Vertical integration of plants within these industries is common, however,
blurring distinctions between' organic chemical plants and plastics/synthetic
fibers plants. As a practical matter, the OCPSF industry is divided among
three types of plants:
• Plants manufacturing only organic chemicals (SIC 2865/2869)
* ooon/S manufacturin£ only plastics and synthetic materials (SIC 2821/
2823/2824)
• Integrated plants manufacturing both organic chemicals and plastics/
synthetic materials (SIC 2865/2869/2821/2823/2824).
Each type of plant is unique not only in terms of product type (e.g., plas-
tics) but also in terms of process chemistry and engineering. Using raw
materials provided by organic chemical plants, plastic plants employ only a
small subset of the chemistry practiced by the OCPSF industry to produce a
limited number of products (approximately 200). Additionally, product re-
covery from process wastewaters in plastic plants generally is possible, thus
lowering raw waste BOD5 concentrations. Plants producing organic chemicals,
on the other hand, utilize a much larger set of process chemistry and engi-
neering to produce approximately 25,000 products; process wastewaters from
these plants are in general not as amenable to product recovery and are gen-
erally higher in raw waste BOD5 concentration and priority pollutant loadings.
Further divisions are possible within these broad groupings. Plastic
materials and synthetic resins manufacturers can be subdivided into thermo-
plastic materials (SIC 28213) producers and thermosetting resin (SIC 28214)
producers. Rayon manufacturers and synthetic organic fiber manufacturers are
also both unique. Again, process chemistry and engineering are broadly con-
sistent within these groupings in terms of BOD .
The organic chemicals industry produces many more products that does the
plastics/synthetic fibers industry and is correspondingly more complex. While
it is indeed possible to separate this industry into product groups, the num-
ber of such product groups is large. Moreover, with few exceptions, plants
produce organic chemicals from several product groups and thus limit the
utility of such an approach.
IV-20
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An alternative to a product-based approach is an approach based on the
type of manufacturing conducted at a plant. Large plants producing primarily
commodity chemicals (the basic chemicals of the industry, e.g., ethylene,
propylene, benzene) comprise the first group of plants. A second tier of
plants- includes plants that produce high-volume, intermediates (bulk chemi-
cals). Plants within this tier typically utilize the products of the com-
modity chemical plants (first tier plants) to produce more structurally com-
plex chemicals. Bulk chemical plants are generally smaller than those in the
first group, but still may produce several hundred million pounds of chemicals
per year (e.g., aniline, methylene dianiline, toluene diisocyanate). The
third group includes those plants that are devoted primarily to manufacture of
specialty chemicals — chemicals intended for a particular end use (e.g., dyes
and pigments). Generally, specialty chemicals are more complex structurally
than either commodity or bulk chemicals.
Chemicals within the three groups — commodity, bulk, and specialty —
are defined on the basis of national production. Commodity chemicals are
those chemicals produced nationally in amounts greater than or equal to 1
billion pounds per year. Bulk chemicals are defined to be those chemicals
produced nationally in amounts less than 1 billion but more than 40 million
pounds per year. Specialty chemicals are those chemicals produced nationally
in amounts less than or equal to 40, million pounds per year. Using these
definitions, there are 35 commodity chemicals, 229 bulk chemicals or bulk
chemical groups, and more than 786 specialty chemicals or specialty chemical
groups.
In general, the rate of biodegradation decreases with increasing molecu-
lar complexity. Because commodity chemical plants produce the least complex
chemicals, a general trend of lower BOD5 effluent concentrations for commodity
chemical plants to higher BOD5 effluent concentrations for specialty chemical
plants is observed.
¥ith regard to subcategorization for BAT, the Agency considered whether
the industry should be subcategorized by evaluating the same subcategorization
approach developed for BPT, which is based primarily on manufacturing product/
processes. The available data for BAT show that plants, in differing BPT sub-
categories can achieve similar low toxic pollutant effluent concentrations by
IV-21
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installing the best available treatment components. Since all plants within
the two BAT technology-based subcategories can achieve compliance with the
same BAT effluent limitations through some combination of demonstrated tech-
nology, the predominant issue relates to the cost of the required treatment
technology. EPA has analyzed these costs and their associated impacts and has
determined them to be reasonable. Therefore, the Agency believes that BAT
subcategorization based on manufacturing product/processes is not necessary
for effective, equitable regulation.
3. Raw Materials
Synthetic organic chemicals can be defined as derivative products of
naturally occurring materials (e.g., petroleum, natural gas, and coal) that
have undergone at least one chemical reaction, such as oxidation, hydrogena-
tion, halogenation, or alkylation. This definition, when applied to the
larger number of potential starting materials and the host of chemical reac-
tions that can be applied, leads to the possibility of many thousands of
organic chemical compounds being produced by a potentially large number of
basic processes having many variations. There are more than 25,000 commercial
organic chemical products derived principally from petrochemical sources.
These are produced from five major raw material classifications: methane,
ethylene, propylene, C4 hydrocarbons and higher aliphatics, and aromatics.
This major raw materials list can be expanded by further defining the aro-
matics to include benzene, toluene, and xylene. These raw materials are
derived from natural gas and petroleum, although a small portion of the
aromatics are derived from coal.
Currently, approximately 90 percent (by weight) of the organic chemicals
used in the world are derived from petroleum or natural gas. Other sources of
raw materials are coal and some naturally occurring renewable material of
which fats, oils, and carbohydrates are the most important.
Regardless of the relatively limited number of basic raw materials util-
ized by the organic chemicals industry, process technologies lead to the for-
mation of a wide variety of products and intermediates, many of which can be
produced from more than one basic raw material either as a primary reaction
IV-22
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product or as a byproduct. Furthermore, primary reaction products are fre-
quently processed to other chemicals that categorize the primary product from
one process as the raw material for a subsequent process.
Delineation between raw materials and products is nebulous at best, since
the product from one manufacturer can be the raw material for another manufac-
turer. This lack of distinction is more pronounced as the process approaches
the ultimate end product, which is normally the fabrication or consumer stage.
Also, many products/intermediates can be made from more than one raw material.
Frequently, there are alternate processes by which a product can be made from
the same basic raw material.
Another characteristic of the OCPSF industry that makes subcategorization
by raw material difficult is the high degree of integration in manufacturing
units.' Since the majority of basic raw materials derive from petroleum and
natural gas, many of the organic.chemical manufacturing plants are either
incorporated into or contiguous to petroleum refineries, and may formulate a
product at almost any point in a process from any or all of the basic raw
materials. Normally, relatively few organic chemical manufacturing facilities
are single product/process plants unless the final product is near the fabri-
cation or consumer product stage.
Because of the integrated complexity of the largest (by weight) single
segment of the organics industry (petrochemicals), it may be concluded that
BPT and BAT subcategorization by raw materials is not feasible for the fol-
lowing reasons:
• The organic chemicals industry is made up primarily of chemical
complexes of various sizes and complexity.
• Very little, if any, of the total production is represented by single
raw material plants.
• The raw materials used by a plant can be varied.widely over short time
spans.
• The toxic, conventional, and nonconventional wastewater pollutant
parameter data gathered for this study were not collected and are not
available on a raw material orientation basis, but rather represent
the mixed end-of-pipe plant wastewaters.
IV-23
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4. Facility Size
Although sales volume, number of employees, area of a plant site, plant
capacity, and production rate might logically be considered to define facility
size, none of these factors alone describes facility size in a satisfactory
manner. Recognizing these limitations, the Agency has chosen total OCPSF
production to define facility size.
The regression model approach allows the Agency to easily test for BPT
subcategorization factors such as facility size as measured by total OCPSF
production. EPA has analyzed total OCPSF production, as discussed previously
in this section, to determine its appropriateness as a subcategorization fac-
tor, and determined that the significance of production is due largely to
plants with only biological treatment that do not meet the 95/40 BPT perform-
ance edit. Consequently, an adjustment factor for production is not incorpo-
rated into the model.
In terms of a BAT subcategorization factor, although facility sizes (as
measured by total OCPSF production) of the waste streams with the OCPSF indus-
try vary widely, ranging from less than 10,000 pounds/day to more than
5 million pounds/day, this definition fails to embody fundamental character-
istics such as continuous or batch manufacturing processes. While equivalent
production rates may be accomplished by either production method, the charac-
teristics of these waste streams in terms of toxic pollutants may vary sub-
stantially because of different yield losses inherent in each process. There-
fore, the Agency has determined that no adequate method exists for defining
facility size and that there is no technical basis for the use of facility
size as a BAT subcategorization factor.
5. Geographical Location
Companies in the OCPSF industry usually locate their plants based on a
number of factors. These include:
• Sources of raw materials
• Proximity of markets for products
• Availability of an adequate water supply
IV-24
-------
• Cheap sources of energy
• Proximity to proper modes of transportation
• Reasonably priced labor markets
In addition, a particular product/process- may be located in an existing facil-
ity based on availability of certain types of equipment or land for expansion.
Companies also locate their facilities based on the type of production
involved. For example, specialty producers may be located closer to their
major markets, whereas bulk producers may be centrally located to service a
wide variety of markets. Also, a company that has committed itself to zero
discharge as its method of wastewater disposal has the ability to locate any-
where, while direct dischargers must locate near receiving waters, and in-
direct dischargers must locate in a city or town that has an adequate POTW
capacity to treat OCPSF wastewaters.:
Because of the complexity and inter-relationships of the factors affect-
ing plant locations outlined above, no clear basis for either BPT or BAT sub-
categorization according to plant location could be found. Therefore, loca-
tion is not a basis for BPT and BAT subcategorization of the OCPSF industry.
Since biological treatment installed to meet BPT effluent limitations is
an important part of both BPT and BAT subcategorization approaches, the Agency
decided to perform an analysis to confirm that temperature (as defined by the
heating-degree day variable to measure winter/summer effects), instead of
location, is not a subcategorization factor. The Agency used a regression
model approach similiar to the analysis for facility size. Analysis on the
following regression model was performed to test for the significance of this
factor: .
= a +
where:
Z wij'Tj +
' (degree days..) + ei
degree days.
the number of. degrees that the mean daily outdoor
temperature is below 65 °F for a given day, accumu-
lated over the number of days in the year that the
IV-25
-------
mean temperature is below 65°F, at plant i (with
associated coefficient J).
.This analysis was performed separately for the four subsets described
previously which partition the 157 full-response, direct discharge OCPSF
plants that have at least biological treatment in place and provided BOD5
effluent and subcategorical production data. The computer analysis for these
regression models is presented in Appendix IV-A, Exhibit 6. In none of these
four subsets was temperature significant, and consequently a temperature
factor is determined to be inappropriate.
6. Age of Facility and Equipment
The age of an OCPSF plant is difficult to define accurately. This is
because production facilities are continually modified to meet production
goals and to accommodate new product lines. Therefore, actual process equip-
ment is generally modern (i.e., 0-15 years old). However, major building
structures and plant sewers are not generally upgraded unless the plant
expands significantly. Older plants may use open sewers and drainage ditches
to collect process wastewater. In addition, cooling waters, steam conden-
sates, wash waters, and tank drainage waters are sometimes collected in these
drains due to their convenience and lack of other collection alternatives.
These ditches may run inside the process buildings as well as between manu-
facturing centers. Therefore, older facilities are likely to exhibit higher
wastewater discharge flow rates than newer facilities. In addition, since the
higher flows may result from the inclusion of relatively clean noncontact
cooling waters and steam condensates as well as infiltration/inflow, raw
wastewater concentrations may be lower due to dilution effects. Furthermore,
recycle techniques and wastewater segregation efforts normally cannot be
accomplished with existing piping systems, and would require the installation
of new collection lines as well as the isolation of.the existing collection
ditches. However, due to water conservation measures as well as ground con-
tamination control, many older plants are upgrading their collection systems.
In addition, the energy crisis of recent years has caused many plants to
upgrade their steam and cooling systems to make them more efficient. Based on
the factors mentioned above, the Agency has determined its only accurate age
IV-26
-------
measurement to be the age of the oldest process at each OCPSF facility.
Analysis on the following regression model was performed to test for the
significance of age:
7
ln(BOD.) = a + E W..-T. + K^age^) + e±
•L • T •*• J J
where:
age
the age of the oldest process at plant i (with associated
coefficient K).
This analysis was performed separately for the four subsets described
previously that partition the 157 full-response, direct discharge OCPSF plants
that have at least biological treatment in place and provided BOD5 effluent
and subcategorical production data. The computer analysis for these regres-
sion models is presented in Appendix IV-A, Exhibit 7. Results of this
analysis are similar to results seen for production, flow, and flow per unit
of production; that is, the only group of plants that exhibit a relationship
between age and effluent BOD5 concentration is the subset of poorly performing
biological-only plants (plants that do not meet the 95/40 BPT editing cri-
teria). Consequently, the Agency has determined that an age factor is not
appropriate.
The extent to which process wastewaters are contaminated with toxic pol-
lutants depends mainly upon the degree of contact that process water has with
reactants/products, the effectiveness of the separation train, and the
physical-chemical properties of those priority pollutants formed in the reac-
tion. Raw wastewater quality is determined by the specific process design and
chemistry. For example, water formed during a reaction, used to .quench a
reaction mixture, or used to wash reaction products will contain greater
amounts of pollutants than does water that does not come into direct contact
with reactants or products. The effectiveness of a separation train is deter-
mined by the process design and the physical-chemical properties of those
pollutants present. ¥hile improvements are continually made in the design and
construction of process equipment, the basic design of such equipment may be
IV-27
-------
quite old. Process equipment does, however, deteriorate during use and re-
quires maintenance to ensure optimal performance. When process losses can no
longer be effectively controlled by maintenance, process equipment is re-
placed. The maintenance schedule and useful life associated with each piece
of equipment are in part determined by equipment age and process conditions.
Equipment age, however, does not directly affect either pollutant concentra-
tions in influent or effluent wastewaters and is therefore inappropriate as a
basis for BAT subcategorization.
7- Wastewater Characteristics and Treatability
a. BPT Subcategorization
The treatability of OCPSF wastewaters is discussed in detail in Section
VII. The treatability of a given wastewater is affected by the presence of
inhibitory materials (toxics), availability of alternative disposal methods,
and pollutant concentrations in, and variability of, the raw wastewater con-
centrations. However, all of these factors can be controlled by sound waste
management, treatment technology design, and operating practices. Examples of
these are:
• The. presence of toxic materials in the wastewater can be controlled by
in-plant treatment methods. Technologies such as steam stripping,
metals precipitation, activated carbon, and reverse osmosis can elimi-
?aufu- Presence of materials in a plant's wastewater that may
inhibit or upset biological treatment systems.
• Although some plants utilize deep well injection for disposal of high-
ly toxic wastes to avoid treatment system upsets, other alternative
disposal techniques such as contract hauling and incineration are
available to facilities that cannot utilize deep well disposal. In
addition, stricter groundwater regulations may eliminate the option of
deep well disposal for some plants and make it uneconomical for
others, forcing facilities to look more closely at these other
options.
• Raw waste concentration variability can easily be controlled by the
use of equalization basins. In some plants, "at-process" storage and
equalization is used to meter specific process wastewaters, on a con-
trolled basis, into the plant's wastewater treatment system.
• Raw waste concentrations can be reduced with roughing biological
filters or with the use of two-stage biological treatment systems.
These techniques are discussed in detail in Section VII.
IV-28
-------
OCPSF wastewaters can be treated by either physical-chemical or biologi-
cal methods, depending on the pollutant to be removed. Also, depending on the
specific composition of the wastewater, any pollutant may be removed to a
greater or lesser degree by technology not designed for removal of this pol-
lutant. For example, a physical-chemical treatment system designed to remove
suspended solids will also remove a portion of the BODg of a wastewater if the
solids removed are organic and biodegradable. It is common in the OCPSF in-
dustry to use a combination of technologies adapted to the individual waste-
water stream to achieve desired results. These concepts are discussed in
detail in Section VII. In general, the percent removals of BOD5 and TSS are
consistent across the seven final subcategories. It is also possible for
plants in these subcategories to achieve high percent removals (greater than
95%) for both BOD5 and TSS (data supporting these removals are presented and
discussed in Section VII). Also, OCPSF plants producing the same products and
generating similiar raw waste BOD5 concentrations are, in general, equally
distributed above and below the pure subcategory long-term averages for BOD5
effluent as determined by the BPT regression equation. Figures IV-1 through
IV-7 present the distribution of plants within each pure subcategory (defined
as full-response direct discharge plants that have at least 80 percent of
their total OCPSF production in one of the seven final subcategories) by
effluent BOD and the product(s) each plant produces. Also included with each
plant's BOD5 effluent is its associated raw waste BOD5 concentration (when
available); in addition, if a plant produces more than one product within a
subcategory, its effluent and raw waste BOD5 values are repeated and noted on
each figure, as multiple effluent and influent, respectively.
In reviewing these figures, it should be noted that for most of the pro-
ducts within a pure subcategory, plants with fairly high raw waste BODg con-
centrations are equally distributed above and below the subcategory long-term
average BOD5 effluent and that even for plants producing the same products
that did not have raw waste BOD5 concentration data, BOD5 effluents are fairly
well-distributed above and below the subcategory median BOD5 effluent for
certain products within selected subcategories. Situations in which there are
a disproportionate number of plants either above or below the subcateogry
long-term average maybe explained by a number of factors, including the con-
tribution of remaining 20 percent of.each plant's product mix to its BOD5
IV-29
-------
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IV-36
-------
effluent, the end-of-pipe treatment systems in place at each plant and the
in-plant controls currently in place at each plant that may cause raw waste
BOD concentrations to be reduced or that may remove toxic pollutants that
inhibit biological activity and cause higher BOD5 effluent concentrations. It
should also be noted in any event that for those plants substantially above
the subcategory long-term average BOD5 effluent value, as well as for other
plants, EPA/s costing methodology and resulting cost estimates and economic
impact estimates have fully accounted for any required treatment improvement.
Based on the distribution of raw waste and effluent BOD5 concentrations,
the relative consistency of percent removal data across the final seven sub-
categories, and BOD5 effluent data within subcategories and product groups
within those subcategories, the Agency has concluded that the adopted BPT
subcategorization accounts sufficiently for wastewater characteristics and
treatability.
b. BAT Subcategorization
Typically, the treatability of a waste stream is described in terms of
its biodegradability, as biological treatment usually provides the most cost-
effective means of treating a high volume, high (organic) strength industrial
waste (i.e., minimum capital and operating costs). Furthermore, biodegrad-
ability serves as an important indicator of the toxic nature of the waste load
upon discharge to the environment. Aerobic (oxygen-rich) biological treatment
processes achieve accelerated versions of the same type of biodegradation that
would occur much more slowly in the receiving water. These treatment pro-
cesses accelerate biodegradation by aerating the wastewater to keep the dis-
solved oxygen concentration high and recycling microorganisms to maintain
extremely high concentrations of bacteria, algae, fungi,(and protozoa in the
treatment system. Certain compounds that resist biological degradation in
natural waters may be readily oxidized by a microbial population adapted to
the waste. As would occur in the natural environment, organic compounds may
be removed by volatilization (e.g., aeration) and adsorption on solid mater-
ials (e.g., sludge) during biological treatment.
IV-37
-------
One of the primary limitations of biological treatment of wastewaters
from the OCPSF industry is the presence of both refractory (difficult to
treat) compounds as well as compounds that are toxic or inhibitory to biologi-
cal processes. Compounds oxidized slowly by microorganisms can generally be
treated by subjecting the wastewater to biological treatment for a longer
time, thereby increasing the overall conventional and toxic pollutant re-
movals. Lengthening the duration of treatment, however, requires larger
treatment tanks and more aeration, both of which add to the expense of the
treatment. Alternatively, pollutants that are refractory, toxic, or inhibi-
tory to biological processes can be removed prior to biological treatment of
wastewaters. Removal of pollutants prior to biological treatment is known as
pretreatment.
The successful treatment of wastewaters of the OCPSF industries primarily
depends on effective physical-chemical pretreatment of wastewaters, the abil-
ity to acclimate biological organisms to the remaining pollutants in the waste
stream (as in activated sludge processes), the year-round operation of the
treatment system at an efficient removal rate, the resistance of the treatment
system to toxic or inhibitory concentations, and the stability of the treat-
ment system during variations in the waste loading (i.e., changes in product
mixes).
However, as discussed earlier in this section, the Agency determined that
a subset of OCPSF plants, based on their low raw waste BOD5 levels, did not
necessarily require biological treatment to comply with BPT effluent limita-
tions. Some of these plants produced chlorinated hydrocarbons that typically
generate 'wastewater characterized, by low raw waste BOD5 concentrations. In
these cases, biological treatment would not be effective in treating refrac-
tory priority pollutants that would not be amenable to biodegradation. There-
fore, the Agency decided that separate BAT effluent limitations based on the
performance of physical-chemical treatment technologies only were appropriate
and has established a separate subcategory for these plants based on their
unique raw wastewater characteristics and treatability.
The Agency also maintains that similar toxic pollutant effluent concen-
trations can be achieved by plants in differing BPT subcategories, i.e.,
IV-38
-------
plants with different product mixes, by installing the best available treat-
ment technologies. These toxic pollutants are being controlled using a combi-
nation of in-plant and end-of-pipe treatment technologies. The in-plant
controls are based upon specific pollutants or groups of pollutants identified
in waste streams and controlled by, technologies for which treatment data are
available or transferred with appropriate basis (see Section VII of this docu-
ment). Thus, subcategory groupings of plants based on product mix for BAT are
not appropriate. Nevertheless, the Agency has attempted to perform a quanti-
tative assessment of treatability of BAT toxic pollutants by BPT subcategory
classification. The capability to perform this assessment is limited because
the frequency of occurrence of BAT toxic pollutants is determined by the pres-
ence of specific product/processes (or reaction chemistry) within plants that
is not totally dependent on BPT subcategory classifications. Table IV-1 pre-
sents a comparison of toxic pollutant mean effluent concentrations achieved by
100 percent plastics and organics .plants contained in the final, edited BAT
toxic pollutant data base that were used in the calculation of BAT effluent
limitations. Also included is thetsame comparison between those 100 percent
"pure" BPT subcategory plants contained in the same data base. The first
comparison shows that, with the exception of two pollutants (#10 and #32),
plastics and organics plants achieve effluent concentrations that approach the
analytical minimum level. The same results are found for the second "pure"
subcategory comparison, even though fewer plants were available for the analy-
sis. For the two pollutants with disparate results, the Agency believes that
these differences are not the result of dissimilar wastewater treatability,
but a lack of effluent concentration data for these pollutants from 100 per-
cent plastics plants. EPA notes that when more than one 100 percent plastics
plant is available for comparison (e.g., pollutant #86),'the effluent concen-
trations are similar.
In addition to each OCPSF plant's ability to achieve similar effluent
concentrations, the Agency also believes that its extensive BAT toxic pollu-
tant data base is representative of OCPSF: wastewaters, treatment technologies,
processes, and products. In total, 186 plants were sampled in the Agency's
screening, verification, 5-plant, and 12-plant studies. After editing the
data base so that only quality data (i.e., having adequate QA/QC) representing
BAT treatment were used, the editedJBAT data base contains sampling data for
IV-39
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TABLE IV-1.
BAT EFFLUENT ESTIMATED LONG-TERM AVERAGE CONCENTRATION COMPARISON
BETWEEN PLASTICS AND ORGANICS PLANTS AND
PURE BPT SUBCATEGORY PLANTS
Plant
Numbers ?
Plastics
883
2221
4051 10
1349
1617
2536
Organ! cs
12 10
296 10
444 10
1609 10
1753
2394
2693
3033
Thermoplastics
883
1617
4051 10
2536
1349
Thermosets
2221
Bulk Organics
444 10
Specialty Organics
1753
Concentrations (ppb) by
Pollutant Number
10 32 38 65 86 "
Plastics vs. Organics
10
10 10 10
1016 923 - _ 103
10
10 10
10 12 10
12 - - 10 10
10
10 18
10
10 59 10
10 13 I 15 I
Pure Subcategory
10
10
1016 923 - _ 103
10 10-
- - 10 10 10
10
10
87
16
10
16
_
-
IV-40
-------
36 OCPSF plants (including industry supplied data) representing 232 product/
processes. These 36 plants account for approximately 26 percent of production
volume and 24 percent of the process wastewater flow of the entire industry.
The types of product/processes utilized by these 36 plants represent approxi-
mately 13 percent of the types of OCPSF product/processes in use. Since the
products manufactured by these facilities are manufactured at other OCPSF
facilities, the data obtained from these plants represent even greater per-
centages of total industry production and flow. Thus, about 68 percent of
OCPSF industry production (in total pounds) is represented and about 57 per-
cent of the OCPSF industry wastewater is accounted for by the products and
processes utilized by the 36 plants in the limitations data base. Products
that could be manufactured by the 232 product/processes utilized at or manu-
factured by the 36 plants account for 84 percent of industry production and
76 percent of process wastewater.
The OCPSF industry manufactures more than 20,000 individual products;
however, overall production is concentrated in a limited number of high-volume
chemicals. Excluding consideration of plastics, resins, and synthetic fibers,
EPA has identified 36 organic chemicals that are manufactured in quantities
greater than 1 billion pounds per year. These chemicals are referred to as
commodity chemicals. Two hundred eighteen organic chemicals are manufactured
in quantities between 40 million and 1 billion pounds per year. These chemi-
cals are referred to as bulk chemicals. Together, these 254 chemicals account
for approximately 91 percent of total annual production volume of organic
chemicals as reported in the 308 Questionnaire survey data base for the OCPSF
industry. By sampling OCPSF plants that manufacture many of these high-volume
chemicals, as well, as other types of OCPSF plants, EPA has, in fact, gathered
sampling data that are representative of production in the entire industry.
Based on the results of its comparison analysis and the adequate coverage
of the OCPSF industry in its sampling programs, the Agency believes that
plants within each of its BAT subcategories can achieve BAT effluent limita-
tions despite differing product/process mix.
The Agency has also determined that because of their unique high raw
wastewater zinc characteristics and treatability noted in Sections V and VII,
IV-41
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respectively, producers of rayon by the viscose process and acrylic fibers by
the zinc chloride/solvent process will receive different BAT effluent limita-
tions for zinc than the remainder of the OCPSF industry, whose BAT limitations
will be based on the performance of chemical precipitation technology used in
the Metal Finishing Point Source Category.
c. Energy and Non-Water Quality Aspects
Energy and non-water quality aspects include the following:
• Sludge production
• Air pollution derived from wastewater generation and treatment
• Energy consumption due to wastewater generation and treatment
• Noise from wastewater treatment.
The basic treatment step, used by virtually all plants in all subcategories
that generate raw wastes containing basically BOD5 and TSS, is biological
treatment. Therefore, the generation of sludges, air pollution, noise, and
the consumption of energy will be homogeneous across the industry. However,
the levels of these factors will relate to the volume of wastewater treated'
and their associated pollutant loads. Since the volumes of wastewater gener-
ated and wastewater characteristics were considered in earlier sections, it is
believed that all energy and nonwater quality aspects have been adequately
addressed in this final subcategorization approach.
IV-42
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SECTION V '•-•-'-
. WATER USE AND WASTEWATER CHARACTERIZATION
A. WATER USE AND SOURCES OF WASTEWATER
The Organic Chemicals, Plastics, and .Synthetic Fibers (OCPSF) industry
uses large volumes of water in the manufacture of products. Water use and
wastewater generation occur at a number of points in manufacturing processes
and ancillary operations, including: 1) direct and indirect contact process
water; 2) contact and noncontact cooling water; 3) utilities, maintenance, and
housekeeping waters; and 4) waters from air pollution control systems such as
Venturi scrubbers.
The OCPSF effluent limitations and standards apply to the discharge of
"process wastewater," which is defined as any water that, during manufacturing
or processing, comes into direct contact with or results from the production
or use of any raw material, intermediate product, finished product,
by-product, or waste product (40 CFR 401.11(q)). An example of direct contact
process wastewater is the use of aqueous reaction media. The use of water as
a medium for certain chemical processes becomes a major high-strength process
wastewater source after the primary reaction has been completed and the final
product has been separated from the water media, leaving residual product and
unwanted by-products formed during secondary reactions in solution.
Indirect contact process wastewaters, such as those discharged from
vacuum jets and steam ejectors, involve the recovery of solvents and volatile
organics from the chemical reaction kettle. In using vacuum jets, a stream of
water is used to create a vacuum, but also draws off volatilized solvents and
organics from the reaction kettle into solution. Later, recoverable solvents
are separated and reused while unwanted volatile organics remain in solution
in the vacuum water, which is discharged as process wastewater. Steam ejector
systems are similar to vacuum jets with steam being substituted for water.
The steam is then drawn off and condensed to form a source of process
wastewater.
V-l
-------
The major volume of water used in the OCPSF industry is cooling water.
Cooling water may be contaminated, such as contact cooling water (considered
process wastewater) from barometric condensers, or uncontaminated noncontact
cooling water. "Noncontact cooling water" is defined as water used for
cooling that does not come into direct contact with any raw material, inter-
mediate product, waste product, or finished product (40 CFR 401.11(n)).
Frequently, large volumes of noncontact cooling water may be used on a once-
through basis and discharged after commingling with process wastewater. Many
of the wastewater characteristics reported by plants in the data bases were
based on flow volumes that included both process wastewater and nonprocess
wastewater such as noncontact cooling water. Other types of nonprocess
wastewater include: boiler blowdown, water treatment wastes, stormwater,
sanitary waste, and steam condensate. An adjustment of the reported volumes
of the effluents was therefore required to arrive at performance of treatment
systems and other effluent characteristics.
This adjustment was made by eliminating the uncontaminated cooling water
volume from the total volume, to arrive at the contaminated wastewater flow at
the sampling site. The concentrations of the conventional pollutants BOD5,
COD, TSS, and TOC were adjusted using the simplifying judgment that the
uncontaminated cooling water did not contribute to the pollutant level.
However, it should be noted that in some cases noncontact cooling water can
contribute pollutant loading, especially to typically low-strength plastics
and synthetic materials wastewaters.
In some cases, effluent priority pollutant and daily conventional
pollutant data submitted by plants were from sample sites that included
nonprocess wastewater. Where this dilution with noncontact cooling water or
other nonprocess wastewater was significant (i.e., >25 percent of total), such
data were considered nonrepresentative of actual treatment systems' daily
performance and were excluded from the data base used for assessing treatment
system performance variability factors.
V-2
-------
B. WATER USE BY MODE OF DISCHARGE
Industry process wastewater flow descriptive statistics are summarized in
Table V-l for 929 OCPSF plants that submitted sufficient information in the
1983 Section 308 Questionnaire. This data base is classified by direct,
indirect, or zero discharge status. "Zero" discharge methods include no
discharge, land application, deep well injection, incineration, contractor
removal, evaporation, off-site treatment by a privately owned treatment
system, and discharge to septic and leachate fields.
Some of the plants in the 308 data base discharge waste streams by more
than one method. However, for purposes of tabulating wastewater data, each
plant was assigned to a single discharge category (i.e., no double counting
appears in the direct, indirect, and zero discharge data columns). A plant
was classified as a zero or alternate discharger only if all of its waste
streams were reported as zero or alternate discharge streams. Plants were
classified as direct dischargers if at least one process wastewater stream was
direct. Plants whose process wastewater streams were discharged to publicly
owned treatment works (POTWs) were classified as indirect dischargers. Many
of the indirect discharge plants discharge noncontact cooling water directly
to surface waters.
Industry nonprocess wastewater flow descriptive statistics are summarized
in Table V-2 for 718 OCPSF plants as classified in Table V-l by process
wastewater discharge status.
C. WATER USE BY SUBCATEGORY
As discussed previously in Section IV, data relating product/process
production information to flow was requested from industry in the 1983 Section
308 Questionnaire to facilitate the flow proportioning of individual product
subcategory limitations for multiple subcategory plants. This information
would have also facilitated the presentation of the wastewater flow data by
subcategory. Unfortunately, much of the production/flow information (when
supplied) was either estimated or grouped with other product/process flows and
was considered too inaccurate or nebulous for use. Since this information
V-3
-------
TABLE V-l.
TOTAL OCPSF PLANT PROCESS VASTEWATER
FLOW CHARACTERISTICS BY TYPE OF DISCHARGE
Process tfastewater
Discharge Status
Direct
Indirect
Descriptive Statistics
Number of Plants*
Percentage of Plants
Total Flow (MGD)
Average Flow (MGD)
Median Flow (MGD)
Frequency Counts (ft of Plants)
By Flow Range
<0.005 MGD
0.005 to 0.01 MGD
>0.01 to 0.10 MGD
>0.10 to 0.50 MGD
>0.5 to 1.0 MGD
>1.0 to 5.0.MGD
>5.0 to 10.0 MGD
>10 MGD (up to a maximum of 19.3 MGD)
*(N) « 929 out of 940 scope facilities
Source: 1983 Section 308 Questionnaire Responses
Zero
304
33%
387
1.31
0.40
393
422
94
0.25
0.04
232
25%
32
0.24
0.007
25
12
54
80
43
75
8
7
106
34
136
77
26
12
1
1
161
11
30
16
4
10
0
0
V-4
-------
TABLE V-2.
TOTAL OCPSF PLANT NONPROCESS WASTEWATER
FLOW CHARACTERISTICS BY TYPE OF DISCHARGE
Nonprocess Wastewater
Discharge Status
Direct
Indirect
Frequency Counts (# of Plants)
By Flow Range
Zero
Descriptive Statistics
Number of Plants*
Percentage of Plants
Total Flow (MGD)
Average Flow (MGD)
Median Flow (MGD)
278
39%
3,973
14.29
0.40
332
46%
353
1.06
0.03
108
15%.
103
0.95
0.05
<0.005 MGD
0.005 to 0.01 MGD
>0.01 to 0.10 MGD
>0.10 to 0.50 MGD
>0.5 to 1.0 MGD
>1.0 to 5.0 MGD
>5.0 to 10.0 MGD
>10 MGD (up to a maximum of 1,732 MGD)
11
14
53
77
32
42
12
37
76
36
117
56
22
19
3
3
21
16
34
20
8
5
1
3
*(N) = 718 out of 940 scope facilities reporting discharge of nonprocess
wastewater
Source: 1983 Section 308 Questionnaire Responses
V-5
-------
could not be used to group these flow data accurately, the Agency has decided
to present these data using two methodologies. The first method utilizes an
approach similar to the regression model used for subcategorization to
proportion these data among subcategories. The second methodology places
individual plants completely in one of the seven final subcategories based on
a prescribed set of rules. These two methodologies are discusssed in more
detail in the following sections.
Tables V-3 through V-16 provide the 1980 process and nonprocess
wastewater flow statistics by subcategory and disposal method. Tables V-3
through V-9 present separate tabulations for primary and secondary producers
and for process and nonprocess wastewater. In each table, the mean and median
flows for multi-subcategory plants have been divided into subcategories using
the regression methodology described in Section IV based on plant production
volume proportions for each subcategory. Thus, mean and median flows given in
some cases may not represent actual plant subcategory flow since, on a unit of
production basis, different products produce different flow volumes. However,
data constraints preclude direct attribution of process and nonprocess flows
to individual products or product subcategory groups. Production weighted
mean subcategory flow values were calculated using the following formula:
Production Weighted Mean = PiFi + P2F2 + P3F3 + ••• + piFi
Where:
Px = Decimal subcategory proportion of total OCPSF plant production for
plant #1 (range = 0 to 1.0)
Fj = Total process flow for plant #1.
In determining the median, the wastewater flow of each plant that has at
least one product within a subcategory are ranked from lowest to highest. The
subcategory decimal production proportions are summed starting from the lowest
flow plant until the sum equals or exceeds 50 percent of the total of all the
decimal production proportions. The wastewater flow of the plant whose
proportions when added to the proportion sum causes the total to exceed
V-6
-------
TABLE V-3
PROCESS WASTEWATER FLOW FOR PRIMARY OCPSF PRODUCERS
BY SUBCATEGORY AND DISPOSAL METHOD
DIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERHOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGAN I CS
MEAN
(MGD)
1.00
0.71
8.04
1.14
2.16
1.53
0.84
MEDIAN
(MGD)
0.43
0.08
8.57
0.57
1.00.
0.29
0.30
STANDARD
DEVIATION
1.70 '
1.66
2.98
2.31
3.73
3.43
1.74
NUMBER OF
OBSERVATIONS.
60.99
12.10
3.19
13.73
48.85
47.53
41.61
NUMBER OF
PLANTS
104
31
5
22
84
113
103
INDIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGAN ICS
MEAN
(MGD)
0.25
0.08
0.05
0.57
0.48
0.34
MEDIAN
(MGD)
0.05
0.02
0.02
0.04
0.05
0.06
STANDARD
DEVIATION
0.65
0.28
0.06
1.71
1.15
1.49
NUMBER OF
OBSERVATIONS
68.57
40.97
7.00
18.43
33.71
106.31
NUMBER OF
PLANTS
108
80
8
36
84
154
V-7
-------
TABLE V-4
PROCESS WASTEWATER FLOW DURING 1980 FOR SECONDARY OCPSF
PRODUCERS BY SUBCATEGORY AND DISPOSAL METHOD
DIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS 0.15
THERMOSETS
ORGAN ICS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGANICS
MEAN
(MGD)
0.15
0.50
0.70
MEAN
(MGD)
0.03
0.03
0.11
MEDIAN
(MGD)
0.08
0.01
0.20
INDIRECT
MEDIAN
(MGD)
0.01
0.00
0.02
STANDARD
DEVIATION
0.26
0.93
1.27
DISCHARGERS
STANDARD
DEVIATION '
0.05
0.08
0.18
NUMBER OF
OBSERVATIONS
8.68
4.03
28.29
NUMBER OF
OBSERVATIONS
16.59
20.90
52.51
NUMBER OF
PLANTS
12
5
30
NUMBER OF
PLANTS
27
30
58
V-8
-------
TABLE V-5
PROCESS WASTEWATER FLOW FOR PRIMARY & SECONDARY
OCPSF PRODUCERS THAT ARE ZERO/ALTERNATIVE DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGAN I CS
MEAN
(MGD)
0.08
0.01
0.42
0.33
0.91
0.31
0.16
MEDIAN
(MGD)
0.01
0.00
0.03
0.08
0.91
0.30
0.11
STANDARD
DEVIATION
0.26
0.08
0.93
0.98
•
0.37 ;
0.19
NUMBER OF
OBSERVATIONS
24.92
33.11
60.71
2.31
0.84
1 .30
2.81
NUMBER OF
PtANTS
36
40
69
3
1
3
4
V-9
-------
TABLE V-6
NON-PROCESS WASTEWATER FLOW DURING 1980
FOR SECONDARY OCPSF PRODUCERS
AND ZERO/ALTERNATIVE DISCHARGERS
BY SUBCATEGORY & DISPOSAL METHOD
SECONDARY AND DIRECT DISCHARGE PLANTS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MEAN
(MGD)
0.320
0.242
3.564
MEDIAN
(MGD)
0.190
0.250
0.255
STANDARD
DEVIATION
0.760
0.242
11.546
SECONDARY AND INDIRECT DISCHARGE
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MEAN
(MGD)
0.072
0.458
1.240
SECONDARY
MEAN
(MGD)
0.242
0.101
0.658
6.455
MEDIAN
(MGD)
0.005
0.020
0.015
AND OTHER
MEDIAN
(MGD)
0.013
0.019
0.031
0.710
STANDARD
DEVIATION
0.206
1.179
6.470
NUMBER OF
OBSERVATIONS
8.72
1.03
27.25
PLANTS
NUMBER OF
OBSERVATIONS
19.50
17.99
46.51
NUMBER OF
PLANTS
12
2
29
NUMBER OF
PLANTS
29
27
52
DISCHARGE PLANTS*
STANDARD
DEVIATION
1.367
0.184
2.960
20.921
NUMBER OF
OBSERVATIONS
18.00
27.01
47.67
1.31
NUMBER OF
PLANTS
26
33
57
2
NOTE: THERE ARE 9 PRIMARY PLANTS NOT INCLUDED IN THIS TABLE
THAT ARE ZERO DISCHARGERS.
V-10
-------
TABLE V-7
TOTAL OCPSF NON- PROCESS WASTEWATER FLOW IN 1980
FOR PRIMARY PRODUCERS BY SUBCATEGORY & DISPOSAL METHOD
DIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MEAN
( MGD )
9.266
5.228
2.295
9.279
55.125
21.990
8.142
MEDIAN
( MGD )
0.280
0.450
2.500
1.910
0.720
0.475
0.200
STANDARD
DEVIATION
67.664
62.392
4.263
17.113
232.600
128.821
42.871
NUMBER OF
OBSERVATIONS
58.905
11.904
2.187
11.851
45.738
46.253
35.162
NUMBER OF
PLANTS
101
33
4
19
78
108
96
INDIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MEAN
( MGD )
0.211
0.141
0.077
3.434
4.808
0.418
DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
BULK ORGANICS
SPECIALTY ORGANICS
MEAN
( MGD )
0.027
0.000
0.150
14.560
MEDIAN
< MGD )
0.027
0.020
0.024
0.311
0.064
0.043
OTHER THAN
. MEDIAN
( MGD )
0.010
0.000
0.150
0.150
STANDARD
DEVIATION
1 .326
0.738
. 0.090
11.510
21.021
1.765
NUMBER OF
OBSERVATIONS
55.056
29.003
4.002
15.329
27.823
74.786
NUMBER OF
PLANTS
85
62
5
30
67
116
DIRECT OR INDIRECT
STANDARD
DEVIATION
0.026
.
.
24.171
NUMBER OF
OBSERVATIONS
2.122
0.878
0.208
2.792
NUMBER OF
PLANTS
3
1
1
3
V-ll
-------
TABLE V-8
NON-PROCESS COOLING WATER FLOW FOR PRIMARY
OCPSF PRODUCERS BY SUBCATEGORY & DISPOSAL METHOD
DIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MEAN
( MGD
0.814
0,259
0.140
0.369
1.097
0.431
0.381
MEDIAN
> ( MGD )
0.182
0.063
0.120
0.337
0.537
0.100
0.077
STANDARD
DEVIATION
2.058
0.661
0.125
0.321
1.651
0.936
1.042
NUMBER OF
OBSERVATIONS
58.415
11.992
2.187
12.153
42.908
43.148
42.196
NUMBER OF
PLANTS
96
33
4
19
75
107
100
INDIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MEAN
( MGD 3
0.085
0.171
0.068
0.776
0.213
0.097
DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MEAN
( MGD )
0.065
0.004
0.121
0.039
0.023
MEDIAN
> ( MGD )
0.012
0.007
0.090
0.118
0.028
0.011
OTHER THAN
MEDIAN
( MGD )
0.043
0.004
0.121
0.003
0.003
STANDARD
DEVIATION
0.204
1.015
0.057
1.781
0.380
0.231
NUMBER OF
OBSERVATIONS
45.578
25.319
4.027
13.479
24.790
68.806
NUMBER OF
PLANTS
73
52
5
25
59
99
DIRECT OR INDIRECT
STANDARD
DEVIATION
0.039
.
.
.
0.036
NUMBER OF
OBSERVATIONS
2.168
0.878
0.838
0.302
2.815
NUMBER OF
PLANTS
4
1
1
2
4
V-12
-------
TABLE V-9
OCPSF MISCELLANEOUS NON-COOLING NON-PROCESS WASTEWATER FLOW
FOR PRIMARY PRODUCERS BY SUBCATEGORY & DISPOSAL HETHOO
DIRECT DISCHARGERS
SUBCATEGORY
'-
THERMOPLASTICS ,
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MEAN
( MGD; )
9.474
4.956
1.671
9.288
52.918
20.449
6.504
MEDIAN
( MGD )
0.485
0.290
0.240
1.585
1 .400
0.660
0.233j
STANDARD
DEVIATION
66.066
59.320
3.467
16.800
226.990
123.687
37.616
NUMBER OF
OBSERVATIONS
62.632
13.183
3.187
12.323
48.535
50.649
46.491
NUMBER OF
PLANTS
107
36
5
' 20
84
118
111
INDIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
:THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MEAN
( MGD >
0.242
0.236
0.116
3.727
4.365
0.434
DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS ;
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MEAN
( MGD )
0.063
0.004
0.121
0.143
14.466
MEDIAN
( MGD }
0.030
0.025
0.063,
0.639
0.106
0.069
OTHER THAN
MEDIAN
( MGD )
0.090
0.004
0.121
0.153
0.153
STANDARD
DEVIATION
• -• t
1.318
1.088
0.130
11.519
19.798
1.708
NUMBER OF
OBSERVATIONS
64.020
35.707
5.002
16.932
31.855
87.483
NUMBER OF
' PLANTS
100
72
6
32
75
131
DIRECT OR INDIRECT
STANDARD
DEVIATION
0.048
"
•
. •
24.107
NUMBER OF
OBSERVATIONS
3.168
0.878
0.838
0.302
2.815
NUMBER OF
PLANTS
5
1
1
2
4
V-13
-------
SUBCATEGORY
THERMOPLASTICS
THERHOSETS
RAYON
FIBERS
COMMODITY ORGAN ICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
TABLE V-10
PROCESS WASTEWATER FLOW FOR PRIMARY OCPSF PRODUCERS
BY SUBCATEGORY AND DISPOSAL METHOD
DIRECT DISCHARGERS
< 95% & 70% RULES )
TOTAL
FLOW
(MGD)'
24.884
3.080
24.639
7.422
25.909
27.146
16.985
194.299
MIN
(MGD)
0.02100
0.00001
5.03000
0.24300
0.00144
0.00020
0.00075
0.00002
MAX
(MGD)
3.450
2.680
11.039
1.482
3.890
18.000
3.450
19.323
MEAN
(MGD)
0.61
0.51
8.21
0.82
0.96
1.04
0.59
2.23
MEDIAN
(MGD)
0.31
. 0.09
8.57
0.63
0.66
0.11
0.26
0.85
STANDARD
DEVIATION
0.73
1.06
3.02
0.46
1.04
3.49
0.91
3.68
NUMBER OF
PLANTS
41
6
3
9
27
26
29
87
INDIRECT DISCHARGERS
TOTAL
FLOW
(MGD)
8.0439
0.7884
0.3768
11.4154
8.1822
32.4242
22.3383
( 95X
MIN
(MGD)
0.0000070
0.0001000
0.0003000
0.0078000
0.0007000
0.0000100
0.0000343
& 70X RULES )
MAX
(MGD)
1.240
0.350
0.160
7.970
2.963
15.439
4.840
MEAN
(MGD)
0.16
0.05
0.05
1.14
0.48
0.36
0.26
MEDIAN
(MGD)
0.05
0.00
0.02
0.28
0.05
0.07
0.03
STANDARD
DEVIATION
0.27
0.10
0.06
2.46
0.92
1.63
0.74 ft
NUMBER OF
PLANTS
49
16
7
10
17
90
86
V-14
-------
TABLE V-11
PROCESS WASTEWATER FLOW DURING 1980 FOR SECONDARY OCPSF
PRODUCERS BY SUBCATEGORY AND DISPOSAL METHOD
< 95 % RULE )
DIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
MINIMUM
(MGD)
0.00016
0.00369
0.00001
0.75000
MINIMUM
(MGD)
0.000300
0.000054
0.000050
0.000200
MAXIMUM
(MGD)
0.20
1.90
4.70
0.97
( 95
INDIRECT
MAXIMUM
(MGD)
0.0920
0.1400
0.6300
0.5585
MEAN
(MGD)
0.08
0.50
0.69
0.86
MEDIAN
(MGD)
0.05
0.06
0.17
0.86
STANDARD
DEVIATION
0.08
0.93
1.30
0.16
NUMBER OF
OBSERVATIONS
8
4
27
2
X RULE )
DISCHARGERS
MEAN
(MGD)
0.02
0.02
0.10
0.07
MEDIAN
(MGD)
0.01
0.00
0.02
0.01
STANDARD
DEVIATION
0.03
0.04
0.17
0.15
NUMBER OF
OBSERVATIONS
11
15
48
16
V-15
-------
TABLE V-12
PROCESS WASTEWATER FLOW FOR PRIMARY & SECONDARY
OCPSF PRODUCERS THAT ARE ZERO/ALTERNATIVE DISCHARGERS
( 95% & 70% RULES )
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGANICS
FIBERS
COMMODITY ORGANIC!
BULK ORGANICS
SPECIALTY ORGANICS 0.00450
MIXED
MINIMUM
(MGD)
0.00001
0.00004
0.00000
0.00010
0.90700
0.29700
0.00450
0.00006
MAXIMUM
(MGD)
0.34
0.02
4.40
0.08
0.91
0.30
0.33
2.20
MEAN
(MGD)
0.05
0.00
0.40
0.04
0.91
0.30
0.15
0.33
MEDIAN
(MGD)
0.01
0.00
0.03
0.04
0.91
0.30
0.11
0.01
STANDARD
DEVIATION
0.09
0.00
0.94
0.06
•
•
0.16
0.70
NUMBER OF
PLANTS
21
27
55
2
1
1
3
16
V-16
-------
TABLE V-13
NOW-PROCESS WASTEWATER FLOW DURING 1980
FOR SECONDARY OCPSF PRODUCERS
AND ZERO/ALTERNATIVE DISCHARGERS
BY SUBCATEGORY & DISPOSAL METHOD
( 9SX & 70% RULES )
SECONDARY lAND DIRECT DISCHARGE PLANTS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAMICS
MIXED
MINIMUM
(MGD)
0.00165
0.25000
0.00200
0.19000
SECONDARY
MINIMUM
(MGD)
0.00010
0.00090
0.00010
0.00050
MAXIMUM MEAN
(MGD) (MGD)
0.710 0.234
0.250 0.250
59.800 3.500
7.600 3.510
MEDIAN
(MGD)
0.120
0.250
0.125
2.740
STANDARD
DEVIATION
0.289
12.038
3.765
NUMBER OF
PLANTS
8
1
25
3
( 95% & 70% RULES )
AND INDIRECT DISCHARGE PLANTS
MAXIMUM MEAN
(MGD) (MGD)
0.250 0.037
5.000 0.492
44.100 1.317
2.100 0.341
MEDIAN
(MGD)
0.003
0.007
0.012
0.059
STANDARD
DEVIATION
0.072
1.372
6.806
0.590
NUMBER OF
PLANTS
14
13
42
15
( 95% & 70% RULES )
SECONDARY AND OTHER DISCHARGE PLANTS*
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
MINIMUM
(MGD)
0.00050
0.00171
0.00001
0.71000
0.08370
MAXIMUM MEAN
(MGD) (MGD)
1.500 0.136
0.590 0.092
5.750 0.360
0.710 0.710
24.700 1.935
MEDIAN
(MGD)
0.010
0.020
0.028
0.710
0.076
STANDARD
DEVIATION
0.381
0.156
0.934
6.559
NUMBER OF
PLANTS
15
22
42
1
14
NOTE: THERE ARE 9 PRIMARY PLANTS NOT INCLUDED IN THIS TABLE
THAT ARE ZERO DISCHARGERS.
V-17
-------
TABLE V-14
TOTAL OCPSF NON-PROCESS WASTEWATER FLOW IN 1980
FOR PRIMARY PRODUCERS BY SUBCATEGORY & DISPOSAL METHOD
DIRECT DISCHARGERS
( 95% & 705! RULES )
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MIXED
MINIMUM
( MGD )
0.00022
0.00007
0.14000
0.07200
0.00200
0.00521
0.00266
0.00010
MAXIMUM
( MGD }
30.744
15.605
2.500
44.364
648.000
38.400
15.626
1731.700
MEAN
( MGD )
2.106
2.659
1.320
10.727
25.595
3.267
1.842
43.023
MEDIAN
( MGD )
0.212
0.218
1.320
4.526
0.409
0.269
0.179
1.281
STANDARD
DEVIATION
5.603
5.741
1.669
15.621
126.949
8.123
3.613
195.531
NUMBER OF
PLANTS
39
7
2
8
26
25
22
83
INDIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
SUBCATEGORY
THERMOPLASTICS
SPECIALTY ORGANICS
MIXED
MINIMUM
( MGD )
0.00000
0.00030
0.01770
0.00520
0.00290
0.00020
0.00010
DISCHARGERS
MINIMUM
( MGD )
0.01000
0.05000
0.00010
< 95% & 70%
MAXIMUM
( MGD )
1.490
0.335
0.210
47.146
111.260
8.830
11.157
OTHER THAN
( 95% & 70%
MAXIMUM
( MGD )
0.047
40.480
0.000
RULES )
MEAN
( MGD )
0.154
0.052
0.077
6.859
8.662
0.439
0.469
DIRECT OR
RULES )
MEAN
( MGD )
0.028
13.560
0.000
MEDIAN
( MGD )
0.021
0.012
0.040
1.159
0.060
0.063
0.030
INDIRECT
MEDIAN
( MGD >
0.028
0.150
0.000
STANDARD
DEVIATION
0.306
0.099
0.090
16.310
30.827
1.271
1.648
STANDARD
DEVIATION
0.026
23.313
m
NUMBER OF
PLANTS
40
11
4
8
13
61
69
NUMBER OF
PLANTS
2
3
1
V-18
-------
TABLE V-15
NON-PROCESS COOLING WATER FLOW FOR PRIMARY
OCPSF PRODUCERS BY SUBCATEGORY & DISPOSAL METHOD
DIRECT DISCHARGERS
( 95% & 70% RULES )
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MIXED
MINIMUM
( MGD }
0.00414
0.00007
0.10000
0.08300
0.00500
0.00165
0.00001
0.00070
MAXIMUM
( MGD )
10.045
1.072
0.120
1.086
3.167
3.300
2.303
12.400
MEAN
< MGD )
0.736
0.290
0.110
0.411
0.884
0.277
0.229
0.843
MEDIAN
( MGD )
0.177
0.038
0.110
0.325
0.468
0.078
0.041
0.288
STANDARD
DEVIATION
1 .969
0.441
0.014
0.351
0.999
0.699
0.456
1.791
NUMBER OF
PLANTS
40
7
2
8
24
22
29
81
INDIRECT DISCHARGERS
SUBCATEGORY
THERMOPLASTICS.
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
MINIMUM
( MGD )
0.00009
0.00010
0.00731
0.02814
0.00300
0.00004
0.00001
( 95% & 70%
MAXIMUM
< MGD )
0.890
0.029
0.135
2.758
0.999
1.600
8.000
DISCHARGERS OTHER THAN
SUBCATEGORY
THERMOPLASTICS
COMMODITY ORGANICS
SPECIALTY ORGANICS
MIXED
MINIMUM
< MGD )
0.04300
0.12100
0.00120
0.00400
( 95% & 70%
MAXIMUM
( MGD )
0.092
0.121
0.060
0.004
RULES )
MEAN
( MGD )
0.077
0.009
0.067
0.786
0.172
0.096
0.247
DIRECT OR
RULES )
MEAN
( MGD )
0.067
0.121
0.021
0.004
MEDIAN
( MGD )
0.012
0.006
0.063
0.481
0.014
0.011
0.016
INDIRECT
MEDIAN
( MGD )
0.067
0.121
0.003
0.004
STANDARD
DEVIATION
0.194
0.009
0.057
0.931
0.320
0.232
1.074
STANDARD
DEVIATION
0.035
•
0.034
NUMBER OF
PLANTS
34
9
4
8
13
58
56
NUMBER OF
PLANTS
2
1
3
1
V-19
-------
TABLE V-16
OCPSF MISCELLANEOUS WON-COOLING NON-PROCESS WASTEWATER FLOW
FOR PRIMARY PRODUCERS BY SUBCATEGORY & DISPOSAL METHOD
DIRECT DISCHARGERS
( 95% & 70% RULES >
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGANICS
BULK ORGAN I CS
SPECIALTY ORGAN I CS
MIXED
MINIMUM
( MGD )
0.00100
0.00015
0.12000
0.22100
0.01200
0.00521
0.00031
0.00080
MAXIMUM
( MGD )
30.896
15.643
2.500
44.447
651.167
41.700
15.703
1739.330
MEAN
( MGD )
2.657
2.949
0.953
11.138
25.432
3.135
1.474
40.435
MEDIAN
( MGD )
0.396
0.290-
0.240
4.929
0.884
0.304
0.173
1.410
STANDARD NUMBER OF
DEVIATION PLANTS
6.235 42
5.687 7
1.341 3
15.500 8
125.062 27
8.264 28
3.097 32
188.898 90
INDIRECT DISCHARGERS ,
SUBCATEGORY
THERMOPLASTICS
THERHOSETS
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MIXED
SUBCATEGORY
THERMOPLASTICS
COMMODITY ORGANICS
SPECIALTY ORGANICS
MIXED
MINIMUM
( MGD )
0.00000
0.00010
0.02411
0.04480
0.00300
0.00004
0.00011
DISCHARGERS
MINIMUM
( MGD }
0.01000
0.12100
0.05120
0.00410
( 95% & 70%
MAXIMUM
( MGD )
2.380
0.350'
0.345
49.904
111.960
9.367
11.417
OTHER THAN
< 95% & 70%
RULES )
MEAN
( MGD >
0.187
0.047
0.115
6.795
7.178
0.449
0.592
DIRECT OR
RULES )
MAXIMUM MEAN
{ MGD )
0.092
0.121
40.540
0.004
( MGD )
0.064
0.121
13.581
0.004
MEDIAN .
( MGD )
0.028
0.018
0.063
0.898
0.081
0.080
0.052
INDIRECT
MEDIAN
( MGD )
0.090
0.121
0.153
0.004
STANDARD NUMBER OF
DEVIATION PLANTS
0.411 47
,0.092 14
0.131 5
16.218 9
27.944 16
1.286 72
1.797 78
STANDARD, NUMBER OF
DEVIATION PLANTS
0.047 3
1
23.347 3
1
V-20
-------
50 percent is then chosen as the.median. If, however, the total equals
50 percent exactly, then the median is the average of the wastewater flow of
that plant and the next plant in the sequence. The tables are divided into
primary and secondary producers because less detailed production data were
collected from secondary producers. Likewise, less detailed data were
collected from both primary and secondary zero discharge plants. Production
data are identified only by Standard Industrial Classification (SIC) code for
secondary or zero discharge producers, ,and thus the organics subcategories
(i.e., bulk, commodity, specialty) must be grouped together.
In each table, the column for "Number of Plants" represents the total
number of plants for whom at least part of their flow .was used to derive the
subcategory statistics. Therefore, double or multiple counting of plants
occurs for multi-subcategory plants. The column for "Number of Observations"
represents the sum of plant subcategory production proportions.
Tables V-10 through V-16 also provide 1980 process and nonprocess
wastewater flow statistics by subcategory and disposal technique, but use a
different method to aggregate plants by subcategory. Plants were placed in
one of five categories (Thermoplastics, Thermosets, Rayon, Organics, Fibers)
if their production was at least 95 percent contained in that category.
Plants having less than 95 percent were placed in a sixth category (Mixed).
The organics category was then further subdivided into three subcategories
(Commodity, Bulk, Specialty) if the plant's organics production was at least
70 percent contained in one of the subcategories. Plants with less than
70 percent production were also placed in the mixed category. As with the
tables generated using the regression methodology, production data are
identified only by SIC code for secondary or zero discharge producers, and
thus the organics subcategories (Commodity, Bulk, Specialty) were grouped
together in the tables for these plants.
Tables V-3 and V-4 provide process wastewater flow statistics for primary
and secondary producers, respectively, with,each divided into direct and
indirect dischargers using the regression methodology. Tables V-10 and V-ll
present the same flow statistics using the 95 percent production basis for
assigning plants to subcategories for the four nonorganics subcategories and
V-21
-------
the 70 percent organics production basis for the three organics subcategories
(95/70 methodology). Table V-5 provides process wastewater flow statistics
for the zero or alternate discharge plants using the regression methodology,
while Table V-12 presents the same flow statistics using the 95/70 methodology.
Tables V-6 through V-9 provide 1980 flow statistics for nonprocess wastewaters
using the regression methodology, while Tables V-13 through V-16 present the
same flow statistics using the 95/70 methodology.
The data in each table are grouped by the disposal method of the plants'
process wastewater. In general, plants that discharge process wastewater
directly will also discharge nonprocess wastewater directly. However, in some
cases, plants that discharge process wastewater indirectly or by zero or
alternate discharge methods may discharge their non-process wastewaters
directly due to the generally lower treatment requirements of many nonprocess
waste streams.
Tables V-6 and V-13 provide the nonprocess flow statistics for secondary
producers and zero and alternate dischargers. Tables V-7 and V-14 provide the
total nonprocess flow statistics for primary producers, while Tables V-8
through V-9 and Tables V-15 through V-16 provide the portions of these flows
that are composed of cooling water versus other miscellaneous nonprocess
wastewater.
fr
The cooling water in Tables V-8 and V-15 include both once-through
noncontact cooling water plus.cooling tower blowdown and for some plants may
include other nonprocess wastewater where flows were reported as a combined
total. It is evident from these tables that cooling water comprises the major
portion of nonprocess wastewater for most plants and that direct dischargers
produce greater quantities of nonprocess wastewater than indirect dischargers.
In general, the summary statistics for wastewater flow by subcategory
that were generated by the two methodologies compare favorably; all of the
differences between subcategory medians calculated by the two methodologies
fell within the standard deviations calculated by either methodology. Reasons
for the differences include the inaccurate nature of assigning individual
plants to subcategories, i.e., the arbitrary assignment of plants based on the
V-22
-------
95/70 rule, which was determined to be insufficient for previous sub-
categorization efforts, as well as the relative contribution of the extra 5 or
30 percent of other subcategories' flows .depending on if the plant is pre-
dominantly plastics or organics, respectively. Based on the inherent
limitations of the 95/70 methodology, the Agency has much more confidence in
the utility of the regression methodology summary statistics, but has included
the 95/70 summary statistics for comparison purposes.
D. WATER REUSE AND RECYCLE
1. Water Conservation and Reuse Technologies
A variety of water conservation practices and technologies are available
to OCPSF plants. Because of the diversity within the industry, no one set of
conservation practices is appropriate for all plants. Decisions regarding
water reuse and conservation depend on plant-specific characteristics, as well
as site-specific water supply and environmental factors (e.g., water avail-
ability, cost, and quality). Therefore, this section will describe the range
of practices and technologies available for water conservation.
Conventional water conservation practices include (McGovern 1973; Holiday
1982);
• Recovery and reuse of steam condensates and process condensates, where
possible
• Process modifications to recover more product and solvents
• Effective control of cooling-tower treatment and blowdown to optimize
cycles of concentration
• Elimination of contact cooling for off vapors
• Careful monitoring of water uses; maintenance of raw water treatment
systems and prompt attention to faulty equipment, leaks, and other
problems
• Installation of automatic monitoring and alarm systems on in-plant
discharges.
V-23
-------
Table V-17 summarizes water conservation technologies, and their applications,
limitations, and relative costs to industry plants. Some of these technolo-
gies, such as steam stripping, are also considered effluent pollution control
technologies. Water conservation, in fact, can often be a benefit of mandated
pollution control.
2. Current Levels of Reuse and Recycle
Data on the amount of water reused and recycled in the OCPSF industry
from the 1978 Census Bureau survey and the 1983 308 Questionnaires are
presented in Tables V-18 and V-19, respectively.
In Table V-18, the Census Bureau defines "recirculated or reused water"
as the volume of water recirculated multiplied by the number of times the
water was recirculated. Seventy-nine percent of the OCPSF plants surveyed by
the Census Bureau reported some recirculation or reuse of water. Census
Bureau statistics show that the bulk of recirculated water is used for cooling
and condensing operations, such as closed-loop cooling systems for heat
transport. Chemical algaecides and fungicides are routinely added to these
cooling waters to prevent organism growth and suppress corrosion, both of
which can cause exchanger fouling and reduction of heat transfer co-
efficients.
As water evaporates and leaks from, such closed systems, the concentration
of minerals in these waters increases, which may lead to scale formation,
reducing heat transfer efficiency. To reduce such scaling, a portion of such
closed system waters is periodically discharged as blowdown and replaced by
clean water. >
t
Table V-19 shows the 1980 recycle flow of process and nonprocess
wastewaters for OCPSF plants that are primary producers, excluding zero and
alternate dischargers as reported in the 1983 Section 308 Questionnaire. The
flow rates shown were for wastewater streams where the final disposal method
was reported as recycle. Thus, the data do not reflect the number of times
the wastewater is recycled (as in Census Bureau data), nor do they include
flow in closed-loop systems such as cooling towers, since water in such
V-24
-------
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r-l .-I O CM
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C3 CM ON rH
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00 CO OO fH
• • • •
O O r-< r-l
CM rH CO VO
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>.i-r>.
fH O rH
C C
O >£ >>
C0rc1
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O Hi di <•
V-28
-------
systems is not considered wastewater until it leaves the system as blowdown.
As a result of these differences, Table V-19 shows a much lower number of
plants reporting recycle.
The fact that Table V-19 excludes plants that are considered zero dis-
chargers may account for some of this discrepancy, since any plant that recy-
cles 100 percent of its process wastewater would be excluded.
D. WASTEWATER CHARACTERIZATION !
1. Conventional Pollutants
A number of different pollutant parameters are used to characterize
wastewater discharged by OCPSF manufacturing facilities. .These include:
• Biochemical Oxygen Demand (BOD5)
9 Total Suspended Solids (TSS)
• pH
0 Chemical Oxygen Demand (COD)
• Total Organic Carbon (TOC) :
• Oil and Grease <0&G).
BOD is one of the most important gauges of the pollution potential of a
wastewater and varies with the amount of biodegradable matter that can be
assimilated by biological organisms under aerobic conditions. Large, complex
facilities tend to discharge a higher BOD5 mass loading, although concentra-
tions are not necessarily different from smaller or less complex plants. The
nature of specific chemicals discharged into wastewater affects the BOD5 due
to the differences in susceptability of different molecular structures to
microbiological degradation. Compounds with lower susceptibility to decom-
position by microorganisms tend to exhibit lower BOD5 values, even though the
total organic loading may be much higher than compounds exhibiting
substantially higher BOD5 values.
V-29
-------
Raw wastewater TSS is a function of the products manufactured and their
processes, as well as the manner in which fine solids that may be removed by a
processing step are handled in the operations. It can also be a function of a
number of other external factors, including stormwater runoff, runoff from
material storage areas, and landfill leachates that may be diverted to the
wastewater treatment system. Solids are frequently washed into the plant
sewer and removed at the wastewater treatment plant. The solids may be
organic, inorganic, or a mixture of both. Settleable portions of the
suspended solids are usually removed in a primary clarifier. Finer materials
are carried through the system, and in the case of an activated sludge system,
become enmeshed with the biomass where they are then removed with the sludge
during secondary clarification. Many of the manufacturing plants show an
increase in TSS in the effluent from the treatment plant. This characteristic
is usually associated with biological systems and indicates an inefficiency of
secondary clarification in removal of secondary solids. Also, treatment
systems that include polishing ponds or lagoons may exhibit this characteristic
due to algae growth. However, in plastics and synthetic materials wastewaters,
formation of biological solids within the treatment plant may cause this
solids increase due to the low strength nature of the influent wastewater.
Raw wastewater pH can be a function of the nature of the processes
contributing to the waste stream. This parameter can vary widely from plant
to plant and can also show extreme variations in a single plant's raw
wastewater, depending on such factors as waste concentration and the portion
of the process cycle discharging at the time of measurement. Fluctuations in
pH are readily reduced by equalization followed by a neutralization system, if
necessary. Control of pH is important regardless of the disposition of the
wastewater stream (i.e., indirect discharge to a POT¥ or direct discharge) to
maintain favorable conditions for biological treatment system organisms, as
well as receiving streams.
COD is a measure of oxidizable material in a wastewater as determined by
subjecting the waste to a powerful chemical oxidizing agent (such as dichro-
mate) under standardized conditions. Therefore, the COD test can show the
presence of organic materials that are not readily susceptible to attack by
biological microorganisms. As a result of this difference, COD values are
V-30
-------
almost invariably higher than BOD5 values for the same sample. The COD test
cannot be substituted directly for the BOD5 test because the COD/BOD5 ratio is
a factor that is extremely variable and is dependent on the specific chemical
constituents in the wastewater. However, a COD/BOD5 ratio'for the wastewater
from a single manufacturing facility with a constant product mix may be
established. This ratio is applicable only to the wastewater from which it
was derived and cannot be utilized to estimate the BOD5 of another plant's
wastewater. It is often established by plant personnel to monitor process and
treatment plant performance with a minimum of analytical delay. As production
rate and product mix changes, however, the COD/BOD, ratio must be Devaluated
for the new conditions. Even if there are no changes in production, the ratio
should be reconfirmed periodically.
TOG measurement is another means of determining the, pollution potential
of wastewater. This measurement shows the presence of organic compounds not
necessarily measured by either BOD or COD tests. TOG can also be related to
delay. As production rate and product mix changes, however, the COD/BOD5
ratio must be reevaluated for the new conditions. Even if there are no
changes in production, the ratio should be reconfirmed periodically.
Tables V-20 through V-27 provide a statistical analysis of raw wastewater
BOD , COD, TOC, and TSS by subcategory and disposal method. For
multi-subcategory plants, the plants' pollutant values have been
production-weighted for calculatipn of mean values and selection of median
values. The following equation illustrates the method for calculating the
production-weighted mean concentrations:
Subcategory:
Production-weighted Mean = P*Ci +
+ P'C» * ' ' ' ' *
Pl + P2 + P3
Where:
P = Decimal subcategory proportion of total plant production for plant
1 #1 (Range 0 to 1.0)
C = Pollutant concentration for plant ttl.
V-31
-------
TABLE V-20
SUMMARY STATISTICS OF RAW WASTEWATER BOD CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
DIR/IND THERMOPLASTICS
THERMOSETS
BULK ORGANICS
SPECIALTY ORGANICS
DIRECT THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
INDIRECT THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
ZERO THERMOPLASTICS
THERMOSETS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
r i\uuuv.CK-r K 1 PIHK I
# OF # OF PLANTS
PLANTS (PRODUCTION
108
44
4
20
51
95
104
1
1
1
2
62
16
4
18
38
53
46
43
26
2
12
40
55
2
1
'1
1
1
WEIGHTED)
65.7538
15.6468
2.1871
13.1475
29.9702
34.9281
60.3664
1.0000
0.0337
0.2863
1.6800
37.1289
4.0231
2.1871
11.1475
21.6020
16.8416
1B.0697
27.4570
10.7119
2.0000
7.5305
17.7067
40.5939
0.1680
0.8781
0.8377
0.0935
0.0228
PRODUCTION
WEIGHTED
MEAN
1328.886
1856.433
169.756
921.281
1724.727
1465.540
1320.423
469.000
577.000
577.000
245.745
725.190
1569.784
169.756
904.556
1504.018
1199.871
1347.053
2182.704
2092.435
1014.500
2518.558
1738.854
1353.627
323.534
340.000
280.000
280.000
280.000
PRODUCTION
WEIGHTED
MEDIAN
351.000
572.000
175.000
986.000
679.000
705.000
715.000
469.000
577.000
577.000
20.500
386.000
668.000
175.000
706.200
694.000
668.000
718.000
198.000
453.800
1014.500
679.000
705.000
715.000
340.000
340.000
280.000
280.000
280.000
PRODUCTION
WEIGHTED
STD. DEV.
4634.526
4824.965
11.139
663.397
2284.493
2120.879
1819.967
429.352
830.834
2119.824
11.139
724.331
2009.651
1399.325
2038.317
7093.989
5779.452
40.305
3042.237
2665.783
1766.617
V-32
-------
TABLE V-21
SUMMARY STATISTICS OF RAW WASTEUATER BOD CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMOSETS
ORGAN I CS
DIR/IND THERMOPLASTICS
ORGAN I CS
DIRECT THERMOPLASTICS
THERMOSETS
ORGAN I CS
INDIRECT THERMOPLASTICS
THERMOSETS
ORGAN I CS
ZERO THERMOPLASTICS
ORGAN I CS
UNKNOWN THERMOPLASTICS
PROOUCER=SECONDARY
# OF # OF PLANTS PRODUCTION
PLANTS
30
24
62
Z
1
9
3
23
17
21
37
1
1
1
(PRODUCTION
WEIGHTED)
17.4317
16.6878
55.8805
1.0567
0.9433
5.6808
2.0319
21 .2874
9.1103
14.6559
33.2337
0.5839
0.4161
1.0000
WEIGHTED
MEAN
673.612
796.882
920.621
42.073
621.500
66.951
39.624
58.193
1194.172
901.867
1492.966
7.000
7.000
434.000
PRODUCTION
WEIGHTED
MEDIAN
117.800 ,
304.000
96.900
9.230
621.500
54.500
24.000
41.000
361.000
360.000
451.000
7.000
7.000
434.000
PRODUCTION
WEIGHTED
STD. DEV.
1698.067
1459.787
2228.595
595.622
•
73.167
22.498
75.010
2276.641
1533.251
2758.663
•
•
V-33
-------
TABLE V-22
SUMMARY STATISTICS OF RAW UASTEWATER COO CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL
METHOD
ALL PLANTS
DIR/IND
DIRECT
INDIRECT
ZERO
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
THERMOPLASTICS
THERMOSETS
BULK ORGANICS
SPECIALTY ORGANICS
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
THERMOPLASTICS
THERMOSETS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
# OF
PLANTS
95
49
4
17
62
79
93
2
1
2
2
56
18
4
15
43
48
41
35
29
2
18
28
49
2
1
1
1
1
# OF PLANTS
(PRODUCTION
WEIGHTED)
53.6896
20.3799
2.1871
11.5417
33.9393
27.2478
46.0146
1.0293
0.0337
1.2533
0.6836
32.0356
6.6961
2.1871
9.5417
24.1352
13.7100
15.6944
20.4567
12.7719
2.0000
8.9665
12.1911
29.6138
0.1680
0.8781
0.8377
0.0935
0.0228
PRODUCTION
WEIGHTED
MEAN
3035.613
7497.533
503.405
1657.671
3457.453
4811.004
3362.890
944.575
6912.000
4794.021
6897.501
2429.787
9414.566
503.405
1632.135
2600.765
3291.938
2354.756
3927.833
4870.899
1779.500
6030.363
6553.362
3817.702
22733.387
31105.000
600.000
600.000
600.000
PRODUCTION
WEIGHTED
MEDIAN
1395.000
2709.000
500.000
1501.000
1645.000
2066.000
1772.500
850.000
6912.000
4167.000
6912.000
1425.000
4094.000
500.000
1217.000
1645.000
3092.000
1756.000
1226.800
2394.000
1779.500
2709.000
1435.000
1772.500
31105.000
31105.000
600.000
600.000
600.000
PRODUCTION
WEIGHTED
STD. DEV.
5851.739
10315.211
83.729
1668.644
5075.267
8651 .988
5231 .467
3269.370
2563.254
4783.865
11736.813
83.729
1847.690
2737.533
3011.197
2418.299
7041.918
7574.041
393.858
8614.405
12603.269
6242.976
V-34
-------
TABLE V-23
SUMMARY STATISTICS OF RAW WASTEWATER COD CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMOSETS
ORGAN I CS
DIR/IND THERMOPLASTICS
ORGAN I CS
DIRECT THERMOPLASTICS
THERMOSETS
ORGAN I CS
INDIRECT THERMOPLASTICS
THERMOSETS
ORGAN I CS
ZERO THERMOPLASTICS
ORGAN I CS
PRODUCER=SECONDARY
# OF # OF PLANTS PRODUCTION
PLANTS
24
19
49
2
1
7
1
19
14
18
28
1
1
(PRODUCTION
WEIGHTED)
11.1848
14.2420
45.5732
1.0567
0.9433
3.7185
1.0000
18.2815
5.8257
13.2420
25.9323
0.5839
0.4161
WEIGHTED
MEAN
1825.124
3282.064
3126.985
795.978
14115.333
272.776
274.500
377.963
3157.083
3509.187
4710.872
284.100
284.100
PRODUCTION
WEIGHTED
MEDIAN
800.000
1808.000
636.700
41.000
14115.333
141.000
274.500
248.000
1995.000
2340.000
1698.000
284.100
284.100
PRODUCTION
WEIGHTED ,
STD. DEV.
2640.893
3996.106
.6883.309
13691 .642
•
219.334
•
571 .528
2823.567
'4059.385
8463.117
•
•
V-35
-------
TABLE V-24
SUMMARY STATISTICS OF RAW WASTEWATER TOC CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
DIRECT THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
INDIRECT THERMOPLASTICS
THERMOSETS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
f
# OF
PLANTS
42
16
7
39
56
55
31
7
7
37
45
41
11
9
2
11
14
'RODUCER=PRIMAR^
# OF PLANTS
(PRODUCTION
WEIGHTED)
18.9470
4.8893
3.8143
20.6337
23.5709
22.1449
14.5154
1.2449
3.8143
19.3261
17.6060
14.4933
4.4316
3.6444
1 .3076
5.9648
7.6516
r
PRODUCTION
WEIGHTED
MEAN
992.384
426.877
475.170
1096.466
989.221
1247.866
1132.305
351.164
475.170
970.419
897.761
1424.170
534.079
452.741
2959.352
1259.177
913.918
PRODUCTION
WEIGHTED
MEDIAN
486.000
349.000
391.200
418.000
484.000
575.000
522.000
349.000
391.200
418.000
358.000
424.000
50.000
654.000
4660.000
505.000
604.000
PRODUCTION
WEIGHTED
STD. DEV.
1997.567
274.541
173.191
1385.640
1749.485
2463.687
2124.494
182.526
173.191
1199.265
1557.493
2965.838
1654.798
322.723
4594.570
2384.023
1120.472
V-36
-------
TABLE V-25
SUMMARY STATISTICS OF RAW WASTEWATER TOC CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMQSETS
ORGAN I CS
DIR/IND THERMOPLASTICS
ORGAN I CS
DIRECT THERMOPLASTICS
THERMOSETS
ORGAN I CS
INDIRECT THERMOPLASTICS
THERMOSETS
ORGAN I CS
PRODUCER=SECONDARY
# OF # OF PLANTS PRODUCTION
PLANTS (PRODUCTION WEIGHTED
9
7
27
2
1
5
2
13
2
5
13
WEIGHTED)
5.4525
4.7260
24.8216
1.0567
0.9433
2.6737
1.0319
11.2945
1.7221
3.6941
12.5838
MEAN
349.877
278.596
1478.439
316.970
5644.333
131.137
68.104
174.445
709.665
337.393
2336.539
PRODUCTION
WEIGHTED
MEDIAN
215.000,
78.000
249.000
15.000
5644.333
118.000
68.000
23.800
500.000
145.500
445.000
PRODUCTION
WEIGHTED
STD. DEV.
698.064
365.633
3094.234
5476.268
87.972
3.298
414.016
381.009
403.957
3957.989
V-37
-------
TABLE V-26
SUMMARY STATISTICS OF RAW WASTEWATER TSS CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGAN I CS
DIR/IND THERMOPLASTICS
THERMOSETS
BULK ORGAN I CS
SPECIALTY ORGANICS
DIRECT THERMOPLASTICS
THERMC.«ETS
RAYON
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
INDIRECT THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
ZERO THERMOPLASTICS
THERMOSETS
F
# OF
PLANTS
113
54
3
15
56
92
109
2
1
2
3
55
15
3
13
36
44
37
55
37
2
20
46
69
1
1
>RODUCER=PRIMAR1
# OF PLANTS
(PRODUCTION
WEIGHTED)
69.2105
21.9417
1.9756
9.8263
29.1388
37.3944
60.5127
1.0293
0.0337
1.2533
1.6836
32.7511
5.4898
1.9756
7.8263
19.4999
14.5703
13.8871
35.3082
15.5401
2.0000
9.6390
21.5708
44.9420
0.1219
0.8781
r
PRODUCTION
WEIGHTED
MEAN
639.742
822.065
399.500
135.510
378.424
1026.209
526.438
66.792
6103.000
1545.294
2485.942
729.522
1756.192
399.500
158.895
302.818
603.532
381.469
564.396
347.309
44.000
531 .376
1281.553
497.827
3181.000
3181.000
PRODUCTION
WEIGHTED
MEDIAN
263.000
212.000
635.000
72.000
157.000
174.000
154.000
63.000
6103.000
196.000
34.700
302.000
1598.000
635.000
156.000
157.000
234.000
194.000
202.000
129.400
44.000
186.000
129.400
151.800
3181.000
3181.000
PRODUCTION
WEIGHTED
STD. DEV.
971.596
1203.909
339.319
126.695
678.674
2990.516
1236,554
131.090
5515.897
4672.420
1115.037
1358.482
339.319
132.934
433.753
913.698
473.399
824.529
739.290
4.243
1028.767
3832.206
1229.205
V-38
-------
TABLE V-27
SUMMARY STATISTICS OF RAW WASTEWATER TSS CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
DISPOSAL SUBCATEGORY
METHOD
ALL PLANTS THERMOPLASTICS
THERMOSETS
ORGAN I CS
DIR/IND THERMOPLASTICS
ORGAN I CS
DIRECT THERMOPLASTICS
THERMOSETS
OR CAN I CS
INDIRECT THERMOPLASTICS
THERMOSETS
ORGANICS
ZERO THERMOPLASTICS
ORGANICS
UNKNOWN THERMOPLASTICS
PRODUCER=SECONDARY
# Of # OF PLANTS PRODUCTION
PLANTS
31
25
64
2
1
9
3
26
18
22
36
1
1
1
(PRODUCTION
WEIGHTED)
18.2239
17.7299
58.0462
1 .0567
0.9433
5.6808
2.0319
24.2874
9.9025
15.6980
32.3995
0.5839
0.4161
1 .0000
WEIGHTED
MEAN
121.241
255.721
800.089
25.286
350.000
32.303
38.924
76.918
164.678
283.782
1365.387
14.600
14.600
360.000
PRODUCTION
WEIGHTED
MEDIAN
64.000
168.000
76.700
6.880
350.000
29.000
26.000
38.900
130.000
168.000
173.000
14.600
14.600
360.000
PRODUCTION
WEIGHTED
STD. DEV.
122.123
262.125
4456.709
333.790
•
20.124
19.618
107.027
112.000
266.163
5943.781
•
•
•
V-39
-------
In determining the median, the actual pollutant concentrations, of each
plant that has at least one product within a subcategory are ranked from
lowest to highest. The subcategory decimal production proportions are summed
starting from the lowest concentration plant until the sum equals or exceeds
50 percent of the total of all the decimal production proportions. The
pollutant concentration of the plant whose proportions when added to the
proportion sum causes the total to exceed 50 percent is then chosen as the
median. If, however, the sum equals 50 percent exactly, then the median is
the average of the pollutant concentrations of that plant and the next plant
in the sequence.
Tables V-28 through V-35 also provide raw wastewater statistics for BOD ,
COD, TOC, and TSS by subcategory and discharge technique, but use the 95/70
methodology discussed earlier in this section to aggregrate plants by subcate-
gory. As in previous tables concerning wastewater volumes, these tables are
separated into primary producers and a few zero/alternate dischargers versus
secondary producers and most zero dischargers. For some indirect and zero
dischargers who pretreat their wastewater, the data used are typically from
the effluent of their pretreatment system rather than strictly raw wastewater.
Most indirect dischargers only sample their wastewater at the point where it
enters the POTO collection system. It should also be noted that, as described
in Section VII, the concentrations of pollutants for raw wastewater of the
primary producers that are direct dischargers have been corrected for dilution
by uncontaminated nonprocess wastewater. This correction was not performed on
secondary producers, nor on indirect and zero dischargers.
As with the summary statistics for wastewater flow by subcategory, the
summary statistics for raw wastewater BOD5, COD, TOC, and TSS concentrations
by subcategory that were generated by the two methodologies compare favorably;
most of the differences between subcategory medians calculated by the two
methodologies fell within the standard deviations calculated by either
methodology. For the reasons stated earlier in this section when discussing
the summary statistics for wastewater flow by subcategory, the Agency has much
more confidence in the accuracy of the summary statistics calculated by the
regression methodology, but has included the summary statistics calculated by
the 95/70 methodology for comparison purposes.
V-40
-------
TABLE V-28
SUMMARY STATISTICS OF RAW WASTEWATER BOD CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
( WITH 95% & 70% RULE )
ALL PLANTS THERMOPLASTICS 48
THERMOSETS 5
RAYON 2
FIBERS 9
COMMODITY ORGANICS 14
BULK ORGANICS 18
SPECIALTY ORGANICS 52 ,
MIXED 74
DIR/IND THERMOPLASTICS 1
BULK ORGANICS 0
SPECIALTY ORGANICS 1
MIXED 1
DIRECT THERMOPLASTICS 26
THERMOSETS 2
RAYON ' 2
FIBERS . 7
COMMODITY ORGANICS 9
BULK ORGANICS 8
SPECIALTY ORGANICS 12
MIXED 45
INDIRECT THERMOPLASTICS 21
THERMOSETS 3
FIBERS 2
COMMODITY ORGANICS 4
BULK ORGANICS 10
SPECIALTY ORGANICS 39
MIXED 27
ZERO THERMOPLASTICS 0
COMMODITY ORGANICS 1
BULK ORGANICS 0
SPECIALTY ORGANICS 0
MIXED 1
iRY --------
MEAN
1088.883
1191.200
169.000
739.244
2099.000
940.156
1263.161
1814.754
469.000
20.500
577.000
647.205
2415.500
169.000
660.600
2209.944
901 .625
1534.810
1079.856
1665.240
375.000
1014.500
2304.125
970.980
1211.440
3140.048
MEDIAN
266.500
250.000
169.000 ;
706.200
629.500
393.500 '
704.500
737.000
469.000
20.500
577.000
380.500
2415.500
169.000
444.000
694.000
264.000
773.500
785.000
138.000
250.000
1014.500
766.500
430.000
694.000
757.000
STD. DEV.
4312.183
1991.833
8.485
531,238
2887.453
1074.395
1623.229
3811.602
•
;
810.973 .
3239.256
8.485
586.126
2959.328
1051.801
2567.712
920.978
6500.336
436.148
40.305
3402.801
1147.855
1249.419
6037.743
280.000
340.000
280.000
340.000
V-41
-------
TABLE V-29
SUMMARY STATISTICS OF RAW WASTEWATER BOD CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
< WITH 95% & 70% RULE )
DISPOSAL
METHOD
ALL PLANTS.
DIR/IND
DIRECT
INDIRECT
ZERO
UNKNOWN
SUBCATEGORY # OF
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
THERMOPLASTICS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
PLANTS
12
13
51
0
14
1
0
1
5
2
20
2
5
11
31
10
0
0
0
0
1
1
0
0
.UIYUHM ----
MEAN
441 .894
623.608
972.029
.
964.434
9.230
_
621.500
70.940
39.950
60.801
24.500
900.960
729.727
1559.918
1282.458
.
.
.
.
7.000
434.000
m
MEDIAN
161 .900
277.000
82.000
302.000
9.230
621.500
54.500
39.950
43.000
' 24.500
651.000
360.000
451.000
402.000
7.000
434.000
STD. DEV.
705.702
871.510
2327.405
2239.655
77.758
22.557
76.557
30.406
938.746
911.519
2848.442
2611.835
V-42
-------
• TABLE V-30
SUMMARY STATISTICS OF RAW WASTEWATER COO CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
( WITH 95% 8 70% RULE )
DISPOSAL
METHOD
ALL PLANTS
DIR/IND
DIRECT
INDIRECT
ZERO
PRODUCER=PRIMARY
SUBCATEGORY # OF MEAN
MEDIAN
STD. DEV.
PLANTS
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGAN I CS
MIXED
THERMOPLASTICS
BULK ORGAN I CS
SPECIALTY ORGANICS
MIXED
THERMOPLASTICS
THERMOSETS
RAYON
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
THERMOPLASTICS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
34
7
2
8
15
11
37
81
1
1
0
1
19
.4
2
6
10
5
12
46
14
3
2
4
5
25
33
0
1
0
0
1
2172.459
5773.143
522.500
1132.000
2914.633
2839.545
2658.803
5450.385
850.000
4167.000
.
. 6912.000
1774.974
8865.250
522.500
916.167
2579.200
5020.200
2173.000
3254.714
. 2806.365
1650.333
1779.500
4331.875
393.400
2891.989
7689.313
.
600.000
.
31105.000
1158.000
1700,000
522.500
1000.000
1943.000
598.000
1692.000
2066.000
850.000
4167.000
6912.000
1286.000
6815.500
522.500
710.000
1971.500
3796.000
1544.500
1689.500
455,500
509.000
1779.500
2229,250
500.000
1692.000
2709.000
•
600.000
-
.
31105.000
3478.292
7882.793
31 .820
875.063
3401 .295
3411.839
2746.715
9051.549
•
•
•
•
1734.512
9586.722
31 .820
904.102
2590.289
3896.203
2220.908
5735.796
507A.226
1984.647
393.858
5387.018
238.931
2980.155
11217.300
•
•
•
•
•
V-43
-------
TABLE V-31
SUMMARY STATISTICS OF RAW WASTEWATER COO CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
( WITH 95% & 70% RULE )
DISPOSAL
METHOD
ALL PLANTS
DIR/INO
DIRECT
INDIRECT
ZERO
UNKNOWN
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
THERMOPLASTICS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
ppnni IPPD— c
r I\\sU U U CK ""5
# OF
PLANTS
8
12
40
0
11
1
0
1
3
1
17
2
4
11
23
7
0
0
0
0
1
0
0
0
•cp/ittn A DV
MEAN
1509.000
3219.000
3007.794
.
3513.803
41.000
_
14115.333
245.333
274.500
393.626
248.200
2823.750
3486.682
4940.004
3393.714
•
•
'.
.
284.100
.
.
.
MEDIAN
646.000
1753.500
582.500
1364.000
41.000
14115.332
141.000
274.500
248.000
248.200
2247.500
2340.000
1698.000
1808.000
284.100
STD. DEV.
2032.859
4181.376
7111.048
4438.984
214.463
587.223
341.957
2234.261
4276.269
8955.829
2962.999
V-44
-------
TABLE V-32
SUMMARY STATISTICS OJ- RAW;WASTEWATER fdC CONCENTRATIONS
BY SUBCATEGORY; GROUP AND,DISPOSAL METHOD
(WITH 95% & 70% RULE ) „
DISPOSAL
METHOD
ALL PLANTS
DIR/IND
DIRECT
INDIRECT
ZERO
PRODUCER=PRIMARY
SUBCATEGORY # OF MEAN
THERMOPLASTICS
THERMOSETS'
RAYON
FIBERS
COMMODITY ORGAN I CS
BULK ORGAN I CS
SPECIALTY ORGANICS
MIXED
THERMOPLASTICS
BULK ORGANICS
, *
SPECIALTY ORGANICS
MIXED . '
THERMOPLASTICS
THERMOSETS '
RAYON
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
THERMOPLASTICS
THERMOSETS
FIBERS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
THERMOPLASTICS
COMMODITY ORGANICS
BULK ORGANICS
SPECIALTY ORGANICS
MIXED
PLANTS
11
0
0
3
10
T9'.
16
45
0
0
0
;' *0 '
8
'•o
i. ' " . '.'
* 0
3
9
6
10
35
3
0
0
1
3
6
10
0
0
0
0
0
470.470
.
.
472.733
1811.067
637.000
1252.500
1017.778
.'
.
.
.
618.396
„
.
472.733
1494.519
758.667
1472.000
994.250
76.000
.
.
4660.000
393.667
886.667
1100.126
.
.
.
.
.
MEDIAN ,
166.000
.
391.200 '
1088.000
308.000
516.500
505.000
,
.
•
-
418.000
.
....
391.200
389.000
238.500
408.000,
486.000
35.000
'•
4660.000
500.000
777.000
579.500
•
.
.
.
.
STD. DEV. ,
770.042 ,
.. . • •
. ', .1 . •
160.829
1860.990
1013.431
2764.300
1774.971
'
.
•
, -
868.222
.
•
160.829
1664.006
1254.864
3514.778
1695.554
74.505
• i, ' .
,
'
195.541
656.135
2128.878
•
•
•
-
•
V-45
-------
TABLE V-33
SUMMARY STATISTICS OF RAW WASTEWATER TOC CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
( WITH 95% & 70% RULE )
DISPOSAL
METHOD
ALL PLANTS
DIR/IND
DIRECT
INDIRECT
ZERO
fr
UNKNOWN
P
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGANICS
FIBERS
MIXED
THERMOPLASTICS
ORGANICS
MIXED
THERMOPLASTICS
THERMOSETS
ORGANICS
MIXED
THERMOPLASTICS
THERMOSETS
ORGANICS
MIXED
THERMOPLASTICS
THERMOSETS
ORGANICS
FIBERS
MIXED
THERMOPLASTICS
THERMOSETS
ORGANICS
'ROOUCER-:
#OF
PLANTS
4
4
22
0
5
1
0
1
2
1
10
2
1
3
12
2
0
0
0
0
0
0
0
0
MEAN
200.337
259.125
1423.514
•
1353.267
15.000
•
5644.333
143.175
68.000
191.480
61.000
500.000
322.833
2450.208
500.000
MEDIAN
143.175
111.750
259.750
118.000
15.000
"•
5644.332
143.175
68.000
30.400
61.000
500.000
145.500
612.500
500.000
STD. DEV.
216.795
325.740
3144.832
•
2434.943
•
•
101.576
m
439.123
80.610
m
367.162
4024.083
707.107
V-46
-------
TABLE V-34 ,
SUMMARY STATISTICS w'kty WASTEWATER TSS CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
( WITH 95% & 70% RULE )
DISPOSAL
METHOD
ALL PLANTS
DIR/IND
DIRECT
INDIRECT
ZERO
SUBCATEGORY
PRODUCER=PRIMARY
# OF
PLANTS
THERMOPLASTICS 49
THERMOSETS 7
RAYON 2
FIBERS 7
COMMODITY ORGAN ICS ,. 10
BULK ORGANICS 20
SPECIALTY ORGANICS 51
MIXED 84
THERMOPLASTICS 1
BULK ORGANICS 1
SPECIALTY ORGANICS 1
MIXED 1
THERMOPLASTICS 21
THERMOSETS 3
RAYON 2
FIBERS 5
COMMODITY ORGANICS 6
BULK ORGANICS 6
SPECIALTY ORGANICS , 10
MIXED 43
THERMOPLASTICS 27
THERMOSETS . 4
FIBERS 2
COMMODITY ORGANICS 4
BULK ORGANICS 13
SPECIALTY ORGANICS 40
MIXED 39
THERMOPLASTICS 0
COMMODITY ORGANICS 0
BULK ORGANICS 0
SPECIALTY ORGANICS 0
MIXED 1
RY •
MEAN
640.032
1212.000
396.500
117.286
247.658
1358.959
445.072
617.603
63.000
196.000
34.700
6103.000
749.452
2590.333
396.500
146.600
194.222
977.333
404.466
452.398
576.299
178.250
44.000
327.813
1624.552
465.482
593.374
MEDIAN
182.000
362.000
396.500
50.000
140.000
124.500
151.800
232.000
63.000
196.000
34.700
6103.000
.... 237.000
"2509.000
396.500
'' 72.000
,'139.000
180.500
193.500
235.000
154.000
155.500
44.000
186.500
83.000
151.400
187.000
STD. DEV.
1066.040
1425.356
337.290
126.805
251 .969
3979.027
1124.192
1020.412
•
•
.
•
1275.399
1035.399
337.290
142.672
143.518
1348.864
528.479
584.672
905.587
154.675
4.243
376.642
4903.910
1245.249
948.802
3181.000 3181.000
V-47
-------
TABLE V-35
SUMMARY STATISTICS OF RAW WASTEWATER TSS CONCENTRATIONS
BY SUBCATEGORY GROUP AND DISPOSAL METHOD
( WITH 95% & 70% RULE )
PRODUCER=SI
DISPOSAL
METHOD
ALL PLANTS
DIR/IND
DIRECT
INDIRECT
ZERO
UNKNOWN
SUBCATEGORY
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
THERMOPLASTICS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
FIBERS
MIXED
THERMOPLASTICS
THERMOSETS
ORGAN I CS
# OF
PLANTS
12
14
53
0
15
1
0
1
5
2
23
2
5
12
30
11
0
0
0
0
1
1
0
0
MEAN
98.348
284.270
861.552
157.557
6.880
350.000
29.860
39.450
79.553
36.400
132.800
325.073
1461.083
175.087
14.600
360.000
MEDIAN
49.200
168.000
76.700
130.000
6.880
350.000
29.000
39.450
38.900
36.400
122.000
189.500
165.500
163.000
14.600
360.000
STD. DEV.
112.008
281.031
4663.029
134.590
•
19.646
19.021
109.397
27.719
86.955
283.886
6174.386
127.525
„ , -
V-48
-------
2. Occurrence and Prediction of Priority Pollutants
The Clean ¥ater Act required the Agency to develop data characterizing
the presence (or absence) of 129 priority pollutants in raw and treated waste-
waters of the OCPSF industry. These data have been gathered by EPA from
industry sources and extensive sampling and analysis of individual OCPSF
process wastewaters. An adjunct to these data-collection efforts was the
correlation of priority pollutant occurrence with product/process sources by a
consideration of the reactants and process chemistry. This approach offers
the advantage of qualitative prediction of organic priority pollutants likely
to be present in plant wastewaters. A systematic means of anticipating the
occurrence of priority pollutants is beneficial to both the development and
implementation of regulatory guidelines:
• Industry-wide qualitative product/process coverage becomes feasible
without the necessity of sampling and analyzing hundreds of effluents
beyond major product/processes.
• Guidance is provided for discharge permit writers, permit applicants,
or anyone trying to anticipate priority pollutants that are likely to
be found in the combined wastewaters of a .chemical plant when the
product/processes operating at the facility are known.
Qualitative prediction of priority pollutants for these industries is possible
because, claims of uniqueness notwithstanding, all plants within the OCPSF
industry are alike in one important sense—all transform feedstocks to
products by chemical reactions and physical processes in a stepwise fashion.
Although each transformation represents at least one chemical reaction,
virtually all can'be classified by,one or more generalized chemical reactions/
processes. Imposition of these processes upon the eight basic feedstocks lead
to commercially produced organic chemicals and plastics. It is the permuta-
tion of the feedstock/process combinations that permit the industries to
produce such a wide variety of products.
Chemical manufacturing plants share a second important similarity;
chemical processes almost never convert 100 percent of the feedstocks to the
desired products; that is, the chemical reactions/processes never proceed to
V-49
-------
total completion. Moreover, because there are generally a variety of reaction
pathways available to reactants, undesirable by-products are often unavoidably
generated. This results in a mixture of unreacted raw materials and products
that must be separated and recovered by unit operations that often generate
residues with little or no commercial value. These yield losses appear in
process contact wastewater, in air emissions, or directly as chemical wastes.
The specific chemicals that appear as yield losses are determined by the feed-
stock and the process chemistry imposed upon it, i.e., the feedstock/generic
process combination.
a. General
Potentially, an extremely wide variety of compounds could form within a
given process. The formation of products from reactants depends upon the
relationship of the free enthalpies of products and reactantsj more important,
however, is the existence of suitable reaction pathways. The rate at which
such transformations occur cannot (in general) be calculated from first
principles and must be empirically derived. Detailed thermodynamic calcu-
lations, therefore, are of limited value in predicting the entire spectrum of
products produced in a process, since both the identity of true reacting
species and the assumption of equilibrium between reacting species are often
speculative. Although kinetic models can in principle predict the entire
spectrum of products fotmed in a process, kinetic data concerning minor side
reactions are generally unavailable. Thus, neither thermodynamic nor kinetic
analyses alone can be used for prediction of species formation.1 What these
analyses do provide, however, is a framework within which pollutant formation
may be considered and generalized.
Prediction of pollutant formation is necessarily of a qualitative rather than
quantitative nature; although reactive intermediates may be identified
without extensive kinetic measurements, their rate of formation (and thus
quantities produced) are difficult to predict without kinetic measurements.
Other quantitative approaches, for example, detailed calculation of an
equilibrium composition by minimization of the free energy 6f a system,
require complete specification of all species to be considered. Because such
methods necessarily assume equilibrium, the concentrations generated by such
methods represent only trends or, perhaps at best, concentration ratios.
V-50
-------
The reaction chemistry of a process sequence is controlled through
careful adjustment and maintenance of conditions in the reaction vessel. The
.physical condition of species present^(liquid, solid, or gaseous phase),
condition of temperature and pressure, the presence of solvents and catalysts,
and the configuration of process equipment are designed to favor a reaction
pathway by which a particular product is produced. From this knowledge, it is
possible to identify .reactive intermediates and thus anticipate species
(potential pollutants) formed.
Most chemical transformations performed by the OGPSF industry may be
reduced to a small number of basic steps or unit processes. Each step or
process represents a chemical modification of the starting matrials and is
labeled a "generic process." For example, the generic process " nitration"
may represent either the substitution or addition of an "-N02" functional
group to an organic chemical. Generic processes may be quite complex
involving a number of chemical bonds being broken and formed, with the overall
transformation passing through a number of distinct (if transitory) i^'^r-
mediates. Simple stoichiometic equations, therefore, ar-
descriptions of chemical reactions arid only rarely account for observed
by-products.
Table V-36 lists the major organic chemicals produced by the OCPSF
industry (approximately 250) by process, and Table V-37 gives the same
information for the plastics/synthetic fibers industry. Certain products
shown in Table V-36 are not derived from primary feedstocks, but rather from
secondary or higher order materials (e.g., aniline is produced by hydrogena-
tion of nitrobenzene that is produced by nitration of benzene). For such
multistep syntheses, generic processes appropriate to each step must be
evaluated separately. For many commodity and bulk chemicals, it is sufficient
to specify a feedstock and a single generic process, because they are gener-
ally manufactured by a one-step process. Nitration of benzene to produce
nitrobenzene, for example, is a sufficient description to predict constituents
of the process wastewater: benzene, nitrobenzene, phenol, and nitrophenols
will be the principal process wastewater constituents. Similarly, oxidation
of butane to produce acetic acid results in wastewater containing a wide
variety of oxidized species, including formaldehyde, methanol, acetaldehyde,
n-propanol, acetone, methyl ethyl ketone, etc.
V-51
-------
GENERIC
PROCESS
AUCOXYLATXX
CONDENSATION
HALOGENATK5N
OXIDATION
POLYMERIZATION
HYDROLYSIS
HYDROCENATJOJ
ESTERimCATWN
PYROLYSB
AIXYLATION
OEHYOROCENATION
AU1NATION (AMMONOLYSIS)
NITRATION
SUIFONATION
AUMOXIDAT10N
CARBONYLATTON
HYDROHALOCENATK3N
DEHYDRATION
OCHYDROHALOCENATION
OXYHALOCENATION
CATALYTIC CRACKING
HYDROOEALKYLATION
PMOSCENATION
EXTRACTION
OlSTn-LATTON
OTHER
HYORATTON
ACIDS ESTERS
2
' « ~
= 8
0 0
••••0 O OO •• «0
OO «
O O O
•
0 00
«
O A •
Hi
liijii! ii.iiU, ,
fl^shiiyisii-l^Hs
llmffiiififtimfii
Miiii{ifi!flf!l!s}|i
pocoooOwBiiJasszas.zKi?
•
}«O»O» OO«OO»OO«» ••
O OO
O • • •
O rraAJO/Pracn. Ulknn No
V-52
-------
The reaction chemistry of a process sequence is controlled through
careful adjustment and maintenance of conditions in the reaction vessel. The
physical condition of species present .(liquid, jsolid, or gaseous phase),
condition of temperature and pressure, the presence of solvents and catalysts,
and the configuration of process equipment are designed to favor a reaction
pathway by which a particular product is produced. From this knowledge, it is
possible to identify .reactive intermediates and thus anticipate species
(potential pollutants) formed.
Most chemical transformations performed by the OCPSF industry may be
reduced to a small number of basic steps or unit processes. Each step or
process represents a chemical modification of the starting matrials and is
labeled a "generic process." For example, the generic process " nitration"
may represent either the substitution or addition of an «-N02" functional
group to an organic chemical. Generic processes may be quite complex
involving a number of chemical bonds being broken and formed, with the overall
transformation passing through a number of distinct (if transitory) !-• ar-
mediates. Simple stoichiometic equations, therefore, ar~
descriptions of chemical reactions and only rarely account for observed
by-products.
Table V-36 lists the major organic chemicals produced by the OCPSF
industry (approximately 250) by process, and Table V-37 gives the same
information for the plastics/synthetic fibers industry. Certain products
shown in Table V-36 are not derived from primary feedstocks, but rather from
secondary or higher order materials (e.g., aniline is produced by hydrogena-
tion of nitrobenzene that is produced by .nitration of benzene). For such
multistep syntheses, generic processes appropriate to each step must be
evaluated separately. For many commodity and bulk chemicals, it is sufficient,
to specify a feedstock and a single generic process, because they are gener-
ally manufactured by a one-step process. Nitration of benzene to produce
nitrobenzene, for example, is a sufficient description to predict constituents
of the process wastewater: benzene, nitrobenzene, phenol, and nitrophenols
will be the principal process wastewater constituents. Similarly, oxidation
of butane to produce acetic acid results; in wastewater containing a *ide
variety of oxidized species, including formaldehyde, methanol, acetaldehyde,
n-propanol, acetone, methyl ethyl ketone, etc.
V-51
-------
[nic Chemical Products
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Table V-36
Generic Processes Used to Manufacture Orga
AUCOXYLATION
CONDENSATION
HALOCENATION
OXIDATION
POLYMERIZATJOM
HYDROLYSIS
HYOROGENATION
ESTERIRCATION
PYROLYSIS
ALKYLATKJN
OEHYOROGENAT10N
AMINAT10N (AMMONOLYSIS)
NTTRATION
SULFONAT1ON
AMMOXIDAT10N
CARBONYLATION
HYDROHALOGENAT10N
DEHYDRATION
DEHYOROHALOCENAT1ON
OXYHALOGENATTON
CATALYTIC CRACKING
HYDRODEALKYLATION
PH05CENATK5N
EXTRACTION
DISTILLATION
OTHER
HYDRATK3M
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V-52
-------
-------
Tabh
Generic Processes Used to
GENERIC
PROCESS
Jl
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ALKOXYLATK3N
CONDENSATION
HALOGENATION
OXIDATION
POLYMERIZATION
HYDROLYSIS
HYDROCENATION
ESTERIFICATION
PYROLYSIS
ALKYLATION
DEHYDROGENATION
AMtNATION (AMMONOLYSIS)
NITRATION
SULFONATION
AMMOXIDATJON
CARBONYLATION
HYDROHALOCENATION
DEHYDRATION
DEHYOROHALOGENAT10N
OXYHALOGENATION
' CATALYTIC CRACKING
.HYDRODEALKYLAT1ON
PHOSCENATJON
EXTRACTION
DISTILLATION
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HYDRATION
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V-53
-------
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i (Continued)
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Specialty chemicals, on the other hand, may involve several chemical
reactions and require a fuller description. For example, preparation of
toluene diisocyanate from commodity chemicals involves four synthetic steps
and three generic processes as shown below:
Phosgenation
N
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This example is relatively simple and manufacture of other specialty chemicals
may be more complex. Thus, as individual chemicals become further removed
from the basic feedstocks of the industry, fuller description is required for
unique specification of process wastewaters. A mechanistic analysis of
individual generic processes permits a spectrum of product classes to be
associated with every generic process provided a feedstock is specified. Each
product class represents compounds that are structurally related to the
feedstock through the chemical modification afforded by the generic process.
b. Product/Process Chemistry Overview
The primary feedstocks of the OCPSF industry include: benzene, toluene,
o,p-xylene, ethene, propene, butane/butene, and methane; secondary feedstocks
include the principal intermediates of the synthetic routes to high-volume
V-55
-------
organic chemicals and plastics/synthetic fibers. Other products that are
extraneous to these routes, but are priority pollutants, are also considered
because of their obvious importance to guidelines development.
Flow charts used to illustrate a profile of the key products of the two
categories were constructed by compositing the synthetic routes from crude oil
fractions, natural gas, and coal tar distillates (three sources of primary
feedstocks) to the major plastics and synthetic fibers. Figures V-l through
V-7 depict the routes through the eight primary feedstocks and various inter-
mediates to commercially produced organic chemicals; Figures V-8 and V-9 show
the combinations of monomers that are polymerized in the manufacture of major
plastics and synthetic fiber products. "Also shown in Figures V-l through V-7
are processes in current use within these industries.
These charts illustrate the tree-shaped structure of this industry's
product profile (i.e., several products derived from the same precursor). By
changing the specific conditions of a process, or use of a different process,
several different groups of products can be manufactured from the same feed-
stock. There is an obvious advantage in having to purchase and maintain a
supply of as few precursors (feedstocks) and solvents as possible. It is also
important to integrate the^product mix at a plant so that one product provides
feedstock for another. A typical chemical plant is a community of production
areas, each of which may produce a different product group. While the product
mix at a given plant is self-consistently interrelated, a different mix of
products may be manufactured from plant to plant. Thus, a plant's product mix
may be independent of, or may complement the product mix at, other plants
within a corporate system.
The synthetic routes to priority pollutants are illustrated in Figures
V-10 through V-14; these flow charts provide a separate scheme for each of the
following five classes of generic groups of priority pollutants:
1. Nitroaromatic compounds, nitrophenols, phenols, benzidines and
nitrosamines
2. Chlorophenols, chloroaromatic compounds, chloropolyaromatic
compounds, haloaryl ethers and PCBs
V-56
-------
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METHANE-
r
*• Methyl* 1-
chloride
Synthesis-
Gas (CO &
Hydrogen)
.Methanol-
Acrylic acid-
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•2-
-3-
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• Methylene*
chloride
—»• Chloroform*
•• Carbon* r
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— Formaldehyde
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Methyl acrylate
Methyl methacrylate
Generic Processes
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Notes
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* Priority pollutant(PRIPOL)
Source: Wise & Fahrenthold, 1981.
Figure V-3
Methane
V-59
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V-63
-------
Monomer(s)
Styrene
Polybutadiene
Acrylonitrile *
4-Vinyl acetate
+Vinyl chloride*
+Methyl methacrylate
+Methyl acrylate
+Acrylamide
Acrylic acid esters
Methyl methacrylate 2ab-
Phenol* 1-
Formaldehyde-
Melamine-
Urea
Epichlorohydrin—1-
Bisphenol A ~
Phosgene •• i -
Generic Processes
Plastics Polymerization
1. Condensation
2. Addition
a. Mass c. Suspension
b. Solution d. Emulsion
Plastics Synthetic
(Resins) Fibers
• Polystyrene Resins
Styrene-Butadiene Resins
(Latex)
SAN Resins
ABS Resins
Polyvinyl alcohol Resins-*—i
Hydrolysis
Polyvinyl acetate Resins '
(Latex)
e —
•^••MMMI
1
Copolymer—3—4 —
(85% Acrylonitrile)
Acrylic Fibers
2d-
• Acrylic Resins(Latex)
• Acrylic Resins
• Phenolic Resins
Melamine Resins
Urea Resins
Epoxy Resins
Polycarbonate Resins
Fibers Spinning Notes
3. Wet ^HZ
4. Dry *
5. Melt +
Synthetic route
Priority pollutant
Variable comonomer
Source: Wise & Fahrenthold, 1981.
Figure V-8
Plastics and Fibers
V-64
-------
Monomer(s)
Terephthalic acid —
Dimethyl terephthalate
Ethylene glycol—
Plastics
(Resins)
•j—•!—* Polyester-
Resins
Synthetic
Fibers
Polyester
Fiber
Glycerin-
Isophthaliq acid——
Phthalic anhydride—
Maleic anhydride-—
Propylene glycol-—
S tyrene • —
Alkyd Resins
Unsaturated
Polyester Resin
Cellulose-
Acetic anhydride-
Diketene —
Coumarone-Indene-
Dicyclopentadiene
ETHYLENE »
•2b-
-2b-
-*• Cellulose xanthate-
-*• Cellulose acetate-
Petroleum
hydrocarbon Resins
-3-*- Rayon Fiber
-4-*- Cellulose
••- acetate
Fiber
PROPYLENE-
-2a—*• LD' Polyethylene Resins
-2b-—•• HD Polyethylene Resins
-2c-
Polypropylene Resins—5-» Polypropylene
Fiber
Vinyl cnioriae"
Hexamethylene— -\
diamine
Tolylene diisoc"
Polymeric MDI —
salt
i _— — —
(_;ia-
,,1
2bcd—*• Polyvinyl chloride Resins
Nylon 66 Resins—• 5-*- Nylon 66 Fiber
Nylon 6 Resins-
Polyurethane Resins
and Foams
-5-—». Nylon 6 Fiber
polyethers
Generic Processes. . .
Plastics Polymerization Fiber Spinning
1. Condensation 3- Wet
2. Addition 4. Dry
a. Mass c. Suspension 5. Melt
b. Solution d. Emulsion
Notes
Synthetic route
Priority pollutant
& Fahrenthold; 1)981.
Figure V-9
Plastics and Fibers
V-65
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-------
3. Chlorinated C2 and C4 hydrocarbons; chloroalkyl ethers
4. Chlorinated C3 hydrocarbons, acrolein, acrylonitrile, isophorone, and
chloroalkyl ethers
5. Halogenated methanes.
The generic processes associated with these synthesis routes are denoted by
numbers individually keyed to each chart.
The precursor(s) for each of these classes is reasonably obvious from the
generic group name. Classes 1 and 2 are, for the most part, substituted
aromatic compounds, while Classes 3, 4, and 5 are derivatives of ethylene,
propylene, and methane, respectively. The common response of these precursors
to the chemistry of a process has important implications, not only for the
prediction of priority pollutants, but for their regulation as well; that is,
group members generally occur together.
It is significant to note that among the many product/processes of the
industry, the collection of products and generic processes shown in Figures
V-10 through V-14 are primarily responsible for the generation of priority
pollutants. The critical precursor-generic process combinations associated
with these products are summarized in Table V-38. While there may be critical
combinations other than those considered here, Table V-38 contains the most
obvious and probably the most likely combinations to be encountered in the
OCPSF industrial categories.
c.
Product/Process Sources of Priority Pollutants
The product/processes that generate priority pollutants become obvious if
the synthesis routes to the priority pollutants are, in effect, superimposed
upon the synthesis routes employed by the industry in the manufacture of its
products. Figure V-15 represents a priority pollutant profile of the OCPSF
industry by superimposing Figure V-l through V-9 and V-10 through V-14 upon
one another so as to relate priority pollutants to feedstocks and products.
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V-73
-------
In any product/process, as typified by Figure V-16, if the feedstock
(reactant), solvent, catalyst system, or product is a priority pollutant, then
it is likely to be found in that product/process wastewater effluent. Equally
obvious are metallic priority pollutants, which are certainly not transformed
to another metal (transmutation) by exposure to process conditions. Since
side reactions are inevitable and characteristic of all.co-products of the
main reaction, priority pollutants may appear among the several co-products of
the main reaction. Subtler sources of priority pollutants are the impurities
in feedstocks and solvents.
Priority pollutant impurities may remain unaffected, or be transformed to
other priority pollutants, by process conditions. Commercial grades of
primary feedstocks and solvents commonly contain 0.5 percent or more of
impurities. While 99.5 percent purity approaches laboratory reagent quality,
0.5 percent is nevertheless equal to 5,000 ppm. Thus, it is not surprising
that water coming into direct contact with these process streams will acquire
up to 1 ppm (or more) of the impurities. It is not unusual to find priority
pollutants representing raw material impurities or their derivatives reported
in the 0.1-1 ppm concentration range in analyses of product/process effluents.
Sensitive instrumental methods currently employed in wastewater analysis have
the ability of measuring priority pollutants at concentrations below 0.1 ppm.
Specifications or assays of commercial chemicals at these trace levels are
seldom available, or were not previously (before BAT) of any interest, since
even 0.5 percent impurity in the feedstock and/or solvent would typically have
a negligible effect on process efficiency or product quality. Only in cases
where impurities affect a process (e.g., poisoning of a catalyst) are contami-
nants specifically limited.
d' Priority Pollutants in Product/Process Effluents
During the Verification sampling program, representative samples were
taken from the effluents of 147 product/processes manufacturing organic chemi-
cals and 29 product/processes manufacturing plastics/synthetic fibers. These
176 product/processes included virtually all those shown in Figures V-l
through V-9. Analyses of these samples, averaged and summarized by individual
product/processes, showed the priority pollutants observed in these effluents
V-74
-------
[Reactant(s)]•
(Impurities)
•Catalyst-
-CHEMICAL-
PROCESS •
Spent Catalyst-
[Product(s)]
• [Solvent ]•*-
Equipment
Cleaning
• Derivatives—
of Impurities
Coproducts-
Byproducts-
Miscellaneous
Res inous
Materials*
Material
Losses
Notes
Limits of the process area in the
plant.
* Still bottoms, reactor coke, etc.
Source: Wise & Fahrenthold, 1981.
Figure V-16
A Chemical Process
V-75
-------
to be consistent with those that can be predicted, based on the precursor
(with impurities) generic process combinations.
Consistency between observation and prediction was most evident at con-
centrations >0.5 ppm. Below that level, an increasing number of extraneous
priority pollutants were reported that were unrelated to the chemistry or
feedstock of the process, and typically reported at concentrations less than
0.1 ppm. These anomalies could usually be attributed to one or more of the
following sources:
• Extraction solvent (methylene chloride), or its associated impurities,
e.g., as residuals in the GC/MS system from previous runs
• Sample contamination during sampling or during sample preparation at
the laboratory (e.g., phthalate leached from anhydrous sodium sulfate
used to dry the concentrated extract prior to injection into the GC)
• In-situ generation in the wastewater collection system (sewer).
In the reconciliation of product/process effluent analytical data, it was
expedient to initially sor.t out the extraneous from the significant priority
pollutants. In most cases, only the latter can be related to the product/
process. Less than half of the effluents of key product/processes manufac-
turing organic chemicals contained priority pollutants at concentrations
greater than 0.5 ppm. The generic groups of priority pollutants associated
with these product/processes are summarized in Table V-39 and are consistent
with those predicted in Table V-36. Many product/process effluents have
little potential to contain greater than 0.5 ppm of priority pollutants,
because they do not involve critical precursor-generic process combinations.
Generic classes of priority pollutants reported at >0.5 ppm in the
effluent of product/processes manufacturing plastics/synthetic fibers are
summarized in Table V-40. The priority pollutants found in polymeric product/
process effluents are usually restricted to the monomer(s) and its impurities
or derivatives. Since all monomers or accompanying impurities are not pri-
ority pollutants, some plastics and synthetic fibers effluents are essentially
free of priority pollutants.
V-76
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V-80
-------
TABLE V-40.
PLASTICS/SYNTHETIC FIBERS EFFLUENTS WITH
SIGNIFICANT CONCENTRATIONS (>0.5 ppm)
OF PRIORITY POLLUTANTS
Product
Monomer(s)
Associated
Priority Pollutants
ABS resins
Acrylic fibers
Acrylic resins (Latex)
Acrylic resins
Alkyd resins
Cellulose acetate
Epoxy resins
Phenolic resins
Polycarbonates
Polyester
Acrylonitrile
Styrene
Polybutadiene
Acrylonitrile
Comonomer (variable)
Vinyl chloride
Acrylonitrile
Acrylate Ester
Me thylme thacrylate
Methylmethacrylate
Glycerine
Isophthalic acid
Phthalic anhydride
Diketene (acetylating
agent)
Bisphenol A
Epichlorohydrin
Phenol
Formaldehyde
Bisphenol A
Terephthalic acid/
Dimethylterephalate
Ethylene glycol
Acrylonitrile
Aromatics
Acrylonitrile
Chlorinated C2's
Acrylonitrile
Acrolein
Cyanide
Acrolein
Aromatics
Polyaromatics
Isophorone
Phenol
Chlorinated C3's
Aromatics
Phenol
Aromatics
(Not investigated)
Predicted: Phenol
Chloroaromatics
Halomethanes
Phenol
Aromatics
V-81
-------
TABLE V-40.
PLASTICS/SYNTHETIC FIBERS EFFLUENTS WITH
SIGNIFICANT CONCENTRATIONS (>0.5 ppm)
OF PRIORITY POLLUTANTS (Continued)
Product
HD Polyethylene resin
Polypropylene resin
Polystyrene
Poly vinyl chloride resin
SAN resin
Monomer (s)
Ethylene
Propylene
Styrene
Vinyl chloride
Stvrene
Associated
Priority Pollutants
Aromatics
Aromatics
Aromatics
Chlorinated C2'
Arnmati r.502)
Polybutadiene
Maleic anhydride
Phthalic anhydride
Propylene glycol
(Styrene added later)
Acrylonitrile
Aromatics
Phenol
Aromatics
V-82
-------
In comparison with effluents from product/processes manufacturing- organic
chemicals, effluents from polymeric product/processes generally contained
fewer priority pollutants at lower concentrations. The polymeric plastics and
fibers considered in this report have virtually no water solubility. Further-
more, the process is designed to drive the polymerization as far to completion
as is practical and to recover unreacted monomer (often with its impurities)
for recycle to the process. Thus, the use of only a few priority pollutant-
related monomers, the limited solubility of polymeric products, and monomer
recovery, results in the reduction of the number of priority pollutants and
their relative loading in plastics/synthetic fibers effluents.
Table V-41 lists priority pollutants detected in OCPSF process
wastewaters by precursor/generic process combinations. Priority pollutants
are generically grouped and the groups are arrayed horizontally. Priority
pollutants reported from Verification analyses of product/process effluents
are noted in four, concentration ranges, reading across from each precursor.
-This arrangement makes it more apparent, particularly at higher concentration
ranges, that reported priority pollutants tend to aggregate within those
groups that would be expected from the corresponding precursor-generic process
combination.
In contrast with organic priority pollutants that are co-produced from
other organic chemicals, metallic priority pollutants cannot be formed from
other metals. Except for a possible change of oxidation state, metals remain
immutable throughout the generic process. Thus, to anticipate metallic
priority pollutants, the metals that were introduced into a generic process
must be known.
Metallic priority pollutants, individually and in combinations, are most
often related to a generic process via the catalyst system. The metals
comprising catalyst systems that are commonly employed with particular
precursor/generic process combinations to manufacture important petrochemical
products have been generally characterized in the technical literature
(especially in patents). An obvious way to offer clues for predicting
metallic priority pollutants was to expand the generic process descriptors in
the listing of Table V-41 to include this information.
V-83
-------
-------
Priority Pollutants in Effluents ofl
PHENOLS
POLYAROMAT1CS
NITROARC
CHLOROPHENOLS
CHLOROAROMATICS HALOARYL E
PRODUCT
PROCESS
CODE
0890-01
0530-01
3393^01
0949-01
3300-01
1244-01
3295-02
3410-03
08.10-01
1650-01
19 80-0 Z
3120-02
35ZO-80
3530-02
1221-01
3535-01
3015-01
3354-01
0185-04
1700-01
1800-01
0820-03
0080-02
2690-01
2265-02
1450-01
\y PRIORITY
N. POLLUTANT
N. GROUPS
\^
^^
N.
>v
N.
N.
PRECURSOR N.
(FEEDSTOCK) \
N.
\
DIRECT CHLORINATION
Benzene 3
Toluene
1,4-Dichlorobenzene
Nitrobenzene
Phthalic anhydride
Ethylene
Ethylene dichloride4
Ethylene dichloride5
Methane6
CHLOROHYDRINATION
Allyl chloride
Ethylene 1
Propylene ^
DEHYDROCHLORINATION
Ethylene dichloride
1,1,2-Trichloroethane
HYDROFLUORINATION
Carbon tetrachloride
1,1,1-Trichloroe thane
PHOSGENATION
Poly MDA8
2,4-Tolylenediamine
AMMONATION
Adipic acid
Ethanol
Ethylene dichloride9
ACETYLATION
Cellulose/Acetic anhyd.
DEHYDRATION
Acetic acid
Cumene hydroperoxide
t-Butanol
Acetic acid
®
c
ID
N
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1. Eitnnituii to pnduct/pfoe««t.
2. Fil» miatlit.
3. 1210-01.1220-01 h«t« ilnllir (Bilytn.
4. 0810-04. hn (lillal >aily»le.
9. Chlorlnitid C2*i «r« ilailm Ira* this iailr>l>-
8. 0830—02.2820—02.2380—03 h«» i.lailir •n»lyl».
a I
lol
V-84
-------
IM,
-------
table V-4J
Priority Pollutants in Effluents of.Precurs
PHENOLS
AROMAT'ICS
POLYAROMATICS
N1TROAROMAT1CS
CHLOROPHENOLS NITROPHENO|
CHLOROAROMATICS HALOARYL ETHERS
\ PRIORITY
\ POLLUTANT
1
PRODUCT
PROCESS
CODE
0890-01 1
0530-01 '
3393-01
0949-01
3300-01
1244-01
3295-02
3410-03
08.10-01
1650-01
1980-02
3120-02
3520-80
3530-02
1221-01
3535-01
3015-01
3354-01
0185-04
1700-01
1800-01
0820-03
0080-02
2690-01
2265-0<
1450-01
\ GROUPS
\
\
\
\
\
PRECURSOR \
(FEEDSTOCK) \
:
1
c y c fl>
o
i = 1 <
<5 '
- i r
• ^ r
\ c = £1 a ± c
\ 1 CO O — I -^ • °
\| m i- lu o
DIRECT CHLORINATION 1 J~
Benzene 3
roluene
1,4-Dichlorobenzene
Nitrobenzene
Phthalic anhydride
Ethylene
Ethylene dichloride4
Ethylene dichloride5
Methane6
CHLOROHYDRDMATION
Allyl chloride
Ethylene 7
Propylene 7
DEHYDROCHLORINATION
Ethylene dichloride
1,1,2-Trichloroe thane
HYDROFLUORINATION
Carbon tetrachloride
1,1,1-Trichloroe thane
PHOSGENATION
Poly MDA8
2,4-Tolylenediamine
AMMONATION
Adipic acid
Ethanol-
Ethylene dichloride9
ACETYLATION
Cellulose/ Acetic anhyd.
DEHYDRATION
. Acetic acid
Cumene hydroperoxide
, t-Butanol
Acetic acid
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V-84
-------
-------
-------
»r-Generic Process Combinations
LS BENZIOINES
POSAMIMES PHTHAUATES HALOGENATEO METHANES
CHLORINATED C3's MISCELLANEOUS
CHLORINATED C2's CHLOROALKYL ETHERS
METALS
\l
m— — 1
Iff!
1
1
1
I
1
1
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o •= £ T> £ 3
1 = 1 o o § o ;
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bis(Chloroethyl)el
bis(2-Chlorolsopr
2-Chloroelhylvlny
bis(2-Chloroatho:
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Acrolein
Acrylonitrlle
Cyanide
Isophorone
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KEY: • = >O.S com
4c=0.1 - O.S ppm
S=.01 - 0.1 pom
= < .01 ppm. or analysis
(ailed lo ilnioct
-------
Table V-41 {Contir
Priority Pollutants in Effluents of Precursor-]
PHENOLS
AROMATICS
POLYAROMATICS
NITROAROMATICS
CHLOROPHENOLS NITROPHENOLS
CHLOROAROMATICS HALOARYL ETHERS NITRIC
PRODUCT
PROCESS
CODE
ESTERJJ
2665-02
3066-01
0240-01
3510-05
0165-09
0165-10
0165-02
0165-11
2470-02
1530-01
3006-21
2883-01
2859-01
2863-01
2886-01
0189-01
3501-01
2951-02
2680-01
2090-01
2090-03
2460-01
3042-80
1660-01
2360-01
0650-01
2460-01
2665-02
0192-04
0185-05
2070-01
3570-02
\v PRIORITY
\ POLLUTANT
\ GROUPS
\
\
\
PRECURSOR \
(FEEDSTOCK) \
\
\
[CATON/POLYMERIZATIO
Acetone cyanohydrin
Acetic acid/n-Piropanol
Acetic acid/Pentanol (Amyl
Acetic acid/Ethylene
Acrylic acid/n-Butanol
Acrylic acid/Ethajiol
Acrylic acid/Isobutanol
Acrylic acid/2-Ethylhexanol
MMA/Butanol
TPA/Methanol
TPA/Ethylene glycol
PA/Ethanol
PA/2-Ethylhexanol
PA/C11-C14 Alcohols
PA/Butanol/Benzyl chloride
PA Glycerin
PA/MA/Propylene glycol
POCl3/Phenol/Isodecanol
Salicylic acid/Methanol
HYDRATTON/HYDROLYSIS
Allyl alcohol
Epichlorohydrin
Acetone cyanohydrin
Polyviny} acetate 2
Ethylene
Propylene
Butene
HYDROCYANA-nON
Acetone
Acetone/Methanol
C13-C19 Olefins
HYDRODIMEREATION
Acrylonitrile
EOMERZZAT7.ON
Maleic acid
m-Xylene
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3. Sty lit etltlbuttbU It c-iy!«n»
of «lild«ntlfleatlon
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4. ViK't pfttutilT htihsr, ttapltd
tlttf ejanlilt rin»I lystn.
9. IMS thu >crilfli»i!ot olteUoi erltariov.
-------
nued)
r-Generic Process Combinations
[NOtS DENZIDIN'ES
H1TROSAMINES PHTHALATES HALOGENATED METHANES
CHLORINATED C3's MISCELLANEOUS
CHLORINATED C2's CHLOROALKYL ETHERS
METALS
I
10
f"
,_
H-Ni»05Od«ro«iriyl am
H-rtttrojod»t>rnnyl am
N-N»troKxI!-n-fWOpyl
1,2-DtplunylhydfiiJna
Bonzldlno
3.3'-DJchto
oo „•—••---- >- >- - I
6 6
6
0
000 0
o oo ooo
0 000
0
6 «
• 0
• 0 0
•
6
0 0 0 0 * * 0
000 00 0
6 6*6
0 0
•ooo 60 o
* *
6
* • 0
6
6 ooo
0 ooo
o 6
.1 66
o
11 ,2-Dichloropropane
1.3-Dichloropropyler
6
6
0 0
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0
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C
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0 0
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1 1 1 1 1 1 1 \ 1 1 N «
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600
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00 0
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0
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6 o
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•rylinll
.tfjllt icU
* =0.1 - O.S ppm
6 =.0t - 0.1 ppm
0 = <.01 ppm, or analysis
failed to delect
-------
Table V-41 (Cont|
Priority Pollutants in Effluents of Precurs<
PHENOLS
POLYAROMATICS
NITROAROMATICS
CHLOROPHENOLS NITROPHf]
CHLOROAROMATICS HALOARYL ETHERS
PRODUCT
PROCESS
CODE
AI
0005-01
3172-01
3235-01
3030-02
3030-04
0153-01
0155-03
2856-01
3008-01
3008-04
3020-03
3040-01
3048-02
3048-01
3048-04
0156-01
3145-01
CONDEN
0560-01
2000-01
1656-01
2443-01
2905-01
3506-01
2825-01
2825-03
3013-01
1830-01
1300-01
3325-02
1666-03
1666-02
3025-01
3025-02
NV PRIORITY
\ POLLUTANT
>v GROUPS
\^
^y
*v
\^
\
PRECURSOR \y
(FEEDSTOCK) \
N.
\
DITION POLYMERIZATION
ACN/Polybutadiene/Styrene
ACN/Styrene
Styrene/Butadiene
Styrene (suspension)
Styrene (bulk)
ACN/AA esters/MMA
tfethylmethacrylate
Mcyclopentadiene
Ethylene (HDPE)
Ethylene (LDPE)
Propylene
Vinyl acetate
Vinyl chloride (susp.)
Vinyl chloride (etnul.)
Vinyl chloride (bulk)
FIBER SPINNING
Acrylic resin
Cellulose
SAT1ON/POLYMERIZATION
Acetone/Phenol
n-Butyraldehyde
Epichlorohydrin/Bisphenol A
Melamine/Formaldehyde
Phenol/Formaldehyde
Urea/Formaldehyde
Caprolactam
Nylon salt
Aniline/For m aldehyde
ETHOXYLAITON
Ethylene oxide/water
Ethylene glycol2
Ethylene glycol still btm's3
Cll, C12 Linear alcohols3
Alkylphenol
PROPOXYLATION
Propylene glycol
Glycerin
CD
C
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N
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1. Exllinaou* to product/proem
2. 3480-01 hit ilill.r indyilt.
, ,
3. 3480-03 hi« «l«llir inilysU.
*. Epe»y fiiln proe.n pl.il.il to ID.I pfoc.t..
ACN - i|
AA - I
UNA - I
V-87
-------
ued)
Generic Process Combinations
BENZIOINES CHLORINATED C3's MISCELLANEOUS
SAMINES PHTHALATES HALOGENATED METHANES CHLORINATED C2's • CHLOROALKYL ETHERS METALS
,i
I H-Wcoiodtptonyl «m»i
I H-Hilrojodi-n-piopyl i
1,2-D»ptvoO.S ppm
*=0.1 - 0.5 ppm
0 =r,01 - 0.1 ppm
0 =<-01 ppm, or analysis
(ailed lo detect
-------
Tabfe V-47 (Contin
Priority Pollutants in Effluents of Preeursor-
PHENOLS
POLYAROMATICS
NITROAROMATICS
CHLOROPHENOLS NITROPHENd
CHLOROAROMATICS HALOARYL ETHERS Nil
PRODUCT
PROCESS
CODE
1770-01
1770-02
1770-04
0130-03
E
0380-02
0380-04
0380-09
0590-01
1171-01
2701-02
2265-01
1710-02
2350-02
.0720-01"
1710-01
1060-01
'0195-01
0380-01
0785-06
0785-09
1171-01
1450-01
3170-01
1550-01
2770-01
Uncodec
Uncodec
Uncodec
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rvr
>v PRIORITY
N. POLLUTANT
\. GROUPS
\^
N.
\^
N.
\
PRECURSOR \^
(FEEDSTOCK) \
\^
\
CRACKING
LPG2
Naphtha/Gas oil
Naphtha/LPG 4
Naphtha/LPG
TRACTION/DISTILLATION
Catalytic reformate 5
Coal tar light oil
Pyrolysis gasoline
C4' Pyrolyzates
C5 Pyrolyzates
?yrolysis gasoline
C4 Pyrolyzates
BTX Extract '-•
C5 Pyrolyzates
C4 Pyrolyzates
ALKYLATION
Benzene/Ethylene
Benzene/Propylene 9
Phenol/Octene/Nonene
HYDRODE ALKYLATION
Toluene/Xylene
OXIMATION
Phenol/Cyclohexanone
Cyclohexane/Cyclohexanon
DIMEREATION
Cyclqpentadiene
Ketene
CARBOXYLATION
Phenol
NITRATION
Toluene
Benzene
DLAZOTIZATION
2,4,6-Trichloroaniline
Aniline
4-Nitro.aniline
2-Nitro aniline
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rsor-Generic Process Combinations
INOtS BENZIOINES
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-------
Table V-41 (C|
Priority Pollutants in Effluents of Preci
PHENOLS
AROMATICS
POLYAROMAT1CS
NITROAROMATICS
CHLOROPHENOLS NlTROPHEl
CHLOROAROMATICS HALOARYL ETHERS
PRODUCT
PROCESS
CODE
2430-01
0091-01
1135-01
0180-80
2960-01
2960-02
3280-01
0030-02
1980-01
0140-01
0160-80
0180-01
2640-07
0070-04
3066-01
2200-01
0130-01
0180-03
0430-01
0200-01
2165-02
0640-02
2500-02
3351-01
0300-04
2000-01
3070-01
0185-04
3230-01
2500-02
2040-01
0090-11
2640-01
HYDRO1
3050-01
2750-01
0640-02
0070-05
0160-03
\ PRIORITY
NV POLLUTANT
N. GROUPS
N.
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OXIDATION
Benzene
Cumene4
Cyclohexane
Cyclohexane/-ol/-one
Naphthalene
o-Xylene
p-Xylene5
ithylene
ithylene
'ropylene 6
Propylene
Cyclohexanol
sec-Butanol/Acrolein
Acetaldehyde
'ropionaldehyde
Aniline
Methane
~yclohexanol/one mix
Toluene 8
• HYDROGENATION -
Acrolein/sec-Butanol
Adiponitrile
n-Butyraldehyde 9
Carbon monoxide
Dinitrotoluene
Nitrobenzene
2-Ethyl-2-hexenal
'ropionaldehyde
DEHYDROGENATION
Adipoamide
Jthylbenzene
•iethane
rlethanol
sopropanol
sec-Butanol
ORMYLATION/CARBONYL
ithylene
sobutylene
*ropylene
ilethanol
Acetylene
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V-86
-------
jed)
aeneric Process Combinations
CHLORINATED C3's MISCELLANEOUS
CHLORINATED C2's CHLOROALKYL ETHERS
METALS
nuanMir
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-------
Copper, chromium, and zinc were the metallic priority pollutants most
frequently reported in the higher concentration ranges for all product/process
effluents. Copper and chromium are used in many catalyst systems. Another
significant source of chromium, as well as zinc, is the "blowdown" that is
periodically wasted from an in-plant production area's recycled noncontact
cooling water. These metals find application in noncontact cooling waters as
corrosion inhibitors. In some wastewater collection systems, it is possible
for the blowdown to become mixed with product/process effluent before the
combined flow leaves the production area to join the main body of wastewater
within the plant. Another source of metallic priority pollutants is the
normal deterioration of production equipment that comes into contact with
process water.
Extraneous or unexpected priority pollutants were also reported in
product/process effluents. Priority pollutants may be considered extraneous
when they cannot be reconciled with the precursor (or its impurities) and the
process chemistry. In Table V-41, extraneous priority pollutants were noted
only when they were reported at greater than 0.5 ppm. Thus, the failure to
flag a priority pollutant at less than 0.5 ppm does not necessarily preclude
it from being extraneous. As a general rule, one extraneous generic group
member indicates that the entire group is probably anomalous. These data are
presented here to assist NPDES permit writers in establishing effective
monitoring requirements for OCPSF plants' end-of-pipe discharges. The
phthalate esters are an example of such a group that persisted throughout the
Verification data. Except for processes that manufacture phthalate esters,
these priority pollutants are now recognized as analytical artifacts and
edited out of the BAT and PSES effluent limitations data base.
E. RAW WASTEWATER CHARACTERIZATION DATA
1. General
As described under "Water Usage" earlier in this section, the OCPSF
industry generates significant volumes of process wastewater containing a
variety of pollutants. Most of this raw wastewater receives some treatment,
either as an individual process waste stream or at a wastewater treatment
V-89
-------
plant serving waste streams from the whole manufacturing facility (see Section
VII). To decide what pollutants merit regulation and evaluate what technol-
ogies effectively reduce discharge of these pollutants, data characterizing
the raw wastewaters were collected and evaluated. This section describes the
Agency's approach to this important task and summarizes the results.
2. Raw ffastewater Data Collection Studies
Section III of this document introduced the many wastewater data
collection efforts undertaken for development of these regulations. Studies
that produced significant data on raw wastewater characteristics include the
308 Surveys, the Phase I and II screening studies, the Verification Study, the
EPA/CMA Five-Plant Study and the New 12-Plant Sampling Program. The 308
Surveys have been described in Section III; the remaining studies are
summarized in Table V-42 and are discussed below. The results of the studies
are presented in the "Wastewater Data Summary" at the end of this Section.
3. Screening Phase I
The wastewater quality data reported in the 1976 Section 308 Question-
naire were the result of monitoring and analyses by each of the individual
plants and their contract laboratories. To expand its priority pollutant data
base and improve data quality by minimizing the discrepancies among sampling
and analysis procedures, EPA in 1977 and 1978 performed its Phase I Screening
Study. The Agency and its contractors sampled at 131 plants, chosen because
they operated product/processes that produce the highest volume organic
chemicals and plastics/synthetic fibers.
Samples were taken of the raw plant water, some product/process influents
and effluents, and influents and effluents at the plant wastewater treatment
facilities. Samples were analyzed for all priority pollutants except
asbestos, and for several conventional and nonconventional pollutants.
Screening samples were collected and analyzed in accordance with procedures
described in the 1977 EPA Screening Procedures Manual. Samples for
liquid-liquid extraction (all organic pollutants except the volatile fraction)
and for metals analyses were collected in glass compositing bottles over a
24-hour period, using an automatic sampler generally set for a constant
V-90
-------
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V-91
-------
lisa
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V-92
-------
aliquot volume and constant time, although flow- or time-proportional sampling
was allowed. For metals analysis, an aliquot of the final composite sample
was poured into a clean bottle. Some samples were preserved by acid addition
in the field, in accordance with the 1977 EPA Screening Procedures Manual;
acid was added to the remaining samples when they arrived at the laboratory.
For purge and trap (volatile organic) analysis, wastewater samples were
collected in 40- or 125-ml vials, filled to overflowing, and sealed with
Teflon-faced rubber septa. Where dechlorination of the samples was required,
sodium thiosulfate or sodium bisulfite was used.
Cyanide samples were collected in 1-liter plastic bottles as separate
grab samples. These samples were checked for chlorine by using potassium-
iodide starch test-paper strips, treated with ascorbic acid to eliminate the
chlorine, then preserved with 2 ml of ION sodium hydroxide/liter of sample
(pH 12).
Samples for total (4AAP) phenol colorimetric analysis were collected in
glass bottles as separate grab samples. These samples .were acidified with
phosphoric or sulfuric acid to pH 4, then sealed.
1 1 -
All samples were maintained at 4°C for transport and storage during
analysis. Where sufficient data were available, other sample preservation
requirements (e.g., those for cyanide, phenol, and VOAs by purge and trap as
described above) were deleted as appropriate (e.g., jif chlorine was known to
be absent). No analysis was performed for asbestos during the Phase I
screening effort.
i
In general, the Phase I Screening Study generated data that were
qualitative in nature due to false positive pollutant identification, which
occurs as a result of the procedures used for interpreting ambiguous pollutant
identification based on the 1977 screening level GC/MS analytical protocols
and QA/QC procedures. These procedures are discussed in more detail in
Section VI of this document.
V-93
-------
4. Screening Phase II
In December 1979, samples were collected from an additional 40 plants
(known as Phase II facilities) manufacturing products such as dyes, flame
retardants, coal tar distillates, photographic chemicals, flavors, surface
active agents, aerosols, petroleum additives, chelating agents, micro-
crystalline waxes, and other low-volume specialty chemicals. As in the
Phase I Screening study, samples were analyzed for all the priority pollutants
except asbestos. The 1977 EPA Screening Procedures Manual was followed in
analyzing priority pollutants. As in Screening Phase I, some samples for
metals analysis were preserved by addition of acid in the field (in accordance
with the 1977 Screening Manual) and acid was added to the remaining samples
when they arrived at the laboratory. In addition, the organic compounds
producing peaks not attributable to priority pollutants with a magnitude of at
least 1 percent of the total ion current were identified by computer matching.
Intake, raw influent, and effluent samples were collected for nearly
every facility sampled. In addition, product/process wastewaters that could
be isolated at a facility were also sampled, as were influents and effluents
from some treatment technologies in place. Fourteen direct dischargers,
24 indirect dischargers, and 2 plants discharging to deep wells were sampled.
Table V-43 lists the product/process and other waste streams sampled at each
plant. «
As with the Phase I Screening Study, data from this study were considered
as qualitative in nature for the same reasons stated for Phase I.
5. Verification Program
The Verification Program was designed to verify the occurrence and
concentrations of specific priority pollutants in waste streams from
individual product/processes and to determine the performance of end-of-pipe
treatment systems.
The product/processes to be sampled were generally chosen to maximize
coverage of the product/processes used to manufacture organic priority pollu-
tants, chemicals derived from priority pollutants, and chemicals produced in
V-94
-------
TABLE V-43.
PHASE II SCREENING - PRODUCT/PROCESS AND OTHER
WASTE STREAMS SAMPLED AT EACH PLANT
Plant Number
Waste Streams Sampled.
1
2
3
4
5
6
7
8
9.
10
11
12
13
14
15
16
17
18
19
Combined raw waste (fluorocarbon)
Anthracene :
Coal tar pitch
Combined raw wastes (dyes)
•
Combined raw wastes (coal tar)
Combined raw wastes (dyes)
Oxide
Polymer
Freon
Freon
Ethoxylation
Nonlube oil additives
Lube oil additives
Combined raw wastes (dyes)
Combined raw wastes (flavors)
Combined raw wastes (specialty chemicals)
Combined raw wastes (flavors)
Hydroquinone
Esters
Polyethylene
Sorbitan monosterate ;
Dyes
Combined raw wastes (surface active agents)
Fatty acids
V-95
-------
TABLE V-43.
PHASE II SCREENING - PRODUCT/PROCESS AND OTHER
WASTE STREAMS SAMPLED AT EACH PLANT (Continued)
Plant Number
Waste Streams Sampled
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Organic pigments
Salicylic acid
Fluorescent brightening agent
Surfactants
Dyes
Combined raw wastes (flavors)
Chlorination of paraffin
Phthalic anhydride
Combined raw waste (unspecified)
Dicyclohexyl phthalate
Plasticizers
Resins
Combined raw waste (unspecified)
Polybutyl phenol
Zinc Dialkyldithiophosphate
Calcium phenate
Mannich condensation product
Oxidized co-polymers
Tris (3-chloroethyl) phosphate
Ether sulfate sodium salt
Lauryl sulfate sodium salt
Cylene distillation
Dyes
Maleic anhydride
Formox formaldehyde
Phosphate ester
Hexamethylenetetramine
V-96
-------
TABLE V-43.
PHASE II. SCREENING - PRODUCT/PROCESS AND OTHER
WASTE,STREAMS SAMPLED AT EACH PLANT (Continued)
Plant Number
Wafste Streams Sampled
35
36
37
38
39
40
Acetic acid
Combined raw Waste (coal tar)
"680" Brominated fire,retardants
Tetrabromophthalic anhydride
Hexabromodyclodpdecane
Hexabromodyclododecane
Fatty acid amine ester
Calcium suylfonate in solvent (alcohol)
Oil field deemulsifier blend
(aromatic solvent)
Oxylakylated phenol—:formaldehyde resin
Ethoxylated monyl phenol
Ethoxylated phfenol—•formaldehyde resin
Combined raw waste (surface active agents)
V-97
-------
excess of 5 million pounds per year. The priority pollutants selected for
analysis in the waste stream from each product/process were chosen to meet
either of two criteria:
• They were believed to be raw materials, precursors, or products, in
the product/process, according to the process chemistry; or
* 5ey<>h!}d bfren.^tected ^ the grab samples taken several weeks before
the 3-day Verification exercise (see below) at concentrations exceed-
ing tne threshold concentrations listed 'in Table V-44.
The threshold concentrations listed in Table V-44 were selected as
follows. The concentrations for pesticides, PCBs, and other organics are
approximate quantitative detection limits. The concentrations for arsenic,
cadmium, chromium, lead, and mercury are one half the National Drinking Water
Standard (40 FR 59556 to 74j December 24, 1975).
The Agency sampled at six integrated manufacturing facilities for the
pilot program to develop the "Verification Protocol." Thirty-seven plants
were eventually involved in the Verification effort. Samples were taken from
the effuents of 147 product/processes manufacturing organic chemicals and 29
product/processes manufacturing plastics/synthetic fibers, as well as from
treatment system influents and effluents at each facility.
Each plant was visited about 4 weeks before the 3-day Verification
sampling to discuss the sampling program with plant personnel, to determine
in-plant sampling locations, and to take a grab sample at each designated
satopling^site. These samples were analyzed to develop the analytical methods
used at each plant for the 3-day sampling exercise and to develop the target
list of pollutants (analytes) for analyses at each site during the 3-day
sampling. Some pollutants that were targeted for Verification, since they
were raw materials, precursors, or co-products, were not detected in the
Verification program grab samples. If such a pollutant was also not detected
in the sample from the first day of the 3-day verification sampling, it was
dropped from the targeted list of analytes for that sample location. Other
compounds were added to the analysis list, since they were found in the grab
sample at a concentration exceeding the threshold criteria in Table V-44.
V-98
-------
Priority pollutants known by plant personnel to be present in the plant's
wastewater were also added to the Verification list.
At each plant, Verification samples generally included: process water
supply, product/process effluents, and treatment facility influent and
effluent. Water being supplied to the process was sampled to establish the
background concentration of priority pollutants. Product/process samples were
taken at locations that would best provide representative samples. At various
plants, samples were taken at the influent to and effluent from both
"in-process" and "end-of-pipe" wastewater treatment systems.
Samples were taken on each of 3 days during the Verification exercise.
Twenty-four hour composite samples for extractable organic compounds and
metals were taken with automatic samplers. Where automatic sampling equipment
would violate plant safety codes requiring explosion-proof motors, equal
volumes of sample were collected every 2 hours over an 8-hour day and manually
composited, Raw water supply samples were typically collected as daily grab
samples because of the low variability of these waters.
Samples for cyanide analysis were collected as either a single grab
sample each day or as an equal-volume, 8-hour composite of four aliquots every
2 hours.
For purge and trap (volatile! organic) analysis, duplicate grab samples
were collected four times over an 8-hour period each day.
The temperature and pH of the sample, the measured or estimated
wastewater flow at the time of sampling, and the process production levels
were all recorded, particularly in connection with operational upsets (in the
production units or wastewater treatment facilities) that could result in the
collection of an unrepresentative sample. ,
It should be noted that for organic priority pollutants, gas chroma-
tography with conventional detectors (GC/CD) was used instead of GC/MS. GC/MS
analysis was used on 10 ten percent of the samples to, confirm the presence or
absence of pollutants whose GC peaks overlapped other peaks. The analytical
V-99
-------
TABLE V-44.
SELECTION CRITERIA FOR TESTING
PRIORITY POLLUTANTS IN VERIFICATION SAMPLES
Parameter
Criterion (ug/1)
Pesticides and PCBs
Other Organics
Total Metals:
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
TOTAL Cyanide
0.1
10
100
25
50
5
25
20
25
1
500
10
5
0
1,000
20
V-100
-------
methods finally developed for a given plant were usually applicable (with
minor modifications) to~all sampling sites at that plant.
Raw data from a laboratory's reporting form were encoded on computer data
tapes. The encoded data were verified to be consistent with the raw data
submitted in the reporting forms. Data across injections, extracts, and
laboratories were averaged to derive a concentration value identified uniquely
by plant, chemical number, sample site, and date.
The data were then reviewed by EPA for consistency with the process
chemistry in operation at the plant during the sampling period. After being
judged acceptable for use in the OCPSF rulemaking, the data were provided to
statisticians for analysis.
6. EPA/CMA Five-Plant Sampling Program
From June 1980 to May 1981, EPA, with cooperation from the Chemical
Manufacturers Association (CMA), and five participating chemical plants,
performed the EPA/CMA Five-Plant Study to gather longer-term data on
biological treatment of toxic pollutants at organic chemical plants. The
three primary objectives of the program were to:
• Assess the effectiveness of biological wastewater treatment for the
removal of toxic organic pollutants
• Investigate the accuracy, precision, and reproducibility of the
analytical methods used for measuring toxic organic pollutants in
OCPSF industry wastewaters
• Evaluate potential correlations between biological removal of toxic
organic pollutants and biological removal of conventional and
nonconventional pollutants.
Since the biological wastewater treatment system influent samples were
taken upstream of any preliminary neutralization and settling of each chemical
plant's combined waste stream, the samples of influent to biological treatment
reflect each facility's raw waste load following any in-plant treatment of
waste streams from individual product/processes.
V-101
-------
EPA selected the five participants because of the specific toxic organic
pollutants expected to be found. The five participating OCPSF plants were
• characterized as having well-designed and well-operated activated sludge
treatment systems. Typically, 30 sets of influent and effluent samples
(generally 24-hour composites) were collected at each plant over a 4- to
6-week sampling period.
Only selected toxic organic pollutants were included in this study;
pesticides, PCBs, metals, and cyanides were not measured. Samples were
analyzed for a selected group of toxic organic pollutants that were specific
to each plant as well as for specified conventional and nonconventional
pollutants. Not all toxic organic pollutants included in this study were
analyzed at all locations.
EPA's contract laboratories analyzed all influent and effluent samples
for toxic organic pollutants using GC/MS or GC/CD procedures (44 FR 69464 et
seq., December 3, 1979, or variations acceptable to the EPA Industrial Tech-
nology Division). One EPA laboratory used GC coupled with flame ionization
detection (GC/FID). Approximately 25 percent of the influent and effluent
samples collected at each participating plant were analyzed by the CMA
contractor using GC/MS procedures (44 FR 69464 et seq., December 3, 1979, or
equivalent). Some variation occurred in the analytical procedures for the
toxic organic pollutants used by both the EPA contract laboratories and CMA
laboratory during this study. An extensive QA/QC program was included to
define the precision and accuracy of the analytical results.
Each participant analyzed conventional and nonconventional pollutants in
their influent and effluent wastewaters using the methods found in "Methods of
Chemical Analysis of Water and Wastes," EPA 600/4-79-020, March 1979.
Additionally, four of the participating plants analyzed from 25 to 100 percent
of the samples collected by EPA for some of the to::ic organic pollutants being
discharged by the plant. The influent concentrations measured in this study
prior to end-of-pipe treatment are discussed later in this chapter. The
biological treatment effluent results are discussed and used in Section VII
and IX.
V-102
-------
7. 12-Plant Long-Term Sampling Program
In response to concerns about the limited amount of long-term toxic
pollutant data contained in the database, EPA conducted a long-term sampling
program from March 1983 through May 1984. Twelve plants were selected based
upon the products manufactured, the pollutants generated, and the in-plant and
end-of-pipe treatment technologies employed. Special emphasis vas placed on
identifying plants with pollutants for which existing data were limited.
The number of sampling days at the 12 plants sampled are presented in
Table V-45. The plants were visited several weeks prior to the long-term
sampling. During these visits, background data were collected, sample sites
were selected, and grab samples were collected. The grab samples enabled EPA
to confirm the presence of suspected pollutants and enabled the laboratory to
determine the proper dilutions to be used during analysis.
Samples were collected for each plant's end-of-pipe treatment system, and
included influent, effluent, and sludge samples. Where plants utilized
in-plant control or tertiary treatment, samples were also collected at the
influent and effluent of these systems. Samples were analyzed for conven-
tional, nonconventional, and priority pollutants.
Organic priority pollutants were analyzed by EPA Method 1624, "Volatile
Organic Compounds by Isotope Dilution GC/MS"; and Method 1625, "Semi-volatile
Organic Compounds by isotope Dilution GC/MS." These methods employ GC/MS for
separation, detection, and quantitation of organic priority pollutants, based
on the capability of the mass spectrometer to distinguish the isotopically
labeled analogs of the organic priority pollutants that were spiked into every
sample prior to extraction. Metal priority pollutants were analyzed by atomic
absorption (AA) spectrophotometry, using the 200 series methods in EPA
publication USEPA 600/4-79-020, "Methods for'Chemical Analysis of Water and
Wastes." Dioxin was analyzed by EPA Method 613. Asbestos was analyzed using
the transmission electron microscopy (TEM) methods described in EPA
publication USEPA 600/4-80-005, "Interim Methodology for Determining Asbestos
in Water."
V-103
-------
TABLE V-45.
NUMBER OF SAMPLING DAYS
FOR 12-PLANT LONG-TERM SAMPLING PROGRAM
Number of Plants
1
7
1
2
1
Number of Days Sampled
20
15
12
10
1
V-104
-------
For the first four plants, data were reported by the laboratory on
manually transcribed data sheets to EPA's Sample Control Center (SCC) for
encoding and quality assurance. For the last eight plants, data were
transmitted by the laboratories to the SCC via magnetic tape. The data were
also reviewed by EPA for consistency with the process chemistry in operation
at the plant during the sampling period. After having been judged to be
acceptable for use in the OCPSF rulemaking, the data were transmitted by SCC
to the IBM computer at EPA's National Computer Center in Research Triangle
Park, North Carolina, for loading into the OCPSF data base.
In addition to data collected in the sampling studies discussed above,
the Agency also received data as part of public comments on the March 1983
Proposal and the July 17, 1985 and December 9, 1986 Federal Register Notices
of Availability (NOA). These data were reviewed by the Agency to determine
their accuracy and validity and selected data were included in EPA's final BAT
toxic pollutant data base, which was used in limitations development. A
discussion of the Agency's review and the selection of plant data for the
final toxic pollutant data base is presented in Section VII.
F. WASTEWATER DATA SUMMARY
1. Organic Toxic Pollutants
The Agency's wastewater data collection studies as well as data submitted
during public comment periods on the proposal and NOAs discussed above yielded
substantial long- and short-term priority pollutant concentration data for
50 data sets from 43 manufacturing plants. Tables V-46 through V-49 provide a
statistical summary of the priority pollutant concentrations in the combined
influent to the end-of-pipe treatment systems for these plants. For illus-
trative purposes, the data for all plants are presented in Table V-46 with
Tables V-47 through V-49 sorted into organics only, plastics only, and
organics and plastics plants, respectively.
V-105
-------
TABLE V-46
SUMMARY STATISTICS FOR INFLUENT CONCENTRATIONS FOR
ALL OCPSF PLANTS
CHEHICAL CHEMICAL
KUH8ER NAME
1 ACENAPHTHENE
2 ACROLEIN
3 ACRYLOHITR1LE
4 BENZENE
6 CARBON TETRACHLORIDE
7 CHLOROBENZENE
8 1,2,4-TRICHLOROBENZENE
9 HEXACHLOR08ENZENE
10 1,2-DICHLOROETHANE
11 1,1,1-TRICHLOROETHANE
12 KEXACHLOROETHANE
13 1,1-DICHLOROETHANE
14 1,1,2-TRICHLOROETHANE
15 1,1,2,2-TETRACHLOROETHANE
16 CHLOROETHANE
18 BIS <2-CHLOROETHYL)ETHER
21 2,4,6-TRICHLOROPHENOL
23 CHLOROFORM
24 2-CHLOROPHENOL
25 1,2-DICHLOROBENZENE
26 1,3-DICHLOROBENZENE
27 1.4-DICHLOR08ENZENE
28 3,3-DICHLOROBEHZIDIHE
29 VINYLIDENE CHLORIDE
30 1,2-TRANSDICHLOROETHYLENE
31 2,4-DICHLOROPHENOt
32 PROPYLENE CHLORIDE
33 1,3-DICHLOROPROPENE
34 2,4-DIHETHYLPHENOL
35 2,4-DINITROTOLUENE
36 2,6-DINlTROTOLUENE
38 ETHYLBEHZENE
39 ' FLUORANTHENE
42 BIS-(2-OHLOROISOPROPYL) ETHER
44 DICHLOROMETHANE
45 CHLOROHETHANE
47 BROHOFORH
52 HEXACHLOR08UTADIENE
54 ISOPHORONE
55 NAPHTHALENE
56 NITROBENZENE
THRESHOLD
VALUE
10
50
50
10
10
10
10
10
10
10
10
10
10
10
50
10
10
10
10
10
10
10
50
10
10
10
10
10
10
10
10
10
10
10
10
50
10
10
16
10
14
FRACTION
BASE/NEUTRAL
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
VOLATILES
BASE/NEUTRAL
VOLATILES
VOLATILES
VOLATILES
VOLATILES
BASE/NEUTRAL
ACIDS
VOLATILES
ACIDS
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
VOLATILES
ACIDS
VOLATILES
VOLATILES
ACIDS
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
VOLATILES
VOLATILES
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
* OF
HOMDETECTS
43
0
2
24
6
40
23
0
39
32
0
20
17
38
30
6
11
66
31
31
3
36
0
49
26
4
4
14
3
0
8
31
2
3
36
7
18
0
1
25
27
* OF
DETECTS
30
3
66
178
30
51
355
18
106
17
18
5
14
5
16
13
79
96
34
399
20
22
10
40
9
27
58
28
42
22
24
143
31
18
109
8
2
18
1
76
382
# OF
PLANTS
8
1
7
23
7
8
4
2
13
6
2
2
4
4
4
2
7
17
5
12
2
4
1
8
4
4
6
4
7
3
4
20
6
2
13
1
1
2
1
14
6
MINIMUM
VALUE
10.00
2500.00
290.00
11.00
10.00
10.00
20.00
13.00
10.00
10.00
38.00
11.00
10.50
10.00
60.00
25.00
10.00
10.00
10.33
10.50
11.50
10.00
371.00
10.50
12.83
60.00
28.50
10.00
10.00
715.00
29.00
15.50
14.87
193.00
10.00
51.00
24.00
83.00
253.00
12.00
86.00
MAXIMUM MEAN
VALUE
7000
34500
890000
713740
44000
49775
2955
920
1272220
7234
3400
640
1201
192
2840
1700
16780
5250
247370
23326
4616
721
38351
1300
515
72912
11000
4850
73537
17500
4675
80000
7175
19486
19000
129
71
9100
253
37145
90500
VALUE
773.8
13633.3
94771.4
24389.6
2203.1
3028.7
571.6
242.9
20730.2
594.1
516.7
163.5
299.4
111.1
522.7
413.5
427.7
643.0
13206.0
1039.6
417.3
105.6
6147.5
348.2
255.9
7153.6
1405.7
447.7
11932.6
3301.3
775.0
2382.5
1249.9
2267.9
2469.7
83.4
47.5
2006.3
253.0
4579.1
3881.6
MEDIAN
VALUE
513.0
3900.0
31500.0
812.3
543.0
382.0
301.0
121.5
410.0
30.5
156.5
15.0
23.3
121.5
104.0
54.0
59.0
216.0
117.5
829.0
25.5
42.0
1700.0
262.5
236.3
665.0
505.0
178.5
4470.0
1659.0
379.5
220.0
1040.0
787.0
1091.0
90.0
47.5
1111.0
253.0
623.6
2802.0
V-106
-------
TABLE V-46
SUMMARY STATISTICS FOR INFLUENT CONCENTRATIONS FOR
ALL OCPSF PLANTS
CHEMICAL CHEMICAL
NUMBER NAME
57 2-NITROPHENOL
58 4-NITROPHENOL
59 2,4-DINITROPHENQL
64 PENTACHLOROPHENOL
65 PHENOL
66 BIS-(2-ETHYLHEXYL> PHTHALATE
68 DI-N-BUTYL PHTHALATE
69 DI-N-OCTYL PHTHALATE
70 01ETHYL PHTHALATE
71 DIMETHYL PHTHALATE
72 BENZO
-------
TABLE V-47
SUMMARY STATISTICS FOR INFLUENT CONCENTRATIONS FOR
ORGANICS-ONLY OCPSF PLANTS
CHEMICAL CHEMICAL
NUMBER NAME
1 ACENAPHTHENE
4 BENZENE
6 CARBON TETRACHLORIDE
7 CHLOROBENZENE
8 1,2,4-TRICHLOROBENZENE
10 1.2-DICHLOROETHANE
11 1.1,1-TRICHLOROETHANE
21 2,4,6-TRICHLOROPHENOL
23 CHLOROFORM
24 2-CHLOROPHENOL
25 1,2-DICHLOROBENZENE
27 1,4-DICHLOROBENZENE
31 2.4-DICHLOROPHENOL
34 2,4-DIHETHYLPHENOL
38 ETHYLBENZENE
39 FLUORANTHENE
47 BROHOFORH
55 NAPHTHALENE
56 NITROBENZENE
57 2-NITROPHENOL
58 4-N1TROPHENOL
59 2.4-DINITROPHENOt
65 PHENOL
72 BENZOPYRENE
74 BENZO-B-FLUORANTHENE
75 BENZO
-------
TABLE V-48
SUMMARY STATISTICS FOR INFLUENT CONCENTRATIONS FOR
PLASTICS-ONLY OCPSF PLANTS
CHEMICAL CHEMICAL
NUMBER NAME
2 ACROLEIN
3 ACRYLONITRILE
4 BENZENE
10 1.2-DICHLOROETHANE
13 1,1-OICHLOROETHANE
14 1.1,2-TRICHLOROETHANE
15 1,1,2,2-TETRACHLOROETHANE
23 CHLOROFORM
29 VINYLIDENE CHLORIDE
32 PROPYLENE CHLORIDE
33 1,3-DICHLOROPROPENE
34 2.4-DJMETHYLPHENOL
38 ETHYLBENZENE
44 DICHLOROMETHANE
55 NAPHTHALENE
65 PHENOL
86 TOLUENE
87 TRICHLOROETHYLENE
88 CHLOROETHYLENE
NUMBER OF DATASETS= 7, NUMBER OF PLANTS= 7
THRESHOLD
VALUE FRACTION
# OF # OF * OF MINIMUM MAXIMUM MEAN MEDIAN
NONDETECTS DETECTS PLANTS VALUE VALUE VALUE VALUE
SO
50
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
50
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
VOLATILES
ACIDS
VOLATILES
VOLATILES
BASE/NEUTRAL
ACIDS
VOLATILES
VOLATILES
VOLATILES
0
0
1
0
0
0
0
0
0
0
0
0
1
2
0
0
0
0
0
3
21
5
1
1
1
1
3
1
1
3
1
25
1
9
24
12
1
3
1
3
2
1
1
1
5
1
3
4
4
1
1
2500.00
1200.00
14.00
1534.00
140.10
21.00
188.20
13.75
52.50
2258.00
175.00
13.50
22.00
10.00
25.00
62.00
60.00
483.70
233.50
34500
414785
190
1534
140
21
188
23
53
2258
1095
14
3565
23
3600
1900
1900
484
2396
13633
154682
81
1534
140
21
188
17
53
2258
550
14
435
17
463
498
525
484
993
3900
163600
62
1534
140
21
188
14
53
2258
380
14
112
17
40
472
230
484
350
V-109
-------
TABLE V-49
SUMMARY STATISTICS FOR INFLUENT CONCENTRATIONS FOR
ORGANICS & PLASTICS OCPSF PLANTS
CHEMICAL CHEMICAL
NUMBER HAME
1 ACEHAPHTHENE
3 ACRYLONITRILE
4 BENZENE
6 CARBON TETRACHLORIDE
7 CHLOROBENZENE
8 1.2,4-TRICHLOROBENZENE
9 HEXACKLOROBENZENE
10 1.2-DICHLOROETHANE
11 1.1,1-TRICHLOROETHANE
12 HEXACHLOROETHANE
13 1.1-OICHLOROETHANE
14 1.1,2-TRICHLOROETHANE
15 1.1,2,2-TETRACHLOROETHANE
16 CHLOROETHANE
18 BIS (2-CHLOROETHYDETHER
21 2,4,6-TRICHLOROPHENOL
23 CHLOROFORM
2* 2-CHLOROPHENOL
25 1.2-DICHLOROBENZENE
26 1.3-DICHLOROBEN2ENE
27 1,4-DICHLOROBENZENE
28 3.3-DICHLOROBENZIDINE
29 VINYLIDENE CHLORIDE
30 1,2-TRANSDICHLOROETHYLENE
31 2,4-DlCHLOROPHENOL
32 PROPYLENE CHLORIDE
33 1.3-D1CHLOROPROPENE
34 2,4-DIHETHYLPHENOL
35 2,4-DIHITROTOLUENE
36 2.6-DINITROTOLUENE
38 ETHYLBENZEHE
39 FLUORANTHENE
42 BIS-C2-CHLOROISOPROPYL) ETHER
44 DICHLOROMETHANE
45 CHLOROHETHAHE
52 HEXACHLOROBUTAOIENE
54 1SOPHORONE
55 NAPHTHALENE
56 NITROBENZENE
57 2-NITROPHENOL
58 4-HITROPHENOL
THRESHOLD
VALUE
10
50
10
10
10
10
10
10
10
10
10
10
10
50
10
10
10
10
10
10
10
50
10
10
10
10
10
10
10
10
10
10
10
10
50
10
16
10
14
20
50
FRACTION
BASE/NEUTRAL
. VOLATILES
VOLATILES
VOLATILES
VOLATILES
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
VOLATILES
BASE/NEUTRAL
VOLATILES
VOLATILES
VOLATILES
VOLATILES
BASE/NEUTRAL
ACIDS
VOLATILES
ACIDS
BASE/NEUTRAL.
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
VOLATILES
ACIDS
VOLATILES
VOLATILES
ACIDS
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
BASE/NEUTRAL
BASE/NEUTRAL
VOLATILES
VOLATILES
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
BASE/NEUTRAL
ACIDS
ACIDS
# OF
NONDETECTS
22
2
22
4
22
6
0
39
31
0
> 20
17
38
30
6
7
66
30
15
3
20
0
49
26
3
4
14
2
0
8
14
1
3
34
7
0
1
7
8
8
15
# OF
DETECTS
6
45
143
29
46
352
18
102
15
18
4
13
' 4
16
13
76
90
32
395
20
18
10
39
9
25
57
25
17
22
24
100
7
18
108
8
18
1
43
381
27
13
# OF MINIMUM
PLANTS VALUE
4
4
16
6
6
3
2
11
5
2
1
3
3
4
2
6
15
4
11
2
3
1
7
4
3
5
3
3
3
4
12
3
2
12
1
2
1
8
5
4
3
10.000
290.000
11.000
10.000
11.500
20.000
13.000
10.000
10.000
38.000
11.000
10.500
10.000
60.000
25.000
10.000
10.000
10.333
10.500
11.500
10.000
371.000
10.500
12.833
60.000
28.500
10.000
10.000
715.000
29.000
15.500
14.870
193.000
10.000
51.000
83.000
253.000
12.000
86.000
26.000
83.000
MAXIMUM MEAN
VALUE
57
890000
713740
44000
49775
2955
920
1272220
7234
3400
640
1201
192
2840
, 1700
16780
5250
247370
23326
4616
220
38351
1300
515
72912
11000
4850
8787
17500
4675
3850
289
19486
19000
129
9100
253
4018
90500
1625
5990
MEDIAN
VALUE VALUE
24.5
66813.2
22706.0
2275.7
3345.7
575.9
242.9
21491.4
642.9
516.7
169.4
320.8
95.7
522.7
413.5
443.5
669.0
13111.7
1025.5
417.3
61.5
6147,5
355.8
255.9
7665.2
1390.8
435.9
3342.0
3301.3
775.0
495.2
69.2
2267.9
2514.3
83.4
2006.3
253.0
797.9
3891.4
219.2
887.6
23.0
23000.0
990.0
666.3
426.0
305.5
121.5
374.5
23.5
156.5
13.5
23.5
120.0
104.0
54.0
59.5
216.0
96.8
824.0
25.5
32.0
1700.0
270.0
236.3
655.0
480.0
173.0
3415.0
1659.0
379.5
223.5
30.0
787.0
1110.5
90.0
1111.0
253.0
399.5
2802.0
147.0
450.0
v-no
-------
TABLE V-49
SUMMARY STATISTICS FOR INFLUENT CONCENTRATIONS FOR
ORGANICS & PLASTICS OCPSF PLANTS
CHEMICAL CHEMICAL
NUMBER NAME
59 2.4-OINITROPHENOL
64 PENTACHLOROPHENOL
65 PHENOL'
66 BIS-<2-ETHYLHEXYL) PHTHALATE
68 DI-N-BUTYL PHTHALATE
69 DI-N-OCTYL PHTHALATE
70 DIETHYL PHTHALATE
71 DIMETHYL PHTHALATE
72 BENZO(A)ANTHRACENE
74 BENZO-B-FLUORANTHENE
75 BENZO
-------
In each table, the number bf nondetects is the number of daily samples
that were taken at or below the threshold concentrations and the number of
detects are the number of da,ily, samples that exceeded the threshold value. In
the calculation of the statistical values, all nondetect samples were assigned
the threshold value (the analytical method nominal detection limit). Specific
pollutant data for each plant were retained only if they were detected in at
least one sample.
2. Toxic Pollutant Metals
There are process sources of certain metal priority pollutants1 in the
process wastewaters of the OCPSF industry. These metals (including cyanide)
and their affiliated process sources may be anticipated from published generic
process chemistry that is typically used to manufacture each of the industry's
products. Analytical data in the Master Process File from verification
sampling, in which the process effluents of 176 of the major product/processes
of the industry were characterized for both metal and organic priority
pollutants, offered confirmation of some of the metals (and cyanide) that were
anticipated. Confirmation was also found in the industry's response to the
1983 '308' Questionnaire, in which plants were asked to affiliate priority
pollutants with each of the product/processes in operation.
Concentrations of metals in wastewater from individual in-plant processes
are typically low (less than 1.0 ppm). Few of the treatment systems in the
OCPSF industry have precipitation technology being applied to a process's
wastewater prior to its joining the combined flow. Many OCPSF wastewater
treatment systems do not have a primary clarifier. This implies the absence
of solids in the combined flow that results from metals fortuitously precipi-
tated by contact with various precipitants, and a concentration of metals in
the combined flow that is typically too low to utilize precipitation technol-
ogy. One obvious exception to this generalization is plants manufacturing
rayon that are controlling zinc losses by chemical precipitation, using lime
or caustic.
For the purposes of this discussion, total cyanide is included in the metal
priority pollutants (or toxic pollutants) term.
V-112
-------
In the 1983 308 Questionnaire, each plant was asked to affiliate priority
pollutants with the various product/processes in operation at the plant in
1980. They were also asked to indicate the priority pollutants' role within
the product process, i.e., catalyst, solvent, raw material, or contaminant in
the raw material, by-product, or waste product. This file, containing
the priority pollutant metal-product/process affiliations, was retrieved from
the 308 data base and a listing was prepared for each metal. Another file,
containing product/process-plant affiliations, was also retrieved and listed
for reference.
Of the five roles, the role of solvent was dismissed for metals. In
addition in contrast to organics chemicals, metals cannot be generated by the
process chemistry, only lost from the process. For this reason, by-product
sources were also ignored. The plants frequently affiliated a metal with the
waste products of the product/process, but affiliation with waste products was
considered to have merit only when the metal was also listed as a catalyst or
raw material for the product/process. Thus, editing focused mainly on
catalyst and raw material roles of the metal in validating the product/
process.
The editing criteria for validation of product/processes and plants were
as follows:
• Invalidate a product/process affiliated with a metal listed as a
by-product or waste product, unless it was also listed as a catalyst
or raw material. Exclude solvent affiliations.
• Invalidate a product/process affiliated with a metal listed as a
catalyst or raw material, if affiliation is inconsistant with the
chemistry of the generic process or is an otherwise anomalous affili-
ation. Add a product/process when a metal is generally associated
with the chemistry of the process (or can be confirmed by plant con-
tact), but was not listed by plants that operate the product/process.
• Invalidate a product/process affiliated with a metal listed as part of
the catalyst system, if the metal is a minor constituent (less than 5%
by weight) of the catalyst, process reactor design severely limits
catalyst losses, -and/or the catalyst is exposed only to non-aqueous
process streams.
V-113
-------
• Invalidate a product/process that is a valid source of a metal, if the
metal is unlikely to emerge in the wastewater from the process at a
treatable level (less than 1 mg/1), before mixing with the wastewater
rrom other processes in operation at the plant.
• Invalidate a product/process, if less than half of the plants that
operate the product/process listed the metal as being affiliated with
the product/process.
• Invalidate a plant affiliated with a valid product/process, if the
plant no longer operates the product/process.
A summary of the results of this validation analysis is presented in
Table V-50. A listing of the product/processes that have been determined to
be process sources of metals and cyanide is presented in Section X of this
document. Based on these results, the Agency determined that a total of eight
toxic pollutant metals (including cyanide) had a substantial number of process
sources in the OCPSF industry. Also, as discussed in the following section,
the remaining seven toxic pollutants (including arsenic) were eliminated from
further consideration for regulation under this rulemaking.
V-114
-------
TABLE V-50.,
SUMMARY OF PRIORITY POLLUTANT METAL-PRODUCT/PROCESS-PLANT VALIDATION
Priority
Pollutant
Metals
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
121 Cyanide
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
No. off PP1
Before
Validation
(Sb)
(As)
(Be) ,
(Cd)
(Cr)
(Cu)
(CN)
(Pb)
(Hg)
(Ni)
(Se)
(Ag)
(Th)
(Zn)
43
46
8
34
116
131
47
46
31
124
20
19
9
152
No. of '
Plants No. of PP ,
Before After
Validation, Validation
126 15
113 ; 25 ' "'
19 ......-,
85 ...
207 24'
240 62
73 41
149 13
93 1
163 63
46
68
20
298 46
No. of
... Plants
After
Validation
29
18
„ 71 ..:-...
.• • 62
37
1
64
81
1 product/processes
V-115
-------
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
A. INTRODUCTION
Specific toxic, conventional, and nonconventional pollutant parameters
were determined to be potentially significant in the Organic Chemicals, Plas-
tics, and Synthetic Fibers (OCPSF) Industry and were selected for evaluation
based on: 1) an industry characterization, 2) data collected from field
sampling efforts, 3) historical data collected from the literature, and 4)
data provided by industry either by questionnaire (Section 308 Questionnaire
Survey) or through public comment on the proposed regulations or subsequent
Federal Register Notices of Availability of New Information.
The U.S. Environmental Protection Agency (EPA) has considered for
regulation the following conventional pollutant parameters for the final BPT
effluent limitations presented in this document: five-day biochemical oxygen
demand (BOD5), total suspended solids (TSS), pH, and oil and grease (O&G).
Nonconventional pollutant parameters considered by the Agency for the final
BPT, BAT, NSPS, PSES, and PSNS effluent limitations guidelines and standards
include chemical oxygen demand (COD) and total organic carbon (TOG).
In developing its BAT, NSPS, PSES, and PSNS effluent limitations guide-
lines and standards for toxic pollutants, the Agency specifically addressed a
list of 126 toxic pollutants, which are presented in Appendix VI-A. As the
list of 65 toxic pollutants and classes of pollutants includes potentially
thousands of specific pollutants, EPA limited its data collection efforts to
the 126 specific compounds referred to as "priority" pollutants. The criteria
that were used in the late 1970's to classify these pollutants as "priority"
pollutants included the frequency of their occurrence in water, their chemical
stability and structure, the amount of the chemical produced, and the avail-
ability of chemical standards and analytical methods for measurement.
VI-1
-------
This section presents descriptions of each of the conventional,
nonconventional, and toxic pollutant parameters considered by the Agency and
discusses the selection criteria used to select pollutants for control under
BPT, BAT, NSPS, PSES, and PSNS.
B. CONVENTIONAL POLLUTANT PARAMETERS
1• Five-Day Biochemical Oxygen Demand (BOD )
The Five-Day Biochemical Oxygen Demand (BOD5) test traditionally has been
used to determine the pollutant strength of domestic and industrial waste-
waters. It is a measure of the oxygen required by biological organisms to
assimilate the biodegradable portion of a waste under aerobic conditions
(6-1). Substances that may contribute to the BODg include carbonaceous
materials usable as a food source by aerobic organisms; oxidizable nitrogen
derived from organic nitrogen compounds, ammonia and nitrates that are
oxidized by specific bacteria; and chemically oxidizable materials such as
ferrous compounds, sulfides, sulfite, and similiar reduced-state inorganics
that will react with dissolved oxygen or that are metabilized by bacteria.
The BODg of a wastewater is a measure of the dissolved oxygen depletion
that might be caused by the discharge of that wastewater to a body of water.
This depletion reduces the oxygen available to fish, plant life, and other
aquatic species. Total exhaustion of the dissolved oxygen .in water results in
anaerobic conditions, and the subsequent dominance of anaerobic species that
can produce undesirable gases such as hydrogen sulfide and methane. The
reduction of dissolved oxygen can be detrimental to fish populations, fish
growth rates, and organisms used as fish food. A total lack of oxygen can
result in the death of all aerobic aquatic inhabitants in the affected area.
The BODg test is widely used to estimate the oxygen demand of domestic
and industrial wastes and to evaluate the performance of waste treatment
facilities by measuring the amount of oxygen depletion in a standard size
flask after 5 days incubation. The test is widely used for measuring poten-
tial pollution, since no other test methods have been developed that are as
suitable or as widely accepted for evaluating the deoxygenation effect of a
waste on a receiving water body.
VI-2
-------
The BOD test measures the weight of dissolved oxygen utilized by
microorganisms as they oxidize or transform the gross mixture of chemical
compounds in the wastewater. The degree of biochemical reaction involved in
the oxidation of carbon compounds is related to the period of incubation and
the rate of biodegradation of the compound(s) within the mixture. When
municipal sewage is tested, BOD5 normally measures only 60 to 80 percent of
the total carbonaceous biochemical oxygen demand of the sample. When testing
OCPSF wastewaters, however, the fraction of total carbonaceous oxygen demand
measured can range from less than 10 percent to more than 80 percent. The
actual percentage for a given waste stream will depend on the degradation
characteristics of the organic components present, the degree to which the
seed is acclimated to these components, and the degree to which toxic or
inhibitory components are present in the'waste (6-1).
2. Total Suspended Solids (TSS)
Suspended solids can.include both organic and inorganic materials. The
inorganic materials include sand, silt, and clay and may include insoluble
toxic metal compounds. The organic fraction includes such materials as
grease, oils, animal and vegetable waste products, fibers, microorganisms, and
many other dispersed insoluble organic compounds (6-2). These solids may
settle rapidly and form bottom deposits that are often a mixture of both
organic and inorganic solids.
Solids may be suspended in water for a time and then settle to the bottom
of a stream or lake. They may be inert, slowly biodegradable materials, or
they may be rapidly decomposable substances. While in suspension, they
increase the turbidity of the water, reduce light penetration, and impair the
photosynthetic activity of aquatic plants. After settling to the stream or
lake bed, the solids can form sludge banks, which, if largely organic, create
localized anaerobic and undesirable benthic conditions. Aside from any toxic
effect attributable to substances leached out by water, suspended solids may
kill fish and shell-fish by causing abrasive injuries, clogging gills and
respiratory passages, screening light, and by promoting and maintaining
noxious conditions through oxygen depletion. Suspended solids may also reduce
the recreational value of a" waterway and can cause problems in water used for
VI-3
-------
domestic purposes. Suspended solids in intake water may interfere with many
industrial processes, and cause foaming in boilers, or encrustations on
exposed equipment, especially at elevated temperatures.
3. pjl
The term pH describes the hydrogen ion-hydroxyl ion equilibria in water.
Technically, pH is a measure of the hydrogen ion concentration or activity
present in a given solution. A pH number is the negative logarithm of the
hydrogen ion concentration. A pH of 7.0 indicates neutrality or a balance
between free hydrogen and free hydroxyl ions. A pH above 7.0 indicates that a
solution is alkaline? a pH below 7.0 indicates that a solution is acidic.
The pH of discharge water is of concern because of its potential impact
on the receiving body of water. Wastewater effluent, if not neutralized
before release, may alter the pH of the receiving water. The critical range
suitable for the existence of most biological life is quite narrow, lying
between pH 6 and pH 9.
Extremes of pH or rapid pH changes can harm or kill aquatic life. Even
moderate changes from acceptable pH limits can harm some species. A change in
the pH of water may increase or decrease the relative toxicity of many mate-
rials to aquatic life. A drop of even 1.5 units, for example, can increase
the toxicity of metalocyanide complexes a thousandfold. The bactericidal
effect of chlorine in most cases lessens as the pH increases.
Waters with a pH below 6.0 corrode waterworks structures, distribution
lines, and household plumbing fixtures. This corrosion can add to drinking
water constituents such as iron, copper, zinc, cadmium, and lead. Low pH
waters not only tend to dissolve metals from structures and fixtures, but also
tend to redissolve or leach metals from sludges and bottom sediments.
Normally, biological treatment systems are maintained at a pH between 6
and 9; however, once acclimated to a narrow pH range, sudden deviations (even
in the 6 to 9 range) can cause upsets in the treatment system with a resultant
decrease in treatment efficiency.
VI-4
-------
4. Oil and Grease (O&G)
Oil and grease analyses do not actually measure the quantity of a
specific substance, but measure groups of substances whose common character-
istic is their solubility in freon. Substances measured may include hydro-
carbons, fatty acids, soaps, fats, oils, wax, and other materials extracted by
the solvent from an acidified sample and not volatilized by the conditions of
the test. As a result, the term "oil and grease" is more properly defined by
the conditions of the analysis rather than by a specific compound or group of
compounds. Additionally, the material identified in the O&G determination is
not necessarily free floating. It may be actually in solution but still
extractable from water by the solvent (6-3).
Oils and greases of hydrocarbon .derivatives, even in small quantities,
cause troublesome taste and odor problems. Scum lines from these agents are
produced on water treatment basin walls and other containers. Fish and water
fowl are adversely affected by oils in their habitat. Oil emulsions may cause
the suffocation of fish by adhering to their gills and may taint the flesh of
fish when microorganisms exposed to waste oil are eaten. Deposition of oil
in the bottom sediments of natural waters can serve to inhibit normal benthic
growth. Oil and grease can also exhibit an oxygen demand.
Levels of oil and grease that are toxic to aquatic organisms vary greatly
depending on the oil and grease components and the susceptibility of the
species exposed to them. Crude oil in concentrations as low as 0.3 mg/1 can
be extremely toxic to freshwater fish. Oil slicks prevent the full aesthetic
enjoyment of water. The presence of oil in water can also increase the
toxicity of other substances being discharged into the receiving bodies of
water. Municipalities frequently limit the quantity of oil and grease that
can be discharged to their wastewater treatment systems.
There are several approved modifications of the analysis for oil and
grease. Each is designed to increase the accuracy or enhance the selectivity
of the analysis. Depending on the procedure and detection method employed,
the accuracy of the test can vary from 88 percent for the Soxhlet Extraction
Method to 99 percent for the Partition-Infrared Method.
VI-5
-------
C. NONCONVENTIONAL POLLUTANT PARAMETERS
1« Chemical Oxygen Demand (COD)
COD is a chemical oxidation test devised as an alternate method of
estimating the oxygen demand of a wastewater. Since the method relies on the
oxidation-reduction system of a chemical reaction rather than a biological
reaction, it is more precise, accurate, and rapid than the BOD5 test. The COD
test is sometimes used to estimate the total oxygen (ultimate rather than the
five-day BOD5) required to oxidize the compounds in a wastewater. In the COD
test, strong chemical oxidizing agents under acid conditions, with the assis-
tance of certain inorganic catalysts, can oxidize most organic compounds,
including many that are not biodegradable. However, it should be noted that
the COD test may not measure the oxygen demand of certain aromatic species
such as benzene, toluene, and pyridine (6-4).
The COD test measures organic components that may exert a biological
oxygen demand and may affect public health. It is a useful analytical tool
Most pollutants measured by the BOD test
for pollution control activities.
will be measured by the COD test. In addition, pollutants resistant to
biochemical oxidation will also be measured as COD.
Compounds resistant to biochemical oxidation are of great concern because
of their slow, continuous oxygen demand on the receiving water and also, in
some cases, because of their potential health effects on aquatic life and
humans. Many of these compounds result from industrial discharges and some of
the compounds have been found to have carcinogenic, mutagenic, and similar
adverse effects. Concern about these compounds has increased as a result of
demonstrations that their long life in receiving water (the result of a low
biochemical oxidation rate) allows them to contaminate downstream water
intakes. The commonly used systems of water purification are not effective in
removing these types of materials and disinfection with chlorine may convert
them into even more objectionable materials.
2. Total Organic Carbon (TOG)
TOC measures all oxidizable organic material in a waste stream, including
the organic chemicals not oxidized (and therefore not detected) in BOD and
VI-6
-------
COD tests. TOC analysis is a rapid test for estimating the total organic
carbon in a waste stream.
¥hen testing for TOC, the organic carbon in a sample is converted to
carbon dioxide (C02) by catalytic combustion or by wet chemical oxidation.
The C02 formed can be measured directly by an infrared detector or it can be
converted to methane (CH4) and measured by a flame ionization detector. The
amount of C02 or CH4 is directly proportional to the concentration of carbo-
naceous material in the sample. TOC tests are usually performed on commer-
cially available automatic TOC analyzers. Inorganic carbons, including
carbonates and bicarbonates, interfere with these analyses and must be removed
during sample preparation (6-5).
D. TOXIC POLLUTANT PARAMETERS
Paragraph 8 of the Settlement Agreement contains provisions authorizing
EPA to exclude toxic pollutants and industry subcategories from regulation
under certain circumstances. Paragraph 8(a)(iii) authorizes the Administrator
to exclude from regulation: toxic pollutants not detectable by Section 304(h)
analytical methods or other state-of-the-art methods; toxic pollutants present
in amounts too small to be effectively reduced by available technologies;
toxic pollutants present only in trace amounts and neither causing nor likely
to cause toxic effects; toxic pollutants detected in the effluent from only a
small number of sources within a subcategory and uniquely related tovonly
those sources; toxic' pollutants that will be effectively controlled by the
technologies upon which are based other effluent limitations and standards; or
toxic pollutants for which more stringent protection is already provided under
Section 307(a) of the Act.
Pursuant to the Paragraph 8(a)(iii) criteria, the Agency decided early in
the rulemaking to eliminate from further consideration 26 toxic pollutants,
consisting of 18 pesticides, seven polychlorinated biphenyls (PCBs), and .
asbestos. These toxic pollutants are listed in Table VI-1, and are excluded
because they are not produced as products or co-products and are unlikely to
appear as raw material contaminants in OCPSF product/processes. At facilities
manufacturing OCPSF product/processes, but where pesticide pollutants are also
VI-7
-------
TABLE VI-1.
TWENTY-SIX TOXIC POLLUTANTS.
PROPOSED FOR EXCLUSION
Aldrin
Dieldrin
Chlordane
4,4'-DDT
4,4'-DDE
4,4'-DDD
alpha-Endosulfan
beta-Endosulfan
Endosulfansulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Toxaphene
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Asbestos
VI-8
-------
synthesized by product/processes inSIC Codes corresponding to the pesticides
category, pesticide discharges wi11»be regulated under effluent limitations
for the separate pesticide category. On occasion, pesticides may appear in
discharges that contain OCPSF effluents only but can be attributed to applica-
tion of pesticide formulations around the plant grounds. PCBs are no longer
manufactured in the United States; however, PCBs may occasionally appear in
OCPSF effluents and are probably the result of leaking transformers containing
PCB-contaminated oil which finds its way into the wastewater through storm-
water runoff or plant floor drains. Asbestos is neither manufactured nor
utilized as a raw material or catalyst by the OCPSF industry. In any event,
none of the 18 pesticides, 7 PCBs, and asbestos are currently related to OCPSF
production.
With the exception of dibxin, all remaining priority pollutants were
considered for regulation; however, as described later in this section, some
were ultimately excluded from regulation under Paragraph 8. Regulation of
dioxin (TCDD) has been reserved even though it was not detected at any of the
sample locations. The minimum detection or analytical threshold level of the
2,3,7,8-tetrachlorodibenzo-p-dioxin analytical method used at the time of the
EPA laboratory studies that included dioxin (March 1983 to May 1984/12-plant
study) was significantly higher than the level presently being used by the
Agency. The minimum detection level used for the OCPSF dioxin analyses was
3 x 10"7 grams/liter, which is five orders of magnitude higher than the
current minimum detection level being used by the Agency to study industrial
sources of dioxin in wastewater discharges. Thus, the Agency decided to
reserve dioxin rather than use the higher analytical detection level as a
basis for exclusion from regulation.
E. SELECTION CRITERIA
1. Conventional Pollutants
The Agency has decided to control five-day biochemical oxygen demand
(BOD5), total suspended solids (TSS), and pH under its final BPT effluent
limitations guidelines. While the Agency considered developing limitations
for oil and grease, EPA determined that the effluent levels of oil and grease
observed at BPT treatment systems were achieved through incidental removal by
VI-9
-------
a treatment system primarily designed to remove BOD5 and TSS. It should be
noted that certain plants install oil and grease treatment technologies to
ensure that subsequent treatment units (e.g., other physical/chemical or bio-
logical treatment) can operate properly. .Therefore, based on these reasons,
the Agency decided not to establish BPT effluent limitations for oil and
grease.
2. Nonconventional Pollutants
While the Agency had considered the development of BPT, BAT, NSPS, PSES,
and PSNS effluent limitations guidelines and standards for specific non-
conventional pollutants, EPA has determined that the regulation of nonconven-
tional pollutants will be deferred. One reason for this deferment is the
enormity of the task of developing analytical methods for many of the noncon-
ventional toxic pollutants. Another reason for not regulating the more famil-
iar nonconventional pollutants such as COD and TOC is that much of the per-
formance data obtained by the Agency is the result of incidental removals by
treatment technologies installed to remove conventional and/or toxic (prior-
ity) pollutants and not designed for the removal of the nonconventional pol-
lutants present, including COD and TOC. The Agency believes that the proper
installation of treatment technologies to meet BPT, BAT, NSPS, PSES, and PSNS
effluent limitations guidelines and standards will result in significant re-
ductions of nonconventional pollutants. For example, nonconventional volatile
pollutants such as xylene that are present in BTX process wastewaters will be
removed by steam strippers installed for removal of benzene and toluene.
3. Toxic Pollutants
i
Toxic pollutant parameters are controlled under BAT and NSPS for direct
dischargers and PSES and PSNS for indirect dischargers and the criteria for
selecting toxic pollutants for regulation for each mode of discharge is dif-
ferent. Therefore, discussion of the selection criteria for BAT and NSPS and
PSES and PSNS are presented separately in the following sections.
a. Selection Criteria for BAT and NSPS Toxic Pollutants
As stated previously, dioxin was reserved from regulation at this time.
In addition, Paragraph 8 of the Settlement Agreement contains provisions
VI-10
-------
authorizing EPA to exclude toxic pollutants and industry subcategories from
regulation under certain circumstances. Pursuant to these criteria (as stated
previously), the Agency eliminated 18 pesticides, 7 PCBs, and asbestos from
further regulatory consideration. The remaining 99 toxic pollutants were then
evaluated based on the specific criteria set forth in Paragraph 8 of the
Settlement Agreement.
Table VI-2 presents the frequency of occurrence of 99 toxic pollutants
sampled for in untreated wastewaters (discharged to the end-of-pipe treatment
systems) during the following EPA toxic pollutant sampling studies: 1) Phase
I Screening, 2) Phase II Screening, 3) Verification, 4) EPA/CMA S^Plant Study,'-
and 5) EPA 12-Plant Study. Also presented are the minimum and maximum
reported concentrations from the last three studies. ;
Only the last three studies for the minimim/maximum values were used
because the analytical methods used for the two screening studies allow the
data only to be used qualitatively. False positive pollutant identification
could occur in the Phase I and II screening studies as a result of the pro-
cedures used for interpreting ambiguous pollutant identification based on the
1977 screening level GC/MS analytical protocols and QA/QC procedures. The
screening level analytical procedures based pollutant identification on three
peaks of the mass spectrum. If these peaks did not agree exactly with the
reference or library, spectrum, then judgement calls were generally made in
favor of compound presence. These judgement calls were made approximately
10 to 20 percent of the time. This was a conservative approach for identify-
ing pollutants of concern for future organic priority pollutant field sampling
and analysis studies because it minimized the occurrence of. false negative re-
porting. Use of the screening analytical protocols also led to the reporting
of a range of analytical threshold levels or "detection limits" for various
toxic compounds. In general, the analytical threshold levels that were
reported as "less than" values are associated with raw waste, sample matrix
interferences. The reporting of data as such does not imply the presence of
the toxic compounds at the reported "less than" values. Rather, it means that
the presence ^«r absence of these compounds cannot be verified due to analyti-
cal limitations. The frequency counts presented in Table VI-2 treats reported
"less than" values as non-detected. (The initial frequency counts presented
VI-11
-------
TABLE VI-2
FREQUENCY OF OCCURENCE AND CONCENTRATION RANGES FOR
SELECTED PRIORITY POLLUTANTS IN UNTREATED WASTEWATER
03S POLLUTANT
NAME
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
(TOTAL)
(TOTAL)
(TOTAL)
ZINC
COPPER
MERCURY
PHENOL
CHROMIUM (TOTAL)
TOLUENE
NICKEL (TOTAL)
BENZENE
ETHYLBENZENE
D1CHLOROHETHANE
CHLOROFORM
ARSENIC (TOTAL)
SILVER (TOTAL)
8IS-(2-ETHYLHEXYL) PHTHALATE
CYAHIDE (TOTAL)
CADMIUM (TOTAL)
LEAD (TOTAL)
ANTIMONY (TOTAL)
NAPHTHALENE
SELENIUM (TOTAL)
1,1,1-TRlCHLOROETHANE
1,2-DICHLOROETHANE
CHLOROBENZENE
THALLIUM (TOTAL)
PERCHLOROETHYLENE
CARBON TETRACHLORIDE
2,4-DIHETHYLPHENOL
VIHYLIDENE CHLORIDE
Dl-N-BUTYL PHTHALATE
TR1CHLOROETHYLENE
ACENAPHTHENE
PHENAHTHRENE
ANTHRACENE
FLUORENE
ACENAPHTHYLENE
BERYLLIUH(TOTAL)
PYRENE
2,4,6-TRICHLOROPHENOL
2-CHLOROPHEHOL
FLUORANTHENE
2,4-DICHLOROPHENOL
1,2-TRAHSDICHLOROETHYLENE
PROPYLEHE CHLORIDE
1,2-DICHLOROBENZENE (0-DICHLOROBENZENE)
1,4-DICHLOROBEHZENE (P-DICHLOR06EHZENE)
DIETHYL PHTHALATE
DIMETHYL PHTHALATE
BUTYLBEHZYL PHTHALATE
1,1,2,2-TETRACHLOROETHANE
BENZO(A)ANTHRACENE
POLLUTANT
FRACTION NUMBER
NUMBER OF MIN MAX
H DET RATIO PLANTS CONCENTRATION CONCENTRATION
M
M
M
A
M
V
H
V
V
V
V
M
«
B
M
M
M
M
B
M,
V
V
V
H
V
V
A
V
B
V
B
B
B
B
B
M
B
A
A
B
A
V
V
B
B
B
8
B
V
B
128
120
123
65
119
86
124
4
38
44
23
115
126
66
121
'm
122
114
55
125
11
10
7
127
85
6
34
29
68
87
1
81
78
80
77
117
84
21
24
39
31
30
32
25
27
70
71
67
15
• 72
137 131 95.620
134 123 91.791
126 95 75.397
148 110 74.324
141 102 72.340
137 96 70.073
126 80 63.492
134 78 56.209
13D 75 57.692
122 69 56.557
131 71 54.198
120 62 51.667
122 58 47.541
127 57 44.882
118 49 41.525
126 48 38.095
131 49 37.405
123 42 34.146
125 42 33.600
119 38 31.933
112 35 31.250
115 34 29.565
115 33 28.696
118 33 27.966
112 28 25.000
113 28 24.779
117 28 23.932
106 25 23.585
118 25 21.186
113 23 20.354
117 23 19.658
117 23 19.658
117 21 17.949
118 21 17.797
118 19 16.102
118 19 16.102
119 18 15.126
113 17 15.044
115 17 14.783
117 17 14.530
114 15 13.158
107 14 13.084
107 14 13.084
116 15 12.931
113 14 12.389
112 13 11.607
113 13 11.504
115 13 11.304
109 12 11.009
112 12 10.714
21
19
13
29
26
26
10
20
18
7
13 .
6
1
1
3
3
8
7
14
4
6
11
7
2
5
6
7
7
1
8
7
10
7
9
8
_
6
6
5
6
4
4
5
9
4
2
1
B
3
5
14.000
23.500
0.500
13.000
60.000
13.000
49.000
12.500
15.500
10.310
11.000
5.000
3.634
11.000
130.000
5.519
103.800
5.000
12.000
3.000
11.000
12.000
11.500
2.000
11.000
15.000
13.500
10.500
19.000
10.222
11.000
18.500
15.000
10.500
12.000
11.000
11.000
10.333
14.870
60.000
12.833
28.500
10.500
10.500
13.500
10.333
34.000
12.030
450000
4834
900
978672
5330
160000
37500
713740
80000
12480
5250
711
18
18830
5063
10
430000
630
37145
250
7234
1272220
49775
5
31500
44000
73537
1300
5930
484
7000
11000
2900
1873
18500
5500
16780
247370
7175
72912
515
11000
23326
721
15000
625
192
2400
ALL CONCENTRATION
RATIO » 100*DET/N(100
IN UNITS OF PPB
* # DETECTED/TOTAL)
VI-12
-------
TABLE VI-2(CON'T.)
FREQUENCY OF OCCURENCE AND CONCENTRATION RANGES FOR
SELECTED PRIORITY POLLUTANTS IN UNTREATED WASTEUATER
08S POLLUTANT
NAME
POLLUTANT
FRACTION NUMBER
-NUMBER OF MIN MAX
N DET RATIO PLANTS CONCENTRATION - CONCENTRATION
51 CHRYSENE
52 OICHLOROBROMOMETHANE
53 BROMOFORH
54 ACRYLOHITRILE
55 NITROBENZENE
56 PENTACHLOROPHENOL
57 , 1,1,2-TRICHLOROETHANE
58 2,6-DIMITROTOLUENE
59 4-NITROPHENOL
60 2-NITROPHENOL
61 CHLOROMETHANE
62 1,1-DICHLOROETHAHE
63 1,3-DICHLOROPROPENG
64 BIS-(2-CHLOROISOPROPYL) ETHER
65 2.4-OINITROPHENOl
66 BIS (2-CHLOROETHYDETHER
67 CHLOROETHANE
68 CHLORODIBROMOMETHANE
69 1,3-DICHLOROBENZnNE (M-DICHLOROBENZENE)
70 OI-N-OCTYL PHTHALATE
71 1,2.4-TRICHLOROBENZENE
72 BENZO-B-FLUORANTHENE
73 HEXACHLOROBENZENE
74 HEXACHLOROETHANE
75 . N-NITROSODIPHENYLAMINE
76 PARA-CHLORO-META-CRESOL
77 2,4-OINITROmUEME
78 • BENZO
-------
in Table VI-2, Vol II of the proposed Development Document (EPA 440/1-83/009,
February 1983) had tabulated "less than" values as detected.)
It should also be noted that the selected untreated wastewater sampling
locations at some plants may be downstream of in-plant controls that may treat
one or more OCPSF product/process sources of wastewater before commingling
with other OCPSF process wastewater at the influent to the end-of-pipe treat-
ment system. Therefore, the end-of-pipe raw wastewater summaries include some
partially treated wastewater. This situation is unavoidable for several
reasons. Foremost is the practical difficulties of accurately sampling and
flow proportioning multiple in-plant sources of wastewater to obtain com-
pletely untreated wastewater characteristics. The Agency's in-plant sampling
efforts often required the cooperation of plant personnel to modify existing
plumbing to accommodate sampling and flow measurement devices. The OCPSF
industry does not measure most in-plant sources of wastewater (the vast major-
ity of in-plant flows reported in the 1983 Section 308 survey were qualified
estimates). In addition, many of these in-plant controls are operated as
product recovery rather than wastewater treatment units. For example, many
existing in-plant controls such as steam stripping were originally installed
for product recovery purposes, but may be operated more efficiently or
upgraded for pollution control purposes. Also, some in-plant controls that
precede biological treatment protect the biota and otherwise ensure that the
biological system functions effectively and consistently. Sampling prior to
product recovery and prior to necessary in-plant control elements of biologi-
cal treatment would tend to overestimate typical raw waste concentrations.
For these reasons, the Agency believes that sampling of raw wastewater prior
to end-of-pipe treatment provides the most reasonable available basis for
assessing typical current OCPSF industry plant-level priority pollutant
concentrations.
• i
In reviewing Table VI-2, two pollutants (hexachlorocyclopentadiene and
N-nitrosodimethylamine) were not detected at any of the 186 OCPSF plants
sampled. An additional five pollutants (2-chloronaphthalene, 4-chlorophenyl
phenyl ether, 4-bromophenyl phenyl ether, methyl bromide, and N-nitrosodi
N-propylamine) were detected at only one OCPSF facility, three pollutants
(2-chloroethyl vinyl ether, acrolein, and bis(2-chloroethoxy)methane) were
VI-14
-------
detected at only two OCPSF facilities, one pollutant (benzidine) was detected
at only three OCPSF facilities, two pollutants (parachlorometa cresol and
1,2,-diphenylhydrazine) were detected at only four OCPSF facilities, and one
pollutant (N-nitrosodiphenylamine) was detected at only five OCPSF facilities.
These pollutants (with the exception of acrolein) were not detected in«any of
the samples from the quantitative ;minimum/maximum data set and were found at
this limited number of plants out of a total plant population of 186 facil-
ities. In addition, one pollutant (butyl benzyl phthalate)., which was found
at a higher percentage of OCPSF facilities was never detected in the quanti-
tative minimum/maximum data set.
Based on the limited number of plants at which these pollutants occur,
the fact that all but one of these pollutants were never quantitatively
identified and that the qualitative data from the two screening studies tend
to exhibit false ;positive values,'the Agency believes that these 15 organic
toxic pollutants described above and an additional 7 priority toxic metals
(discussed later in this section) and listed in Table VI-3 should be excluded
as follows: two pollutants should be excluded from regulation under BAT on
the basis of Paragraph 8(a)(iii) of the Settlement Agreement because these
pollutants were "... not detected by Section 304(h) analytical methods or
other state-of-the-art methods ..." and the remaining 13 organic toxic
pollutants and 7 metals should be excluded from regulation under BAT on the
basis of Paragraph 8(a)(iii) of the Settlement Agreement because these pollu-
tants were "... detected in the effluent from a small number of sources and
are uniquely related to those sources ..."
Also, three toxic pollutants (benzo (ghi) perylene, dibenzo (a,,h)
anthracene, and ,indeno (l,2,3-c,d) pyrene) were detected in two or fewer OCPSF
plants in the qualitative frequency of occurrence data base, were reported at
less than 25 ppb in the quantitative minimum/maximum concentration data base
and are part of the polynuclear aromatic (PNA) pollutant class, which gener-
ally occur together and for which 11 of 14 pollutants in the class are being
regulated under BAT. Based on these factors, the Agency has decided to ex-
clude these three toxic pollutants (also presented in Table VI-3) from regula-
tion under BAT on the basis of Paragraph 8(a)(iii) of the Settlement Agreement
because these pollutants were "...effectively, controlled by the technologies
upon which are based other effluent limitations guidelines and standards..."
' VI-15
-------
TABLE VI-3.
TWO TOXIC POLLUTANTS EXCLUDED FROM REGULATION FOR BAT
SUBCATEGORIES ONE AND TWO UNDER PARAGRAPH 8(a)(iii) OF THE
cr,^TJE^xuENT AGREEMENT BECAUSE THEY WERE "... NOT DETECTED BY
SECTION 304(h) ANALYTICAL METHODS OR OTHER STATE-OF-THE-ART METHODS
Hexachlorocyclopentadiene
N-Ni trosodimethylamine
TWENTY TOXIC POLLUTANTS EXCLUDED FROM REGULATION FOR BAT
„ SUBCATEGORIES ONE AND TWO m»ER PARAGRAPH 8(a)(iii) BECAUSE THEY
WERE "... DETECTED IN THE EFFLUENT FROM A SMALL NUMBER OF SOURCES AND
ARE UNIQUELY RELATED TO THOSE SOURCES ..."
Acrolein
2-Chloronaph thalene
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
Methyl Bromide
N-Ni trosodi-n-propylamine
2-Chloroethyl vinyl ether
Bis (2-chloroethoxy) ether
Benzidine
Parachlorometa Cresol
1,2-Diphenylhydrazine
N-Nitrosodiphenylamine
Butyl Benzyl Phthalate
Arsenic
Beryllium
Cadmium
Mercury
Selenium
Silver
Thallium
THREE TOXIC POLLUTANTS EXCLUDED FROM REGULATION FOR BAT
SUBCATEGORIES ONE AND TWO UNDER PARAGRAPH 8(a)(iii)
OF THE SETTLEMENT AGREEMENT BECAUSE THEY WERE
"...EFFECTIVELY CONTROLLED BY TECHNOLOGIES UPON WHICH ARE BASED
OTHER EFFLUENT LIMITATIONS, GUIDELINES, AND STANDARDS "
Benzo(ghi)Perylene
Dibenzo(a,h)Anthracene
Indeno(l,2,3-c,d) Pyrene
VI-16
-------
TABLE VI-3. (Continued)
EIGHT TOXIC POLLUTANTS EXCLUDED FROM REGULATION FOR BAT SUBCATEGORIES
ONE AND TWO UNDER PARAGRAPH 8(a)(iii) OF THE SETTLEMENT AGREEMENT
BECAUSE THEY WERE "...PRESENT ONLY IN TRACE AMOUNTS AND NEITHER
CAUSING NOR LIKELY TO CAUSE TOXIC EFFECTS..."
1,1,2,2-Tetrachlproethane
Bis(2-Chloroethyl)Ether
Chlorqdibromomethane
Isopho.rone
Pentachlorophenol
Di-n-Octyl Phthalate
Bromoform
Di chlorobromome thane
VI-17
-------
In addition to the 18 organic toxic pollutants (listed in Table VI-3)
that vere excluded for the reasons mentioned above, another eight organic
toxic pollutants (also shown in Table VI-3) are being excluded after examining
the Agency's toxic pollutant wastevater loadings estimates for direct and
indirect dischargers. Table VI-4 presents a summary of the toxic pollutant
wastewater loadings estimates by direct and indirect dischargers for these
eight toxic pollutants. Three toxic pollutants (bis(2-chloroethyl)ether,
bromoform, and dichlorobromomethane), while being detected at a relatively
high number of plants (8, 10, and 11 plants, respectively) in the qualitative
frequency of occurrence data base, were'estimated never to occur in the Agen-
cy's current toxic pollutant wastewater loadings calculations for direct and
indirect dischargers. These wastewater loadings were calculated on a plant-
by-plant basis utilizing each plant's current product/process mix as reported
in the 1983 Section 308 Questionnaire Survey and are considered an up-to-date
quantitative measurement of a toxic pollutant's industry-wide presence. Five
toxic pollutants (1,1,2,2-tetrachloroethane, chlorodibromomethane, isophorone
pentachlorophenol, and di-n-octyl phthalate) had relatively low current waste-
water loadings predicted using this up-to-date product/process mix information
with average current discharge loadings ranging from 0.007 to 0.237 Ibs/day.
Based on these factors, the Agency has decided to exclude these eight toxic
pollutants from regulation under BAT on the basis of paragraph 8(a)(iii) of
the Settlement Agreement because these pollutants were "...present only in
trace amounts and neither causing nor likely to cause toxic effects,.."
In addition to the 26 organic toxic pollutants excluded from regulation
above under BAT, the Agency had intended to reserve 10 pollutants (in addition
to dioxin) in the subcategory with end-of-pipe biological treatment (BAT Sub-
category One) and 14 toxic pollutants (in addition to dioxin) from regulation
in the subcategory without end-of-pipe biological treatment (BAT Subcategory
Two) because the in-plant control performance data for carbon adsorption and
chemical precipitation that had been collected via the sampling programs,
Section 308 Questionnaire Survey or technology transfer orior to promulgation
was not adequate in the Agency's judgment to support regulation of these
pollutants. However, based on an analysis of pollutant loading estimates for
these pollutants at direct discharge OCPSF facilities, seven pollutants (all
metals) did not appear in the wastewater loadings estimates revised by EPA
VI-18
-------
TABLE VI-4.
WASTEWATER LQADDKS FOR EIGHT TOXK POLLUTANTS
BEING CONSIDERED FOR PARAGRAPH EIGHT EXCLUSION
Direct
Indirect
Total
Pollutant Pollutant
Number Name
Current Current Average
No. of Daily No. of Daily Plant Daily ,
Plants Loading* Plants Loading* Loading
(Ibs/day) (Ibs/day) (Ibs/day/plant)
15 1,1,2,2-Tetrachloroethane 30 5.358 —
18 Bis(2-chloroethyl) ether — — —
47 Bromoform — —
48 Dichlorobromomethane — — , —
51 Chlorodibromotnethane 64 0.436 —
54 Isophorone 34 8.055 —
64 Pentachlorophenpl — 13
69 Di-N-Octyl Phthalate 45 2.681 —
— 0.179 >
•. — ' — •
— —
— . — -
— 0.007
— 0.237
0.318 0.024
— 0.060
loadings are calculated from annual loadings assuming discharge 365 days per
year.
VI-19
-------
after conducting a thorough analysis, which was discussed in Section V, to
validate the Verification Master Process File to include only the metals
concentration data for product/processes that are confirmed process sources.
This validation found a limited number of plants that utilized these seven
metals in their processes. Therefore, based on the analysis and validation
activities, the Agency has decided to exclude an additional seven pollutants
(arsenic, beryllium, cadmium, mercury, selenium, silver, and thallium) because
they were "...detected in the effluent from a small number of sources and are
uniquely related to those sources ..." (see Table VI-3).
This leaves a total of four pollutants that the Agency intends to reserve
from regulation under BAT Subcategory One and eight pollutants that the Agency
intends to reserve from regulation under BAT Subcategory Two. Tables VI-5 and
VI-6 present the pollutants which have been reserved from regulation under the
two BAT subcategories. Based on these decisions, the Agency will regulate a
total of 63 toxic pollutants in BAT Subcategory One and 59 toxic pollutants in
BAT Subcategory Two.
b* Selection Criteria for PSES and PSNS Toxic Pollutants
As discussed in Section XI, Pretreatment Standards for Existing Sources
(PSES) and Pretreatment Standards for New Sources (PSNS), indirect dischargers
need only address those pollutants that upset, inhibit, pass-through, or
contaminate sludges at Publicly Owned Treatment Works (POTWs). The Agency has
assumed for purposes of this analysis and based upon the available data, that
within each Subcategory, the raw wastewaters at indirect discharging OCPSF
plants are not significantly different from those at direct discharging OCPSF
plants. In selecting pollutants regulated for pretreatment standards, the
toxic pollutants that the Agency considered as candidates for BAT regulation
in both subcategories were evaluated with respect to the pass-through cri-
teria. In the final regulation, the Agency addressed the 59 pollutants regu-
lated for BAT Subcategory Two because it was determined that the end-of-pipe
biological treatment used for BAT Subcategory One was not the appropriate PSES
technology. The Agency evaluated data on removal of these pollutants at POTWs
and at industrial treatment plants meeting BAT, to establish which pollutants
pass through POTWs. Pollutants found not to pass through were eliminated from
VI-20
-------
TABLE VI-5.
FOUR TOXIC POLLUTANTS RESERVED FROM REGULATION
UNDER BAT FOR SUBCATEGORY ONE
2,4,6-Trichlorophenol
3,3'-Dichlorobenzidine
Antimony
Dioxin (TCDD)
TABLE VI-6.
EIGHT TOXIC POLLUTANTS RESERVED FROM
REGULATION UNDER BAT FOR SUBCATEGORY TWO
2,4,6 - Trichlorophenol
2 - Chlorophenol
3,3' - Dichlorobenzidine
2,4 - Dichlorophenol
2,4 - Dinitrotoluene
2,6 - Dinitrotoluene
Antimony
Dioxin (TCDD)
VI-21
-------
consideration for regulation under PSES and PSNS. The remaining pollutants
were then selected as candidates for regulation. The procedure used for the
pass-through analysis is described below. Results of this procedure for both
BAT subcategories are shown in Tables VI-7 and VI-8.
c. PSES Pass-Through Analysis
Prior to establishing pretreatment standards for a toxic pollutant, the
Agency must determine whether the pollutant passes through POTWs or interferes
with POTW operation or sludge disposal practices. In determining whether
pollutants pass through a POTW, the Agency generally compares the percentage
of a pollutant removed by POTWs with the percent of a pollutant removed by
direct discharging industrial facilities applying BAT. Under this approach, a
pollutant is deemed to pass through the POTW when the average percentage
removed by POTWs nationwide is less than the percentage removed by direct
discharging industrial facilities applying BAT for that pollutant.
This approach to the definition of pass-through satisfies two competing
objectives set by Congress: that standards for indirect dischargers be analo-
gous to standards for direct dischargers, and that the treatment capability
and performance of POTWs be recognized and taken into account in regulating
the discharge of pollutants from indirect dischargers. Rather than compare
the mass or concentration of pollutants discharged by POTWs with the mass or
concentration of pollutants discharged by direct dischargers, EPA compares the
percentage of the pollutants removed with POTWs' removals. EPA takes this
approach because a comparison of mass or concentration of pollutants in a POTW
effluent with pollutants in a direct discharger's effluent would not take into
account the mass of pollutants discharged to the POTW from nonindustrial
sources nor the dilution of the pollutants in the POTW effluent to lower con-
centrations from the addition of large amounts of nonindustrial wastewater.
Presented below are brief descriptions of PSES pass-through analysis
methodologies utilized for proposal and the two Federal Register NOAs as well
as a more detailed discussion of the methodology and results of the PSES pass-
through analysis used for the final regulation.
VI-22
-------
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VI-25
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VI-26
-------
March 1983 Proposal Approach
In the March 21, 1983 proposal (48 FR 11828), the Agency modified the
general pass-through analysis methodology discussed above. Cognizant of the
analytical variability typical of organic toxic pollutants in POTW and OCPSF
wastewater, EPA proposed to find that pass-through occurs only if the percent-
age removed of a certain pollutant by direct dischargers applying BAT is at
least 5 percent greater than the percent removed by well-operated POTWs
("Five percent differential"). The methodology used for calculating POTW and
industrial percent removals was as follows: 1) for an individual POTW or
OCPSF plant, the influent and effluent data around the particular treatment
system were paired on a daily basis; 2) daily percent removals were calculated
for each pollutant; 3) an average daily "percent removal was calculated for
each pollutant by OCPSF plant or POTW; and 4) for each pollutant, a median
percent removal was calculated using average daily percent removals for each
OCPSF plant or POTW. Also, the Agency assumed pass-through for all pollutants
that did not have POTW percent removals, but were regulated under BAT and had
OCPSF industry percent removal data.
Using the above methodology, EPA determined that six pollutants in the
Plastics-Only subeategory and 29 pollutants in the Not Plastics-Only subcate-
gory should be controlled under PSES and PSNS on the basis of pass-through.
(These subcategories appeared in the proposal, but have not been retained in
the final regulation.)
July 1985 NOA Approach
In the July 17, 1985 Federal Register NOA, the Agency retained the same
methodology used for the March 1983 proposal, but introduced several different
approaches for public comment and included additional OCPSF sampling data
(i.e., the EPA 12-Plant Sampling Study) in the OCPSF percent removal calcula-
tions. These approaches included the use of either a 0 percent differential
or a 10 percent differential between POTW and OCPSF percent removals in deter-
mining pass-through and the possible finding of pass-through for selected
volatile pollutants that are air stripped in POTW collection and treatment
systems, regardless of whether they passed through using the traditional pass-
VI-27
-------
through analysis. A list of these volatile pollutants is presented in Table
VI-9. Section VIII discusses air emissions from wastewater treatment systems
and the derivation of this list.
Based on this methodology, the Agency proposed control of 48 toxic pol-
lutants under PSES and PSNS using the traditional pass-through methodology and
identifying pollutants of concern for which POTW percent removal data were not
available. The Agency also proposed to find pass-through for 12 toxic vola-
tile and seraivolatile pollutants on' the basis of volatilization.
December 1986 NOA Approach
After assessing the public comments on the July 17, 1985 NOA, a number of
different pass-through analysis methodology changes were examined, including:
1) the use of all published literature sources in determining a representative
POTW percent removal for all pollutants without full-scale POTW percent
removal data; 2) the continued finding of pass-through for pollutants volatil-
ized rather than treated by POTWs; 3) modifying the typical pass-through
analysis in order to not regulate certain acid and base/neutral pollutants
that were regulated based on pass-through analysis results, but might be shown
not to pass-through based on certain means of evaluating industry and POTW
removals for comparable ranges of influent pollutant concentrations; 4) chang-
ing the methodology for calculating the POTW and OCPSF percent removals; and
5) modifying the 5 percent differential rule between POTW and OCPSF percent
removals.
The first revision of the original POTW pass-through analysis incorpor-
ated literature, pilot- and bench-scale plant percent removal data for POTWs
for those toxic-pollutants that were not adequately covered by the 40 POTW
Study data base. In the previous pass-through analyses, toxic pollutants with
no full-scale POTW percent removal data were considered to pass through POTW
treatment systems, requiring them to be regulated under PSES. For those pol-
lutants without full-scale POTW removal data, the PSES cost estimates for the
December 1986 NOA were based on POTW percent removals from a number of sources
that were utilized to perform the revised pass-through analysis. These
sources included a report to Congress that presented the results of a study
VI-28
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TABLE $1-9.
VOLATILE AND SEMIVOLATILE TOXIC POLLUTANTS
TARGETED FOR CONTROL DUE TO AIR STRIPPING
(1) Acenaphthene*
(3) Acrylonitrile*
(4) Benzene
(6) Carbon Tetrachloride
(7) Chlorobenzene
(8) 1,2,4-Trichlorobenzene
(9) Hexachlorobenzene
(10) 1,2-Dichloroethane
(11) 1,1,1-Trichloroethane
(12) Hexachloroethane
(13) 1,1-Dichloroethane
(14) 1,1,2-Trichloroethane
(16) Chloroethane
(23) Chloroform
(25) 1,2-Dichlorobenzene
( 26 ) 1,3-Di chlorobenzene
(27) 1,4-Dichlorobenzene
(29) 1,1-Dichloroethylene
(30) 1,2-Trans-dichloroethylene
(32) 1,2-Dichloropropane
(33) 1,3-Dichloropropylene
(38) Ethylbenzene
(42) Bis (2-chloroisopropyl) Ether*
(44) Methylene Chloride
(45) Methyl Chloride
(48) Dichlorobromomethane
(52) Hexachlorobutadiene
(55) Naphthalene*
(85) Tetrachloroethylene
(86) Toluene
(87) Trichloroethylene
(88) Vinyl Chloride
*These pollutants were determined to be less susceptible to air stripping and
removed from the list of volatiles for which volatilization overrides the
percent removal pass-through analysis.
VI-29
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examining the discharge of listed hazardous wastes to POTtfs (the February 1986
Domestic Sewage Study), the General Pretreatment Regulations (40 CFR 128 and
403), and the best professional judgment estimates of EPA's Wastewater Engi-
neering Research Laboratory (EPA-WERL) and other Agency personnel based on
various pilot-plant studies performed by or for EPA-WERL.
The second revision involved the permanent incorporation of the finding
of pass-through for volatile pollutants that are air stripped rather than
treated in POTtfs (see Table V-9).
In addition to evaluating alternative data sources to replace missing
full-scale POTtf percent removals, the Agency also performed further analyses
using the 40 POTtf Study and the OCPSF data bases to evaluate treatability of
toxic pollutants as it relates to influent concentration levels. Specific-
ally, these data were first plotted to show a relationship between percent
removal and influent concentration and then a comparison of the POTW and OCPSF
plots were made. To facilitate the analysis, the toxic pollutants were
combined into groups that have previously been used in the calculation of
toxic pollutant variability factors (See Section VII). In general, few of the
groups had both adequate POTtf and OCPSF data to draw any firm conclusions.
Since POTtfs and OCPSF facilities do not have equivalent influent concentra-
tions for most pollutants (because of the dilution effects of domestic sewage
and other industry wastewaters on POTW influents), POTtf percent removals tend
to be based upon calculations using lower average influent concentration.
Thus, the percent removal results may be strongly influenced by the influent
concentration. Another factor influencing the percent removals is related to
effluent concentration. From the groups with adequate data, a definite asymp-
totic relationship was observed for certain groups, that generally occurs
because of the analytical minimum levels ("limits of detection") at the low
end of the concentration range. For many of the pollutant groups, this does
not indicate an inability to remove pollutants but the lack of quantification
below the analytical minimum level that limits the maximum percent removal
that can be calculated.
Based on these results, selected pollutants were identified for further
analysis from the following groups:
VI-30
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« Group 1 - Halogenated Methanes
• Group 2 - Chlorinated C2s
• Group 11 - Aromatics
• Group 12 - Polyaromatics (PNAs)
• Group 13 - Chloroaroraatics
« Group 16 - Phthalate Esters j
• Group 18 - Benzidienes
• Group 19 - Phenols.
Comparing POTW and OCPSF percent removals at individual influent ranges,
a detailed pass-through analysis was performed for each selected pollutant.
The results of this analysis were that seven pollutants (acenaphthene, ben-
zene, chloroform, phenol, anthracene, phenanthrene, and toluene) that had
previously been considered to require regulation based on pass-through analy-
sis results were now shown not to pass-through. However, since all but three
of these pollutants were contained in the list of volatile pollutants, only
phenol, anthracene, and phenanthrene were selected for consideration in this
alternative regulatory option as not passing through.
The fourth revision involved the evaluation of the methodology used to
calculate the POTW and OCPSF percent removals used in the PSES pass-through
analysis, which was revised to conform with other calculations being used for
limitations development and to avoid the use of daily influent/effluent pairs
in order to accommodate retention times in treatment systems larger than
24 hours. The new data editing methodology was as follows: 1) all influent
and effluent data around the biological treatment system were assembled;
2) average influent and effluent concentrations were calculated for each
pollutant; 3) an average percent removal was calculated for each pollutant
(instead of an average daily percent removal); and 4) for each pollutant, a
median percent removal was calculated using the average percent removals for
each OCPSF plant or POTW. Also, based on revised BAT industry data editing
techniques, industrial percent removal data were no longer available for six
toxic pollutants (1,1-dichlbroethane, bromoform, dichlorobromomethane, penta-
chlorophenol, cadmium, and silver). Therefore, these pollutants were elimi-
nated. Also, these revised BAT data editing techniques eliminated some indus-
trial data, thus changing (raising or lowering, depending on the pollutant)
the calculated industrial percent removals.
VI-31
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Finally, the Agency decided not to use a 5 or 10 percent differential and
concluded that the most reasonable approach is to accept the available data as
the best information on the relative percent removals of BAT and POTWs and to
perform BAT/POTW comparisons directly based on that data. EPA decided that
such an approach was unbiased in that it does not favor either the over-
statement or under-statement of pass-through for the pollutants.
Adopted Approach and Rationale
After reviewing public comments received on the December 1986 NOA pass-
through methodology revisions, the Agency again examined its procedures and
instituted a final set of changes. As stated previously, the Agency decided
not to use a 5 or 10 percent differential. In urging EPA to adopt a 5 or
10 percent differential, commenters stated that use of the differential would
address the problem of low POTW effluent concentrations that may mask the full
extent of POTW treatment. These commenters also supported the rationale that,
in addition to analytical variability, a differential was supported by the
fact that POTW influent concentrations are typically much lower than industry
treatment system influent concentrations, and many POTW effluent samples are
below detection, preventing a complete accounting of all pollutants removed by
the POTW.
The problem with using a differential is that it is uncertain whether the
POTWs are treating to levels substantially below detection or not, since the
data analyses results were from measurements only to the detection limits.
Thus, it is difficult to determine the extent to which POTW removals are
underestimated and the degree to which compensation is justified. (It should
be noted that the risk of underestimation exists also with respect to calcu-
lating BAT removals with data reflecting effluent levels below the detection
level.) Moreover, a 5 or 10 percent differential, unless restrictively
drafted, would often result in overcompensating for the uncertainty. It
should be noted that to allow even a few pollutants to go unregulated based on
the 5 percent differential could be significant in terms of the number of
pounds of unregulated toxic pollutants discharged. Finally, the potential
effect discussed by the commenters will be greatly mitigated by changes in the
data editing criteria, which are discussed below.
VI-32
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EPA has modified the criteria under which the full-scale POTW data for
conducting the pass-through comparison test were selected. In previous analy-
ses, EPA used data when influent concentrations exceeded 20 ppb. For pollu-
tants with low influent concentrations, i.e., not much higher than 20 ppb, the
effluent concentrations were consistently below the detection level and could
not be precisely quantified. The conservative technique of estimating the
effluent by rounding it up to the detection limit had the effect of understat-
ing the POTW's percent removal. In many cases, in fact, both POTW and BAT
treatment systems with relatively low influent concentrations yielded efflu-
ents below detection, and the resulting percent removals were not true mea-
sures of treatment effectiveness, but rather were primarily functions of the
influent concentrations. The percent removal comparison thus had the effect
of determining pass-through if and only if the POTW had a lower pollutant
influent concentration, rather than basing the determination on true treat-
ability criteria. A second concern with the 20 ug/1 criterion is its incon-
sistency with the criteria used to select industry data that EPA considers
generally acceptable for assessing treatability and calculating BAT effluent
limitations. One of EPA's criteria for using industry data to set effluent
limitations is that the influent data must exceed 10 times the pollutant's
minimum analytical threshold level for that plant. When an influent concen-
tration is below this level, effluent concentrations below the pollutant's
analytical minimum level often may be achieved using less than BAT level
treatment. The editing criterion ensures that effluent limitations generally
reflect the technical capability of BAT level treatment rather than low influ-
ent concentrations.
Consistent with the general BAT editing approach, EPA has used the "ten
times the minimum level" (i.e., 100 ppb for most pollutants) criterion for BAT
and POTW influents for purposes of selecting the data used to perform pass-
through comparisons for the final rule when available. When BAT or POTW
influents greater than "ten times the minimum level" were not available,
pass-through comparisons were made using the 20 ppb criterion for BAT and POTW
influents. For the final pass-through determination, 28 of the pollutants
were found to pass-through using data edited at 10 times the minimum level;
three pollutants demonstrated no pass-through at this level of editing.
VI-33
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EPA also retained the modified approach of calculating plants' percent
removals using average plant removals. Previously, for each plant, EPA had
averaged daily percent removals. This is technically inappropriate. First,
many OCPSF treatment systems have retention times exceeding one day's time.
Thus, it is improper to compare influent and effluent samples taken on the
same day. Second, even if the retention time is shorter than a full day, any
sampled influent, after mixture and dispersal within the treatment system,
cannot be traced to a particular sample leaving the system. In fact, in the
typical biological treatment system, a portion of the biological solids are
recirculated within the system. Thus again, it is improper to compare any
influent and effluent samples as a pair. Third, due to the low concentrations
found in both OCPSF treatment and POTW biological systems (due to dilution by
other wastewaters), small daily changes in pollutant concentrations yield a
misleading picture of variability in the daily efficiency of these systems.
Therefore, EPA has modified its approach to calculate a plant's percent
removal by averaging all influent samples, averaging all effluent samples, and
calculating percent removals using these averages.
The Agency also decided to retain the use of qualified bench- or pilot-
scale POTW percent removal data in the absence of sufficient full-scale POTW
removal data on specific pollutants to perform the removal comparison. A
summary of the bench/pilot-scale data results and the studies that are the
sources of these data is presented in Table VI-10. Despite the fact that EPA
sampled 50 POTWs in addition to conducting many OCPSF sampling efforts, there
are 12 pollutants regulated at BAT for which EPA lacks sufficient full-scale
POTW data to perform this analysis. In the 1983 proposal, EPA adopted the
approach of assuming pass-through in the absence of data to the contrary.
Some industrial commenters objected to this approach arguing that Section
307(b) authorizes EPA to promulgate pretreatment standards only for pollutants
that pass-through or interfere with the POTW, and that EPA is thus required
to affirmatively find pass-through or interference as a precondition to pro-
mulgating pretreatment standards. Environmental groups argued to the contrary
saying that EPA has an obligation to require pretreatment if there may be
pass-through or interference and that in the absence of adequate data, the
possibility of pass-through must be assumed. In subsequent notices, EPA
requested comment on an alternative approach of using qualitative data to
determine POTW removal rates in the absence of full-scale quantitative data
VI-34
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and to use that data for the comparative analysis. EPA made the alternative
approach data available for comment. After considering public comments on
this approach and on the data to be used, EPA has decided in the final rule to
use certain pilot- and bench-scale .data when adequate full-scale POTW data are
lacking. These alternative data were used for seven pollutants, and four of
these pollutants were found to pass-through.
EPA disagrees with the comment that it must assume pass-through in the
absence of quantitative data to the contrary. Section 307(b) of the Act
requires EPA to promulgate pretreatment standards "for those pollutants which
are determined not to be susceptible to'treatment by (the POTW) or which would
interfere with the operation of such treatment works." Thus, at least one
reasonable interpretation of the statute is that EPA must make a determination
of pass-through or interference prior to promulgating pretreatment standards,
rather than assume pass-through. In any event, the statute does not prohibit
the use of bench- or pilot-scale data when they are the best available data.
Certainly, EPA has a preference for full-scale POTW data and has expended
considerable resources to obtain such data for the OCPSF rulemaking. However,
to address remaining full-scale POTW data gaps, EPA believes that it is
appropriate to use the besjt alternative information available. Some industry
commenters objected that the alternative data are of lesser quality than the
full-scale POTW data and have a larger range of potential error. EPA acknow-
ledges that this may be the case with estimates not based on pilot- or bench-
scale studies. However, EPA believes that the pilot- or bench-scale data used
for the seven pollutants for which, pass-through is evaluated for this rule-
making are of sufficient technical quality to use in the comparative analysis
and may thus be used in the absence of adequate full-scale POTW data. Fur-
ther, EPA does not agree that the use of a 5 or 10 percent differential to
compare BAT and POTW removal efficiencies is compelled when using alternative
data. As discussed previously, any error in the data, whether full-scale or
not, can affect results in either direction.
Finally, the Agency has retained the override of the pass-through analy-
sis results for three volatile pollutants where the overall percent removal
includes in substantial part the emission of these pollutants to air rather
VI-37
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than actual treatment. As discussed in Section VIII, EPA has decided to
regard these three pollutants (hexachlorobenzene, hexachloroethane, and hexa-
chlorobutadiene), as passing through the POTW due to volatilization and thus
warranting promulgation of pretreatment standards.
Table VI-11 presents the results of the final PSES pass-through analysis
for the 59 toxic pollutants being regulated under the non-end of pipe biologi-
cal subcategory (BAT Subcategory TWo). Based on the results of this final
analysis, 47 toxic pollutants have been determined to pass-through POWs and
thus require regulation under PSES and PSNS. Summaries of the results for
pollutants not regulated are presented in Tables VI-12 through VI-16.
The Agency performed an additional PSES pass-through analysis, which used
the same methodology as discussed above except that OCPSF percent removals
were calculated using the end-of-pipe biological (BAT Subcategory One) per-
formance data base. The results of this alternative pass-through analysis
(presented in Table VI-8) show that a total of 47 toxic pollutants pass
through. Because the final PSES are based upon physical-chemical treatment
(including in-plant biological treatment for certain organip pollutants),
unlike the proposed PSES which were based upon biological treatment, the final
pass-through analysis calculated OCPSF percent removals based upon the per-
formance required by BAT Subcategory Two (noh-end-of-pipe biological treat-
ment). This ensured that PSES would be required only if the PSES limits
(which are based upon BAT Subcategory Two limits) would result in percent
removals exceeding those achieved by POTWs. These results are reflected in
Table VI-7. The six toxic pollutants, listed in Table VI-12, could not be
evaluated by the PSES pass-through analysis because estimated volatilization
rates are low and POTtf percent removal data could not be obtained. An analy-
sis was conducted of pollutant loading estimates for these pollutants at indi-
rect, full response OCPSF facilities revealed that the toxic pollutants 2,4-
dinitrophenol, benzo(k) fluoranthene, and acenapthylene would be treated by an
appropriate in-plant control installed on the same waste streams for other
toxic pollutants that have been determined to pass through. Table VI-14 pre-
sents the results of this analysis. Therefore, the Agency has decided to
exclude three of these toxic pollutants from regulation under PSES and PSNS on
the basis of Paragraph 8(a) (iii)(4) of the Settlement Agreement since they
VI-38
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TABLE VI-11.
FORTY-SEVEN TOXIC POLLUTANTS DETERMINED TO INTERFERE WITH,.INHIBIT,,
OR PASS-THROUGH POTWS, AND REGULATED UNDER PSES AND PSNS
BASED ON TABLE VII-7
Pollutant Name
Reason For Regulation
Acenaphthene
Benzene
Carbon Tetrachloride
Chlorobenzene
1,2,4-Trichlorobenzene
Hexachlorobenzene
1,2-Dichloroethane
1,1,1-Trichloroethane
Hexachloroe thane
1,1-Dichloroethane
1,1,2-Trichloroethane
Chloroethane
Chloroform
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethylene
1,2-Trans-Dichloroethylene
1,2-Dichloropropane
1,3-Dichloropropylene
2,4-Dimethylphenol
Ethylbenzene
Fluoranthene
Methylene Chloride
Methyl Chloride
Hexachlorobu tadi ene
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
4,6-Dini tro-0-Cresol
Phenol
Bis(2-Ethylhexyl)Phthalate
Di-N-Butyl Phthalate
Diethy1 Phthalate
Dimethyl Phthalate
Anthracene
Fluorene
Phenanthrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride
Cyanide
Lead
Zinc
Pass-through Comparison; @ 10 x MDL
Pass-through Comparison @ 10 x MDL
Pass-through Comparison @ 10 x MDL
Pass-through Comparison @ 10 ,x MDL
Pass-through Comparison @ 10 x MDL
Volatilization "
Pass-through Comparison @ 10 x MDL
Pass-through Comparison @ 10 x MDL
Volatilization
Pass-through Comparison @ 20 ppb
Pass-through Comparison i@ 20 ppb
Pass-through Comparison @ 20 ppb
Pass-through Comparison @ 10 x MDL
Pass-through Comparison @ 10 x MDL
Pass-through Comparison @ 20 ppb
Pass-through Comparison @ 20 ppb
Pass-through Comparison @ 10 x MDL
Pass-through Comparison
-------
TABLE VI-12.
SIX TOXIC POLLUTANTS DETERMINED NOT TO INTERFERE
WITH, INHIBIT, OR PASS-THROUGH POWs, AND EXCLUDED
FROM REGULATION UNDER PSES AND PSNS
Benzo(A)Anthracene
Benzo(A)Pyrene
Chrysene
Chromium
Copper
Nickel
TABLE VI-13.
SIX TOXIC POLLUTANTS THAT DO NOT
VOLATILIZE EXTENSIVELY AND DO NOT HAVE
POTtf PERCENT REMOVAL DATA
Acrylonitrile
Bis(2-Chloroisopropyl)Ether
2,4-Dini trophenol
3,4-Benzofluoranthene
Benzo(K)Fluoran thene
Acenaph thylene
VI-40
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'TABLE VI-14.
RESULTS OF PSES ANALYSIS TO DETERMINE IF TOXIC
POLLUTANT REMOVALS WERE "... SUFFICIENTLY
CONTROLLED BY, EXISTING TECHNOLOGIES
Percent of. plants at .which the pollu-
tant is adequately treated or costed
Pollutant
Number
3
42
59
74
75
77
Pollutant due td presence
Name treatable
Acrylonitrile
Bis(2-Chloroisopropyl)Ether
2 , 4-Dini trophenol
3 , 4-Benzof luoranthene
Benzo ( k) Fluoran thene
Acenaphthylene
of: .another similarly
toxic pollutant
39%
50%
;ioo%
*
100%
87%
* Analysis could not be performed
VI-41
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TABLE VI-15.
THREE TOXIC POLLUTANTS EXCLUDED FROM PSES AND PSNS
REGULATION UNDER PARAGRAPH 8(a)(iii) OF THE
SETTLEMENT AGREEMENT BECAUSE THEY WERE "... SUFFICIENTLY
CONTROLLED BY EXISTING TECHNOLOGIES ..."
2,4-Dini trophenol
Benzo(K)Fluoranthene
Acenaph thylene
TABLE VI-16.
THREE POLLUTANTS RESERVED FROM REGULATION UNDER
PSES AND PSNS DUE TO LACK OF POTW
PERCENT REMOVAL DATA
Acrylonitrile
Bis(2-Chloroisopropyl)Ether
3,4-Benzofluoran theme
VI-42
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will be "...sufficiently controlled by existing technologies." The Agency has
also decided to reserve the three remaining toxic pollutants from regulation
under PSES and PSNS in addition to the seven pollutants shown in Table VI-6
(see Tables VI-15 and VI-16, respectively).
VI-43
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SECTION VI
REFERENCES
6-1 U!CTKT™ ^HVPCR' STANDARD METHODS FOR EXAMINATION OF WATER AND
WASTEWATER, 4TH EDITION, WASHINGTON, DC, APHA, 19076, P. 549
6-2 Ibid., p. 94
6-3 Ibid., p. 516, 517, 519, 521.
6-4 Ibid., p. 554
6-5 Ibid., p. 534
VI-44
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VII. CONTROL AND TREATMENT TECHNOLOGIES
A. INTRODUCTION
This section identifies and describes the principal Best Management
Practices (BMPs) and in-plant and end-of-pipe wastewater control and treatment
technologies currently used or available for the reduction and removal of
conventional, nonconventional, and priority pollutants discharged by the OCPSF
industry. Many OCPSF plants have implemented programs that combine elements
of BMPs, in-plant wastewater treatment, and end-of-pipe wastewater treatment
to minimize pollutant discharges from their facilities. Due to the diversity
of the OCPSF industry, the configuration of these controls and technologies
differs widely from plant to plant.
BMPs are in-plant source controls and general operation and maintenance
(O&M) practices that prevent or minimize the potential for the release of
toxic pollutants or hazardous substances to surface waters or POTWs (7-1).
The following pages describe these in-plant source controls (i.e., process
modifications; instrumentation; solvent recovery; and water reuse, recycle,
and recovery) and O&M practices that are employed, or could potentially be
employed, at OCPSF plants.
Physical/chemical in-plant treatment technologies are used selectively in
the OCPSF industry on certain process wastewaters to recover products or
process solvents, to reduce loadings that may impair the operation of a
biological treatment system, or to remove certain pollutants that are not
sufficiently removed by biological treatment systems. The in-plant treatment
technologies currently used or available to the OCPSF industry and available
performance data for these technologies are described and presented in Part C
of this section.
End-of-pipe treatment systems in the OCPSF industry employ physical,
biological, and physical/chemical treatment, and often consist of a
combination of primary (neutralization and settling), secondary (biological
high rate aeration and clarification), polishing, and/or tertiary (ponds,
filtration, or activated carbon adsorption) unit operations. The end-of-pipe
VII-1
-------
treatment technologies currently used or available to the OCPSF industry and
available performance data for these technologies are described and presented
in Part D of this section.
The performance of selected BPT and BAT total treatment systems,
including nonbiological treatment systems, are presented in Part E of this
section. tfastewater discharge or disposal methods (other than direct to
surface waters and indirect through POTWs) used by OCPSF plants, frequently
called zero or alternate discharge methods, are presented in Part F. Part G
presents treatment and disposal options for the sludges resulting from certain
wastevater treatment operations. Finally, Part H presents the procedures used
to develop the effluent limitations guidelines and standards for the OCPSF
industry.
The Environmental Protection Agency (EPA) developed three technology
options for promulgating BPT. BPT Option I consists of biological treatment,
which usually involves either activated sludge or aerated lagoons, followed by
clarification (and preceded by appropriate process controls and in-plant
treatment to ensure that the biological system may be operated optimally).
Many of the direct discharge facilities have installed this level of treat-
ment. BPT Option II is based on Option I with the addition of a polishing
pond to follow biological treatment. BPT Option III is based on multimedia
filtration as an alternative basis (in lieu of BPT Option II polishing ponds)
for additional total suspended solids (TSS) control after biological
treatment.
EPA has selected BPT Option I-biological treatment with secondary
clarification-as the technology basis for BPT limitations controlling BOD
and TSS for the OCPSF industry. This option has been previously described'by
EPA as "biological treatment." However, a properly designed biological treat-
ment system includes "secondary clarification" which usually consists of a
clarifier following the biological treatment step of activated sludge, aerated
lagoons, etc. The rationale for the selection of BPT Option I as the basis
for the final BPT effluent limitations is discussed in detail in Section IX.
VII-2
-------
EPA developed three final options for BAT effluent limitations. BAT
Option I would establish concentration-based BAT effluent limitations for
priority pollutants based on using BPT-level biological treatment for tHe
end-of-pipe biological treatment subcategory. Since some plants do not have
sufficient BOD5 in their wastewater to support (or require) biological
treatment, there is a non-end-of-pipe biological treatment subcategory. The
plants in this subcategory db not use end-of-pipe biological treatment.; their
BAT Option I treatment involves in-plant controls that consist of physical/
chemical treatment and in-plant biological treatment to achieve toxic
pollutant limitations, with end-of-pipe TSS control if necessary.
' BAT Option II would establish concentration-based BAT effluent
limitations based on the performance of the end-of-pipe treatment component
(biological treatment for the end-of-pipe biological treatment subcategory and
physical/chemical for the non-end-of-pipe biological treatment subcategory),
plus in-plant control technologies that remove priority pollutants prior to
discharge to the end-of-pipe treatment system. The in-plant technologies
include steam stripping to remove selected volatile and semivolatile (as
defined by the analytical methods) priority pollutants, activated carbon for
various base/neutral priority pollutants, chemical precipitation for metals,
alkaline chlorination for cyanide, and in-plant biological treatment for
removal of selected priority pollutants, including several polynuclear
aromatics (PNA), several phthalate esters, and phenol.
BAT Option III adds activated carbon to the end-of-pipe treatment to
follow biological treatment or physical/chemical treatment in addition to the
BAT Option II level of in-plant controls.
The Agency has selected Option II as the basis for BAT limits for both
subcategories. The rationale for the selection of BAT Option II as the basis
for the final BAT effluent limitations for both subcategories is discussed in
detail in Section X.
The Agency is promulgating PSES for all indirect dischargers*based on the
same technology basis as the BAT non-end-of-pipe biological treatment
subcategory. The rationale for selection of this technology basis for the
final PSES effluent limitations guidelines is discussed in Section XII.
VII-3
-------
A review of waste management practices and well-designed and -operated
wastewater treatment system configurations currently in use by the OCPSF
manufacturing facilities, reveals that there are numerous approaches for
implementing effective pollutant control practices. Since the Agency does not
specify what technology must be used to achieve the promulgated numerical
effluent limitations and standards, the following portions of this section
describe the unit operations and treatment practices that provide the bases of
the selected technical options, as well as alternative unit operations and
treatment systems that may also be utilized to achieve pollutant reduction
goals. As noted in Section VIII, the Agency's methodology for estimating the
engineering costs of compliance for individual facilities is based on costing
one or more of the treatment unit operations included in the selected
technology option, depending on the difference between current effluent pollu-
tant concentrations and target effluent concentrations that would be required
to achieve compliance with regulatory requirements.
B. BEST MANAGEMENT PRACTICES
Best Management Practices (BMPs) consist of a variety of procedures to
prevent or minimize the potential for the release of toxic pollutants or
hazardous substances to surface waters or POTWs (7-1). Specific practices
that limit the volume and/or contaminant concentration of polluted waste
streams, such as solvent recovery, water reuse, and various pretreatment
options, involve applying BMPs to facility design. O&M procedures such as
preventive'maintenance measures, monitoring of key parameters, and equipment
inspections that minimize the potential for unit process failures and
subsequent treatment plant upsets are also considered part of BMPs. The
following discussion is divided into two parts: in-plant source controls
(i.e., process modifications; instrumentation; solvent recovery; and water
reuse, recycle, and recovery) and general O&M practices. Several specific
examples of how wastewater treatment plants improved their performances
through minor modifications are also included.
!• In-Plant Source Controls
In-plant source controls include processes or operations that reduce
pollutant discharges within a plant. Some in-plant controls reduce or
VII-4
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eliminate waste streams, while others recover valuable manufacturing
by-products.
In-plant controls provide several advantages: income from the sale of
recovered material, reduction of end-of-pipe treatment costs, and removal of
pollutants that upset or inhibit end-of-pipe treatment processes (7-2).
While many newer chemical manufacturing plants were designed to reduce
water use and pollutant generation, improvements can often be made in older
plants to control pollution from their manufacturing activities. The major
in-plant source controls that are effective in reducing pollutant loads in the
OCPSF industry are described below.
a. Process Modifications
Most manufacturers within the OCPSF industry use one or more toxic prior-
ity pollutants in various stages of production. In some cases, problems per-
taining to a difficult-to-treat pollutant can be solved by finding less toxic
or easier to treat substitutes for that compound. In many cases, a suitable
substitute can be found at no or minor additional cost.
In some situations, plants can improve their effluent quality by shifting
from batch processes to continuous operations, thus eliminating the waste-
waters generated between batches by cleanup with solvents or caustic. Such
modifications increase production yields and reduce wastewater generation.
Effluent quality at a facility can sometimes be improved by taking advan-
tage of'unused equipment or by simply reconfiguring existing equipment and
structures. Some plant-specific approaches are as follows:
• Floor drains likely to receive spills can be designed to flow into a
collection sump instead of directly into an industrial sewer system.
This allows concentrated wastes to be recovered, treated, or
equalized prior to being pumped or transferred to the wastewater
treatment plant.
• Highly acidic or basic waste streams can be neutralized or diluted by
being mixed together upstream of the wastewater treatment plant.
VII-5
-------
Unused tanks at a facility can be fitted to intercept shock loadings
and allow concentrated pollutants to be gradually mixed in with
process wastewater at a high dilution rate. Excess tank or lagoon
capacity can also be used to increase detention times and improve
equalization of wastewaters.
An abandoned steam stripper from a closed process line can be con-
Preheating or cooling waste streams designated for biological treat-
ment can also be a great asset as activated sludge systems generally
Two examples of process modifications from other industries may be appli-
cable to the OCPSF industry. The first involves biological degradation.
Although anaerobic digestion is common at the mesophilic temperature of 30°C,
use of thermophilic digestion has gained popularity of late because of poten-
tially increased solids destruction. New York City, in its wastewater treat-
ment operation, conducted thermophilic digestion directly after mesophilic
digestion. This has led to increased sludge solids destruction, and when
employed with increased decanting, has led to a reduction in sludge volume and
more efficient operation (7-3).
Another modification involves the use of a step-feed operating program.
Having a variety of feed points enables the protection of effluent quality
while steps are taken to correct malfunctions in the biological treatment
process.
b. Instrumentation
Process upsets resulting in the discharge of products, raw materials, or
by-products are important sources of pollution in the OCPSF industry. Well-
designed monitoring, sensor, and alarm systems can enable compensatory action
to be taken before an unstable condition results in such process upsets.
Some common parameters that can be monitored and controlled using various
types of sensors and equipment include flow (both open channel and closed
conduit), pump speed, valve position, and tank level. Analytical measurements
such as PH, dissolved oxygen (DO), suspended solids, and chemical residuals
VII-6
-------
can also be monitored and regulated using feedback control equipment. At many
facilities, the overpressurization of reaction kettles, the bursting of
rupture-disks, and the discharge of chemical pollutants could be controlled
with a proper early warning system.
c. Solvent Recovery
The recovery of waste solvents has become a common practice among plants
using solvents in their manufacturing processes. In some cases> solvents can
be recovered in a sufficiently pure form to be used in the same manner as new
solvents. Solvents of lesser quality may still be usable in other areas of
manufacturing or be sold to another facility for use in applications not
requiring a high level of purity. Also, many private companies exist that
collect and reclaim spent solvents which are then sold back to the same or
other OCPSF facilities.
Solvents that cannot be recovered or reused can be destroyed through
incineration. Incineration may also be the best disposal method for used
solvents that cannot be economically recovered and for wastes such as bottoms
from solvent recovery units.
Solvent recovery, off-site reclaiming, reuse, and incineration are
methods of removing solvents from waste streams before they arrive at an end-
of-pipe treatment system or a POTW. Therefore, they contribute to protecting
biological treatment units from toxic shocks which could cause poor effluent
quality. In addition, as the cost for disposal of hazardous liquid waste
increases, solvent recovery becomes more economical.
d. Water Reuse, Recycle, and Recovery
Water conservation through reuse, recycle, and recovery can result in
more efficient manufacturing operations and a significant reduction in indus-
trial effluent requiring treatment. Recycling cooling water through the use
of cooling towers is a common industrial practice that dramatically decreases
total discharge volume. While noncontact cooling water may require little or
no treatment prior to recycling (other than reducing the water temperature in
cooling towers and adding corrosion inhibitors), treatment of the wastewater
VII-7
-------
prior to reuse is usually necessary to ensure a return stream of sufficient
quality for use in the process. In some cases, the treatment required is
simple, and facilities may already exist on-site (e.g., sedimentation).
fiy reducing the volume of wastewater discharged, recycling often allows
the use of abatement practices that are uneconomical on the full waste stream.
Further, by allowing concentrations to increase, the opportunities for recov-
ery of waste components to offset treatment cost (or even achieve profitabil-
ity) are substantially improved. In addition, pretreatment costs of process
water (and in some cases, reagent use) may be reduced. For example, removal
efficiencies for metals in chemical precipitation units are increased at
higher raw waste concentrations and proper chemical coagulant dosage. More
economical recovery of solvents is obtained from a properly designed steam
stripper at elevated solvent feed levels. Recycling also enables many plants
to achieve zero discharge, eliminating the need for ultimate disposal or
surface discharge.
Recycling systems can achieve significant pollutant load reductions or
zero discharge at relatively low cost. The systems are easily controlled by
simple instrumentation, and relatively little operator attention is required.
The most important design-parameter is the recycle rate (rate of return) to
the process stream or blowdown rate from closed loop recycle systems to avoid
build-up of dissolved solids.
Recycling limitations include the potential for plugging and scaling of
the process lines and excessive heat build-up in the recycled water which may
require cooling prior to reuse. Chemical aids are often used in the recycle
loops to inhibit scaling or corrosion.
Other approaches to reducing industrial discharge volumes include equip-
ment modifications and separation of stormwater and process wastewater. The
use of barometric condensers can result in significant water contamination,
depending upon the nature of the materials entering the discharge water
streams. As an alternative, several plants use surface condensers to reduce
hydraulic or organic loads. Water-sealed vacuum pumps can also create water
pollution problems. These problems can be minimized by using a water recircu-
lation system to reduce the amount of water being discharged.
VII-8
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Separation of stormwater and process wastewater enables each waste stream
to receive only the treatment required, and prevents problems caused by large
volumes of stormwater being contaminated by process wastewater, which sub-
sequently requires specialized treatment. If stormwater contains polluted
runoff from contaminated areas of a site, it may be possible to collect the
stormwater in retention basins and then gradually blend it in with process
wastewater in an equalization basin at the beginning of the wastewater treat-
ment cycle.
2. Operation and Maintenance (O&M) Practices
Many O&M practices minimize the potential for unit process failures and
subsequent treatment plant upsets. Inspections of those aspects of site
operation that have the highest potential for uncontrolled chemical releases
should be conducted by qualified maintenance or environmental engineering
staff members. Construction records should be reviewed to assure that under-
ground tanks and pipes have coatings or cathodic protection to inhibit
corrosion. Storage tanks and pipelines should be regularly inspected for
leaks, corrosion, deterioration of foundation or supports, pitting, cracks,
deformation, or any other abnormalities. Seams, rivets, nozzle connections,
valve function and position, and any associated ancillary equipment should.
also be inspected regularly to check for deterioration as well as potential
leaks from human error (e.g., valve not closed, loose pipe connections).
Training is important to assure that an operator reacts properly to upset
conditions. Treatment plant personnel should receive on-the-job and classroom
training covering the fundamental theories of wastewater treatment, specific
information about the equipment in use at that facility, the nature of
manufacturing processes and potential for upset, and prearranged procedures
for responding to upset conditions. Plants with operational flexibility may
be able to compensate to some degree for sudden changes in weather conditions
or inflow volume and quality by adjusting factors such as hydraulic retention
times and clarifier overflow rates through altering recycling rates, putting
backup units on-line, or directing excess wastewater to a holding basin until
flow rates return to normal. In addition, manufacturing personnel upstream of
a treatment plant should be trained in the proper disposal of waste chemicals
VII-9
-------
and the restrictions associated with disposal of wastes in industrial sewers
or storm drains.
Facilities handling a wide range of chemicals should be particularly
sensitive to potential problems arising from incompatible materials mixing in
tanks or pipelines. Monitoring storm sewers and industrial sewers on a
regular basis for toxic and hazardous pollutants is useful in identifying
potential misuse of sewers or evidence of infiltration of industrial wastes.
This type of internal housekeeping helps to reduce the potential for uncon-
trolled releases from a facility or shock loadings to an on-site treatment
plant.
At some facilities, waste treatment operations can be improved by
bringing in private contractors to handle some or all facets of operations.
Contractors experienced in treatment plant operations may have greater avail-
able technical resources to draw from than typical plant personnel in the
event of an operational problem. For example, a company specializing in
sludge handling may be able to improve that aspect of treatment plant
operations with a higher level of expertise and a lower cost than plant
personnel. In addition, a contractor operating several treatment plants may
be able to reduce costs for all facilities through bulk purchasing of
chemicals and pooling parts inventories.
If properly applied, certain O&M practices can compensate for cold
weather temperatures. Plants operating in cold weather conditions must
recognize that unnecessary storage of wastewater prior to treatment may reduce
the temperature of the biotreatment system. Cold weather operation may
require insulation of treatment units, covering of open tanks, and/or tracing
of chemical feed lines. Maintenance of higher mixed liquor suspended solids
(MLSS) concentrations and a reduced food-to-microorganism (F/M) ratio may be
necessary. Plant-specific techniques are presented in the summer/winter
discussion in the secondary treatment technology section.
VII-10
-------
C. IN-PLANT TREATMENT TECHNOLOGIES
1. Introduction
In-plant treatment is directed toward removing certain pollutants from
segregated product/process waste streams before these waste streams are com-
bined with the plant's remaining wastewaters. In-plant technologies, usually
designed to treat toxic or priority pollutants, could often be used for
end-of-pipe treatment of the plant's combined waste streams. Using these
technologies on segregated internal waste streams is usually more cost-
effective, since treatment of low volume, concentrated, and homogenous waste
streams generated by specific product/processes is more efficient.
In-plant treatment is frequently employed to protect the plant's end-
of-pipe treatment by removing the following types of pollutants (7-2):
• Pollutants toxic or inhibitory to biological treatment systems
• Biologically refractive pollutants
• High concentrations of specific pollutants
• Pollutants that may offer an economic recovery potential (e.g., sol-
vent recovery)
• Pollutants that are hazardous if combined with other chemicals down-
stream
• Pollutants generated in small volumes in remote areas of the plant
• Corrosive pollutants that are difficult to transport.
>• Many technologies have proven effective in removing specific pollutants
from the wastewaters produced by OCPSF plants. The selection of a specific
in-plant treatment scheme depends on the nature of the pollutant to be
removed, and on engineering and cost considerations.
The frequency of in-plant treatment technologies in the OCPSF industry is
presented in Table VII-1. This information was compiled from the 546 OCPSF
manufacturers that responded to all three parts of the Section 308 Question-
naire and the 394 Part A plants that responded to only Part A of the Section
308 Questionnaire. OCPSF manufacturers are defined as "full-response" if
VII-11
-------
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over 50 percent of their total plant production includes OCPSF products; if
they treat their OCPSF was testers in a separate treatment system; or if only
one treatment system is employed, the non-OCPSF wastewaters contribute less
than 25 percent of the total process flow. Part A plants are those that meet
the definition of being zero dischargers or do not meet the full-response
requirements stated above as direct or indirect dischargers. The 1983 Section
308 Questionnaire requested information on the plant's general profile
(Part I); detailed production information (Part II); and wastewater treatment
technology, disposal techniques, and analytical data summaries (Part III).
In-plant controls frequently used by OCPSF plants for the treatment of
individual waste streams include steam stripping (82 plants), distillation
(72), filtration (54), chemical precipitation (50), solvent extraction (29),
and carbon adsorption (18).
This section presents a general description and performance data for
selected in-plant treatment processes that are currently used or that may be
applicable to treat wastewaters from the OCPSF industry. General descriptions
of the treatment technologies are based largely upon material found in the EPA,
Treatability Manual, most recently revised in February 1983 (EPA-600/2-82-
OOla). Performance data specific to various technologies are derived from
four sources. The first source is OCPSF data compiled from responses to the
1983 OCPSF Section 308 Questionnaire, responses to the Supplemental Question-
naire sent to 84 facilities, and data collected by EPA in several sampling
studies previously detailed in Section V. The second source is data obtained
from other point source categories found in EPA technical development
documents and the Treatability Manual. The third source is data submitted as
part of public comments, on the proposal and NOAs. Technical literature serves
as the final source of performance data.
2. Chemical Oxidation (Cyanide Destruction)
Oxidation is a chemical reaction process in which one or more electrons
are transferred from the chemical being oxidized to.the chemical initiating
the transfer (the oxidizing agent). The primary function performed by oxida-
tion is detoxification. For instance, oxidants are used to convert cyanide to
VII-13
-------
the less toxic cyanate or completely to carbon dioxide and nitrogen. Oxida-
tion has also been used for the removal of phenol and organic residues in
wastewaters and potable water. Oxidation can also be used to assure complete
precipitation, as in the oxidation of iron from the ferrous (Fe*2) to the
ferric (Fe+3) form where the more oxidized material has a lower solubility
under the reaction conditions. Cyanide destruction (the oxidation of cyanide
to carbon dioxide and nitrogen) is a form of chemical oxidation and will be
used to illustrate the oxidation process, which is discussed in detail below.
Cyanide Destruction. Chlorine in elemental or hypochlorite salt form is
a strong oxidizing agent in aqueous solution, and is used in industrial waste
treatment facilities primarily to oxidize cyanide. Chemical oxidation equip-
ment often consists of an equalization tank followed by two reaction tanks,
although the reaction can be carried out in a single tank. The cyanide alka-
line chlorination process uses chlorine and a caustic to oxidize cyanides to
cyanates and ultimately to carbon dioxide and nitrogen. The oxidation
reaction between chlorine and cyanide is believed to proceed in two steps, as
follows :
(1) CN" + .01, « CNC1 + Cl
(2) CNC1 + 20H~
CNO"
H20
The cyanates can be further decomposed into nitrogen and carbon dioxide by
excess chlorination:
(3) 2CNO" + 40H~ + 3C1,
ecr
2C0
N
2H20
According to the Section 308 Questionnaire data base, 30 OCPSF plants use
chemical oxidation as an in-plant treatment technology; of these, 11 plants
use chemical oxidation for cyanide destruction. Performance data for chemical
oxidation are not available for the OCPSF industry. However, data for cyanide
destruction from the metal finishing industry are available, and can be
applied to the OCPSF industry as discussed in detail later in this section and
in Tables VII-2 and VII-3.
VII-14
-------
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VII-15
-------
TABLE VII-3.
PERFORMANCE DATA FOR TOTAL CYANIDE OXIDATION USING CHLORINATION
Plant ID
Adjusted Average Total CN
Effluent Concentration (mg/1)
12065
21051
38051
06075
36623
19050
20079
05021
20078
20080
15070
33073
09026
31021
33024
0.14
0.0
0.0
0.039
0.103
0.031
17.54
0.035
0.083
0.949
0.323
0.707
0.119
0.708
0.204
Source: Development Document for Effluent Limitations Guidelines
New Source Performance Standards for the Metal Finishing
Point Source Category, June 1983.
VII-16
-------
As shown in Table VII-2, removal efficiency for plant #30022 using ozone
as an oxidant varies between 87 and 96 percent. The oxidation of cyanide
using ozone results in high capital and energy costs, and its efficiency is
limited when treating wastewaters containing more than one pollutant. Cyanide
can also be destroyed using hydrogen peroxide, but this results in high energy
costs because the wastewater must be heated prior to treatment. Furthermore,
peroxide only partially oxidizes cyanide to cyanate, and the addition of a
formaldehyde catalyst results in a higher strength (BOD5 level) wastewater.
Results of cyanide oxidation using chlorination from a number of metal
finishing plants can be seen in Table VII-3. Average effluent cyanide
concentrations range from 0.0 (plant #2.1051) to 17.54 mg/1 (plant #20079).
EPA indicated in its December 8, 1986, Notice that it was considering
using the performance data for cyanide destruction from the metal finishing
industry to develop cyanide limitations and standards. These data are based
on alkaline chlorination (a type of chemical oxidation). Public comments on
this notice suggested that EPA should transfer cyanide destruction performance
data from the pharmaceutical manufacturing industry rather than from the metal
finishing industry because of the similarity in wasfew'ater characteristics
shared by the OCPSF and pharmaceutical categories. EPA has evaluated the
pharmaceutical cyanide destruction performance data and has rejected transfer
of these.data for use in the development of OCPSF cyanide limitations because
the cyanide(destruction performance data from the pharmaceutical industry are
from a cyanide hydrolysis system that utilizes high temperatures and pressures
to hydrolyze free cyanide; this particular type of cyanide destruction tech-
nology has not yet been demonstrated to be effective on OCPSF cyanide-bearing
wastewater. EPA believes that the cyanide destruction by alkaline chlor-
ination data from the metal finishing industry are more appropriate for
transfer to the OCPSF industry since this technology is used on cyanide waste
streams in the OCPSF industry.
Another significant issue raised concerning the use of alkaline
chlorination technology in the OCPSF industry was the contention that while
this technology may effectively reduce concentrations of free cyanide in OCPSF
wastewaters, it cannot reduce concentrations of metal-complexed cyanides.
VII-17
-------
Industry comraenters have stated that the limitations and standards should be
for amenable cyanide only. EPA has evaluated the expected amount of cyanide
complexing resulting from the presence of certain transition metals (i.e.,
nickel, copper, silver, and cobalt in OCPSF cyanide-bearing waste streams),
and has concluded that only cyanide complexed by copper, silver, or nickel
could present a problem for treatment by alkaline chlorination. However,
silver is found at such low levels in the process wastewater of so few
product/processes that cyanide complexing would not present a problem, and
only a limited number of product/process waste streams would contain combina-
tions of either copper and cyanide (four sources), or nickel and cyanide (two
sources). For these six product/process sources, a potential for cyanide
complexing is present. However, no data have been submitted to demonstrate
that the actual levels of complexing interfere with the ability of the plant
to meet the total cyanide limitations. Thus, EPA believes that limitations and
standards controlling total cyanide are appropriate for all dischargers
subject to this regulation. A discussion identifying the sources of cyanide
and the product/processes with a potential for complex formation with nickel
and copper are contained in Section V of this document.
3. Chemical Precipitation
Chemical precipitation is a principal technology used to remove metals
from OCPSF wastewaters. Most metals are relatively insoluble as hydroxides,
sulfides, or carbonates, and can be precipitated in one of these forms. The
sludge formed is then separated from solution by physical means such as sedi-
mentation or filtration. Hydroxide precipitation is the conventional method
of removing metals from wastewater. Most commonly, caustic soda (NaOH) or
lime (Ca(OH)2) is added to the wastewater to adjust the pH to the point where
metal hydroxides exhibit minimum solubilities and are thus precipitated.
Sulfide precipitation has also been demonstrated to be an alternative to
hydroxide precipitation for removing metals from certain wastewaters.
Sulfide, in the form of hydrogen sulfide, sodium sulfide, or ferrous sulfide,
is added to the wastewater to precipitate metal ions as insoluble metal
sulfides. Carbonate precipitation, while not used as frequently as hydroxide
VII-18
-------
or sulfide precipitation, is another method of removing metals from waste-
water. A carbonate reagent such as calcium carbonate is added to the waste-
water to precipitate metal carbonates. The solubility of metal hydroxides and
sulfides as a function of pH is shown in Figure VII-1. The solubility of most
metal carbonates is between hydroxide and sulfide solubilities.
Chemical precipitation has proven to be an effective technique for
removing many industrial wastewater pollutants. It operates at ambient
conditions and is well suited to automatic control. Hydroxide precipitation
has been used to remove metal ions such as antimony, arsenic, chromium,
copper, lead, mercury, nickel, and zinc; Sulfide precipitation has mainly
been used to remove mercury, lead, and silver from wastewater, with less
frequent use to remove other metal ions. Carbonate precipitation has been
used to remove antimony and lead from wastewater. To achieve maximum
pollutant removals, chemical precipitation should be 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
stirring to promote particle growth by various coagulation mechanisms
(flocculation); apd 4) clarification (or sedimentation or filtration) to
remove the flocculated solid particles.
The use of chemical precipitation technology as well as the availability
of performance data may be limited for several reasons. First, treatable raw
waste concentrations of product/process sources of priority pollutant metals
are not prevalent throughout the industry. Furthermore, plants that generate
process sources of metals and plants that utilize in-plant chemical precipi-
tation unit operations also tend to rely on co-dilution of metal-bearing
wastestreams by non-metal-bearing process wastewater as well as incidental
metal removals in end-of-pipe treatment systems. Fifty OCPSF plants in the
Section 308 Questionnaire data base report using chemical precipitation as an
in-plant treatment technology; however, very few facilities reported in-plant
chemical precipitation performance data.
Second, sulfide precipitation technology may generate toxic hydrogen
sulfide and may result in discharges of wastewaters containing residual levels
of sulfide. The generation of toxic hydrogen sulfide can be controlled by
VII-19
-------
ci
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1
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102..
10° -•
10-2 . .
Pb (CH)2
Cr (OH)3
Zn (CH)2
2 34 5 6 7 8 9 10 11 12 13 14
Figure VII-1: Solubility of Metal Hydroxides and Sulfides
as a Function of pH
Source: Treatability Manual. 1981.
VII 20
-------
maintaining the pH of the solution between 8 and 9.5. The discharge of waste-
waters containing sulfide can be controlled by carefully monitoring the amount
of sulfide added.
Third, in some instances, chemical precipitation may be limited by inter-
ference of chelating agents and complexed metal ions. Because of the varying
stabilities,of metal complexes and the wide variety of organic ligands in
OCPSF wastewaters, each plant with highly stable complexes has adapted or
should adapt its treatment system to control the concentrations of the metals
present in its process wastewater. Thus, control options for complexed
metals, and the degree to which control is necessary or cost-effective, are
unique to individual plants.
Several of the strategies employed by the OCPSF industry for treating
complexed metals in process wastewater are as follows:
• Destabilize the complex by chemically reducing the metal's valence to
zero. The released non-rionic metal is insoluble and can be captured
via agglomeration with other solids that are being separated from the
wastewater. Reductive destabilization is also effected by electro-
plating, in which case the metal is captured on the cathode.
• Destabilize the complex by degrading the organic ligand. The released
metal is then captured a's an insoluble salt by subsequent addition of
a reagent (e.g., lime, caustic, or sodium sulfide). In special cases,
ion exchange could be used to capture the metal ion.
• Capture the metal directly from the complex through the addition of a
reagent (e.g., sodium sulfide to a copper complex) that forms an
exceedingly insoluble salt of the metal.
• Concentrate the wastewater (e.g., in an evaporator) beyond the typi-
cally limited solubility of the metal-dye complex, so that it and
other solids separate as a sludge.
• Use carbon adsorption technology to capture the complexed metal from
the wastewater.via the organic ligand, which will adsorb on the carbon
as if it were not complexed.
Specific examples of the abovementioned precipitation technologies are
detailed below:
• Plant 1647. Complexed copper (cuprous, +2) in a dyestuff process
wastewater could not be precipitated effectively in a plant's combined
VII-21
-------
wastewater by lime addition. The segregated wastewater from the
dyestuff process was pretreated with sodium borohydride. Although
relatively expensive, the pretreatment destabilized the complex by
reducing the metal ion to copper (0), which was no longer amenable to
complexation by the organic ligand. Since copper (0) is insoluble,
the plant was then able to effectively remove the metal from the
combined wastewater via agglomeration with other solids precipitated
by the lime addition.
• Plant 1593. Copper (+2) and trivalent chromium (+3) are complexed
with organic ligands in metallized dyes manufactured at the plant.
The product is captured as a presscake on a plate-and-frame filter.
The filtrate, together with wastewater from floor drains and other
processes, is segregated into dilute and concentrated wastewater.
Concentrated wastewater is concentrated still further in an
evaporator, where most of the complexed metals separate as a residue
which is sent to a surface impoundment. Condensed overhead from the
evaporator and the dilute wastewater from a surge lagoon (flow
equalization), neither of which now contains concentrations of
complexed metals above their toxic thresholds, are combined as
influent to a powdered activated carbon (PAC) biological treatment
system.
Prior to segregating the dilute and concentrated wastewaters, the
combined process wastewater flow had to be pretreated with activated
carbon columns to protect the biota from the toxic effects of metals
released after complexing organic ligands had been biodegraded. Since
most of the combined flow was dilute wastewater that did not contain
complexed metals at toxic levels, the treatment system was modified to
segregate the concentrated wastewater for pretreatment to eliminate
the carbon column. Substantial operating cost savings were achieved
by these modifications.
• Plant 1572. Cadmium (+2) chelated with an unknown organic ligand is
used as a catalyst in a reactor. Reactor washout is treated with
sodium hydrosulfide to form a cadmium sulfide precipitate directly
from the complexed cadmium. The solids are captured by centri-
fugation, and the centrifugate is passed - through a rapid sand filter
to capture any fines. The solids from the centrifuge are saved and
are1 available to the plant as a cadmium reclaiming option with the
catalyst supplier.
• Plant 1769. Two organometallic products, tetraethyl lead (TEL) and
tetramethyl lead (TML), are produced at this plant. Although the
chemical bonding in organometallies differs from the metallized dye
complexes discussed previously, the treatment technology is the same
in principle. After adjusting the wastewater to a pH of 8 to 10 with
dilute sulfurie acid, sodium borohydride is added to reduce the ethyl
groups to ethane by hydride transfer. The released lead (+4) then
reacts with water to precipitate lead dioxide, which is captured in a
clarifier. The lead dioxide is recycled to refiners, which regenerate
the lead for sale to the market.
VII-22
-------
• Plant 2447. This plant manufactures oil-soluble dialkyl dithio-
carbamates and water-soluble dithiocarbamates of antimony, cadmium,
nickel, lead, and zinc. The metals in this plant's wasteyater are not
present as stable complexes but as salts of organic acids. This
example is given only to illustrate the wide variety of treatment
strategies used by the OCPSF industry to control metals.
Since metal dithiocarbamates have low solubility in water, a
precipitating reagent is readily available that is effective for con-
trolling these metals in the wastewater. The wastewater .is generated
in batches as washout from mixing tanks and reactors, and is collected
in a storage tank. Depending on the characteristics; of the batch, the
plant will either incinerate the waste, or route it to the wastewater
treatment system. Treatment consists of adding sodium dithiocarbamate
to precipitate the metals, and a coagulant (ferrous sulfate) to aid
settling of the solids in a clarifier.-
Wastewaters from the OCPSF industries generally do not contain high con-
centrations of metal ions. Rayon and certain acrylic fibers manufacturing,
however, generate elevated levels of zinc in wastewaters. Other industrial
processes may also have metals in their wastewaters due to use of metals in
chemical processing and as trace contaminants from raw materials and
equipment.
In the December 8, 1986, Federal Register Notice of Availability, the
Agency proposed to establish limitations for metals, from OCPSF plants with and
without end-of-pipe biological treatment in-place for BAT and PSES based upon
the use of hydroxide precipitation data from several metals industries. For
OCPSF waste streams with complexed metals, EPA proposed the use of sulfide
precipitation to achieve the same limitations. ,
Industry commenters strongly criticized several aspects of EPAfs proposed
approach. First, they argued that most priority pollutant metals are not
present in significant quantities in OCPSF wastewaters. They criticized^the
data base upon which EPA had estimated loadings for these pollutants. They
argued that these pollutants resulted not from OCPSF,processes, many,of which
do not use metals, but rather from non-process wastewaters (e.g., zinc and
chromium used as corrosion inhibitors and .often contained in cooling water
blowdown) or due to their presence in intake waters. The commenters concluded
that EPA should regulate only those metals present in OCPSF process waste-
waters as a result of the process use of the metals, applying the limits to
those wastewaters only.
VII-23
-------
To address these comments, EPA has conducted a detailed analysis of the
process wastewater sources of metals in the OCPSF industry. In response to
criticism that EPA has relied too heavily on limited Master Process File
metals data, EPA reviewed the responses to the 1983 Section 308 Questionnaire
to examine which metals were used as catalysts in particular OCPSF product/
processes, or were for other reasons likely to be present in the effluent from
these processes. When necessary, EPA contacted plant personnel for additional
information. The results of EPA's analysis, together with supporting documen-
tation, are set forth in Section V of this document.
Based upon this analysis, EPA has concluded that chromium, copper, lead,
nickel, and zinc are discharged from OCPSF process wastewaters at frequencies
and levels that warrant national control. However, EPA agrees that many OCPSF
wastewaters do not contain these pollutants or contain them only at insignif-
icant levels. At most plants, process wastewater flows containing these
metals constitute only a small percentage of the total plant OCPSF process
wastewater flow. As a result, end-of-pipe data obtained by EPA often do not
reflect treatment but rather reflect the dilution of metal-bearing process
wastewater by nonmetal-bearing wastewater. Thus, these data are unreliable
for the purpose of setting effluent limitations reflecting the use of best
available technology. Consistent with the comments, EPA has decided to focus
its regulations on metal-bearing process wastewaters only.
The concentration limitations are based upon the use of hydroxide
precipitation technology, which is the standard metals technology that forms
the basis for virtually all of EPA's BAT metals limitations for metal-bearing
wastewaters. Because very little OCPSF data on the effectiveness of hydroxide
precipitation technology are available, EPA has decided to transfer data for
this technology from the metal finishing industry point source category. A
comparison of the metals raw waste data from the metal finishing industry
data base with the validated product/process OCPSF raw waste data indicates
that the concentrations of the metals of concern are generally within an
acceptable range of concentrations found at metal finishing plants, except for
lead. Table VII-4 presents this comparison of available OCPSF and metal
finishing raw waste metals concentrations. With respect to lead, some OCPSF
plants' raw waste concentrations exceed the range of metal finishing raw waste
VII-24
-------
TABLE VII-4.
COMPARISON OF OGPSF AND METAL FINISHING
RAW WASTE METALS AND CYANIDE CONCENTRATIONS
Parameter
Range of OCPSF
Raw Waste Concen-
trations (mg/1)
Metal Finishing
Range of Effluent Long-
Metal Finishing Term Average
RaV Waste Concentration
Concentrations (mg/1) (mg/1)
Total Chromium (119)
Total Copper (120)
Total Cyanide (121)
Total Lead (122)
Total Nickel (124)
Total Zinc (L28)3
0.200-0.799
0.100-14.500
0.140- 5200.000
50.060-218.9002
0.270-4.000
0.400-20.000 ,
p.650-393.000
0.880-108.000
0.045-1680.000
0.052-9.701
!
1,070-167.000
0.630-175.000
0.572
0.815
0.180
0.197
0.942
0.549
1OCPSF raw, waste concentration data are limited to data from the Master
Process File for only product/processes that are validated process sources of
metals. ._
2OCPSF raw waste concentration data for lead are from two validated product/
processes that occur at the same plant. These values compare to the raw
waste concentrations for a lead battery manufacturing facility (identified as
plant #672 in the battery manufacturing industry study). The lead battery
plant raw waste concentration range was 2.21 to 295 mg/1 for lead; its
effluent long-term average concentration (after lime/hydroxide precipitation)
was 0.131 mg/1. The effluent data ranged from 0.01 to 0.81 mg/1.
3Excludes raw waste zinc concentrations from rayon and acrylic fiber
manufacturers. , ;,
VII-25
-------
concentrations. A comparison was made between the available OCPSF raw waste
concentrations and the data from the lead battery subcategory of the battery
.manufacturing point source category.. This comparison, as noted in Table
VII-4, shows that the battery manufacturing lead raw waste concentrations
encompass the range of OCPSF raw waste concentrations. Since hydroxide
precipitation achieves lead effluent concentrations at battery manufacturing
facilities that are as good as or better than those demonstrated by metal
finishing plants, EPA.believes that transfer of metal finishing lead data is
appropriate.
In addition, the metal finishing wastewater matrices contain organic
compounds that are used as cleaning solvents and plating bath additives. Some
of these compounds serve as complexing agents, and their presence is reflected
in the metal finishing industry data base. This data base contains hydroxide
precipitation performance results from plants with waste streams from certain
operations (electroless plating, immersion plating, or printed circuit board
manufacturing) containing complexing agents. This is important because the
data base reflects both treatment of waste streams containing complexing
agents and segregation of these waste streams prior to treatment.
The transfer of technology and limitations from the metal finishing
industry is further supported by the theory of precipitation. Given suffi-
cient retention time and the proper pH (which is frequently achieved by the
addition of a lime hydroxide), and barring the binding up of meta.ls in unusual
organic complexes (see discussion below), a metal exceeding its solubility
level in water can be removed to a particular concentration (i.e., the
effluent can be treated to a level approaching solubility for each constituent
metal). This is a physical/chemical phenomenon that is relatively independent
of the type of wastewater, barring the presence of complexing agents.
Some product/processes do have wastewaters that contain organic compounds
that bind up the metals in stable complexes that are not amenable to optimal
settling through the use of lime. EPA asked for comments in the December 1986
Notice on the use of sulfide precipitation in these situations. Industry
commenters argued that the effectiveness of this technology has not been
demonstrated for highly stable, metallo-organic chemicals. EPA agrees.
VII-26
-------
Strongly complexed priority pollutant metals are used or created, for
instance, in the manufacture of metal complexed dyestuffs (metallized dyes) or
metallized organic pigments. The most common priority pollutant metals found
in these products are trivalent chromium and copper. The degree of complexing
of these metals may vary among different product/processes. Consequently,
each plant may need to use a different set of unique technologies to remove
these metals. Thus, metals limits are not set by this regulation and must be
established by permit writers on a case-by-case basis for certain product/
processes containing complexed metals. These product/processes are listed in
Appendix B to the regulation and in Table X-5.
The list in Table X-5 has been compiled based upon the analysis
summarized in Section V of this document. EPA has concluded that all other
metal-bearing process wastewaters (whether listed in Table"X^5 or established
as metal-bearing by a permit writer) can be treated using hydroxide
precipitation to the levels set forth in the regulation.
As noted previously, since certain manufacturers of rayon and acrylic
fibers have significantly higher raw waste zinc concentrations than any other
OCPSF process wastewaters, the lime precipitation performance data received
from the subject facilities are only applicable to certain types of processes.
Table VII-5 presents a summary of zinc raw waste concentration data and lime
precipitation performance data from three rayon facilities, as well.as one
acrylic fibers plant that uses a zinc chloride/solvent process. Acrylic
fibers facilities using the zinc chloride/solvent process have been combined
with rayon facilities for the purpose of establishing BAT zinc limitations
because ,of their high raw waste zinc concentrations. By comparing the raw
waste concentrations and resulting effluent concentrations for zinc in Tables
VII-4 and VII-5, the fairly distinct differences in the two data sets are
obvious.
4. Chemical Reduction (Chromium Reduction)
Reduction is a chemical reaction process in which one or more electrons
are transferred to the chemical being reduced from the chemical initiating the
transfer (the reducing agent). The major application of chemical reduction
VII-27
-------
TABLE VII-5.
RAW WASTE AND TREATED EFFLUENT
ZINC CONCENTRATIONS FROM RAYON
AND ACRYLIC FIBERS MANUFACTURING
Plant No. Plant Type
Average
Influent Zinc No. of
Concentration .of Influent
(mg/1) Observations
Average
Effluent Zinc
Concentration
(mg/1)
No. of
Effluent
Observations
63 Rayon 143.471
387 Rayon 135.257
1012 Acrylic Fibers 287.686
1774 Rayon 15.570
365
354
363
346
3.847
2.198
2.291
2.409
253
258
358
346
VII-28
-------
involves the treatment of chromium wastes. To illustrate the reduction
process, the conversion of hexavalent chromium to trivalent chromium (chromium
reduction) is discussed below.
Chromium Reduction. A common chemical used in industrial plants for the
reduction of chromium is sulfur dioxide. Chemical reduction equipment usually
consists of one reaction tank where gaseous sulfur dioxide is mixed with the
wastewater. The reduction occurs when sulfurous acid, produced through the
reaction of sulfur dioxide and water, reacts with chromic acid as follows:
(1) 3S02 + 3H20 = 3H2S03
(2) 3H2S03 + 2H2Cr04 = Cr2(S04)3 + 5H20
According to the Section 308 Questionnaire data base, 11 OCPSF plants use
chromium reduction as an in-plant treatment technology.
5. Gas Stripping (Air and Steam)
Stripping, in general, refers to the removal of^relatively volatile com-
ponents from a wastewater by the passage of air, steam, or other gas through
the liquid. The stripped volatiles are usually processed further by recovery
or incineration.
Stripping processes differ according to the stripping medium chosen for
the treatment system. Air and steam are the most common media, with inert
gases also used. Air and steam stripping are described below.
Air Stripping. Air stripping is essentially a gas transfer process in
which a liquid containing dissolved gases is brought into contact with air and
an exchange of gases takes place between the air and the solution. In
general* the application of air stripping depends on the environmental impact
of the resulting air emissions. If sufficiently low concentrations are
involved, the gaseous compound can be emitted directly to the air. Otherwise,
air pollution control devices may be necessary.
'VII-29
-------
The exchange of gases takes place in the stripping tower. The tower
consists of a vertical shell filled with packing material to increase the
surfade area for gas-liquid contact, and fans to draw air through the tower.
The towers are of two basic types-countercurrent towers and crossflow towers.
In countercurrent towers, the entire airflow enters at the bottom of the
tower, while the water enters the top of the tower and falls to the bottom.
In crossflow towers, the air is pulled through the sides of the tower along
its entire height, while water flow proceeds down the tower.
The removal of pollutants by air stripping is adversely affected by low
temperatures, because the solubility of gases in water increases as
temperature decreases.
Steam stripping. Steam stripping is essentially a fractional
distillation of volatile components from a wastewater stream. The volatile
component may be a gas or an organic- compound that is soluble in the waste-
water stream. More recently, this unit operation has been applied to the
removal of water immiscible compounds (chlorinated hydrocarbons), which must
be reduced to trace levels because of their toxicity.
Steam stripping is usually conducted as a continuous operation in a
packed tower or conventional fractionating distillation column (bubble cap or
sieve tray) with more than one stage of vapor/liquid contact. The preheated
wastewater from the last exchanger enters near the top of the distillation
column and then flows by gravity countercurrent to superheated steam and
organic vapors (or gas) rising up from the bottom of the column. As the
wastewater passes down through the column, it contacts the vapors rising from
the bottom of the column. This contact progressively reduces the concen-
trations of volatile organic compounds or gases in the wastewater as it
approaches the bottom of the column. At the bottom of the column, the waste-
vater is heated by the incoming steam, which also reduces the concentrations
of volatile components to their final level. Much of the heat in the
wastewater discharged from the bottom of the column can then be recovered by
preheating the feed to the column.
VII-30
-------
Reflux (condensing a portion of the vapors from the top of the column and
returning it to the column) may be practiced if it is desired to alter the
composition of the vapor stream that is derived from the stripping column
(e.g., increase the concentration of the stripped material for recovery ,
purposes). There also may be advantages to introducing the feed to a tray
below the top tray when reflux is used. Introducing the feed at a lower tray
(while still using the same number of trays in the stripper) will have the
effect of either reducing steam requirements, as a result of the need for less
reflux, or yielding a vapor stream richer in the volatile components. The
combination of using reflux and introducing the feed at a lower tray will
increase the concentration of the volatile organic components in the overhead
(vapor phase) beyond that obtainable by reflux alone and increase the poten-
tial for recovery.
Stripping of the organic (volatiles) constituents of the wastewater
stream occurs because the organic volatiles tend to vaporize into the steam
until its concentration in the vapor and liquid phases (within the stripper)
are in equilibrium. The height of the column and the amount of packing
material and/or the number of metal trays along with steam pressure in the
column generally determine the amounts of volatiles that can be removed and
the effluent pollutant levels that can be attained by the stripper. After the
volatile pollutant is extracted from the wastewater into the superheated
steam, the steam is condensed to form two layers of generally immiscible
liquids—the aqueous and volatile layers. The aqueous layer is generally
recycled back to the steam stripper influent feed stream because it may still
contain low levels of the volatile. The volatile layer may be recycled to the
process, incinerated on-site, or contract hauled (for incineration,
reclaiming, or further treatment off-site) depending on the specific plant's
requirements.
Steam stripping is an energy-intensive technology in which heat energy
(boiler capacity) is required to both preheat the wastewater and to generate
the superheated steam needed to extract the volatiles from wastewater. In
addition, some waste streams may require pretreatment such as solids removal
(e.g., filtration) prior to stripping because accumulation of solids within
the column will prevent efficient contact between the steam and wastewater
VII-31
-------
phases. Periodic cleaning of the column and its packing materials or trays is
a necessary part of routine steam stripper maintenance to assure that low
effluent levels are consistently achieved.
Steam strippers are designed to remove individual volatile pollutants
based on a ratio (Henry's Lav Constant) of their aqueous solubility (tendency
to stay in solution) to vapor pressure (tendency to volatilize). The column
height and diameter, amount of packing or number of trays, the operating steam
pressure, and temperature of the heated feed (vastevater) are varied according
to the strippability (using Henry's Lav Constant) of the volatile pollutants
to be stripped. Volatiles vith lover Henry's Lav Constants require greater
column.height, more trays or packing material, greater steam pressure and
temperature, more frequent cleaning, and generally more careful operation than
do volatiles vith higher strippability (7-4). Although the degree to vhich a
compound is stripped can depend to some extent upon the vastevater matrix, the
basis for the design and operation of steam strippers is such that matrix
differences are taken into account for the volatile compounds the Agency has
evaluated.
Since Henry's Lav Constants vere such important design parameters, the
Agency initially proposed that, for consolidation purposes, toxic pollutants
could be grouped into three general ranges of Henry's Lav Constants termed
high, medium, and low; these groups are presented in Table VII-6. The pollu-
tants in the lov Henry's Lav Constant group vere determined to require
treatment other than steam stripping (i.e., carbon adsorption or in-plant
biological treatment). The remaining groups vere then used in the development
of^team stripping cost curves and in the transfer of steam stripping perfor-
mance data to toxic pollutants vithout performance data, depending on vhether
they fell vithin the high or medium grouping. For the purposes of this docu-
ment, these groupings are designated "strippability" groups.
According to the Section 308 Questionnaire data base, eight OCPSF plants
report using air stripping and 82 report using steam stripping as an in-plant
treatment technology. Steam stripping performance data collected during the
EPA 12-Plant Study or submitted by industry for selected volatile organic
compounds are presented in Table VII-7. The data indicate that high removal
VII-32
-------
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efficiencies (e.g., most plant-pollutant combinations are over 992) can be
achieved for these volatile organic compounds. It should also be recognized
.that most treatment systems consist of several unit processes and that addi-
tional removal of organic compounds will likely occur, especially in systems
with biological treatment units.
Nitrobenzene performance data .from two plants in the OCPSF industry that
employed steam stripping followed by activated carbon are presented in Table
VII-8. The data indicate that a high removal efficiency (e.g., approximately
99*) can be obtained for this semi-volatile organic compound by using these
two processes. However, the data shown in Table VII-9 also indicate that com-
petitive adsorption may be occurring among nitrobenzene, the dinitrotoluenes
(2,4- and 2,6-dinitrotoluene), and the nitrophenols (2- and 4-nitrophenol and
2,4-dinitrophenol) which seem to favor adsorption of nitrophenols over nitro-
benzene because of their more attractive chemical affinity to the carbon. The
nitrotoluene data are not available because matrix interferences prevented
quantitation with the analytical methods that had been used.
6. Solvent Extraction
Solvent extraction, also referred to as liquid-liquid extraction, involves
the separation of the constituents of a liquid solution by contact with
another immiscible liquid for which the impurities have a high affinity. The
separation can be based either on physical differences that affect differen-
tial solubility between solvents or on a definite chemical reaction.
The end result of solvent extraction is to separate the original solution
into two streams-a treated stream and a recovered solute stream (which may
contain small amounts of water and solvent). Solvent extraction may thus be
.considered a recovery process since the solute chemicals are generally
recovered for reuse, resale, or further treatment and disposal. A process for
extracting a solute from solution will typically include three basic steps:
1) the actual extraction, 2) solvent recovery from the treated stream, and
3) solute removal from the extracting solvent. The process may be operated
continuously.
VII-36
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Solvent extraction is presently applied in two main areas: 1) the
recovery of phenol frpm aqueous wastes, and 2) the recovery of halogenated
hydrocarbon solvents from organic solutions containing other water-soluble
components. ,
Although effective in recovering solvents and other organic compounds for
recycle and reuse, solvent extraction is not a widespread wastewater treatment
technology because effluent concentration levels that are acceptable for
recycle and reuse are generally too high for wastewater discharge. According
to the Section 308 Questionnaire data base, 29 OCPSF plants use solvent
extraction as an in-plant control or a raw material reclamation technology.
Performance data are summarized for petroleum refining and organic chemical
manufacturing plants in Volume III of the Treatability Manual. The data show
a wide variation in removal efficiency, varying from 12 to 99 percent. Most
volatile organics are removed with greater than 90 percent efficiency, but
base/neutrals show removal efficiencies generally below 75 percent.
7. Ion Exchange
Ion exchange involves the process of removing anions and cations from
wastewater. Wastewater is brought in contact with a resin that exchanges the
ions in the wastewater with a set of substitute ions. The process has four
operations carried out in a complete cycles service, backwash, regeneration,
and rinse. The wastewater is passed through the resin until the available ex-
change sites are filled and the contaminant appears in the effluent (break-
through point). When this point is reached, the service cycle is stopped and
the resin bed is. backwashed with water in a reverse direction to that of the
service cycle. Next, the exchanger is regenerated (converted to original
form) by contacting the resin with a sufficiently concentrated solution of the
substitute ion. Finally, the bed is rinsed to remove excess regeneration
solution prior to the next service step.
Ion exchange is used in several ways. In industrial wastewaters, ion
exchange may be used to remove ammonia, arsenic, chromium, and nickel. It is
commonly used to recover rinse water and process chemicals, or to reduce salt
concentrations in incoming water sources.
VIIv-39
-------
According to the Section 308 Questionnaire data base,' only seven OCPSF
plants use ion exchange as an in-plant treatment technology. Based on the
limited number of OCPSF plants employing ion exchange and the absence of OCPSF
ion exchange performance data, ion exchange was not considered as a BAT or
PSES -candidate technology. Performance data for ion exchange systems in the
metal finishing industry are presented in Table VII-10. Although removal
efficiencies are greater for the electroplating and printing circuit board
plants (e.g., 91 to greater than 99%) than for plant #11065 (e.g., zero
removal to greater than 99%), the influent pollutant concentrations are also
much greater.
8. Carbon Adsorption
Activated carbon adsorption is a proven technology primarily used for the
removal of organic chemical contaminants from individual process waste
streams. Carbon has a very large surface area per unit mass and removes
pollutants through adsorption and physical separation mechanisms. In addition
to removal of many organic chemicals, activated carbon achieves limited
removal of other pollutants such as BOD5 and metals. Carbon used in a fixed
column, as opposed to being directly applied in granular or powdered form to a
waste stream, may also act as a filtration unit.
Activated carbon can be used as an in-plant treatment technology in order
to protect downstream treatment units such as biological systems from high
concentrations of toxic pollutants that could adversely affect system
performance. In-plant activated carbon treatment also enables removal of
pollutants from low volume waste streams before the waste streams mix with and
contaminate much larger volumes of wastewater, which would be more difficult
and costly to treat.
According to the Section 308 Questionnaire data base, 18 OCPSF plants are
known to use activated carbon as an in-plant treatment technology. Although
performance data for a specific individual in-plant carbon adsorption unit
prior to biological treatment were not available, the Agency collected
performance data from a carbon adsorption unit following steam stripping at an
OCPSF facility for which the carbon adsorption unit treated a separate process
VII-40
-------
TABLE, yn-io.
TYPICAL ICN EXCHANGE PERFORMANCE DATA.
Electroplating Plant ^,
Parameter
Zinc (Zn)
Cadmium (Cd)+3
Chromium (Cr+ )
Chromium (Cr )
Copper (Cu)
Iron (Fe)
Nickel (Ni)
Silver (Ag)
Tin (Sn)
Cyanide (CM)
Manganese (Mn)
Aluminum (A3.)
Sulfate (S04)
Lead (Pb)
Gold (Au) .
Prior To
Purifi-
cation
14.8
5.7
3.1
7.1
4.5
7.4
6.2
1.5
.1.7
9.8
4.4
5.6
After
Purifi-
cation
0.40
0.00
0.01
0.01
0.09
0.01 ,
0.00
0.00
0.00
0.04
0.00
0.20 ..
Removal
Efficiency
.<*>'.
• 97
100
100
100
98
100
100
•100
100,
100
100
96
Printed Circuit Board Plant
Prior To
*' Purifi-
, cation
_
-
• -
43.0
1.60
9.10
. 1.10
3.40
—
210.00
" 1.70
2.30
After
Purifi-
cation
-
—
—
o.io
0.01
o!io
0.09 :
*•"
2.00
0.01
. 0.10
Removal
Efficiency
(%)
100
99 .
*1 /Vv
100
91
97
99
99
% .
Plant #11065, which was visited and sampled, employs an ion exchange unit to remove metals
from rinsewater. The results of the sampling are displayed below.
POLLUTANT CONCHM33ATION (mg/1)
"~ Plant #11065 ~^~~
Parameter
TSS
Cu
Ni
Cr, Total
Cd
Pb
Day.l
Input To
Ion Exchange
6.0
52.080
0.095
0.043
0.005
0.010
Day 2
Effluent From
Ion Exchange
.4.0
0.118
0.003
0.051.
0.005
0.011
Removal
Efficiency
(%)
33
'100 "
97
0
0
0
Input To
Ion Exchange
1.0
189.3
0.017
0.026
0.005
0.010
Effluent From
Ion Exchange
1.0 -
0.20
0.003
0.006
0.005
0.010
Removal
Efficiency
(%)
0
100
82
77
0
0
Sources Development Document for Effluent Limitations Guidelines New Source Performance
Standards for the Metal Finishing Point Source Category, June 1983.
1Concentrations in mg/1.
vn-4i
-------
waste stream prior to discharge. This unit was sampled during the EPA
12-Plant Study. This plant manufactures only interrelated products whose
similar waste streams are combined and sent to a physical/chemical treatment
system consisting of steam stripping followed by activated carbon. The toxic
pollutants associated with these waste streams are removed by either steam
stripping or activated carbon, or a combination of both.
The Agency has decided to use this available performance data from the
end-of-pipe carbon adsorption unit as the basis for establishing BAT limits
for four pollutants (2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, and
4,6-dinitro-o-cresol), and the combination of steam stripping and activated
carbon adsorption for nitrobenzene. Table VII-11 presents the performance
data for the carbon adsorption unit at this plant. These data show very good
removals (greater than 99%) for the carbon adsorption unit for 4,6-dinitro-
o-cresol, 2-nitrophenol, 4-nitrophenol, and 2,4-dinitrophenol. However, the
concentration data indicate that for 2,4-dinitrophenol and nitrobenzene the
carbon adsorption unit is experiencing competitive adsorption phenomena. As
shown in Table VII-9, this condition exists when a matrix contains adsorbable
compounds in solution that are being selectively adsorbed and desorbed.
9. Distillation
Distillation is a unit process usually employed to separate volatile
components of a waste stream or to purify liquid organic product streams. ' The
process involves boiling a liquid solution and collecting and condensing the
vapor, thus separating the components of the solution. The vapor is collected
in a vessel where it is condensed, resulting in a separation of materials in
the feed stream into two streams of different composition.
The distillation process is used to recover solvents and chemicals from
industrial wastes that otherwise would be destroyed by waste treatment.
Although effective in recovering solvents and other organic compounds for
recycle and reuse, distillation is not a widespread wastewater treatment tech-
nology because effluent levels that are acceptable for recycle and reuse are
generally too high for wastewater discharge. According to the Section 308
Questionnaire, 72 OCPSF plants use distillation as an in-plant control and/or
secondary product or raw material reclamation technology.
VII-42
-------
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No performance data are available for distillation as a wastewater
control technology.
10. Filtration
Filtration is a proven technology for achieving the removal of suspended
solids from wastewaters. The removal is accomplished by the passage of water
through a physically restrictive medium (e.g., sand, coal, garnet, or diato-
maceous earth) with resulting entrapment of suspended paniculate matter by a
complex process involving one or more removal mechanisms, such as straining,
sedimentation, interception, impaction, and adsorption. In-plant filtration
can serve to remove suspended solids and subsequently improve the performance
of downstream treatment units that may be adversely affected by larger parti-
cles in the waste stream. In addition, filtration units can serve to collect
solids with reclamation value from specific waste streams.
According to the Section 308 Questionnaire data base, 54 OCPSF plants use
filtration as an in-plant treatment technology. Performance data for filtra-
tion as an in-plant technology were not available in the OCPSF industry; how-
ever, performance data for hydroxide precipitation plus in-plant filtration
from the metal finishing point source category for TSS and selected metals are
presented in Table VII-12, along with the hydroxide precipitation performance
data from metal finishing for comparison purposes.
11. Reverse Osmosis
Reverse osmosis is a pressure-driven membrane process that separates a
wastewater stream into a purified "permeate" stream and a residual "concen-
trate" stream by selective permeation of water through a semipermeable
membrane. This occurs by developing a pressure gradient large enough to
overcome the osmotic pressure of the ions within the waste stream. This
process generates a permeate of relatively pure water, which can be recycled
or disposed, and a concentrate stream containing most of the pollutants
originally present, which can be treated further, reprocessed, or recycled.
Reverse osmosis systems generally require extensive pretreatment (pH
adjustment, filtration, chemical precipitation, activated carbon adsorption)
of the wastewater stream to prevent rapid fouling or deterioration of the
membrane surface.
VII-44
-------
TABLE VII-12.
PERFORMANCE DATA FROM HYDROXIDE PRECIPITATION AND
HYDROXIDE PRECIPITATION PLUS FILTRATION FOR
METAL FINISHING FACILITIES
Parameter
Hydroxide Precipitation
only
(mg/1)
Hydroxide Precipitation
Plus Filtration
(mg/1)
Total Suspended Solids
Chromium, Total
Copper
Lead
Nickel
Zinc
16.8
0.572
0.815
0.051
0.942
0.549
12.8
0.319
0.367
0.031
0.459
0.247
Source: Development Document for Effluent Limitations Guidelines New Source
Performance Standards ffcr the Metal Finishing Point Source Category,
June 1983.
VII-45
-------
Reverse osmosis has been used in industry for the recovery and recycle of
chemicals. Metals and other reusable materials can easily be separated from a
waste stream. Although reverse osmosis is slightly more effective than chemi-
cal precipitation for metals removal, it is very expensive and appropriate
only for low volume waste streams high in'dissolved solids.
12. Ultrafiltration
Ultrafiltration is a physical unit process, similar to reverse osmosis,
that is used to segregate dissolved or suspended solids from a liquid stream
through the use of semipermeable polymeric membranes. The membrane of an
ultrafilter forms a molecular screen that separates molecular particles based
on their differences in size, shape, and chemical structure. A hydrostatic
pressure is applied to the upstream side of a membrane unit, which acts as a
filter, passing small particles such as salts while blocking larger emulsified
and suspended matter. Ultrafiltration differs from reverse osmosis in the
size of contaminants passed. Ultrafiltration generally retains .participates
and materials with a molecular weight greater than 500, while reverse osmosis
membranes generally pass only materials with a molecular weight below 100.
Ultrafiltration has been used in oil/water separation and for the removal
of macromolecules such as proteins, enzymes, starches, and other organic
polymers. Ultrafiltration is presently not a widely used process but has
potential application to OCPSF wastewater treatment. Summary performance data
are available from EPA's Volume III Treatability Manual for the aluminum
forming, automobile and other laundries, rubber manufacturing, and timber
products processing industries and are presented in Table VII-13. The data
show a wide variation in removal efficiencies and effluent levels. An experi-
mental combined Ultrafiltration and carbon adsorption system does show
promise. This system consists of powdered activated carbon suspended in
wastewater. The mixture is then pumped through 20 ultrafilter modules
arranged in two parallel trains. Heavy metal removal data for this system are
presented in Table VII-13.
VII-46
-------
TABLE VII-13.
ULTRAFILTRATION PERFORMANCE DATA FOR METALS
IN LAUNDRY WASTEVATER-OPA LOCKA, FLORIDA
Parameter (mg/1)
Zinc
Copper
Lead
Chromium (total)
Cadmium
Raw
0.52
0.51
0.4
0.1
0.03
Supernatant
<0.20
0.14
0.1
<0.01
<0.02
Permeate
<0.20
0.06
0.01
' <0.01
<0.02
Source: Van Gils, G. and M. Pirbazari. August 1986. Development of *
Combined Ultrafiltration and Carbon Adsorption System for Industrial
Wastewater Reuse and Priority Pollutant Removal. Environmental
Progress 5(3):167-170.
VII-47
-------
13. Resin Adsorption
Resin adsorption is a process that may be used to extract and, in some
cases, recover dissolved organic solutes from aqueous wastes. Waste treatment
by resin adsorption involves two basic steps: 1) contacting the liquid waste
stream with the resin, allowing the resin to adsorb the solutes from the
solution, and 2) subsequently regenerating the resin by removing the adsorbed
chemicals, often accomplished by simply washing with the proper solvent.
Resin adsorption is similar in nature to activated carbon adsorption; the most
significant difference being that resins are chemically regenerated while
carbon is usually thermally regenerated, eliminating the possibility of mater-
ial recovery. Resins generally have a lower adsorptive capacity than carbon,
and are not likely to be competitive with carbon for the treatment of high
volume waste streams containing moderate or high concentrations of mixed
wastes with no recovery value.
Current applications of resin adsorption include removal of copper and
chromium both as salts and organic chelates, removal of color associated with
metal complexes and organics, and the recovery of phenol from a waste stream.
According to the Section 308 Questionnaire data base, no plants reported using
resin adsorption. No data, are available from other industries.
14. In-Plant Biological Treatment
For certain segregated waste streams and pollutants, in-plant biological
treatment is an effective and less costly alternative to carbon adsorption for
control of toxic organic pollutants, especially those which are effectively
absorbed into the sludge and are relatively biodegradable. In-plant
biological treatment may require longer detention times and certain species of
acclimated biomass to be effective as compared to end-of-pipe biological
treatment that is predominantly designated to treat BOD5. EPA has determined
that in-plant biological treatment with an acclimated biomass is as effective
as activated carbon adsorption for removing priority pollutants such as
polynuclear aromatics (PNAs) like naphthalene, anthracene, and pyrene; phenol;
and 2,4-dimethylphenol as shown in the sampling data collected at plant #1293
of the 12-Plant Sampling Study, which are presented later in this section.
Plant #1293 is a coal tar facility with flows of less than 50,000 gallons per
VII-48
-------
day (gpd), which generates the highest raw waste concentrations of these toxic
pollutants. Its treatment system consists of equalization, extended above-
ground aerated lagoon, and secondary clarification prior to discharge to a
POTW. This treatment system reduces the concentrations of all the above-
mentioned toxic pollutants to their respective analytical minimum levels.
After reviewing the performance data from this plant, the Agency deter-
mined that other relatively biodegradable toxic pollutants could also be
controlled by this type of dedicated biological treatment system (i.e., with a
minimum amount of dilution with other process wastewaters). This determina-
tion was made after review of performance data from selected end-of-pipe
biological treatment systems (plant 1948 and #2536) receiving wastewaters
whose main toxic pollutant constituents included the following: acrylo-
nitrile, bis (2-ethylhexyl) phthalate, di-N-butyl phthalate, diethyl
phthalate, and dimethyl phthalate.
The Agency has determined that these data are appropriate for use in
characterizing the performance of in-plant biological treatment based upon the
waste stream characteristics of the influent to the treatment systems. The
selected plants generate major sources of these pollutants.
According to the Section 308 Questionnaire data base, 33 OCPSF plants
report using some form of biological, treatment prior to discharge to an end-
of-pipe treatment system (direct dischargers) or POTW (indirect dischargers).
Table VII-14 presents the performance data for the three plants chosen by the
Agency to represent the performance of in-plant biological treatment.
D. END-OF-PIPE TREATMENT TECHNOLOGIES
1. Introduction
End-of-pipe treatment systems in the OCPSF industry often consist of
primary, secondary, and polishing or tertiary unit operations. In primary
treatment, physical operations are used to remove floating and settleable
solids found in wastewater. In secondary treatment, biological and chemical
processes are used to remove most of the organic matter. In polishing or
tertiary treatment, additional combinations of unit operations and processes
VII-49
-------
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are used to remove other constituents that are not removed by primary or
secondary treatment. Many technologies have proven effective in removing
specific pollutants from the wastewaters produced by OCPSF plants. The selec-
tion of a specific end-of-pipe treatment scheme depends on the nature of the
pollutant to be removed and on engineering and cost considerations,: Data on
the frequency of application of specific primary, secondary, and polishing or
tertiary end-of-pipe treatment technologies are presented in Tables VII-15,
VII-16, and VII-17, respectively. Primary treatment technologies used by the
OCPSF plants to remove floating and settleable solids, to protect the biolog-
ical segment of the system from shock loadings, and to assure the efficiency
of biological treatment include neutralization (365 plants), equalization
(297), primary clarification (144), and nutrient addition (114). Secondary
treatment technologies used by OCPSF plants to remove organic matter include
secondary clarification (174 plants), activated sludge (143), and aerated,
lagoons (89). Polishing or tertiary treatment technologies used to remove
certain constituents not sufficiently removed by the primary and secondary
systems include polishing ponds (64 plants), filtration (41), and carbon
adsorption (21).
2. Primary Treatment Technologies
Although the final BPT, BAT, and PSES effluent limitations guidelines are
not based on these primary treatment technologies, many OCPSF facilities uti-
lize one or some combination of these technologies to enhance the performance
of subsequent treatment steps (e.g., biological). The Agency encourages the
use of any of the primary treatment technologies discussed to improve the
removal efficiency of the overall treatment system. <
a. Equalization
Equalization involves the process of dampening flow and pollutant
concentration variation of wastewater before subsequent downstream treatment.
By reducing the variability of the raw waste loading, equalization can: ;
significantly improve the performance of downstream treatment processes that
are more efficient if operated at or near uniform hydraulic, organic, and
solids loading rates and that reduce effluent variability associated with slug
VII-51
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raw waste loadings. Equalization is accomplished in a holding tank manufac-
tured from steel or concrete, or in an unlined or lined pond. The retention
time of the tank or pond should be sufficiently long to dilute the effects of
any highly concentrated continuous flow or batch discharges on treatment plant
performance. -
Equalization is reliable from both equipment and process standpoints, and
is used to increase the reliability of the flow-sensitive treatment processes
that follow by reducing the variability of flow and pollutant concentrations.
Equalization is a common treatment technology to the OCPSF industry. Accor-
ding to the Section 308 Questionnaire data base, 297 OCPSF plants use
equalization as a primary treatment technology.
b. Neutralization
Neutralization involves the process of adjusting either an acidic or a
basic waste stream closer to a neutral pH. Neutralization may be accomplished
in either a collection tank, rapid mix tank, or an equalization tank by mixing
acidic and alkaline wastes, or by the addition of chemicals. Alkaline waste-
waters are typically neutralized by adding sulfuric or hydrochloric acid, or
compressed carbon dioxide. Acidic wastewaters may be neutralized with
limestone or lime slurries, soda ash, or caustic soda. The selection of
neutralizing agents depends upon cost, availability, ease of use, reaction
by-products, reaction rates, and quantities of sludge formed. The most
commonly used chemicals are lime (to raise the PH) and sulfuric acid (to lower
the pH).
Neutralization of an excessively acidic or basic waste stream is
necessary in a variety of situations, including 1) the precipitation-of
dissolved heavy metals; 2) the prevention of metal corrosion and damage to
other construction materials; 3) preliminary treatment allowing effective
operation of the biological treatment process; 4) the providing of neutral pH
water for recycle uses; and 5) the reduction of detrimental effects in the
receiving water.
VII-55
-------
Neutralization is highly reliable with proper monitoring, control, and
proper pretreatment to control interfering substances. Neutralization is a
common treatment technology to the OCPSF industry; according to the Section
308 Questionnaire data base, 365 OCPSF plants neutralize their wastewaters.
c. Screening
Screening is the process of removing coarse and/or gross solids from
wastewater before subsequent downstream treatment, and is usually accomplished
by passing wastewater through drum- or disk-type screens. Typically, coarse
screens are stainless steel or nonferrous wire mesh with openings from 6 to
20 mm. Fine screens have openings that are less than 6 mm. Solids are raised
above the liquid level by rotation of the screen and are backflushed into
receiving troughs by high-pressure jets.
Screening has proven to be a very reliable process when properly designed
and maintained. According to the Section 308 Questionnaire data base,
49 OCPSF plants use screening as a primary treatment technology.
d. Grit Removal
Grit removal is achieved in specially designed chambers. Grit consists
of sand, gravel, cinders, or other heavy solid materials that have subsiding
velocities or specific gravities substantially greater than those of the
organic putrescible solids in wastewater. Grit chambers are used to protect
moving mechanical equipment from abrasion; to reduce formation of heavy de-
posits in pipelines, channels, and conduits; and to reduce the frequency of
digester cleaning that may be required as a result of excessive accumulations
of grit in such units.
Normally, grit chambers are designed to remove all grit particles with a
0.21 mm diameter, although many chambers have been designed to remove grit
particles with a 0.15 mm diameter. According to the Section 308 Questionnaire
data base, 41 OCPSF plants use grit removal as a primary treatment process.
e. Oil Separation (Oil Skimming, API Separation)
Oil separation techniques are used to remove oils and grease from waste-
water. Oil may exist as free or emulsified oil. The separation of free oils
VII-56
-------
and grease is accomplished by gravity, and normally involves retaining the
oily waste in a holding tank and allowing oils .and other materials less dense
than water to float to the surface. This oily top layer is skimmed off the
wastewater surface by.a mechanism such as a rotating drum-type or a belt-type
skimmer. Emulsified oil, after it has gone through a "breaking" step
involving chemical or thermal processes to generate free oil, can also be
separated using a skimming system.
Oil separation is used throughout the OCPSF industry to recover oil for
use as a fuel supplement or for recycle, or to reduce the concentration of
oils, which reduces any deleterious effects on subsequent treatment or
receiving waters. In the OCPSF industry, oil separation also removes many
toxic organic chemicals (typically :large non-polar molecules) that tend to
concentrate in oils and grease. However, since the removal of these toxic
pollutants is incidental to oil separation/removal, this treatment process was
not used as the technology basis for this final regulation. Still, the Agency
encourages its use to improve the performance of the overall treatment system
for removing unwanted floating oils and greases.
According to the Section 308 Questionnaire data base, 86 OCPSF plants use
oil separation; 58 use API separation (a common gravity oil separation based
upon design standards published by the American Petroleum Institute); and
111 practice oil skimming as a preliminary treatment technology. No OCPSF
performance data are available; however, data from the iron and steel manufac-
turing and electrical and electronic components industries are presented in
Volume III of the EPA Treatability Manual. The data show generally high
removal efficiencies for metals and toxic organics.
f. Flotation
Flotation is a process by which suspended solids, free and emulsified
oils, and grease are separated from wastewater by releasing gas bubbles into
the wastewater. The gas bubbles attach to the solids, increasing their
buoyancy and causing them to float. A surface layer of sludge forms, and is
usually continuously skimmed for disposal. Flotation may be performed in
several ways, including foam (froth), dispersed air, dissolved air, vacuum
VII-57
-------
flotation, and flotation with chemical addition. The principal difference
between these variations is the method of gas bubbles generation.
Flotation is used primarily in the treatment of wastewater streams that
carry heavy loads of finely divided suspended solids or oil. Solids having a
specific gravity only slightly greater than water, which would require abnor-
mally long sedimentation times, may be removed in much less time by flotation.
Thus, it is often an integral part of standard clarification.
According to the Section 308 Questionnaire data base, 31 OCPSF plants
used dissolved air flotation as a primary treatment technology. No OCPSF
performance data are available. The Volume III EPA Treatability Manual
presents performance data from textile mills, pulp and paper mills, auto and
other laundries, and petroleum refineries. The data show a median removal
efficiency of 61 percent for BOD5 and a median effluent concentration of
250 rag/1. Toxic removal efficiencies show large variations.
8> Clarification (settling, sedimentation)
Qlarification is a physical process used to remove suspended solids from
wastewater by gravity settling. Settling tanks, clarifiers, and sedimentation
ponds or basins are designed to let wastewater flow slowly and quiescently,
providing an adequate retention time to permit most solids more dense than
water to settle to the bottom. The settling solids form a sludge at the
bottom of the tank or basin. This sludge is usually pumped out continuously
or intermittently from settling tanks or clarifiers, or scraped out period-
ically from sedimentation ponds or basins.
Settling is used alone or as part of a more complex treatment process.
It is usually the first process applied to wastewaters containing high
concentrations of settleable suspended solids. Settling is also often used in
conjunction with other treatment processes such as removal of biomass after
biological treatment or removal of metal precipitates after chemical
precipitation. Clarifiers, in conjunction with chemical addition, are used to
remove materials such as dissolved solids that are not removed by simple
sedimentation (chemically assisted clarifiers are discussed later in this
section under polishing and tertiary treatment).
VII-58
-------
Clarification (or sedimentation or settling) is a common primary
treatment technology in the OCPSF industry; according to the Section 308 -
Questionnaire data base, 144 OCPSF plants use primary clarification.
h. Coagulation and Flocculation
Chemical coagulation and flocculation are terms often used interchange-
ably to describe the physiochemical process of suspended particle aggregation
resulting from chemical additions to wastewater. Technically, coagulation
involves the reduction of electrostatic surface charges and the formation of
complex hydrous oxides. Coagulation is essentially instantaneous in that the
only time required is that necessary for dispersing the chemicals in solution.
Flocculation is the time-dependent physical process of the aggregation of
wastewater solids into particles large enough to be separated by sedimenta-
tion. ' ' . ...... , .-., •... .. . '< •••• ,.
The purpose of coagulation is to overcome electrostatic repulsive surface
forces and cause small particles to agglomerate into larger particles, so that
gravitational and inertia! forces will predominate and affect the settling of
the, particles. The process can be grouped into two sequential mechanisms:
• Chemically induced destabilization of the repulsive surface-related
forces, thus allowing particles to stick together when contact, .between
particles is made.
• Chemical bridging and physical enmeshment between the non-repelling
particles, thus allowing for the formation of large particles.
'. " ~ . -.'''-
There are three different types of coagulants: inorganic electrolytes,
natural organic polymers, and synthetic polyelectrolytes.
Inorganic electrolytes are salts or multivalent ions such as alum
(aluminum sulfate), lime, ferric chloride, and ferrous sulfate.' The
inorganic coagulants act by neutralizing the charged double layer of colloidal
particles and by precipitation reactions. Alum is typically added to the
waste stream as a solution. At an alkaline pH and upon mixing, the alum
hydrolyzes and forms fluffy gelatinous precipitates of aluminum hydroxide.
These precipitates, partially as a result of their large surface area, act to
VII-59
-------
enmesh small particles and thereby create large particles. Lime and ion
salts, as well as alum, are used as flocculants primarily because of this
tendency to form large fluffy precipitates of "floe" particles.
Natural organic polymers derived from starch, vegetable materials, or
monogalactose act to agglomerate colloidal particles through hydrogen bonding
and electrostatic forces. These are often used as coagulant aids to enhance
the efficiency of inorganic coagulants.
Synthetic polyelectrolytes are polymers that incorporate ionic or other
functional groups along the carbon chain in the molecule. The functional
groups can be either anionic (attract positively charged species), cationic
(attract negatively charged species), or neutral. .Polyelectrolytes function
by electrostatic bonding and the formation,of physical bridges between
particles, thereby causing them to agglomerate. These are also most often
used as coagulant aids to improve floe formation.
The coagulation/flocculation and sedimentation process entails the
following steps:
• Addition of the coagulating agent to the liquid
• Rapid mixing to dispense the coagulating agent throughout the liquid
ml?lng ,t0 allov for cont*ct between small particles
and agglomeration into larger particles.
Coagulation and flocculation are used for the clarification of industrial
wastes containing colloidal and suspended solids. Coagulants are most
commonly added upstream of sedimentation ponds, clarifiers, or filter units to
increase the efficiency of solids separation. This practice has also been
shown to improve dissolved metal removal as a result of the formation of
denser, rapidly settling floes, which appear to be more effective in absorbing
and adsorbing fine metal hydroxide precipitates. Coagulation may also be used
to remove emulsified oil from industrial wastewaters. Emulsified oil and
grease is aggregated by chemical addition through the processes of coagulation
and/or acidification in conjunction with flocculation. Performance data for
VII-60
-------
coagulation/flocculation units are presented in the context of TSS and metals
removal in the section on chemical precipitation.
According to the Section 308 Questionnaire data base, 42 OCPSF plants
utilize coagulation and 66 OCPSF plants utilize flocculation as part of their
preliminary treatment systems.
3. Secondary Treatment Technologies
a. Activated Sludge ,
The activated sludge process is a biological treatment process primarily
used for the removal of organic material from wastewater. It is characterized
by a suspension of aerobic and-facultative microorganisms maintained in a
relatively homogenous state by mixing or by the turbulence induced by aera-
tion. These microorganisms oxidize soluble organics and agglomerate colloidal
and particulate solids in the presence of dissolved molecular oxygen. The
process can be preceded by sedimentation to remove larger and heavier solid
particles if needed. The mixture of microorganisms, agglomerated particles,
and wastewaters (referred to as mixed liquor) is aerated in an aeration basin.
The aeration step is followed by sedimentation to separate biological sludge
from treated wastewater. The major portion of the microorganisms and solids
removed by sedimentation are recycled to the aeration basins to be recombined
with incoming wastewater, while the excess, which constitutes the waste
sludge, is sent to sludge disposal facilities.
The activated sludge biomass is made up of bacteria, fungi, protozoa, and
rotifers. The bacteria are the most important group of microorganisms as they
are responsible for stabilization of the organic matter and formation of the
biological floe. The function of the biomass is to convert the soluble
organic compounds to cellular material. This conversion consists of transfer
of organic matter (also referred to as substrate or food) through the cell
wall into the cytoplasm, oxidation of substrate to produce energy, and
synthesis of protein and other cellular components from the substrate. Some
of the cellular material undergoes auto-oxidation (self-oxidation or
endogenous respiration) in the aeration basin, the remainder forming net
growth or excess sludge. In addition to the direct removal of dissolved
VII-61
-------
organics by biosorption, the biomass can also remove suspended matter and
colloidal matter. The suspended matter is removed by enmeshment in the
biological floe. The colloidal material is removed by physiochemical
adsorption on the biological floe. Volatile compounds may be driven off to a
certain extent in the aeration process. Metals are also partially removed,
and accumulate in the sludge.
The effectiveness of the activated sludge process is governed by several
design and operation variables. The key variables are organic loading, sludge
retention time, hydraulic or aeration detention time, oxygen requirements, and
the biokinetic rate constant (K). The organic loading is described as the
food-to-microorganism (F/M) ratio, or the kilograms of BOD5 applied daily to
the system per kilogram of mixed liquor suspended solids (MLSS). The MLSS in
the aeration tank is determined by the rate and concentration of activated
sludge returned to the tank. The organic loading (F/M ratio) affects the BOD5
removal, oxygen requirements, biomass production, and the settleability of the
biomass. The sludge retention time (SRT) or sludge age is a measure of the
average retention time of solids in the activated sludge system. Sludge
retention time is important in the operation of an activated sludge system as
it must be maintained at a level that is greater than the maximum generation
time of microorganisms in the system. If adequate sludge retention time is
not maintained, the bacteria are washed from the system faster than they can
reproduce themselves and the process fails. The SRT also affects the degree
of treatment and production of waste sludge. A high SRT results in carrying a
high quantity of solids in the system and obtaining a higher degree of treat-
ment and also results in the production of less waste sludge. The hydraulic
detention time is used to determine the size of the aeration tank and should
be determined by use of F/M ratio, SRT, and MLSS. The biokinetic rate
constant (or K-rate) determines the speed of the biochemical oxygen demand
reaction and generally ranges from 0.1 to 0.5 days'1 for municipal waste-
waters. The value of K for any given organic compound is temperature-
dependent; because microorganisms are more active at higher temperatures, the
value of K increases with increasing temperatures (7-5). Oxygen requirements
are based on the amount required for BOD5 synthesis and the amount required
for endogenous respiration. The design parameters will vary with the type of
vastewater to be treated and are usually determined in a treatability study.
VII-62
-------
The oxygen requirement to satisfy BOD5 synthesis is established by the
characteristics of the wastewater. the oxygen requirement to satisfy
endogenous respiration is established by'the total solids maintained in the
system and their characteristics. A detailed discussion of typical design
parameters used in the OCPSF industry and how these parameters are used in the
Agency's compliance cost estimates are presented in Section VIII.
Modifications of the activated sludge process are common, as the process
is extremely versatile and can be adapted for a wide variety of organically
contaminated wastewaters. The typical modification may represent a variation
in one or more of the key design parameters, including the F/M loading, aera-
tion location and type, sludge return, and contact basin configuration. The
modifications in practice have been identified by the major characteristics
that distinguish the particular configuration. The characteristic types and
modifications are briefly described as follows:
• Conventional. The aeration tanks are long and narrow, with plug flow
(i.e., little forward or backwards mixing).
• Complete Mix. The aeration tanks are shorter and wider, and the
aerators, diffusers, and entry points of the influent and return
sludge are arranged so that the wastewater mixes completely.
• Tapered Aeration/"' A modification of the conventional process in which
the diffusers are arranged to supply more air to the influent end of
the tank, where the oxygen demand is highest.
• Step Aeration. A modification of the conventional process in which
the wastewater is introduced to the aeration tank at several points,
lowering the peak oxygen demand.
, High Rate Activated Sludge. A modification of conventional or tapered
aeration in which the aeration times are shorter, the pollutants
loadings are higher per unit mass of microorganisms in the tank. The
rate of BOD removal for this process is higher than that of conven-
tional activated sludge processes, but the total removals are lower.
• Pure Oxygen. An activated sludge variation in which pure oxygen
instead of air is added to the aeration tanks, the tanks are covered,
and the oxygen-containing off-gas is recycled. Compared to normal air
aeration, pure oxygen aeration requires a smaller aeration tank volume
and treats high-strength wastewaters and widely fluctuating organic
loadings more effectively.
• Extended Aeration. A variation of complete mix in which low organic
loadings and long aeration times permit more complete wastewater
degradation and partial aerobic digestion of the microorganisms.
VII-63
-------
• Contact Stabilization. An activated sludge modification using two
aeration stages. In the first, wastewater is aerated with the return
sludge in the contact tank for 30 to 90 minutes, allowing finely
suspended colloidal and dissolved organics to absorb to the activated
sludge. The solids are settled out in a clarifier and then aerated in
the sludge aeration (stabilization) tank for 3 to 6 hours before
flowing into the first aeration tank.
• Oxidation Ditch Activated Sludge. An extended aeration process in
which aeration and mixing are provided by brush rotors placed across a
race track-shaped basin. Waste enters the ditch at one end, is
aerated by the rotors, and circulates.
Activated sludge is the most common end-of-pipe biological treatment
employed in the OCPSF industry. According to the Section 308 Questionnaire
data base, 143 OCPSF plants reported using activated sludge, 2 plants reported
using an oxidation ditch, and 8 plants reported using pure oxygen activated
sludge. Performance data for BOD5 and TSS removal are from the OCPSF Master
Analysis File and are presented in Table VII-18. The data show that activated
sludge treatment results in a median removal efficiency of 96 percent for BOD5
and 81 percent for TSS. For those plants meeting the BPT performance edit of'
95 percent removal of BOD5 or having an effluent BOD5 concentration no greater
than 40 mg/1, the BOD5 median removal efficiency is 98 percent and the TSS
median removal efficiency is 82 percent. (A detailed discussion of EPA's BPT,
data editing criteria is presented later in this section.)
b. Lagoons
A body of wastewater contained in an earthen dike and designed for
biological treatment is termed a lagoon or stabilization pond or oxidation
pond. While in the lagoon, the wastewater is biologically treated to reduce
the degradable organics and also reduce suspended solids by sedimentation.
The biological process taking place in the lagoon can be either aerobic or
anaerobic, depending on the design of the lagoon. Because of their low
construction and operating costs, lagoons offer a financial advantage over
other treatment methods and for this reason have become popular where
sufficient land area is available at reasonable cost.
Lagoons are used in industrial wastewater treatment for stabilization of
suspended, dissolved, and colloidal organics either as a main biological
VII-64
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treatment process or as a polishing treatment process following other
biological treatment systems. Aerobic, facultative, and aerated lagoons are
generally used for industrial wastewater of low and medium organic strength.
High strength wastewaters are often treated by a series of ponds; the first
one will be virtually all anaerobic, the next facultative, and the last
aerobic.
The performance of lagoons in removing degradable organics depends upon
detention time, temperature, and the nature of waste. Aerated lagoons gener-
ally provide a high degree of BOD5 reduction more consistently than the
aerobic and facultative lagoons. Typical problems associated with .lagoons are
excessive algae growth, offensive odors from anaerobic ponds if sulfates are
present and the pond is not covered, and seasonal variations of effluent
quality.
There are four major classes of lagoons that are based on the nature of
biological activity.
Aerobic Lagoons. Aerobic lagoons are shallow ponds that contain
dissolved oxygen (DO) throughout their liquid volume at all times. These
lagoons may be lined with concrete or an impervious flexible lining, depending
on soil conditions and wastewater characteristics. Aerobic bacterial
oxidation and algal photosynthesis are the principal biological processes.
Aerobic lagoons are best suited to treating soluble organics in wastewater
relatively free of suspended solids. Thus, they are often used to provide
additional treatment of effluents from anaerobic ponds and other partial
treatment processes.
Aerobic lagoons depend on algal photosynthesis, natural reaeration,
adequate mixing, good inlet-outlet design, and a minimum annual air temper-
ature above about 5°C (41°F), for a major portion of the required DO. Without
any one of these conditions, an aerobic pond may develop anaerobic conditions
or be ineffective or both. Because light penetration decreases rapidly with
increasing depth, aerobic pond depths are restricted to 0.2 to 0.3 m (0.6 to
1.0 ft) to maintain active algae growth from top to bottom. In order to
achieve effective pollutant removals with aerobic lagoons, some means of
VII-66
-------
removing algae (coagulation, filtration, multiple-cell design) is sometimes
necessary.
Anaerobic Lagoons. Anaerobic lagoons are relatively deep ponds (up to
6 meters) with steep sidewalls in which anaerobic conditions are maintained
by keeping organic loading so high that complete deoxygenation is prevalent.
Some oxygenation is possible in a shallow surface zone. If floating materials
in the waste form an impervious surface layer, complete anaerobic conditions
will develop. Treatment or stabilization results from anaerobic digestion of
organic wastes by acid-forming bacteria that break down organics. The
resultant acids are then converted to carbon dioxide, methane, and other end
products. Anaerobic lagoons are capable of providing treatment of high
strength wastewaters and are resistant to shock loads. These lagoons are
sometimes used to digest the waste sludge from an activated sludge plant.
In the typical anaerobic lagoon, raw wastewater enters near the bottom of
the pond (often at the center) and mixes with the active microbial mass in the
sludge blanket, which can be as much as 2 meters (6 feet) deep. The discharge
is located near one of the sides of the pond, submerged below the liquid
surface. Excess sludge is washed out with the effluent and recirculation of
waste sludge is not required.
Anaerobic lagoons are customarily contained within earthen dikes.
Depending on soil and wastewater characteristics, lining with various
impervious materials, such as rubber, plastic, or clay may be necessary. Pond
geometry may vary, but surface area-to-volume ratios are minimized to enhance
heat retention.
Facultative Lagoons. Facultative lagoons are intermediate depth ponds of
1 to 2.5 m (3 to 8 feet) in which the wastewater is stratified into three
zones. These zones consist of an anaerobic bottom layer, an aerobic surface
layer, and an intermediate zone. Stratification is a result of solids
settling and temperature-water density variations. Oxygen in the surface
stabilization zone is provided by reaeration and photosynthesis. The photo-
synthetic activity at the lagoon surface produces oxygen diurnally, increasing
the DO content during daylight hours, and decreasing it during the night. In
VII-67
-------
general, the aerobic surface layer serves to reduce odors while providing
treatment of soluble organic by-products of the anaerobic processes operating
at the bottom. Sludge at the bottom of facultative lagoons will undergo
anaerobic digestion, producing carbon dioxide and methane.
Facultative lagoons are customarily contained within earthen dikes.
Depending on soil and wastewater characteristics, lining the lagoon with vari-
ous impervious materials, such as .rubber, plastic, or clay, may be necessary.
Aerated Lagoons. Aerated lagoons are medium-depth basins of 2.5 to 5 m
(8 to 15 ft) in which oxygenation is accomplished by mechanical or diffused
aeration units and from induced surface aeration. Surface aerators may be
high speed, small diameter or low speed, large diameter impeller devices,
either fixed-mounted on piers or float-mounted on pontoons. Diffused aerators
may be plastic pipe with regularly spaced holes, static mixers, helical
diffusers, or other types. Aerated lagoons can be either aerobic or fac-
ultative. Aerobic ponds are designed to maintain complete mixing. Thus, all
solids are in suspension and separate sludge settling and disposal facilities
are required to separate the solids from the treated wastewater.
According to the Section 308 Questionnaire data base, lagoons are a
common secondary treatment technology in the OCPSF industry; 89 plants
reported using aerated lagoons, 24 plants reported using aerobic lagoons, and
12 plants reported using anaerobic lagoons. Performance data for BOD5 and TSS
removal from these lagoon systems were obtained from the OCPSF Master Analysis
File and are presented in Table VII-19. The data show that lagoon treatment
results in a median removal efficiency of 89 percent for BOD5 and 66 percent
for TSS, when all plants using only this secondary treatment process are
considered. For those plants meeting the BPT performance edit, the median
BOD5 removal efficiency is 90 percent and the median TSS removal efficiency is
75 percent,
c. Attached Growth Biological Systems
Attached growth biological treatment systems are used to biodegrade the
organic components of a wastewater. In these systems, the biomass adheres to
VII-68
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the surfaces of rigid supporting media. As wastewater contacts the supporting
medium, a thin-film biological slime develops and coats the surfaces. As this
film (consisting primarily of bacteria, protozoa, and fungi) grows, the slime
periodically breaks off the medium and is replaced with new growth. This
phenomenon of losing the slime layer is called sloughing and is primarily a
function of the organic and hydraulic loadings on the system. The effluent
from the system is usually passed to a clarifier to settle and remove the
agglomerated solids. Attached growth biological treatment systems are appli-
cable to industrial wastewaters amenable to aerobic biological treatment in
conjunction with suitable pre- and post-treatment. The process is effective
for the removal of suspended or colloidal materials, but less effective for
the removal of soluble organics. The two major types of attached growth
biological treatment processes used in the OCPSF industry are trickling
filters and rotating biologic contactors. These processes are described
below:
Trickling Filters. The physical unit of a trickling filter consists of a
suitable structure packed with an inert medium (usually rock, wood, or
plastic) on which a biological mass is grown. The wastewater is distributed
by either.a fixed-spray nozzle system or a rotating distribution system over
the upper surface of the medium and as it flows through the medium covered
with biological slime, both dissolved and suspended organic matter are removed
by adsorption. The adsorbed matter is oxidized by the organisms in the slime
during their metabolic processes. Air flows through the filter by convection,
thereby providing the oxygen needed to maintain aerobic conditions. Most
trickling filters are classified as either low- or high-rate, depending on the
organic and hydraulic loading. A low-rate filter generally has a media bed
depth of 1.5 to 3 meters (5 to 10 feet) and does not use recirculation.
High-rate filter media bed depths can vary from 1 to 9 meters (3 to 30 feet)
and require recirculation. The recirculation of effluent in high-rate filters
is necessary for effective sloughing control. Otherwise, media clogging and
anaerobic conditions could develop as a consequence of the high organic
loading rates employed.
Rotating Biological Contactors. The most common types of rotating
biological contactors consist of a plastic disk or corrugated plastic medium
VII-70
-------
mounted on horizontal shafts. The medium slowly rotates in wastewater (with
40 to 50% of its surface immersed) as the wastewater flows past. During rota-
tion, the .medium picks up a thin layer of wastewater, which flows over its
surface absorbing oxygen from the.air. A biological mass growing on the
medium surface adsorbs and coagulates organic pollutants from the wastewater.
The biological mass biodegrades the organic matter. Excess microorganisms and
other solids are continuously,removed from the film on the disk by shearing
forces created by the rotation of the disk in the wastewater. This rotation,
also mixes ,the wastewater, keeping sloughed solids in suspension until they
are removed by final clarification. :
According to the Section 308, Questionnaire data base, 8 plants report
using rotating biological contactors and 12 plants report using trickling
filters as a secondary treatment technology. Performance data fqr BOD5 and
TSS removal are from the OCPSF Master Analysis File and are presented in Table
VII-20. The data show that attached growth biological treatment results in a
median removal efficiency of 92 percent for BOD5 and 70 percent for TSS, when
all plants using only this secondary treatment process are considered. For
those plants meeting the BPT performance edits, the median BOD5 removal , .
efficiency is 92 percent and the median TSS removal efficiency is 70 .percent.
d. Secondary Clarification
The function of secondary clarifiers varies with the method of,biological
treatment utilized. Clarifiers in an activated sludge system serve a dual
purpose. In addition to providing a clarified effluent, they must also
provide a concentrated source of return sludge for process control. Adequate
area and depth must be provided to allow this compaction to occur while
avoiding rejection of solids into the tank effluent (7-6). Secondary clari-
fiers dn activated sludge systems are also sensitive to sudden changes -in flow
rates. Therefore, the use of multispeed pumps for in-plant wastewater lift
stations is strongly recommended where adequate flow equalization is not
provided (7^7).
Clarifiers in activated sludge systems must be designed not only for
hydraulic overflow rates, but also for solids loading rates. This is due
VII-71
-------
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VII-72
-------
mainly to the need for both clarification and thickening in activated sludge
clarifiers to provide both a well clarified effluent and a concentrated return
sludge (7-6).
When the MLSS concentration is less than about 3,000 mg/1, the clarifier
size will normally be governed by hydraulic overflow rates. At higher MLSS
values, the ability of the clarifier .to thicken solids becomes the governing
factor. Therefore, solids loading rates become more critical in determining
tank size. Design size should be computed for both average and peak condi-
tions to ensure satisfactory effluent quality at all times (7-6).
Depth of clarifiers in activated sludge systems is extremely important.
The depth must be sufficient to permit the development of a sludge blanket,
especially under conditions when the sludge may be bulking. At the same time,
the interface of the sludge blanket and the clarified wastewater should be
well below the effluent weirs (7-6).
For long rectangular tanks, it is common practice to locate the sludge
withdrawal hopper about l/3«?to 1/2 the distance to the end of the tank to
reduce the effects of density currents (7-6, 7-7).
Typical design parameters for clarifiers in activated sludge systems
treating typical domestic wastewaters are also presented in Table VII-21. The
design of these clarifiers should be based upon an evaluation of average and
peak overflow rates and solids loadings. That combination of parameters that
yields the largest surface area should be used (7-6).
Clarifiers following trickling filters must effectively separate
biological solids sloughed from the filter media. .The design of clarifiers
following trickling filters is based on hydraulic overflow rates similar to
the method used for primary clarifiers. Design overflow rates must include
recirculated flow where clarified secondary effluent is used for recir-
culation. Because the influent SS concentrations are low, tank solids
loadings need not be considered. Typical design parameters for clarifiers
following trickling filters are also presented in Table VII-21 (7-6).
VII-73
-------
TABLE VII-21.
TYPICAL DESIGN PARAMETERS FOR SECONDARY CLARIFIERS
TREATING DOMESTIC WASTEWATER
Type of Treatment
Overflow Rate
(gpd/sq ft)
Average Peak
Settling Following
Trickling Filtration 400-600
Settling Following Air-
Activated Sludge
(Excluding Extended
Aeration) 400-800
Settling Following
Extended Aeration
Settling Following
Oxygen-Ac t i va t ed
Sludge with Primary
Settling
200-400
1,000-1,200
1,000-1,200
800
400-800 1,000-1,200
Solids Loading1 Depth
(Ib solids/day/sq ft) ft
Average Peak
20-30
20-30
25-35
10-12
<50 12-15
<50 12-15
<50 12-15
Allowable solids loadings are generally governed by sludge settling
characteristics associated with cold weather operations. e"-Ling
Source: Process Design Manual for Upgrading Existing Wastewater Treatment
Plants, EPA 625/l-71-004a, October 1974.
VII-74
-------
e. Operating, Managing, and Upgrading Biological Treatment Systems
This section identifies methods by which biological treatment systems in
the OCPSF industry may modify their existing facilities in order to upgrade or
improve performance. Most of the upgrades discussed pertain to activated
sludge and aerated lagoon systems, since these are the biological treatment
systems most commonly used in the OCPSF industry and the systems most amenable
to operational and design modifications. Approaches to upgrading biological
treatment units include adding unit treatment processes, modifying the design
and operational parameters of existing units, acclimating existing bacteria to
certain toxicants or using bioaugmentation (the addition of acclimated types
of bacteria bred to remain active under a variety of adverse conditions),
particle size reduction, nutrient addition, and the addition of powdered
activated carbon (PAC) to aeration units.
In some cases, the only means of improving the performance of a
biological treatment system is to add additional unit treatment processes.
Aeration basins and clarifiers are sometimes added to accommodate higher waste
loads or to address inadequacies in the original treatment plant design. The
addition of primary.unit treatment such as equalization improves system
performance by diluting slugs of concentrated wastes, minimizing routine
variations in influent wastewater flow and pollutant concentration, and
removing suspended particles. Preaeration basins are often added to raise
wastewater DO levels and improve the treatability and settling characteristics
of the wastes. Postaeration basins are added to systems to raise the DO in
treatment plant effluent before it flows into receiving streams. Microscreen
and filtration units can be added to improve suspended solids removal prior to
effluent discharge. In summary, there are a number of unit processes
available that can be added to a facility, provided that land is available, to
address specific treatment problems.
Upgrading existing bioreactor facilities can include adding chemical and
physical treatments such as the addition of polyelectrolytes to clarifiers to
improve solids settling or the installation of a surface skimmer to a pre-
treatment unit to accomplish oil and scum removal. Operational changes
affecting the quantity and species of microorganisms in a system, however, are
VII-75
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often the most significant with regard to improving the removal of pollutants
and increasing a treatment system's capacity to handle large raw waste loads.
Experience at some facilities indicates that operation of an activated sludge
plant to maintain a stable mixed liquor fauna (i.e., maintain a specific
distribution of bacterial species), rather than operation based on a constant
aeration rate or MLSS concentration, yields more consistent treatment of BOD
and priority pollutants (7-8). Thus, operational changes and unit treatment
modifications should be planned giving appropriate consideration to this
approach. Many of the concepts for improving the performance of biological
units discussed below are presented in the context of activated sludge and
aerated lagoon systems; however, in many cases they also apply to other types
of biological units, such as fixed film reactors.
As previously discussed, flow equalization is important in improving the
treatability of a waste stream by minimizing variations in wastewater
characteristics, such as temperature, pH, and pollutant concentrations. One
facility in the OCPSF industry improved the equalization of its wastewater by
removing several feet of sedimentation from a primary clarifier, thus
increasing the wastewater detention time. This plant also added heat
exchangers upstream of the treatment units to lower the wastewater temperature
and provide a more uniform wastewater temperature year round.
Modifications to the operations of activated sludge units include
changing influent flow patterns; altering the division, mixing, and aeration
characteristics of the tanks; and recycling sludge from the secondary
clarifier to one or more locations in the treatment train. Step aeration,
introducing primary effluent at several locations in the aeration basin, can
be used to upgrade the performance of a plant with high pollutant loadings
(7-9). Distribution of the waste equalizes the loading in the aeration basin
and enables the microorganisms to function more efficiently.
In situations where a treatment system needs to be modified to handle an
increased waste load, a conventional single tank activated sludge process can
be converted into a two-stage contact stabilization process. The main advan-
tage of contact stabilization is that it operates with a much shorter
hydraulic retention time and hence enables the facility to treat a larger
VII-76
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waste load. In other situations where oxygen requirements are not being met
and the facility has extra capacity, oxygen supply can be improved by creating
a complete mix activated sludge system from a contact stabilization or
conventional activated sludge unit. Another approach to improving oxygen
supply is to convert a standard air supplied aeration system to a pure oxygen
system.
Pure oxygen systems are recommended for situations where wide fluctua-
tions occur in the organic loading to a plant and for strong industrial waste-
water. Since they are more efficient than conventional aeration systems, they
can be used to increase the treatment capacity of existing plants. A means of
further improving a pure oxygen or air supplied aeration system is to use
diffusers that produce smaller diameter bubbles (and hence increase the
surface area to bubble volume ratio), and to increase the contact time between
the bubble and the wastewater.
In some treatment train configurations, it is possible to create a second
biological treatment unit by recycling sludge from a secondary clarifier to a
preaeration unit. As presented in the discussion of summer/winter issues,
this was done by plant #2394 in the OCPSF industry to improve the performance
of its treatment plant during cold weather. An additional benefit of
recycling sludge in this manner is that there is usually a decrease in the
total sludge volume generated. Plant #2394 used 100 percent recycle and hence
had no waste sludge during winter months.
Fixed film biological treatment units sometimes have problems associated
with waste distribution and waste loading. Low flows in trickling filter
plants may result in poor distribution of wastewater over the filter media.
Recirculation of part of the treatment plant effluent will increase the flow
through the plant and improve the motion of the distribution arm. An approach
to increasing the capacity or improving the performance of some trickling
filter plants is to replace traditional filter media usually consisting of
stones with synthetic media designed to have a much larger surface area.
Efficient operation of a bioreactor is dependent on maintaining viable
populations of bacteria. Organic priority pollutant removal is often
VII-77
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problematic as the pollutants often inhibit the growth of organisms respon-
sible for their degradation (7-10). To efficiently degrade these organics,
the inhibitory levels should be determined and should not be exceeded in plant
operations. In addition, bacteria can be acclimated to certain toxicants by
subjecting the activated sludge to an acclimation program or by using
"pre-acclimated" bacteria, the latter process being called bioaugmentation.
Bioaugmentation has also been used to supplement plants in cold weather with
specialized bacteria that maintain high levels of biodegradation activity at
wastewater temperatures as low as 40°F. In addition, bioaugmentation has been
proven to improve oxygen transfer, reduce sludge generation, and improve
sludge settling characteristics. Furthermore, bioaugmentation will greatly
reduce the time needed for recovery from a shock loading. Preserved bacteria
can be added to a biological treatment system as needed to maintain existing
populations and to increase biodegradation capabilities in the event of a
chemical upset.
The efficiency of a biological system can be improved by reducing the
particle size of solids in the influent through pretreatment with coagulation/
flocculation, sedimentation, or other processes. Rates of adsorption,
diffusion, and biochemical reaction are all enhanced by smaller particle size.
Particles smaller than 1 x 10~6 meter in diameter can be biochemically
degraded at a much faster> rate than larger particles (7-11). This is due to
the increase in surface area to mass ratio as particle size decreases. Higher
quality secondary effluent from the biological treatment unit will result in
subsequent improvements in the performance of downstream units such as filtra-
tion and activated carbon units.
Secondary clarification systems can also be modified or operated
differently in order to upgrade or improve TSS effluent performance. An
Agency study of full-scale municipal treatment systems shows that rectangular
clarifier modifications such as reaction baffles and other flow-modifying
structures at clarifier inlets resulted in a 13.8 percent reduction in
effluent TSS. Also, the additional installation of a stop-gate in a channel
upstream of the aeration basins to reduce large flow transients to a rectang-
ular secondary clarifier resulted in 31.5 percent lower effluent TSS levels
than the unmodified clarifier without the stop-gate. In another case, this
VII-78
-------
study also shows that slowing the rotational speed of hydraulic sludge removal
mechanisms .in circular clarifiers to 56 percent of its design speed reduced
effluent TSS by 10,5 percent. Also, the additional installation of a
cylindrical ring baffle/flocculation chamber in secondary clarifiers resulted
in 38.5 percent lower effluent TSS levels than the unmodified secondary
clarifier (7-7).
For a biological system to function properly, nutrients such as organic
carbon, nitrogen, and phosphorus must be available in adequate amounts. While
domestic wastewaters usually have an excess of nutrients, industrial waste-
waters are sometimes deficient. If a deficiency is identified, the perfor-
mance of an industrial wastewater treatment plant can be improved through
nutrient addition. According to the Section 308 Questionnaire data base,
114 OCPSF plants utilize nutrient addition prior to biological treatment.
Removal of organics can be enhanced by mixing powdered activated carbon
(PAC) in the aeration basin of a biological treatment system (7-12). PAC
improves treatment in the activated sludge process because of its adsorptive
and physical properties. Lighter weight organics, such as phenols, appear to
adsorb reversibly on the carbon. Use,of PAC can dampen the shock effects of
concentrated slugs of inhibiting organics on the bacteria culture, as the
organics will initially adsorb on the carbon. The PAC can be bioregenerated
as these lighter weight organic species desorb from the PAC and are degraded.
Heavier organics, such as the residual metabolic end products, appear to
adsorb irreversibly on the PAC. PAC also helps to remove pollutants by
extending the contact time between the pollutant and the biomass. When
adsorbed by the carbon, pollutants settle into the sludge and contact time
with the biomass is extended from hours to days. The waste sludge that
contains powdered carbon is removed from the activated sludge system,
dewatered, and either disposed of or regenerated. The regenerated carbon may
require an acid wash to remove metals as well as other inorganic materials to
improve the adsorption capacity.
e.
Summer/Winter
In commenting on the 1983 proposal and subsequent notices, many commen-
ters asserted that EPA incorrectly evaluated the effect of temperature on
VII-79
-------
Diological treatment systems and incorrectly concluded that temperature is ,,„,
important in the context of effluent limitations guidelines. They claimed
that one element of this incorrect analysis was EPA's deletion of nine plants
from the data base simply because they had been issued "Best Professional
Judgement" NPDES permits with separate compliance standards for summer and
winter months. They claim that this is an arbitrary decision that virtually
ensures that the effect of temperature will not be considered in estimating
effluent variability.
EPA has studied the effects of temperature variations on biological
treatment system performance, in the OCPSF industry and disagrees with these
comments. With regard to operations in warm climates, the Agency believes
that warmer than average temperatures do not have any significant effect on
biological treatment efficiency or variability. However, algae blooms in
ponds can be a wastewater treatment problem in ponds located in warm climates.
Nonetheless, polishing ponds are not part of the technology basis for BPT
limitations. Also, EPA was not able to associate algae bloom problems'with
any elements of biological treatment (aerated lagoons, clarification, equali-
zation basins, etc.). Consequently, EPA believes that algae growth problems
in warm climates are not relevant to the promulgated BPT regulations.
In order to evaluate winter performance of biological treatment systems,
EPA has analyzed BOD5 removal efficiency, BOD5 effluent concentration, and
operational changes for 21 plants reporting daily data and other plants
located in various parts of the country. These analyses indicated that there
is a slight reduction in average BOD5 removal efficiency and a small increase
in average effluent BOD5 concentrations during winter months for some plants.
However, other plants were able to maintain a BOD5 removal efficiency of
95 percent or greater and effluent BOD5 concentrations characteristic of good
operation during the entire year. The analysis also suggests that the plants
with lower efficiencies are affected as much by inefficient operation
practices as by winter temperature considerations. A discussion of
inefficient operating practices used by some plants as well as practices
employed by plants achieving superior all year performance is presented below.
The adoption of practices used by plants with higher winter efficiencies
should result in improved winter effluent quality.
VII-80
-------
EPA has determined that temperature effects can be mitigated by opera-
tional and technological changes so that compliance with BPT limitations using
biological treatment is possible for all OCPSF plants with well-designed and
well-operated biological systems. As also discussed below, the potential
effects of winter operations are included in the plant-specific factors that
affect derivation of the variability factors used to establish effluent
limitations guidelines. In addition, EPA has developed costs for plants that
need to upgrade their winter-time biological treatment operation to comply
with the promulgated BPT limitations.
: .Regarding the deletion of nine summer/winter plants' data from the data
base, the Agency notes that because these plants were subject to meeting two
different sets of permit limits, they had no incentive to attempt to achieve
uniform limitations throughout the year. Not suprisingly then, the daily data
from these plants exhibit a two-tier pattern. These data can be characterized
by-two means, and the variability of these data over a 12-month period is
fundamentally different from the data from plants required to meet only one
set of permit limits. Consequently, the data generated during these periods
are not representative of well-operated biological treatment, which as noted
ibove, is capable of uniform treatment throughout the year as demonstrated by
£ number of plants. Another problem with daily data from these plants is that
during certain periods of the spring and fall, these plants may be able to
Operate their treatment plants at less than full efficiency because they are
required to meet the less stringent set of permit limits.
: In summary, the Agency believes that it has accounted adequately for the
effect of temperature changes on biological treatment performance in its
variability analysis by including in the variability data, base a number of
well-designed and well-operated plants from climates with significant tempera-
ture variation. The inclusion of data from plants with summer/winter permits
would result in an overestimate of the variability of biological treatment
operations in the OCPSF categories.
The detailed analyses described below are based on two sets of data that
were analyzed in order to determine the effect of temperature on the treatment
of BOD and TSS. The first set included the OCPSF daily data base, which
VII-81
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contained daily data from 69 plants. Of these, 48 were excluded from the
final BPT daily data base analysis for a variety of reasons, including greater
than 25 percent non-process wastewater dilution, summer/winter NPDES permit
limits, changes in treatment system during sampling, non-representative
treatment, and effluent data after post-biological tertiary treatment. As a
result, daily data from 21 plants formed the basis of the variability
component of the BPT limits and were included in the summer/winter analysis.
These 21 plants are #s 387, 444, 525, 682, 741, 908, 970, 1012, 1062, 1149,
1267, 1407, 1647, 1973, 1977, 2181, 2430, 2445, 2592, 2626, and 2695. The
second data set includes 131 plant responses to a Section 308- Survey question
regarding average winter and average summer performance and operating para-
meters that were gathered to highlight practices used to accommodate cold
weather conditions.
The principal parameters evaluated for correlation with temperature were
average effluent BOD5 and TSS concentration, and BOD5 removal efficiency. In
addition, two plants that had made operational changes to increase winter
efficiency were also evaluated.
525s Removal Efficiency. Of the 21 plants with long-term daily data,
14 had sufficient BOD5 influent and effluent data (total BOD5 values were
used) to enable the calculation of BOD5 monthly removal efficiencies. Six
plants <#s 387, 444, 1149, 1267, 2626, and 2695) were not used because they
had no BOD5 influent values, and plant ;#908 was eliminated because its
geographic location in Puerto Rico made any seasonal distinctions meaningless
The plants that were used had a minimum of three influent and effluent
values each month; if there were time periods where fewer values were avail-
able, these specific time periods were excluded from the analysis (Plant 1062
had only one influent measurement between 1-1-79 and 7-31-79 and plant 2592
had no influent sampling between 12-1-79 and 7-9-80). For each plant where
sampling occurred over a period exceeding 1 year, values for the same month
but different years were averaged together.
The monthly efficiencies were derived by use of the formula
VII-82
-------
Fraction removed = 1 -
[average BOD effluent for the month]
average BOD influent for the monthJ
'The result of the efficiency analysis is presented in Table VII-22.
As can be seen, the annual average BOD5 removal efficiency is 95 percent.
Seven of the.fourteen plants (#s 682, 970, 1062, 1647, 1977, 2181, and 2430)
had greater than.95 percent removal of BOD5 throughout the year. If the '
winter months are defined to be January-February-March and the summer months
are defined to be June-July-August, two plants had removal efficiencies in the
winter months that were greater than or equal to those in the summer: months.
Plant 1062 had 97 percent removal efficiency in both the winter and summer
months, and Plant 2430 had 99 percent removal efficiency in the winter months
and 98 percent removal efficiency in the summer. In addition, five plants
(ts 682, 970, 1647, 1977 «and 2181) had average winter removal efficiencies
within 1 percent of their average summer removal efficiencies.
The 14 plants are located in three different geographical regions. Plant
data were analyzed by region, with subset I including data from,the five
plants located in the ncnrth (W, IL, RI, lA, IN), subset II including data
from the six plants located in the south '(TX, GA, LA, SC), and subset III
including data from the three plants located in the middle-latitudes (VA, NG).
These results are presented in Tables VII-23, VII-24, and VII-25. Monthly
average removal efficiencies for each plant were obtained, and these were
combined into an overall monthly average for each subset. Plants located in
the northern region had the highest average removal efficiency (northern
plants - 98 percent; southern plants - 95 percent; middle latitude - 89
percent). In the northern region, four of the five plants (682, 1062, 1647,
and 2181) had removal efficiencies greater than 95 perc.ent throughout the ;
^Although it was also possible to obtain monthly efficiencies by calculating
daily efficiencies and-averaging them for each month, such a method would
have resulted in elimination of many data points when only influent or efflu-
ent values, not both, were available for a specific day- Also, because
retention times are generally greater than 1 day, and because wastewaters are
mixed during treatment, an effluent value cannot necessarily be correlated
with an influent value for that same day or for any other particular time.
VII-83
-------
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year. In the southern region, only two of the six plants (1977 and 2430) had
greater than 95 percent removal efficiencies throughout the year; in the
middle latitudes, one.out of the three plants (970) had greater than 95
percent removal efficiency. This analysis shows that removal efficiency was
affected primarily by nonclimate-related factors.
A similar analysis was performed using the data base derived from plants
that responded to the OCPSF 308 Questionnaire on summer/winter operations.
Question C-12 of the questionnaire 'asked each respondent to select a 3-month
period in the summer and a 3-month period in the winter of the same year. The-
summer period was generally selected as-June-July-August or July-August-
September, although a few respondents selected May-June-July. The winter
period was generally selected as January-February-March, although some
respondents selected various other 3-month periods from October through
February. For these two periods, the respondent was to provide summary data
for a variety of parameters, including average daily,total BOD5 influent and
effluent concentrations, TSS influent and effluent concentrations, MLSS con-
centration, mixed liquor volatile suspended solids (MLVSS) concentration, and
food to microorganism ratio (F/M). Plants were included in the analysis if
there were both influent and effluent total BOD5 values so that a BOD5 removal
efficiency could be calculated. Of all plants for which information was
available from Question C-12, 131 had sufficient information to enable the
calculation of BOD5 removal efficiency. When estimated values were given,
they were used. For the four plants using recycled waste streams (296, 2551,
1617, 2430), only the initial influent and final effluent values were used;
although this might result in artificially high efficiencies, it represented
the only logical approach. Two plants (1038 and 1389) had two different sets
of values, so each set was used. Two plants (227 and 909) had influent data
from one biological treatment system and 'effluent data from another, and were
not used in the analysis.
VII-88
-------
The results of the analysis are as follows:
Summer
Winter
Plant Category
All Plants
Southern Plants
Northern Plants
Middle Latitude
Plants
N !
131
52
46
33
Avg
Sfficiencj
0.89
0.91
0.86
0.89
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r Dev Efficiency Dev
0.31
0.14
0.48
0.18
0.86
0.86
0.85
0.87
0.25
0.21
0.32
0. 19
Southern plants were located in Alabama, Florida, Georgia, Louisiana,
Mississippi, South Carolina, and Texas. Northern plants were located in
Connecticut, Iowa, Illinois, Indiana, Michigan, New Jersey, New York, Ohio,
Pennsylvania, Rhode Island, and West Virginia. Middle latitude plants were
located in Arkansas, Delaware, Kentucky,. Maryland, North Carolina, Oregon,
Tennessee, Virginia, and Washington.
These results are consistent with the results of the 14-plantdaily data
analysis discussed previously. The BOD5 removal efficiencies for all plants
are 3 percent less during the winter period than the .summer period (86% vs.
89%). The regional removal efficiencies are 1 to 5 percent less in the winter
period than in the summer period. The greatest regional variation in
efficiency occurs in the south. The standard deviation.of the efficiency is
large relative to the efficiency difference within each category, reflecting
the large variations among plants within the same category. These results
tend to indicate that while northern and middle latitude plants would have
larger swings in temperature going from season to season, these swings have
been compensated for through operation and process modifications as indicated
by the similar summer and winter removal efficiencies (86% vs. 85%). The
larger difference between summer and winter removal efficiencies for southern
plants (91% vs. 86%) indicate that these facilities have not "adequately
addressed the smaller temperature swings by operational and process modifica-
tions.
VII-89
-------
These findings support several conclusions. There may be differences
between efficiencies attainable in summer and in winter, but these differences
are nonetheless small. The large standard deviations obtained reflect differ-
ences in operating practices among plants. Plants that operate efficiently do
so year-round, and have been able to minimize or at least partially compensate
for temperature effects through equipment and operational treatment system
adjustments. In addition, plants located in the colder northern climate show
minimal efficiency differences between winter and summer months, which
provides further evidence that temperature effects are minimal. The daily
data assessment also indicates minimal efficiency variations during the spring
and autumn months, when temperature fluctuations would tend to be greatest;
this result casts doubt on the theory that fluctuations, rather than continued
cold, would reduce BOD5 removal efficiency by preventing the formation of a
stable microbial population.
Average Effluent BOD., and TSS
The effect of temperature on effluent BOD5 and TSS levels was evaluated
previously in the July 1985 document entitled "Selected Summary of Information
in Support of the OCPSF Point Source Category Notice of Availability of New
Information." EPA calculated rank correlation by subcategory for BOD5 efflu-
ent and TSS effluent versus heating degree days, a measure typically used by
power companies to estimate heating bills. The results of the analysis were
consistent with the assumption that temperature is not a factor. With the
exception of effluent TSS for specialty chemicals, all calculated rank
correlations were not significant. In the case of specialty chemicals, the
correlation was positive and significant. However, the positive correlation
implies that TSS increases as temperature decreases. Since engineering
considerations dictate that TSS should not decrease as temperature increases,
this result is considered spurious.
A new analysis was conducted, employing data from. 20 of the 21 plants in
the data base used for the calculation of BPT variability factors. The only
plant not used was #908, because of its location in Puerto Rico. BOD, and TSS
effluent averages were compared to months rather than heating degree days (see
Tables VII-26 and VII-27). The annual average BCD, and. TSS effluent concen-
trations are 22 mg/1 and 31 mg/1, respectively. Seven of the 20 plants (525,
VII-90
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682, 970, 1062, 1973, 2181, and 2430) have monthly average BOD5 effluent
concentrations less than 22 rag/1 throughout the year, while four of the
20 plants (387, 1012, 1407, and 2626) have monthly average. BOD5 effluent
concentrations less than 37 mg/1 throughout the year. Also, if winter months
are defined as January-February-March and summer months are defined as
June-July-August, three plants (1062, 1149, and 2430) have lower average BOD5
effluent concentrations for the winter months than for the summer months. In
addition, two plants (387 and 2626) have average BOD5 effluent concentrations
for the winter within 3 mg/1 of the summer average BODg effluent concentra-
tions, while four plants (444, 1973, 2626, and 2695) have average TSS effluent
concentrations for the winter months within 3 mg/1 of the summer average TSS
effluent concentrations.
Another analysis was performed comparing each plant's average BODg and
TSS effluent concentrations in the winter and summer months to its annual
average BOD5 and TSS effluent targets that provide the basis for BPT effluent
limitations. These annual compliance targets are presented in Appendix VII-A
of this document. Eight of the 20 plants (525, 682, 1062, 1407, 1647, 1973,
2181, and 2430) had both winter and summer average BOD5 effluent concentra-
tions below their annual average; BOD5 effluent compliance targets, while eight
plants (387, 444, 525, 1CTL2, 1407, 1973, 2181, and 2626) had both summer and
winter average TSS effluent concentrations below their annual average TSS
effluent compliance targets.
The plants were then divided into geographical regions,and the same
analyses performed. Subset I consisted of six northern plants from West
Virginia, Illinois, Rhode Island, Iowa, and Indiana; subset II consisted of
10 southern plants from Texas, Georgia, Louisiana, and South Carolina; and
subset III consisted of four middle latitude plants from Virginia and North
Carolina (see Tables VII-28, VII-29, VII-30, VII-31, VII-32, and VII-33). The
annual average BOD5 effluent concentrations were 13 mg/1, 30 mg/1, and 16 mg/1
for the northern, southern, and middle latitude plants, respectively; annual
average TSS effluent concentrations were 38 mg/1, 31 mg/1, and 19 mg/1 for the
northern, southern, and middle latitude plants, respectively. Approximately
66 percent, 70 percent, and 50 percent of the plants in the northern,
southern, and middle latitude regions, respectively, have annual average BOD5
VII-93
-------
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VII-99
-------
concentrations less than the regional annual average BOD5 effluent concentra-
tion; approximately 66 percent, 66 percent, and 50 percent of the plants in
the northern, southern, and middle latitude regions, respectively, have annual
average TSS effluent concentrations below the regional annual average TSS
effluent concentrations.
Additional Parameters
Evaluating other parameters using the 21-plant daily data base was not
possible since BODg, TSS, and flow were the only parameters monitored. The
Question C-12 data base provides average summer and winter values for MLSS,
HLVSS, and F/M. For all plants used in the previous C-12 data analysis for
BOD5 efficiency and for which values for MLSS, MLVSS, or F/M were available
for both summer and winter periods, average values for MLSS, MLVSS, and F/M
were determined.
Several editing rules were used. If estimates were given, they were
used. For Plant #1340, two different biological treatment processes had the
same BOD5 values, but had two different sets of MLSS, MLVSS, and F/M values.
Both sets were used. For Plant #296, which recycled waste streams, the MLSS,
MLVSS, and F/M values for each recycled stream were used. For Plants #1389
and #1038, -where two sets of BOD5 values were used, two sets of MLSS, MLVSS,
and F/M values were also used.
Based on these rules, average MLSS, MLVSS, and F/M values are as follows:
HLSS (mg/1)
Summer
4634
Winter
4950
MLVSS (mg/1)
Summer
3003
Winter
3444
Summer
1.024
F/M
Winter
0.863
An attempt was made to correlate the summer and winter values for MLSS,
MLVSS, and F/M to the summer and winter values for BOD5 removal efficiency.
This exercise yielded no conclusive results; the analysis found some plants
with poor winter performance to have higher MLSS concentrations and lower F/M
ratios (which should help to compensate for lower temperatures), while other
poor winter performers had the opposite trend in operating conditions. There
also appeared to be no correlation between plant location (northern or
VII-100
-------
southern) and seasonal operating parameters. This exercise also found plants
in northern climates achieving high year-round performance with very little
variation in seasonal MLSS, MLVSS, and F/M values. Therefore, it seems that
good plant performance is a function of a combination of factors (including
system design, operating parameters, and operating procedures) whose separate
contributions cannot be readily determined based on the level of information
gathered in this segment of the Section 308 Questionnaire.
Operational Changes
Two plants (948 and 2394) were identified as having made operational or
process changes in an effort to improve efficiency and provide at least
partial compensation for temperature.
Plant #948, which has a warm process effluent, has instituted several
operational changes in winter months to improve the performance of its
biological treatment system. First, it turns off some of its cooling towers
to compensate for greater heat loss during winter months. The facility also
decreases the number of aerators by 5 percent since there is significant heat
loss during the aeration process. The MLSS level and sludge age are increased
by decreasing the sludge wastage rate. These measures increase the sludge's
capacity to oxidize and metabolically assimilate organic material. A disad-
vantage of the increased sludge age is that sludge settling characteristics
are adversely affected. The plant largely compensates for this by increasing
the pplyelectrolyte dosage to the influent to the clarifier in the winter.
A second facility, Plant #2394, has also instituted process modifications
to improve the performance of its activated sludge system in the winter. In
the summer,-the plant uses a preaeration basin followed by a single stage
activated sludge unit and secondary elarifiers. In the summer, sludge from
the elarifiers is recycled ,to the activated sludge unit. In the winter,
sludge from the elarifiers is recycled to the preaeration unit, thus con-
verting it.into a second biological unit. In summary, the installation of
additional piping to allow flexibility in the sludge recycle point allows the
plant to have a one-stage biological treatment system in the summer and a
two-stage system in the winter.
VII-101
-------
Data are not available for Plant #948 to correlate its operational
changes with removal efficiency. Monthly monitoring data are available for
Plant 12394, although the plant was excluded from the 21-plant data base for
calculating BPT variability factors because the treatment system was modified
during the period of record and the effluent data were collected after terti-
ary treatment. Monthly BOD5 influent and effluent levels (IBOD5 and EBOD ),
TSS effluent levels (ETSS), and removal efficiencies for Plant #2394 are
presented in Table VII-34 for the period December 1981 to March 1984. The
results are inconclusive. They show reduced efficiency during the months of
January and February. They also show an efficiency increase of 19 percent
between January 1982 and January 1983, and an increase of 13 percent between
February 1982 and February 1983. The efficiency for January 1984 then drops
by 7 percent from the preceding January, but the February 1984 efficiency of
95 percent is the same as the efficiency of the preceding February. The sharp
efficiency increase between winter 1982 and winter 1983 suggests the effec-
tiveness of the operational changes, but the reasons for the decrease between
January 1983 and January 1984 cannot be determined from the available data.
It is not known if production changes occurred during that period.
Conclusion
Results of the BOD5 removal efficiency, BOD5 effluent, and operational
changes analyses performed above show a slight reduction in efficiency at some
plants during the months of January"and February. Efficiencies vary widely
among plants, and many plants have attained efficiencies of 95 percent or
greater for all months of the year. This suggests that the plants with lower
efficiencies are affected as much by inefficient operating practices as by
winter temperature considerations. Adoption of certain practices used by
plants with higher winter efficiencies by these plants should result in
improved winter efficiency.
Technologies and operating techniques exist that, if properly applied,
can compensate for temperature. Plants operating in cold weather conditions
should recognize that excessive storage prior to treatment may reduce the
temperature of the biotreatment system. Cold weather operation may require
insulation of treatment units, covering of open tanks, and tracing of chemical
VII-102
-------
TABLE VII-34.
MONTHLY DATA FOR PLANT #2394
1981
1982
1983
1984
December
January
February
March
April
May
June
July
August
September
October
November
December
January
February
March
April
May
June
July
Augus t
September
October
November
December
January
February
March
Average
Influent
BOD
(mg/1)
396
311
475
484
468
364
416
350
608
427
570
530
521
377
457
420
387?
404
436
332
474
364
415
388
351
295
397
354
Average
Effluent
BOD
(mg/1)
59
76
84
38
1 9
5
5
2
2
3
9
9
14
20
21
13
8
'5
4
3
3
3 .
4
8
11
35
21
15
Average
Effluent
TSS
(mg/1)
26
20
20
22
24
14
19
13
8
7
8
10
15
15
14
14
22
17
17
13
8
10
13
21
15
24
25
26
BOD5
Removal
Efficiency
(%)
0.85
0.76
0.82
0.92
0.98
0.99
0.99
0.99
1.00
0.99
0.98
0.98
0.97
0.95
0.95
0.97
0.98
0.99
0.99 ' •• •'
0.99 ,
0.99
0.99
0.99
0.98
0.97
0.88
• 0.95
0.96
VII-103
-------
feed lines. Insulation may include installing tanks in the ground rather than
aboveground, using soil around the walls of aboveground units, or enclosing
treatment units. During colder periods, maintenance of higher MLSS concen-
trations and suitable, reduced F/M may be necessary. Plant-specific
techniques, such as those used at Plants #948 and #2394, should also be
applied.
Another case study, cited in vendor literature, discusses cold weather
modifications for a biological treatment system at a West Virginia polyester
resin manufacturer. During the winter, the plant uses its equalization basin
for biological contact stabilization before the wastewater enters the
biological aeration basin. The plant replaced some of its aerators with
mechanical aerators especially designed for cold weather operation and added
similar aerators to the equalization basin for winter use. The new aerators
designed specifically for winter conditions provide "aeration, mixing, and 02
transfer without the temperature loss of conventional aerators during cold
weather." The West Virginia facility now achieves "a 99 percent BOD removal,
with influent BOD at 2,500 mg/1 and effluent at 20 mg/l~even in the winter."
Part of the improvement in effluent quality was attributed to warmer basin
temperature (7-13).
Two other points should be made. First, temperature is only one of many
factors that impacts wastewater treatment performance. Waste load variations,
biomass acclimation, flow variations, waste treatability, and temperature of
the wastewater as well as adequacy of treatment system design and operation
must all be considered. The interaction among these factors makes it diffi-
cult to isolate any one factor separately. Temperature considerations must be
viewed as specific to a given site in the context of these factors, rather
than as specific to a given geographic area.
Secondly, EPA has taken the cost of improving winter efficiency into
account by using the minimum State temperature in the K-rate equation for
estimating costs for full-scale and second-stage biological systems and by
adding a cost factor for biological upgrades. The cost factor ranges from
1.0 to 2.0 and is also based upon a State's minimum average ambient
temperature. Both State minimum temperature and the biological upgrade cost
factor are discussed in more detail in Section VIII.
VII-104
-------
4. Polishing and Tertiary Treatment Technologies
Polishing technologies consist of polishing ponds, filtration, and
chemically assisted clarification (CAC). Tertiary treatment includes only
activated carbon treatment.
a. Polishing Ponds
Polishing ponds are bodies of wastewater, generally limited to 2 to
3 feet in depth, used for the removal of residual suspended solids by
sedimentation. They are usually used as a tertiary treatment step following
biological treatment. Depending on the nature of the pollutant to be removed
and the degree of removal required, the polishing treatment system can consist
of one unit operation or multiple unit operations in series.
, According to the Section 308 Questionnaire data base, 64 OCPSF plants
reported using polishing ponds as an end-of-pipe treatment. Originally, 18 of
these 64 plants were used to establish treatment performance limits for BPT
Option II. However, following the December 9, 1986, Federal Register Notice
of Availability, the Agency carefully reviewed the BPT data base identifying
plants that reported having polishing ponds, and evaluated the data that they
provided. The 18 plants used to calculate BPT Option II effluent limitations
met the preliminary BFT effluent criteria, which was 95 percent removal of
BOD5 across the treatment system or an effluent BOD5 concentration equal to or
less than 50 mg/1 and an effluent TSS concentration .equal to or less than
100 mg/1.
The Agency reviewed the information provided in response to the Section
308 Questionnaires and contacted permit writers in the Regions and/or States
in which the facilities were located. The results of this effort identified
16 of the 18 plants as not containing BPT Option II treatment systems. Only
two plants are actually using their ponds as a final polishing step to remove
suspended solids and BOD5 from the effluent produced by a biological system
operating at a BPT Option I level. A summary of the results of this evalu-
ation is given in Table VII-35. A' description of the 16 plants without the
BPT Option II technology follows. Seven of the 16 plants combine treated
wastewater from the biological treatment system with other wastewaters in a
VII-105
-------
TABLE VII-35.
MATRIX OF 18 PLANTS WITH POLISHING
PONDS USED AS BASIS FOR BPT OPTION II LIMITATIONS
Plant ID
157
267
284
384
500
811
866
948
990
1020
1061
1438
1695
1698
1717
2471
2528
4017
Pond
Serves as
Equalization
Basin
X
X
X
X
X
X
X
Pond Pond Pond Pond
Serves as Serves as Known to Serves as
Secondary Reaeration Have Algae a Final
Clarifier Basin Problem Polish
X
X
X
X
X
X
X
X
X
X
X
TOTAL
VII-106
-------
final pond. Since these ponds mix different wastewaters, they achieve some
dilution of treated process wastewater prior to discharge. Because the actual
removal of the pollutants through biodegradation or settling cannot be
demonstrated, these ponds cannot be characterized as polishing ponds. Another
plant uses a "polishing pond" as a reaeration basin to increase the level of
dissolved oxygen (DO) in its effluent and to prevent a depressed oxygen level
from occurring in the receiving stream. Finally, one plant is known to have
an algae problem associated with its pond operation during the summer months,
that indicates that this plant may not be meeting the BPT Option II criteria
during part of the year.
As for the remaining 30 plants that reported having polishing ponds that
were not used to form the basis for the BPT Option II limits, four plants that
reported effluent BOD5, TSS, and flow data did not meet the BPT Option II
criteria. Fifteen plants did not report any BOD5 or TSS data; seven of these
15 plants use their ponds as a secondary clarification step, and six plants
use their ponds as a final mixing step. The remaining 11 plants were not used
because three plants have BPT Option III treatment (filtration); one plant
recycles water back to its production processes from the pond; one plant is an
indirect discharger; two plants discharge from their polishing ponds into
subsequent treatment stages; and four plants do not use biological treatment.
Based on the above information, the Agency concluded that the use of polishing
ponds to provide additional removal ,of conventional pollutants (BODg and TSS)
beyond that achievable by well-designed and well-operated biological treatment
(Option I) is not successfully demonstrated in the OCPSF industry.
b. Filtration
Filtration is an established unit operation for achieving the removal -of
suspended solids from wastewaters. The removal is accomplished by the passage
of water through a physically restrictive medium (e.g., sand, coal, garnet, or
diatomaceous earth) with resulting entrapment of suspended particulate matter
by a complex process involving one or more removal mechanisms, such as
straining, sedimentation, interception, impaction, and adsorption. Continued
filtration reduces the porosity of the bed as particulate matter removed from
the wastewater accumulates on the surface of the grains of the media and in
VII-107
-------
the pore spaces between grains. This reduces the filtration rate and
increases the head loss across the filter bed. The solids must be removed by
"backwashing" when the head loss increases to a limiting value. Backwashing
involves forcing wash water through the filter bed in the reverse direction of
the original fluid flow so that the solids are dislodged from the granular
particles and are discharged in the spent wash water. When backwashing is
completed, the filter is returned to service.
Filtration is an established -wastewater treatment technology currently in
full-scale use for industrial waste treatment. Filtration has several
applications: 1) pretreatment to remove suspended solids prior to processes
such as activated carbon adsorption, steam stripping, ion exchange, and
chemical oxidation; 2) removal of residual biological floe from settled
treatment process effluents; 3) removal of residual chemically coagulated floe
from physical/chemical treatment process effluents; and 4) removal of oil from
oil separation and dissolved air flotation effluents.
According to the Section 308 Questionnaire data base, 41 OCPSF plants use
filtration as a polishing technology. EPA evaluated BPT Option III (bio-
logical treatment plus multimedia filtration) technology to determine if this
option could achieve, in'°a practicable manner, additional conventional pollu-
tant removal beyond that achievable by well-designed, well-operated biological
treatment with secondary clarification. Eleven plants in the BPT data base
use BPT Option III technology and meet the final BPT editing criteria. Thus,
this option would require EPA to regulate all seven subcategories based upon a
very small data set. As shown in Table VII-36, the median effluent TSS
concentration value for these plants is 32 mg/1. Even if three additional
plants are included in this data base because they use Option I treatment plus
either ponds or activated carbon followed by1filters, the resulting median TSS
value is 34 mg/1. These results, when compared to the performance of
clarification only following biological treatment (median value of 30 mg/1),
clearly show that the efficiency of filtration following good biological
treatment and clarification is not demonstrated for this industry. Moreover,
on the average, OCPSF plants with more than Option I treatment in EPA's data
base (biological treatment plus filtration) have not demonstrated significant
BOD5 removal beyond that achievable by Option I treatment alone. The median
VII-108
-------
TABLE VII-36.
OPTION III OCPSF PLANTS WITH BIOLOGICAL TREATMENT
PLUS FILTRATION TECHNOLOGY THAT PASS THE BPT EDITING CRITERIA
Plant ID
2551
1943
102
2536
883
2376
1343
2328
909
1148
844
Median value
Effluent TSS
(mg/1)
9
16
18
18
27
32
36
37
41
46
54
32
Effluent BOD
(mg/1)
11
22
7
3
20
27
8
19
21
37
5
19
VII-109
-------
concentration value for these plants is 19 mg/1 compared to a median
BOD,
value of 23 mg/1 BOD5 for the plants with Option I technology in place which
meet the 95 percent/40 mg/1 BOD5 editing criteria. Therefore, EPA does not
believe that the data support any firm estimate of incremental pollutant
removal benefits and incremental costs for BPT Option III.
One commenter suggested that, in light of the apparent poor incremental
performance of filters in the OCPSF industry, EPA should transfer data from
non-OCPSF filtration operations, specifically from domestic sewage treatment.
EPA has evaluated the additional removal achievable by multimedia filtration
on the effluent from the biological treatment of domestic sewage. Data found
in EPA's "Process Design Manual for Suspended Solids Removal" (EPA 625/1-
75-003, January 1975) indicates that multimedia filtration achieves a median
of 62 percent removal of TSS from biological treatment effluent TSS levels of
25 mg/1 or less.
The Agency also considered transferring multimedia filtration performance
data from the pharmaceutical manufacturing point source category for use in
the development of BPT Option III (biological treatment plus filtration)
limitations. Daily data across multimedia filtration systems at three
pharmaceutical plants demonstrated that effluent concentrations of TSS from
advanced biological treatment in that industry could be reduced by 50 percent
over a 15 to 100 mg/1 influent concentration range by multimedia filtration
(no removal of BOD5 across multimedia filtration was demonstrated). This
concentration range covers the range of performance of OCPSF plants that meet
the Agency's Option I 95 percent/40 mg/1 (BOD5) and 100 mg/1 (TSS) editing
criteria to define well-designed and well-operated biological treatment.
However, the OCPSF industry filtration data do not indicate any
substantial TSS or BOD5 removal beyond that achieved by Option I technology.
This indicates that differences in the biological solids in the OCPSF industry
may be responsible for the lack of filtration effectiveness. For example, if
the OCPSF biological floe (solids) were to break into smaller sized or
colloidal particles, they could pass through the filter substantially
untreated. While EPA cannot be certain.whether this occurs, the data indicate
VII-110
-------
that filters in this industry are not as effective in removing OCPSF waste-
water solids as they may be for domestic sewage or certain other industry
wastewater solids. EPA does not believe that the appropriateness of
transferring data from these other wastewaters to the OCPSF industry is
demonstrated.
c. Chemically Assisted Clarification (GAG)
Coagulants are added to clarifiers (chemically assisted clarifiers) to
enhance liquid-solid separation, permitting solids denser than water to settle
to the bottom and materials less dense than water (including oil and grease)
to flow to the surface. Settled solids form a sludge at the bottom of the
clarifier, which can be pumped out continuously or intermittently. Oil and
grease and other floating materials may be skimmed off the surface.
Chemically assisted clarification may be used alone or as part of a more
complex treatment process. It may also be used as:
• The first process applied to wastewater containing high levels of
settleable suspended solids.
• The second stage of most biological treatment processes to remove the
settleable materials, including microorganisms, from the wastewater;
the microorganisms can then be either recycled to the biological
reactor or discharged to the plant's sludge handling facilities.
9 The final stage of most chemical precipitation (coagulation/
flocculation) processes to remove the inorganic floes from the
wastewater.
As discussed in Section VIII, chemically assisted clarification was a
component of the model wastewater treatment technology for estimating the BPT
engineering costs of compliance. First, when biological treatment was in
place (with or without secondary clarification), an additional chemically
assisted clarification unit operation iwas costed if the reported TSS effluent
concentration was more than 3 mg/1 above the plant's long-term average
compliance target. Second, for plants that do not need biological treatment
to comply with their BOD5 compliance targets, chemically assisted clarifi-
cation unit operations were costed if the reported TSS effluent concentrations
were more than 3 mg/1 above the long-term average compliance target.
VII-111
-------
Although chemical addition was not frequently reported by plants in the
OCPSF industry, chemically assisted clarification is a proven technology for
the removal of BOD5 and TSS in a variety of industrial categories, partic-
ularly in the pulp and paper industry. Case studies of full-, pilot-, and
laboratory-scale chemically assisted clarification systems in the pulp and
paper industry as well as other industrial point source categories are
discussed in the following sections.
Full-Scale Systems
Several full-scale, chemically assisted clarification systems have been
constructed in the pulp, paper, and paperboard industry and in other indus-
trial point source categories. Data on the capability of full-scale systems
to remove conventional pollutants are presented below.
Recent experience with full-scale, alum-assisted clarification of
biologically treated kraft mill effluent suggests that final effluent levels
of 15 mg/1 each of BODg and TSS can be achieved. The desired alum dosage to
attain these levels can be expected to vary depending on the chemistry of the
wastewater to be treated. The optimum chemical dosage is dependent on pH.
Chemical clarification following activated sludge treatment is currently
being employed at a groundwood (chemi-mechanical) mill. According to data
provided by mill personnel, alum is added at a dosage .of about 150 mg/1 to
bring the pH to an optimum level of 6.1. Polyelectrolyte is also added at a
rate of 0.9 to 1.0 mg/1 to improve flocculation.
Neutralization using NaOH is practiced prior to final discharge to bring
the pH within acceptable discharge limits. The chemical/biological solids are
recycled through the activated sludge system with no observed adverse effects
on biological organisms. Average reported results for 12 months of sampling
data (as supplied by mill personnel) show a raw wastewater to final effluent
BOD5 reduction of 426 to 12 mg/1, and TSS reduction of 186 to 12 mg/1.
VII-112
-------
Treatment system performance at the mill was evaluated as part of a study
conducted for the EPA (7-14). Data obtained over 22 months show average final
effluent BOD5 and TSS concentrations of 13 and 11 mg/1, respectively. As part
of this study, four full-scale chemically assisted clarification systems in
other industries were evaluated. Alum coagulation at a canned soup and juice
plant reduced final effluent BOD5 concentrations from 20 to 11 mg/1, and TSS
levels from 65 to 22 mg/1. Twenty-five mg/1 of alum plus 0.5 mg/1 of poly-
electrolyte are added to the biologically treated wastewater to achieve these
final effluent levels. Treatment plant performance was evaluated at a winery
where biological treatment followed by chemically assisted clarification was
installed. Final effluent levels of 39.6 mg/1 BOD5 and 15.2 mg/1 TSS from a
raw wastewater of 2,368 mg/1 BOD5 and 4,069 mg/1 TSS were achieved. The
influent wastewater concentrations to the clarification process were not
reported. The chemical dosage was 10 to 15 mg/1 of polymer (7-14). A
detailed summary of the results of the study of full-scale systems is pre-
sented in Table VII-37 (7-14).
In October'1979, operation of a full-scale chemically assisted
clarification system treating effluent from an aerated stabilization basin at
a northeastern bleached kraft mill began. This plant was designed and
constructed after completion of extensive pilot-scale studies. The purpose of
the pilot plant was to demonstrate that proposed water quality limitations
could be met through the use of chemically assisted clarification.' After
demonstrating that it was possible to meet the proposed levels, studies were
conducted to optimize chemical dosages. The testing conducted showed that the
alum dosage could be reduced significantly by the addition of acid for pH
control, while still attaining substantial TSS removal. In the pilot-scale
study, it was shown that total alkalinity, a measure of a system's buffering
capacity, was a reliable indicator of wastewater variations and treatability.
Through this study, a direct relationship between total alkalinity and alum
demand was shown. High alkalinity (up to 500 mg/1) caused by the discharge of
black liquor or lime mud results in high alum demands. Therefore, a sub-
stantial portion of alum dosage can be used as an expensive and ineffective
means of reducing alkalinity (pH) to the effective pH point (5 to 6) for
optimum coagulation. The use of acid to assist in pH optimization can mean
substantial cost savings and reduction in the alum dosage rate required to
VII-113
-------
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effect coagulation. In one instance, use of concentrated sulfuric acid for pH
reduction decreased alum demand by 45 percent. Acid addition was also
effective in reducing alum dosage for wastewaters with low alkalinity
(approximately 175 mg/1) (7-15).
Table VII-38 summarizes effluent quality of the full-scale system since
startup; this system has been operated at an approximate alum dosage rate of
350 mg/1 without acid addition. Recent correspondence with a mill represen-
tative indicated that, with acid addition, this dosage rate could be reduced
to 150 mg/1 (7-16). However, this lower dosage rate has not been confirmed by
long-term operation.
Scott et al. (7-17) reported on a cellulose mill located on the shore of
Lake Baikal in the USSR. The mill currently produces 200,000 kkg (220,000
tons) of tire cord cellulose and 11,000 kkg (12,100 tons) of kraft pulp per
year. Average water usage is 1,000 kl/kkg (240 kgal/t). The mill has strong
and weak wastewater collection and treatment systems. The average BOD5 for
the weak wastewater system is 100 mg/1, while the strong wastewater BOD5 is
400 mg/1. Only 20 percent of the total wastewater flow is included in the
strong wastewater system. Each stream receives preliminary treatment con-
sisting of'neutralization of pH to 7.0, nutrient addition, and aerated
equalization. Effluent from equalization is discharged to separate aeration ,
and clarification basins. These basins provide biological treatment using a
conventional activated sludge operation. Aeration is followed by secondary
clarification. Suspended solids are settled, and 50 percent of the sludge is
returned to the aeration process. Waste sludge is discharged to lagoons. The
separate streams are combined after clarification and are treated for color
and'suspended solids removal in reactor clarifiers with 250 to 300 mg/1 of
alum and 1 to 2 mg/1 of polyacrylamide flocculant, a nonionic polymer. The
clarifiers have an overflow rate of approximately 20.4 m per day/m
(500 gpd/ft2).
Chemical clarification overflow is discharged to a sand filtration
system. The sand beds are 2.9 m (9.6 ft) deep with the media arranged in five
layers (7-18). The sand size varies from 1.3 mm (0.05 in) at-the top to 33 mm
(1.3 in) at the bottom. The filter is loaded at 0.11 m3 per minute/m
VII-115,
-------
TABLE VII-38.
FINAL EFFLUENT QUALITY OF A CHEMICALLY ASSISTED
CLARIFICATION SYSTEM TREATING BLEACHED KRAFT WASTEWATER
Date
Average
for Month
BOD. (mg/1)
Maximum Day
Average
for Month
TSS (mg/1)
Maximum Day
September 1979
October 1979
November 1979
December 1979
January 1980
February 1980
March 1980
April 1980
May 1980
11
8
9
21
8
7
13
9
11
21
12
18
83
16
14
46
16
22
87
40
28
21
28
31
44
32
38
254
92
47
56
36
68 -
113
96,
80
VII-116
-------
(2.7 gpm/ft2). Effluent from sand filtration flows to a settling basin and
then to an aeration basin; both basins are operated in series and provide a
7r-hour detention time.
The effluent quality attained is as follows:
Parameter ". Raw Waste
BOD5 (mg/1) 300
Suspended Solids (mg/1) 60
PH -
Final Effluent
2
• '• 5
6.8 - 7.0
Individual treatment units are not monitored for specific pollutant
parameters. '
Pilot- and Laboratory-Scale Systems ,
Several laboratory- and pilot-scale studies of the application of
chemically assisted clarification have been conducted. Available data on this
technology to remove conventional pollutants based on laboratory- and pilot-
scale studies are presented below.
As part of a study of various solids reduction techniques, Great Southern
Paper Co. supported a pilot-scale study of chemically assisted clarification
(7-19). Great Southern operates an integrated unbleached kraft mill,
Treatment consists of primary clarification and aerated stabilization followed
by a holding pond. The average suspended solids in the discharge from the
holding pond were 65 mg/1 for the period January 1, 1973, to December 31,
1974. In tests on this wastewater, 70 to 100 mg/1 of alum at a pH of 4.5
provided optimum dosages; the removals after 24 hours of settling ranged from
83 to 86 percent. Influent TSS of the sample tested was 78 mg/1. Effluent
TSS concentrations ranged from 11 to 13 mg/1;
- In a recent EPA-sponsored laboratory study, alum, ferric chloride, and
lime in combination with five polymers, were evaluated in further treatment of
biological effluents from four pulp and paper mills (7-20). Of the three
chemical coagulants, alum provided the most consistent flocculation at minimum
dosages, while lime was the least effective of the three. However, the study
VII-117
-------
provides the optimum chemical dosage for removal of TSS from biologically
treated effluents. These, inconclusive findings are the result of a number of
factors, including the lack of determination of optimum pH to effect removal
of TSS; the lack of consideration of higher chemical dosages when performing
laboratory tests even though data for some mills indicated that better removal
of TSS was possible with higher chemical dosage (a dosage of 240 mg/1 was the
maximum considered for alum and ferric chloride, while 200 mg/1 was the
maximum dosage used for lime); the testing of effluent from one mill where the
TSS concentration was 4 mg/1 prior to the addition of chemicals; and the elim-
ination of data based simply on a visual determination of proper flocculation
characteristics.
Laboratory data on alum dosage rates for chemically assisted
clarification have been submitted to the Agency in comments on the pulp,
paper, and paperboard contractor's draft report (7-21). Data submitted for
bleached and unbleached kraft pulp and paper wastewaters indicate that
significant removals of suspended solids occur at alum dosages in the range of
100 to 350 mg/1 (7-22, 7-23, 7-24). For wastewaters resulting from the
manufacture of dissolving 'sulfite pulp, effluent BOD5 and TSS data were
submitted for dosage rates of 250 mg/1; however, it was stated that dosages
required to achieve an effluent TSS concentration on the order of 15 mg/1
would be in the range of 250 to 500 mg/1 (7-25). During the pulp, paper, and
paperboard rulemaking, NCASI assembled jar test data for several process types
and submitted it to the Agency (7-26). Data for chemical pulping subcategories
indicated that alum dosages in the range of 50 to 700 mg/1 will effect
significant removals of TSS. The average dosage rate for all chemical pulping
wastewaters was 282 mg/1. Data submitted for the groundwood, deink, and
nonintegrated-fine papers subcategories indicate that dosages in the range of
100 to 200 mg/1 .will significantly reduce effluent TSS.
Data on the frequency of this technology are not available for the OCPSF
industry although data on the frequency of other similar technologies
(coagulation, flocculation, clarification, chemical precipitation) have been
previously presented. However, based upon the above information and upon the
general performance of clarifiers in treating TSS, EPA has concluded that
chemically assisted clarification can treat TSS in non-end-of-pipe biological
plants to meet the BPT TSS limits.
VII-118
-------
d. Activated Carbon Adsorption
Activated carbon adsorption is a physical separation process in which
organic and inorganic materials are removed from wastewater by sorption or the
attraction and accumulation of one substance on,the surface of another. There
are essentially three consecutive steps in the sorption of dissolved materials
in wastewater by activated carbon. The first step is the transport of the
solute through a surface film to the: exterior of the carbon. The second step
is the diffusion of solute within the pores of the activated carbon. The
third and final step is sorption of the solute on the interior surface bound-
ing the pore and capillary spaces of the activated carbon, ,While the primary
removal mechanism is adsorption, biological degradation and filtration also
may reduce the organics in the solution.
Activated carbon is considered to be a non-polar sorbent and tends to
.sorb the least.polar and least soluble organic compounds; it will sorb most,
but not all, organic compounds. As activated carbon adsorbs organics from
wastewater, the carbon pores eventually become saturated and the exhausted
carbon must be regenerated for reuse or replaced with fresh;carbon. The
adsorptive capacity of the carbon can be restored by chemical or thermal
regeneration. :_•'-••
s t f ;, * '. - '
There are two forms of activated carbon in common use—granular and
powdered. Granular carbon is generally preferred for.most wastewater applica-
tions because it can be readily regenerated. The two forms of carbon used and
different process configurations are described below.
Granular Activated Carbon. Granular carbon is about 0.1 to 1 mm in
diameter and is contacted with wastewater in columns or beds. The water to be
treated is either filtered .down (downflow) or forced up (upflow) through the
carbon column or bed. Additional design configurations of carbon contact
columns include gravity or pressure flow, fixed or moving beds, and single
(parallel) or multi-stage (series) arrangements. In a typical downflow
countercurrent operation, two columns are operated.in series with a common
spare column. When breakthrough occurs for the second column (i.e., the
concentration of a, target pollutant in the effluent is higher than the
VII-119
-------
desired concentration), the exhausted column is removed from service for
regeneration of the carbon. The partially exhausted second column becomes
the lead column, and the fresh spare column is added as a second column in the
series. When breakthrough is again reached, the cycle is repeated. The fixed
bed downflow operation, in addition to adsorption, provides filtration but
may require frequent backwashing. In an upflow configuration, the exhausted
carbon is removed at the bottom of the column, and virgin or regenerated
carbon is added at the top, thereby providing countercurrent contact in a
single vessel.
Powdered Activated Carbon. Powdered carbon is about 50 to 70 microns in
diameter and is usually mixed with the wastewater to be treated. This
"slurry" of carbon and wastewater is then agitated to allow proper contact.
Finally, the spent carbon carrying the adsorbed impurities is settled out or
filtered. In practice, a multi-stage, countercurrent process is commonly used
to make the most efficient use of the carbon's capacity.
Carbon adsorption systems have been demonstrated as practical and
economical for the reduction of dissolved organic and toxic pollutants from
industrial wastewaters. Activated carbon can be used to remove chemical
oxygen demand (COD), biochemical oxygen demand (BOD), and related parameters;
to remove toxic and refractory organics; to remove and recover certain
organics; and to remove selected inorganic chemicals from industrial waste-
water. Compounds that are readily removed by activated carbon include
aromatics, phenolics, chlorinated hydrocarbons, surfactants, organic dyes,
organic acids, higher molecular weight alcohols, and amines. Activated carbon
can also be used to remove selected inorganic chemicals, such as cyanide,
chromium, and mercury. A summary of classes of organic compounds adsorbed on
carbon are presented in Table VII-39, and a summary of carbon adsorption
capacities (the milligram of compound adsorbed per gram of carbon) is
presented for powdered carbon in Table VII-40.
The major benefits of carbon treatment involve its applicability to a
wide variety of organics and its high removal efficiencies. The system is
compact, and recovery of adsorbed materials is sometimes practical. The
limitations of the process include ineffective removal of low molecular weight
VII-120
-------
TABLE VII-39.
CLASSES OF ORGANIC COMPOUNDS ADSORBED ON CARBON
Organic Chemical Class
Examples of Chemical Class
Aromatic Hydrocarbons
Polynuclear Aromatics
Chlorinated Aromatics
Phenolics
Chlorinated Phenolics
High Molecular Weight Aliphatic
and Branch Chain Hydrocarbons*
Chlorinated Aliphatic Hydrocarbons
High Molecular Weight Aliphatic
Acids and Aromatic Acids*
High Molecular Weight Aliphatic
Amines and Aromatic Amines*
High Molecular Weight Ketones,
Esters, Ethers, and Alcohols*
Surfactants
Soluble Organic Dyes
benzene, toluene, xylene
naphthalene, anthracenes ,
biphenyls
chlorobenzene, polychlorinated
biphenyls, aldrin, endrin,
toxaphene, DDT
phenol, cre'sol, resorcenol, and
polyphenyls
trichlorophenol,
pentachlorophenol
gasoline, kerosene
1,1,1-trichloroethane,
trichloroethylene, carbon
tetrachloride, perchloroethylene
tar acids, benzoic acid
aniline, toluene diamine
hydroquinone, polyethylene
glycol
alkyl benzene sulfonates
methylene blue, Indigo carmine
*High Molecular Weight includes compounds in the range of 4 to 20 carbon atoms
VII-121
-------
TABLE VII-40.
SUMMARY OF CARBON ADSORPTION CAPACITIES
Compound
bis(2-Ethylhexyl)
phthalate
Butylbenzyl phthalate
Heptachlor
Heptachlor epoxide
Endosulfan sulfate
Endrin'
Fluoranthene
Aldrin
PCB-1232
beta-Endosulfan
Dieldrin
Hexachlorobenzene
Anthracene
4-Nitrobiphenyl
Fluorene
DDT
2-Acetylaminofluorene
alpha-BHC
Anethole*
3,3-Dichlorobenzidine
2-Chloronaph thalene
Phenylmercurie Acetate
Hexachlorobutadiene
gamtna-BHC (lindane)
p-Nonylphenol
4-Dimethylaminoazobenzene
Chlordane
PCB-1221
DDE
Acridine yellow*
Benzidine dihydrochloride
beta-BHC
N-Bu tylph thalate
N-Ni trosodiphenylamine
Adsorption8
Capacity (mg/g)
Compound
Adsorption*
Capacity (mg/g)
11,300
1,520
1,220
1,038
686
666
664
651
630
615
606
450
376
370
330
322
318
303
300
300
280
270
258
256
250
249
, 245
242
232
230
220
220
220
220
Phenanthrene• 215
Dimethylphenylcarbinol* 210
4-Aminobiphenyl 200
beta-Naphthol* 200
alpha-Endosulfan 194
Acenaphthene 190
4,4' Methylene-bis-
(2-chloroaniline) 190
Benzo(k)fluoranthene 181
Acridine orange 180
alpha-Naphthol IQQ
4,6-Dinitro-o-cresol 169
alpha-Naphthylamine 160
2,4-Dichlorophenol 157
1,2,4-Trichlorobenzene 157
2,4,6-Trichlorophenol 155
beta-Naphthylamine 150
Pentachlorophenol 150
2,4-Dinitrotoluene 146
2,6-Dinitrotoluene 145
4-Bromophenyl phenyl ether 144
p-Nitroaniline* 140
1,1-Diphenylhydrazine 135
Naphthalene 132
l-Chloro-2-nitrobenzene 130
1,2-Dichlorobenzene 129
p-Chlorometacresol 124
1,4-Dichlorobenzene 121
Benzothiazole* 120
Diphenylamine 120
Guanine* 120
Styrene 12Q
1,3-Dichlorobenzene 118
Acenaphthylene 115
4-Chlorophenyl phenyl ether 111
Diethyl phthalate no
VII-122
-------
TABLE Vli-40.
SUMMARY OF CARBON ADSORPTION CAPACITIES (Continued)
Compound
Adsorption3
Capacity (mg/g)
Compound
Adsorption3
Capacity (mg/g)
2-Nitrophenol
Dimethyl phthalate
Hexachloroethane
Chlorobenzene
p-Xylene
2,4-Dimethylphenol
4-Nitrophenol
Acetophenone
1,2,3,4-Tetrahydro-
naphthalene
Adenine*
Dibenzo(a,h)anthracene
Nitrobenzene
3,4-Benzofluoranthene
1,2-Dibromo-3-chloro-
propane
Ethylbenzene
2-Chlorophenol
Tetrachloroethene
o-Anisidine*
5 Bromouracil
Benzo(a)pyrene
2,4-Dini trophenol
Isophorone
Trichloroethene
Thymine*
Toluene
5-Chlorouracil*
N-Ni trosodi-n-propylamine
bis(2-Chloroisopropyl)
ether
Phenol
99
97
97
91
85
78
76
74
74
7.1
69
68
57
53
53
51
51
50
44
34
33
32
28
27
26
25
24
24
21
Bromoform 20
Carbon tetrachloride 11°
bis(2-Chloroethoxy)
methane H
Uracil* . . 11
Benzo(ghi)perylene 11
1,1,2,2-Tetrachloroethane li
1,2-Dichloropropene 8.2
Dichlorobromomethane 7.9
Cyclohexanone* 6.2
1,2-Dichloropropane 5.9
1,1,2-Trichloroethane 5,-8
Trichlorofluorome thane ->.6
5-Fluorouracil* 5.5
1,1-Dichloroethylene 4.9
Dibromochloromethane 4^8
2-Chloroethyl vinyl
ether 3.9
1,2-Dichloroethane 3.6
1,2-trans-Dichloroethene 3.1
Chloroform ' ; 2.6
1,1,1-Trichloroethane 2.5
1,1-Dichloroethane
Acrylonitrile
Methylene chloride
Acrolein
Cytosine*
Benzene
Ethylenediaminetetra-
acetic acid
Benzoic acid
Chloroethane
N-Dimethylnitrosamine
1.8
1.4
1.3
1.2
1.1
1.0
0.86
0.76
' 0.59
6.8 x 10-5
VII-123
-------
TABLE VII-40.
SUMMARY OF CARBON ADSORPTION CAPACITIES (Continued)
NOT ADSORBED
Acetone cyanohydrin
Butylamine
Cyclohexylamine
Ethanol
Hydroquinone
Triethanolamine
Adipic acid
Choline chloride
Diethylene glycol
Hexamethylenediamine
Morpholine
Ion
Na+
K+
Ca++
Mg++
^ "mineralized" distilled water containing the following
Cone, (mg/1)
92
12.6
100
25.3
Ion
P04
S04
Cl-
Alkalinity
Cone, (mg/1)
10
100
177
200
Source:
concentration of
Isotherms for Toxic Organics." MERL, April 1980.
VII-124
-------
or highly soluble organics, low tolerance for suspended solids in the waste-
water, and relatively high capital and operating costs. Preliminary treatment
to reduce suspended solids and to remove oil and grease will often improve the
effectiveness of the activated carbon system.
Treatability tests should be performed on specific waste streams to
determine actual performance of an activated carbon unit. The degree of
removal of different organic compounds varies depending on the nature of the
adsorbate, the pH of the solution, the temperature of the solution, and the
wastewater characteristics. If the wastewater contains more than one organic
compound, these compounds may mutually enhance adsorption, may act relatively
independently, or may interfere.with one another.
According to the Section 308 Questionnaire data base, 21 OCPSF plants
reported using carbon adsorption as a tertiary treatment technology. Table
VII-41 presents tertiary activated carbon performance data for an OCPSF plant
sampled during the EPA 12-Plant Study.
E. Total Treatment System Performance
1. Introduction
The last two sections presented descriptions and performance data for
those in-plant and end-of-pipe treatment technologies currently used or avail-
able for the reduction and removal of conventional, nonconventional, and
priority pollutants discharged by the OCPSF industry. The performance data
presented were primarily for those pollutants that the technologies were
primarily designed to remove. For example, BOD5 and TSS data were presented
for activated sludge; metals data were presented for chemical precipitation;
and volatile priority pollutant data were presented for steam stripping.
This section discusses the removal of pollutants from all treatment
technologies by presenting the performance of total treatment systems. The
treatment systems studied are those used to promulgate the BPT and BAT
effluent limitations. In addition,- the performances of those treatment
systems within the OCPSF industry that do not use biological treatment are
also presented.
VII-125
-------
TABLE VII-41.
END-OF-PIPE CARBON ADSORPTION PERFORMANCE
DATA FROM PLANT NO. 3033
Pollutant
Name
Average
Influent Concentration
to Activated Carbon
(ug/1)
Average
Effluent Concentration
from Activated Carbon
(ug/1)
Bis(2-chloroethyl)ether (18)
1,2-Dichloropropane (32)
2,4-Dimethylphenol (34)
Methylene Chloride (44)
Phenol (65)
Bis(2-ethylexyl)Phthalate (66)
13.64
10.46
13.92
12.21
11.42
14.31
10.00 (ND)
10.00 (ND)
10.00 (ND)
11.46
10.00 (ND)
13.00
VII-126
-------
2. BPT Treatment Systems
EPA has promulgated concentration-based BPT effluent limitations based on
selected biological end-of-pipe technologies that are designed primarily to
address the conventional pollutants BOD5 and TSS. These are supplemented by
those in-plant controls and technologies that are commonly used to assure the
proper and efficient operation of the end-of-pipe technologies, such as steam
stripping, activated carbon, chemical precipitation, cyanide destruction, and
in-plant biological treatment. Activated sludge and aerated lagoons are the
primary examples of such biological treatment.
The. performance of BPT treatment systems is represented by the long-term
BOD and TSS averages for each subcategory and the overall maximum monthly and
daily maximum variability factors presented in the limitations development
part of this section.
3. Nonbiological Treatment Systems
Approximately 84 plants rely exclusively upon end-of-pipe physical/
chemical treatment or did not report any in-place treatment at all. These
facilities must comply with the BPT effluent limitations guidelines based on
biological treatment system performance. Some of these plants generate low
levels of BOD5, thus finding physical/chemical treatment more effective in
reducing TSS loadings. Without nutrient addition, biological systems
generally cannot function unless influent BOD5 is high enough to sustain their
biota. Other plants have determined, based on an analysis of the types and
volumes of pollutants that they discharge, that physical/chemical treatment is
more economical, easier to operate, or otherwise more appropriate. Some of
these plants can control conventional pollutants effectively without using the
biological component of the BPT Option I technologies. However, other plants
seem to rely on dilution of process wastewater prior to discharge rather than
the appropriate Option I treatment. A listing of available BOD5 and TSS
effluent data and in-place controls reported by those plants with nonbiolog-
ical treatment systems is presented in Table VII-42. Forty-one of the
physical/chemical treatment only plants reported discharge BOD5 concentration
data, and 46 provided TSS concentration data. After adjusting the reported
wastewater concentration data for non-process wastewater dilution, 29 percent
VII-127
-------
TABLE VII-42.
TREATMENT TECHNOLOGIES FOR DIRECT NONBIOLOGICAL PLANTS*
Plant
ID
76
87
105
114
155
159
225
259
260
294
373
447
451
502
536
Effluent BOD.
(mg/1)
-
929
-
15
-
429
96
350
20
57
62
23,628
-
93
31
Effluent TSS
(rag/I) Type of Controls Reported
Neutralization
44 Equalization, neutralization, primary
clarification, carbon adsorption
Str-eam stripping, neutralization, primary
clarification
89 Filtration
282 Neutralization, API separation, dissolved
air flotation
Filtration, chemical precipitation, steam
stripping, equalization, coagulation,
neutralization, oil separation, primary
clarification, filtration, carbon adsorp-
tion, second stage of an indicated
treatment unit
s>
46 Steam stripping, distillation, equaliza-
tion, settling pond, neutralization,
screening, oil skimming
Filtration, coagulation, API separation,
surface impoundment
8 Cooling tower, API separation
119 Reuse for steam, coagulation, flocculation,
neutralization, oil separation, primary
clarification
155 Neutralization, oil separation, oil
skimming
22,898 Neutralization, filtration
Chemical precipitation, primary clarifi-
cation, flocculation
38 Water scrub, neutralization
1 Neutralization
VII-128
-------
TABLE VII-42.
TREATMENT TECHNOLOGIES FOR DIRECT NONBIOLOGICAL PLANTS
(Continued)
Plant Effluent BOD5
ID (mg/1)
Effluent TSS
(mg/1)
Type of Controls Reported
569
614
657
663
669
709
727
775
814
819
859
876
16
7
56
91
84
225
90
Steam stripping, primary clarification
Distillation, equalization, acidification/
aeration, neutralization, filtration,
equalization
17 Collection basin, neutralization, oil
separation
47 Equalization, flocculatioh, neutralization,
dissolved air flotation, mechanical skim-
ming, spray cooling, polishing pond
42 Filtration, steam stripping, neutraliza-
tion, oil skimming, dissolved air flota-
tion, air stripping
98 Settling pond, neutralization, API separ-
ation, filtration, carbon adsorption
108 Equalization, flocculation, chemical pre-
cipitation, grit removal, oil skimming,
clarification, air stripping,
neutralization, polishing pond
6 Chemical precipitation, neutralization,
primary clarification
Carbon adsorption, neutralization, oil
skimming, oil separation, API separation,
coagulation, flocculation
128 Chemical precipitation, equalization, neu-
tralization, oil separation, carbon adsorp-
tion
4,369 Equalization, neutralization, primary
clarification
76 Formaldehyde treatment, carbon absorption,
equalization, neutralization, primary
clarification
VII-129
-------
TABLE VII-42.
TREATMENT TECHNOLOGIES FOR DIRECT NONBIOLOGICAL PLANTS*
(Continued)
Plant Effluent BOD,.
ID (mg/1)
Effluent TSS
(rag/1)
Type of Controls Reported
877
913
938
1618
1688
1774
4
142
8
54
27
942
962
991
992
1249
1439
1532
1569
71
17
-
-
-
302
110
18
66
25
-
-
-
1,463
-
44
11
46
Dissolved air flotation
Chemical oxidation, steam stripping, equal-
ization, phase separation, neutralization
Steam stripping, equalization, floccula-
tion, hypochlorite addition, filtration,
neutralization, primary clarification,
settling pond
Steam stripping, neutralization, oil skim-
ming, primary clarification
Equalization, primary clarification
Solvent decantation
Distillation, equalization, neutralization
Equalization, neutralization
Settling, solvent extraction, equalization,
neutralization, steam stripping
Steam stripping, mercury treatment, neu-
tralization, carbon adsorption
Distillation, equalization, neutralization,
primary clarification, blending and air
stripping, filtration
Oil skimming
Steam stripping, equalization, floccula-
tion, neutralization, primary clarification
Equalization, flocculation, neutralization,
primary clarification, filtration
VII-130
-------
TABLE VII-42.
TREATMENT TECHNOLOGIES FOR DIRECT NONBIOLOGICAL PLANTS
(Continued)
Plant Effluent BOD.
ID
(mg/1)
Effluent TSS
(mg/1)
Type of Controls Reported
1776
1785
1794
1839
2030
2055
2062
2073
2090
2206
2268
2345
168
6
862
50
2400 5,640
2419
2527
100 Steam stripping, grit removal, oil skim-
ming, neutralization
- Chemical precipitation, chromium reduction,
steam stripping, ion exchange, carbon ad-
sorption, equalization, neutralization
Oil skimming, API separation
Steam stripping, gravity settling
Chemical precipitation, chromium reduction,
air stripping, neutralization, flocculation
Steam stripping, coagulation, flocculation,
recycle basin, clarification, polishing
pond
Chemical precipitation, steam stripping,
carbon adsorption, coagulation, floccula-
tion, neutralization, pH adjustment .
40 HOPE skimmer, polishing pond, pH adjustment
50 Distillation, equalization, neutralization,
grit removal
Oil skimming, oil separation
264 Equalization, sedimentation, neutraliza-
tion, filtration
29 Steam stripping, solvent extraction, floc-
culation, redox reactor, redox towers,
neutralization, polishing pond, noncontact
coolers
1,175 Solvent extraction, distillation
Equalization, neutralization, oil skimming,
dissolved air flotation
Oil skimming, aerobic spray field
VII-131
-------
TABLE VII-42.
TREATMENT TECHNOLOGIES FOR DIRECT NONBIOLOGICAL PLANTS*
(Continued)
Plant Effluent BOD,
ID
(mg/1)
2735
2767
2770
2771
2786
16
140
80
4010
Effluent TSS
(rag/1)
Type of Controls Reported
2531
639
145
Equalization,
flocculation,
neutralization.
primary clarification, carbon adsorption
2533
2590
-
16
31
13
Equalization,
Sulfur recovei
screening
:y, single stac
re flash .
2606
2647
2668
2680
-
47
939
48
-
51
5,866
26
21
31
17
13
55
176
equalization, stormwater impoundment, neu-
tralization, oil separation, filtration,
carbon adsorption
Neutralization
Filtration, distillation
Steam stripping, distillation
Decant sump, equalization, steam stripping,
neutralization, carbon adsorption
Pellet skimming, neutralization, oil
skimming, dissolved air flotation,
clarification
Neutralization
Distillation, equalization, neutralization,
oil skimming, primary clarification
Equalization, neutralization, primary
clarification
Filtration, chemical precipitation, air
stripping, steam stripping, equalization,
neutralization, oil skimming, oil
separation, API separation, dissolved air
flotation, polishing pond, (nutrient
addition prior to a septic tank for part of
the plant flow)
Depolymerization, distillation, pH adjust-
ment, neutralization, centrifugation
n ' 446'.601' 611' 664> 956, 1033, 1327, 1593, 1670, 1986,
, and 2660 report no in-place treatment technology.
VII-132
-------
of the physical/chemical treatment plants were determined to require no
further treatment to comply with the individual plant BPT Option I BOD5 long-
term average effluent compliance targets (discussed later in this section and
in Section VIII). For another 69 percent of the plants, the engineering costs
of compliance were based on activated sludge treatment systems because their
discharge BOD5 concentrations (after correction for non-process wastewater
dilution) ranged from 15 to 23,600 mg/1 above their individual plant BPT
Option I BOD5 long-term average effluent compliance targets. The remaining
2 percent of the plants were costed for contract hauling because their
wastewater flows were less than 500 gallons per day (gpd).
In the case of TSS, 38 percent of the 46 physical/chemical treatment only
plants that reported TSS data were determined to require no further treatment
to comply with the individual plant BPT Option I TSS long-term average efflu-
ent compliance targets. For 49 percent of the plants, the engineering, costs
of TSS compliance were associated with the activated sludge treatment-system
costed for BOD5.control. For another 7 percent of the plants, t>e engineering
costs of TSS compliance were based on chemically assisted clarification
treatment systems} for 4'percent of the plants, costs were based on copper
sulfate addition to polishing ponds; and for 2 percent, on contract hauling
because the wastewater flows were less than 500 gpd.
Currently, 14 plants do not report any in-place treatment at all; of
these/two plants reported BOD5 and TSS concentrations. One plant would
require no treatment and the other plant would require biological treatment to
comply with their respective BPT compliance targets.
The Agency did not establish alternative limitations for facilities that
do not utilize or install biological treatment systems to comply with the BPT
effluent limitations. Some industry commenters criticized the Agency for not
exempting,or establishing, alternative BOD5 limitations for stand-alone
"chlorosolvent" manufactures. They claim that "chlorosolvent" wastewaters
cannoV sustain a biomass and should not be subject to limitations based on
biological treatment, but did not provide supporting data. The Agency
identified only three stand-alone "chlorosolvent" facilities (plants 569, 913,
and 2062) using the commenters definition of "chlorosolvents" as chlorinated
VII-133
-------
Cl and C2 hydrocarbons. These three plants use only physical/chemical
controls to achieve their current discharge levels. However, of these three
plants, only plant 913 reported BODS data that provided a long-term average of
4 mg/1 BOD5. Since this is significantly below the plant's BPT long-term
effluent compliance target of 21 mg/1 BOD5, the Agency concluded that plant
913 would comply with the BOD5 effluent limitations without the use of
biological treatment. The only other identified stand-alone chlorinated
organics plant that did not use biological treatment was plant 1569, a manu-
facturer of chlorinated benzenes. This plant reported a long-term average
BOD5 discharge concentration of 18 mg/1, a level already below its BPT long-
term effluent compliance target of 27 mg/1 BOD5. The Agency also identified
three other manufacturers that produced "chlorosolvents" along with other
products (plants 1532, 2770, and 2786); they reported long-term average BOD5
discharge concentrations of 110, 140, and 80 mg/1, respectively—sufficient5
levels to sustain biota. In fact, the Agency identified 13 OCPSF plants that
utilize biological treatment systems with reported influent BOD5 concentration
less than 125 mg/1. The influent concentrations for seven of these plants
range from 60 to 80 mg/1 BOD5. Furthermore, another plant (725) sampled by
EPA has an activated sludge system that treats wastewater with a 37 mg/1 BOD5
average influent concentration. The product mix at this facility included
tetrachloroethylene and chlorinated paraffins.
•Gfr
The nonbiologicar wastewater treatment performance information for OCPSF
plants that reported influent and effluent BOD5 and/or TSS data is listed in
Table VII-43. As shown, the ranges of BOD5 and TSS percent removals are 27 to
98 percent and 0 to 91 percent, respectively. Some of these systems include
clarification treatment, but in combination with other physical/chemical
wastewater treatment unit operations.
In an effort to identify performance data for physical/chemical
clarification treatment systems treating BOD5 and TSS, the Agency was able to
obtain influent and effluent BOD5 and TSS data for clarification systems at
pulp, paper, and paperboard mills. Table VII-44 presents performance data for
clarification systems at 27 mills, and the data show that clarification
systems can obtain significant removals of both TSS and BOD5 as well as
reducing TSS levels in raw wastewaters to levels comparable to BPT Option I
VII-134
-------
', TABLE VII-43.
PERFORMANCE OF OCPSF NONBIOLOGICAL WASTEWATER TREATMENT SYSTEMS
Plant ID
Reported Reported
Pollutant Influent Efficient .•%,•;. In-Place
Parameter (mg/1) (mg/1) Removal Treatment*
657
669
938
BOD
TSS
BOD
TSS
BOD
TSS
22
47
2804
451
226
1688
1776
2055
BODC
TSS"
BODC
TSS"
BOD
TSS
235
100
237
16 27 Collection basin,
17 i - 64 neutralization, oil
separation
56 98 Filtration, steam
42 91 stripping, neutralization,
oil skimming, dissolved air-
flotation, air stripping
Steam stripping, equaliza-
27 88 tion, flocculation,
hypochlorite addition,
filtration, neutralization,
primary clarification,
settling pond
142 — Steam stripping, equaliza-
46 80 tion, flocculation,
neutralization, primary
clarification
Steam stripping, grit
100 0 removal, oil skimming,
neutralization , .
168 29 Steam stripping, coagula-
tion,, flocculation, recycle
basin, secondary clarifi-
cation, polishing pond
individual plants may treat all process wastevater or a portion of the
process wastewater by the reported treatment unit operations. Reported
influent data may not precede all listed unit operations.
VII-135
-------
8
E
-
^
wT!
Q Q C
cn co c
C; b; fc? S3 E?
O» O» CT* \7\ CM
rH T-l i-l rH <-H
in
r-l rH M CM
i u-i
' CO CO
CM CM
I CM sj-
en
VII-136
-------
long-term average levels in a wastewater matrix containing low BODg levels.
In addition, for these plants BOD5 effluent values are also comparable to BPT
Option I long-term average levels.
Based on the discussion and the performance data presented above, the
Agency concludes that:
• There are a limited number of OCPSF plants with either no treatment or
physical/chemical treatment in-place (which have BOD and TSS effluent
data) that are not in compliance with the BOD5 and TSS BPT long-term
average effluent compliance targets and have not had BPT compliance
costs estimated based on biological treatment.
• There are a limited number of OCPSF plants with either no treatment or
physical/chemical treatment in-place (which have BOD5 and TSS effluent
data) that are in compliance with BOD5 but not in compliance with TSS
BPT Option I long-term average effluent compliance targets.
• BPT Option I long-term averages for BOD5 and TSS, which are based on
the performance of biological treatment, can be attained by physical/
chemical treatment systems either in-place or used by the Agency to
estimate BPT compliance costs (i.e., chemically assisted clarifica-
tion).
Furthermore, compliance with BAT toxic pollutant effluent limitations
guidelines based on installation of physical/chemical or biological treatment
or improvements in the design and operation of in-place treatment would also
result in incidental reductions of conventional pollutants.
For these reasons, the Agency has decided not to establish a separate set
of BPT effluent limitations for OCPSF plants that do not require biological
treatment to comply with BPT.
A. BAT Treatment Systems
The Agency promulgated BAT limitations for two subcategories that were
largely determined by raw waste characteristics. First, the end-of-pipe
biological treatment subcategory includes plants that have or will install
biological treatment to comply with BPT limits. Second, the non-end-of-pipe
biological treatment subcategory includes plants that either generate such low
levels of BOD5 that they do not need biological treatment or choose to use
VII-137
-------
physical/chemical treatment alone to comply with the BPT limitations for BOD5.
The BAT limitations are based on the performance of the biological treatment
component plus in-plant control technologies that remove priority pollutants
prior to discharge to the end-of-pipe treatment system. These in-plant
technologies include steam stripping to remove volatile and semivolatile
priority pollutants, activated carbon for various base/neutral priority
pollutants, chemical precipitation for metals, cyanide destruction for
cyanide, and in-plant biological treatment for removal of polynuclear aromatic
(PNA) and other biodegradable priority pollutants. Table VII-45 presents a
list of the regulated BAT toxic pollutants and the technology basis for the
final BAT Subcategory One and Two effluent limitations for each. Tables
VII-46 and VII-47 present a summary of the long-term weighted average effluent
concentrations for the final BAT toxic pollutant data base for BAT Subcategory
One and Subcategory Two. The minimum, maximum, and median of the plant's
weighted average effluent concentrations were calculated for each pollutant to
display the performance of well-operated treatment systems in the OCPSF
industry.
F. WASTEWATER DISPOSAL
1. Introduction
The method of treatment for direct and indirect dischargers was discussed
in Sections C and D. In this section the treatment processes and disposal
methods associated with zero or alternate discharge in the OCPSF industry are
described. Zero or alternate discharge at the OCPSF plant is defined as no
discharge of contaminated process wastewater to either surface water bodies or
to POTWs. Table VII-48 presents the frequency of waste stream final discharge
and disposal techniques. This section describes deep well injection (56 OCPSF
plants), contract hauling (128 plants), incineration (93 plants), evaporation
(29 plants), surface impoundment (25 plants), and land application (19 plants).
2. Deep Well Injection
Deep well injection is a process used for the ultimate disposal of
wastes. The wastes are disposed by injecting them into wells at depths of up
to 12,000 ft. The wastes must be placed in a geological formation that
prevents the migration of the wastes to the surface or to groundwater
VII-138
-------
TABLE VII-45.
LIST OF REGULATED TOXIC POLLUTANTS AND THE TECHNOLOGY BASIS
FOR BAT SUBCATEGORY ONE AND TWO EFFLUENT LIMITATIONS
Poll't.
No. Pollutant Name
BAT
Subcategory One
End-of-Pipe
Biological Treatment Plus
BAT
Subcategory Two
1 Acenaphthene
3 Acrylonitrile
4 Benzene
6 Carbon Tetrachloride
7 Chlorobenzene
8 1,2,4-Trichlorobenzene
9 Hexachlorobenzene
10 1,2-Dichloroethane
11 1,1,1-Trichloroethane
12 Hexachloroethane n
13 1,1-Dichloroethane
14 1,1,2-Trichloroethane
16 Chloroethane
23 Chloroform
24 2-Chlorophenol
25 1,2-Dichlbrobenzene
26 1,3-Dichlorobenzene
27 1,4-Dichlorobenzene
29 1,1-Dichloroethylene
30 1,2-Trans-Dichloroethylene
31 2,4-Dichlorophenol
32 5 1,2-Dichloropropane
33 1,3-Dichloropropene
34 2,4-Dimethylphenol
35 2,4-Dinitrotoluene
36 2,6-Dinitrotoluene
38 Ethylbenzene
In-,Flant Biological
In-Plant Biological
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping**
Steam Stripping
Steam Stripping
Steam Stripping
(Biological Only)
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
(Biological Only)
Steam Stripping
Steam Stripping
InrPlant Biological
(Biological Only)
(Biological Only)
Steam Stripping
In-Plant Biological
In-Plant Biological
Steam Stripping
Steam Stripping*
Steam Stripping*
Steam Stripping*
Steam Stripping
Steam Stripping*
Steam Stripping
Steam Stripping*
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Reserved
Steam Stripping*
Steam Stripping*
Steam Stripping*
Steam Stripping
Steam Stripping
Reserved
Steam Stripping*
Steam Stripping*
In-Plant Biological
Reserved
Reserved
Steam Stripping*
VII-139
-------
TABLE VII-45.
LIST OF REGULATED TOXIC POLLUTANTS AND THE TECHNOLOGY BASIS
FOR BAT SUBCATEGORY'ONE AND TWO EFFLUENT LIMITATIONS
(Continued)
Poll't.
No. Pollutant Name
BAT
Subcategory One
End-of-Pipe
Biological Treatment Plus
BAT
Subcategory Two
39 Fluoranthene
42 Bis(2-Chloroisopropyl)Ether
44 Methylene Chloride
45 Methyl Chloride
52 Hexachlorobutadiene
55 Naphthalene
56 Nitrobenzene
57 2-Nitrophenol
58 4-Nitrophenol
59 2,4-Dinitrophenol
60 4,6-Dini tro-o-Cresol
65 Phenol
66 Bis(2-Ethylhexyl)Phthalate
68 Di-N-butyl Phthalate
70 Diethyl Phthalate
71 Dimethyl Phthalate
72 Benzo(a)Anthrancene
73 Benzo(a)Pyrene
74 3,4-Benzofluoranthene
75 Benzo(k)Fluoranthene
76 Chrysene
77 Acenaphthylene
78 Anthracene
80 Fluotene
81 Phenanthrene
In-Plant Biological
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
In-Plant Biological
Steam Stripping and
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon**
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological'
Steam Stripping*
Steam Stripping
Steam Stripping
Steam Stripping*
In-Plant Biological
Steam Stripping and
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
Activated Carbon
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
In-Plant Biological
VII-140
-------
TABLE VII-45.
LIST OF REGULATED TOXIC POLLUTANTS AND THE TECHNOLOGY BASIS
FOR BAT SUBCATEGORY ONE AND TWO EFFLUENT LIMITATIONS
(Continued)
Poll't.
No. Pollutant Name
BAT
Subcategory One
End-of-Pipe
Biological Treatment Plus
BAT
Subcategory Two
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
88 Vinyl Chloride
119 Total Chromium
120 Total Copper
121 Total Cyanide
122 Total Lead
124 Total Nickel
128 Total Zinc
In-Plant Biological
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Hydroxide Precipi-
tation***
Hydroxide Precipi-
tation***
Alkaline Chlori-
nation***
Hydroxide Precipi-
tation***
Hydroxide Precipi-
tation***
Hydroxide Precipi-
tation***
In-Plant Biological
Steam Stripping
Steam Stripping
Steam Stripping
Steam Stripping
Hydroxide Precipi-
tation***
Hydroxide Precipi-
tation***
Alkaline Chlori-
nation***
Hydroxide Precipi-
tation***
Hydroxide Precipi-
tation***
Hydroxide Precipi-
tation***
*Steam stripping performance data transferred based on Henry's Law Constant
groupings.
**Transferred from Subcategory Two.
***Metals and cyanide limitations based on hydroxide precipitation and
alkaline chlorination, respectively, only apply at the process source.
VII-141
-------
TABLE VH-46.
SIMWRY OF THE LOWS-TERM WEIGHED AVERAGE EFFLUENT OONCEmMTICNS FOR THE
FINAL BAT TOXEC POLLUTANT DATA BASE FOR BAT SUBGATBGORY ONE
Pollutant
Umber
1
3
4
6
7
8
9
10
11
12
14
16
23
24
25
26
27
29
30
31
32
33
34
35
36
38
39
42
44
45
52
Pollutant Name
Acenaphthene
Acrylonitrile
Benzene
Carbon Tetrachloride
Chlorobenzene
1,2, 4-Trichlorobenzene
Hexachlorobenzene
1, 2-Dichloroethane
1, 1, 1-Trichloroethane
Hexachloroethane
1, 1,2-Tridiloroethane
Chloroethane
Chloroform
2-Chlorophenol
1, 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1,4-Dichlorobenzene
1 , 1-Dichloroethylene
1 , 2-Trans-dichloroe'thylene
2,4-Wchlorophenol
1 , 2-Dichloropropropane
1 , 3-Dichloropropene
2,4-Dimethylphenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Ethylbenzene
Fluoranthene
Bis(2-Chloroisopropyl)Ether
Methylene Chloride
Methyl Chloride
Hexachlorobutadiene
Number of
Plants
3
5
17
3
2
3
1
9
2
2
3
4
8
3
7
1
1
5
3
3
6
3
4
2
2
14
3
1
8
1
2
Median of
Est. Long-
Term Means
(ppb)
10.000
50.000
10.000
10.000
10.000
42.909
10.000
25.625
10.000
10.000
10.000
50.000
12.208
10.000
47.946
24.800
10.000
10.000
10.000
17.429
121.500
23.000
10.794
58.833
132.667
10.000
11.533
156.667
22.956
50.000
10.000
Minimum of
Est. Long-
Term Means
(ppb)
10.000
50.000
10.00
10; 00
10.00
10.00
10.00
10.00
10.00
10.00
10.00
50.00
10.00
10.00
10.00
24.80
10.00
10.00
10.00
10.00
13.19
10.25
10.00
10.00
10.00
10.00
10.13
156.67
10.00
50.00
10.00
Maximum of
Est. Long-
Term Means
(ppb)
13.00
122.67
16.62
10.00
10.00
69.46
10.00
1228.33
10.00
10.00
10.00
50.00
43.00
93.30
88.20
24.80
10.00
11.60
77.67
21.62
923.00
63.33
13.47
107.67
255.33
10.00
12.27
156.67
206.67
50.00
10.00
Vn-142
-------
TABLE VIP-46.
SUMMARY OF 1HE LOWS-TERM WEIGHTED AVERAGE EFFLUENT CONCHflEATIONS FCR THE
FINAL BAT TOXLC POLLUTANr DATA BASE FOR BAT SUBCATEGORY ONE
(Continued)
Pollutant
Number
55
56
57
58
59
65
66
68
70
71
72
73
74
75
76
77
78
80
81
84
85
86
87
88
Pollutant Name
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
Phenol
Bis(2-Ethylhe5^1)Phthalate
Di-N-Butyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
Benzo(a)Anthracene
Benzo(a)Pyrene
3, 4-Benzofluoranthene
Benzo(K)Fluoranthene
Chrysene
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride
Number of
Plants
10
4
2
3
3
22
2
2
2
2
2
1
1
1
3
3
3
3
6
3
3
24
4
3
Median of
Est. Long-
Term Means
(ppb)
10.000
14.000
27.525
50.000
50.000
10.363
47.133
17.606
42.500
10.000
10.000
10.333
10.267
10.000
10.000 .
10.000
10.000
10.000
10.000
11.333
10.423
10.000
10.000
50.000
Minimum of
Est. Long-
Term Means
(ppb)
10.00
14.00
20.00
50.00
50.00
10.00
43.45
13.09
23.67
10.00
10.00
10.33
10.27
10.00
10.00
10.00
10.00
10.00
10.00
10.33
10.00
10.00
10.00
50.00
Maximum of
Est. Long-
Term Means
(ppb)
10.21
149.67
35.05
145.00
105.35
120.00
50.81
22.12
61.33
10.00
10.00
10.33
10.27
10.00
10.00
13.00
10.00
10.00
17.92
16.00
227.00
102.67
16.00
174.00
VH-143
-------
TABLE VII-47.
SUflfiRY OF THE LONG-TERM WEIGHTED AVERAGE EFFLUENT COMmRATIONS FOR THE
FINAL BAT TOXIC POLLUTANT DATA. BASE FOR BAT SUBCATEQORY TWO
Pollutant
foiriber
1
3
4
6
7
8
9
10
11
12
13
14
16
23
25
26
27
29
SO
32
33
34
38
39
42
44
45
52
Pollutant Name
Acenaphthene
Acrylonitrile
Benzene
Carbon Tetrachloride
Chlorobenzene
1,2, 4-Tridilorobenzene
Hexachlorobenzene
1 , 2-Dichloroethane
1, 1, 1-Trichloroethane
Hexachloroe thane
1 , 1-Dichloroethane
1, 1, 2-Trichloroethane
Chloroe thane
Chloroform
1 , 2-Dichlorobenzene
1,3-Dichlorobenzene
l,4^chlorobenzene
1 , 1-Dichloroethylene
1, 2-Trans-dichloroethylene
1 , 2-Dichloropropane
1 , 3-^ti.chloropropene
2,4-Dimethylphenol
Ethylbenzene
Fluoranthene
Bis(2-Chloroisopropyl)Ether
Methylene Chloride
Methyl Chloride
Hexachlorobutadiene
Number of
Plants
1
1
4
_
_
_
_
2
1
_
1
2
2
2
_
_
_
2
2
_
_
1
_
1
_
3
1
:
Median of
Est. Long-
Term Means
(ppb)
10.000
50.000
28.576
64.500
64.500
64.722
64.722
64.722
10.000
64.722
10.000
10.293
50.000
44.108
64.722
64.500
64.500
10.052
11.052
64.722
64.722
10.000
64.500
11.533
64.722
10.800
50.000
64.500
Minimum of
Est. Long-
Term Means
(ppb)
10.000
50.000
10.00
64.50
64.50
64.72
64.72
62.77
10.00 '
64.72
10.00
10.00
50.00
11.81
64.72
64.50
64.50
10.00
10.00
64.72
64.72
10.00
64.50
11.53
64.72
10.00
50.00
64.50
Maximum of
Est. Long-
Term Means
(ppb)
10.00
50.00
200.33
64.50
64.50
64.72
64.72
66.67
10.00
64.72
10.00
10.59
50.00
76.41
64.72
64.50
64.50
10.10
12.10
64.72
64.72
10.00
64.50
11.53
64.72
30.33
50.00
64.50
VLT-144
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TABLE Vn-47.
SUMMARY OF THE LONG-TERM WEIGHTED AVERAGE EFFLUENT CONCENTRATIONS FOR THE
FINAL BAT TOXIC POLLUTANT DATA BASE FOR BAT SUBCATBQORY TWO
(Continued)
Pollutant
Number
55
56
57
58
59
60
65
66
68
70
71
72
73
74
75
76
77
78
80
81
84
85
86
87
88
Pollutant Name
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2 , 4-Dini trophenol
4 , 6-Dini tro-0-Cresol
Phenol.
Bis(2-Ethylhe?yl)Phthalate
Di-N-Butyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
Benzo(a)Anthracene
Benzo(a)Pyrene
3 , 4-Benzofluoranthene
Benzo(k)Fluoranthene
Chrysene
Acenaphtnylene
Anthracene
Fluorene
Phenanthrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride
Number of
Plants
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
Median of
Est. Long-
Term Means
(ppb)
10.000
948.675
20.000
50.000
373.000
24.000
10.000.
43.455
13.091
23.667
10.000
10.000
10.333
10.267
10.000
10.000
10.000
10.000
10.030
10.000
10.333
18.429
12.418
11.586
64.500
Minimum of
Est. Long-
Term Means
(ppb)
10.00
712.60
20.00
50.00
373.00
24.00
10.00
43,45 ,
13.09
23.67
10.00
10.00
10.33
10.27
10.00
10.00
10.00
10.00
10.00
10.00
10.33
18.43
10.951
10.00
50.00
Maximum of
Est. Long-
Term Means
(ppb)
10.00
1184.75
20.00
50.00
373.00
24.00
10.00
43.45
13.09
23.67
10.00
10.00
10.33
10.27
10.00
10.00
10.00
10.00
10.00
10.00
10.33
18.43
13.88
13.17
79.00
VH-145
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TABLE VII-48.
FREQUENCY OF WASTE STREAM FINAL DISCHARGE
AMD DISPOSAL TECHNIQUES
Disposal Technique
No. of Plants No. of Plants Total No.
(Full Response) (Part A) of Plants
Direct Discharge to Surface Water
Discharge to Publicly
Owned Treatment Works
Discharge to Privately Owned
Off-Site Treatment Facilities
Deep Well Injection
Contract Hauling
Incineration
Land Application
Evaporation
Surface Impoundment
Recycle
250
287
6
32
82
63
0
13
8
36
54
106
35
24
46
30
19
16
17
0
304
393
41
56
128
93
19
29
25
36
NOTE: Combined direct and indirect discharges have been counted with the
direct dischargers; otherwise, remaining disposal techniques can be
double-counted for applicable plants.
. VII-146
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supplies. The most suitable site for deep well. injection is a porous zone of
relatively low to moderate pressure that is sealed above and-below by unbroken
impermeable strata. Limestones, sandstones, and dolomites are among the rock
types most frequently used because of their relatively high porosity. The
formation chosen must have sufficient volume to contain the waste without
resulting in an increase in the hydraulic pressure, which could lead to a
crack in the confining rock layers. .
The most significant hindrance to the application of deep well injection
is the potential for groundwater and surface water contamination; -Careful ..,-.
control of the process is necessary to prevent any contamination, and
injection should only be used in certain geographically acceptable areas. The
process is also limited to waste streams with low levels of suspended solids
to prevent plugging of the well screen which can cause unstable operation.
Pretreatment such as filtration can prevent .clogging of the screen and the
disposal aquifer. Another practical limitation is that waste streams to be
injected should have a pH value between 6.5 and 8.0 to prevent equipment
corrosion. In general, all streams subject to deep well injection are.treated
through equalization, neutralization, and filtration before disposal. Deep
well injection may be particularly attractive for disposal of inhibitory or
toxic organic waste streams.
According to the Section 308 Questionnaire data base, 56 OCPSF plants use
deep well injection as a means for ultimate disposal for all or a portion of
their wastes. . . --.. ;:.:.... •;.•...,,..-•. -..•..-.--••- :•,;..•. • -,._ . -r , ; - 4..-v
3. Off-Site Treatment/Contract Hauling
Off-site treatment refers to wastewater treatment at a site other than
the generation site. Off-site treatment may occur at a cooperative or
privately owned centralized facility. Often a contract hauler/disposer is
paid to pick up the wastes at the generation site and to haul them to the
treatment facility. The hauling may.be accomplished by truck, rail, or barge.
VII-147
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Off-site treatment/contract hauling is usually limited to low volume
wastes, many.of which may require specialized treatment technologies for
proper disposal. Generators of these wastes often find it more economical to
treat the wastes at off-site facilities than to install their own treatment
system. Sometimes, adjacent plants find it more feasible to install a
centralized facility to handle all wastes from their sites. The costs usually
are shared by the participants on a prorated basis.
According to the Section 308 Questionnaire data base, 128 plants use con-
tract hauling and off-site treatment as a final disposal technique for part or
all of their wastes.
4. Incineration
Incineration is a frequently used zero discharge method in the OCPSF
industry. The process involves the oxidation of solid, liquid, or gaseous
combustible wastes primarily to carbon dioxide, water, and ash. Depending
upon the heat value of the material being incinerated, incinerators may or may
not require auxiliary fuel. The gaseous combustion or composition products
may require scrubbing, particulate removal, or another treatment to capture
materials that cannot be discharged to the atmosphere. This treatment may
generate a waste stream tnat ultimately will require some degree of treatment.
Residue left after oxidation will also require some means of disposal.
Incineration is usually used for the ultimate disposal of flammable
liquids, tars, solids, and hazardous waste materials of low volume that are
not amenable to the usual end-of-pipe treatment technologies. To achieve
efficient destruction of the waste materials by incineration, accurate and
reliable information on the physical and chemical characteristics of the waste
must be acquired in order to determine appropriate operating conditions for
the process (e.g., feed rates, residence time, and temperature) and the
required destruction efficiency.
VII-148
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According to the Section 308 Questionnaire data base, 93 OCPSF plants use
incineration as an ultimate disposal technique.
5. Evaporation
Evaporation is a concentration process involving removal of water from a
solution by vaporization to produce a concentrated residual solution. The
energy source may be synthetic (s.team, hot gases, and. electricity) or natural
(solar and geothermal). Evaporation equipment can range from simple open
tanks or impoundments to sophisticated multi-effect evaporators capable of
handling large volumes of liquid. The evaporation process is designed on the
basis of the quantity of water to be evaporated, the quantity of heat required
to evaporate water from solution, and the heat transfer rate. The process
offers the possibility of total wastewater elimination with only the remaining
concentrated solution requiring disposal and also offers the possibility of
recovery and recycle of useful chemicals from wastewater.
According to the Section 308 Questionnaire date base, 29 OCPSF plants use
evaporation as a final disposal technique.
6. Surface Impoundment ,
Impoundment generally refers to wastewater storage in large ponds.
Alternate or zero discharge from these facilities relies on the natural losses
by evaporation, percolation into the ground, or a combination thereof.
Evaporation is generally feasible if precipitation, temperature, humidity, and
wind velocity combine to cause a net loss of liquid in the pond. Surface
impoundments are usually of shallow depth and large surface area to encourage
evaporation. If a net loss does not exist, recirculating sprays, heat, or
aeration can be used to enhance the evaporation rate to provide a net loss.
The rate of percolation of water into the ground is dependent on the subsoil
conditions of the area of pond construction. Since there is a great potential
for contamination of the shallow aquifer from percolation, impoundment ponds
are frequently lined or sealed to avoid percolation and thereby make the
basins into evaporation ponds. Solids that accumulate over a period of time
in these sealed ponds will eventually require removal. Land area requirements
are a major factor limiting the amount of wastewater disposed of by this
method.
VII-149
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According to the Section 308 Questionnaire data base, 25 OCPSF plants
report using surface impoundments as a final disposal technique.
7. Land Application
Land treatment is the direct application of wastewater onto land with
treatment being provided by natural processes (chemical, physical, and
biological) as the effluent moves through a vegetative cover or the soil.
Land application greatly reduces or eliminates BOD5 and suspended solids,
results in some nutrient removal, may result in some heavy metal removal, and
can recharge groundvater. A portion of the wastewater is lost to the atmo-
sphere through evapotranspiration, part to surface water by overland flow, and
the remainder percolates to the groundwater system.
Land disposal of industrial wastewaters must be compatible with land use
and take into consideration the potential for environmental pollution, damage
to crops, and entrance into the human food chain. To protect soil fertility
and the food chain during land disposal, it is necessary to determine the
capacity of soils to remove nitrogen, the potential toxicity of organic and
inorganic contaminants to plant life and soil, and the deleterious effects of
dissolved salts, including sodium, on plants and soil.
According to the Section 308 Questionnaire data base, 19 OCPSF plants
report using land application as a final disposal technique.
G. SLUDGE TREATMENT AND DISPOSAL
Solid residues (sludge) are generated by many wastewater treatment
processes discussed in previous sections of this chapter. Sludge is generated
primarily in biological treatment, chemical precipitation (coagulation/
flocculation), and chemically assisted clarifiers. Sludge must be treated to
reduce its volume and to render it inoffensive before it can be disposed.
Sludge treatment alternatives include thickening, stabilization, conditioning,
and dewatering. Disposal options include combustion and disposal to land.
The frequency of these treatment and disposal alternatives, according to the
Section 308 Quesionnaire data base, is presented in Table VII-49.
VII-150
-------
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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. The principal
purposes of stabilization are to make the sludge less odorous and putrescible,
and to reduce the pathogenic organism content. The technologies available for
sludge stabilization include chlorine oxidation, lime stabilization, heat '
treatment, anaerobic digestion, and aerobic digestion. Conditioning involves
the biological, chemical, or physical treatment of a sludge to enhance
subsequent dewatering techniques. The two most common methods used to
condition sludge are thermal and chemical conditioning. Dewatering, the
removal of water from solids to achieve a volume reduction greater than that
achieved by thickening, is desirable to prepare sludge for disposal and to
reduce the sludge volume and mass to achieve lower transportation and disposal
costs. Some common dewatering methods include vacuum filtration, filter
press, belt filter, centrifuge, thermal, drying beds, and lagoons. Combustion
serves as a means for the ultimate disposal of organic constituents found in
sludge. Some common equipment and methods used to incinerate sludge include
fluidized bed reactors, multiple hearth furnaces, atomized spray combustion,
flash drying incineration, and wet air oxidation. Environmental impacts of
combustion may include discharges to the atmosphere (particles and other toxic
or noxious emissions), surface waters (scrubbing water), and land (ash).
Disposal of sludge to land may include the application of the sludge (usually
biological treatment sludge) on land as a soil conditioner and as a source of
fertilizer for plants, or the stockpiling of sludge in landfills or permanent
lagoons. In selecting a land disposal site, consideration must be given to
guard against pollution of groundwater or surface water supplies.
According to the Section 308 Questionnaire data base, 116 plants report
treating their sludge by thickening or dewatering (26 by thickening, 4 by
centrifugation, 4 by filtration, 22 by digestion, and 50 by dissolved air
flotation). Of the 104 plants reporting sludge disposal methods, 21 use
on-site landfills, 15 employ incineration, 18 use contract hauling, and 50
dispose of sludge at off-site landfills.
VII-152
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H. LIMITATIONS DEVELOPMENT
This section describes the methodology used to develop BPT, BAT, and PSES
effluent limitations and standards and includes discussions of data editing
criteria, derivation of long-term averages, and derivation of "Maximum for
Monthly Average" and "Maximum for Any One Day" variability factors.
1. BPT Effluent Limitations
As discussed in Section VI, the Agency decided to control BOD5 and TSS
under BPT. This section discusses the data editing rules and methodology used
to derive the final BPT effluent limitations guidelines for BOD5 and TSS.
a. Data Editing Criteria
Two sets of data editing rules were developed for BPT; one set was used
to edit the data base, which was utilized to calculate the long-term averages
(LTA) BOD5 and TSS values for each subcategory, while the second set was used
to edit the BPT daily data base, which was utilized to derive variability
factors.
b. LTA Data Editing
The two major forms of data editing performed on the LTA data base
obtained through the 1983 Section:308 Questionnaire were the dilution adjust-
ment assessments made for each full-response, direct discharge OCPSF facility
which submitted BOD,., or"TSS influent and/or effluent data and a BPT perform-
ance edit.
Dilution Adjustment - Since the limitations apply to all process
wastewater as defined in Section V, the Agency grouped all volumes of process
and non-process wastewater for the purpose of adjusting reported plant-level
BOD and TSS concentrations for dilution by nonprocess wastewater. This also
permitted the Agency to estimate engineering costs of compliance based on the
proper process wastewater flows and conventional pollutant concentrations.
For example, if BOD5 was reported as 28 mg/1 at the final effluent sampling
location with 1 MGD of process wastewater flow that was combined with 9 MGD of
unconlaminated nonprocess cooling water flow, then the BOD5 concentration in
VII-153
-------
the process wastewater alone was actually 280 mg/1 before dilution. This
conservatively assumes that the cooling water flow is free of BODg and TSS.
However, in the Agency's judgment, many of the sources and flows reported
as nonprocess wastewater by plants in their respective Section 308 Question-
naires are contaminated by process sources of BOD5 and TSS. Table VII-50
presents a list of the miscellaneous wastewaters reported in the Section 308
Questionnaires as nonprocess, which EPA has determined to be either contam-
inated (and therefore process wastewater) or uncontaminated with conventional
pollutants. The Agency reviewed this list after receiving public comments on
both NOAs criticizing some of its assignments and determined that, in general,
its assignments were correct.
Since the limitations apply to process wastevater (which includes
"contaminated nonprocess" wastewater) only, the relative contributions of
process wastewater versus "uncontaminated nonprocess" wastewater were deter-
mined at the influent and effluent sample sites. These data were used to
calculate plant-by-plant "dilution factors" for use in adjusting pollutant
concentrations at influent and effluent sampling locations as appropriate.
The general procedure for determining sample-site dilution factors and
adjusting BOD5 and TSS values was as follows:
• Sum uncontaminated nonprocess wastewater flows for an individual plant
(e.g., Plant No. 61 uncontaminated nonprocess wastewater flow =
0.280 MGD)
• Sum process wastewater flow for an individual plant (e.g., Plant No
61 process wastewater flow =0.02 MGD)
• Divide the sum of uncontaminated nonprocess wastewater flows by the
total process wastewater flow to determine dilution factor (e.g., for
Plant No. 61, 0.280 MGD/ 0.02 MGD = 14.0)
• Apply the sample-site dilution factor (plus 1) by multiplying by the
reported BOD or TSS value to be adjusted (e.g., for Plant No. 61,
196 mg/1 effluent BOD5 x (14.0 + 1) = 2,940 mg/1 effluent BOD .
VII-154
-------
TABLE VII-50.
CONTAMINATED AND UNCONTAMINATED MISCELLANEOUS "NONPROCESS" WASTEWATERS
REPORTED IN THE 1983 SECTION 308 QUESTIONNAIRE
Contaminated "Nonprocess" Wastewaters
(therefore designated as
process wastewater)
Uncontaminated Nonprocess Wastewaters
Air Pollution Control Wastewater (B5)
Sanitary (receiving biological treat-
ment) (B4)
Boiler Slowdown
Sanitary (indirect discharge)
Steam Condensate
Vacuum Pump Seal Water
Wastewater Stripper Discharge
Bi from Vertac
Boiler Feedwater Lime
Softener Slowdown
Contaminated Water Offsite
Condensate
Storage, Lans, Shops
Laboratory Waste
Steam Jet Condensate
Water Softener Backwashing
Miscellaneous Lab Wastewater
Raw Water Clarification
Landfill Leachate
Water Treatment
Technical Center
Scrubber Water
Utility Streams
Washdown N-P Equipment
Contact Cooling Water
Vacuum Steam Jet Slowdown
Densator Slowdown
Bottom Ash-Quench Water
! ,
Demineralizer Washwater
Non-Contact Cooling Water (Bl)
Sanitary (no biological treatment,
direct discharge) (B4)
Cooling Tower Slowdown (B2)
Stormwater Site Runoff (S3).
Deionized Water Regeneration
Miscellaneous Wastewater (conditional)
Softening Regeneration
Ion Exchange Regeneration
River Water intake
Make-up Water
Fire Water Make-up
Tank Dike Water
Demineralizer Regeneranf'
Dilution Water
Condensate Losses
Shipping Drains
Water Treatment Slowdown .
Cooling Tower .Overflow
Chilled Water Sump Overflow
Air Compressor and Conditioning Blow
Firewall Drainings
Other Non-contact Cooling
Miscellaneous Leaks and .Drains
Boiler House Softeners ' .
Fire Pond Overflow
Boiler Regeneration Backwash
Groundwater (Purge)
Firewater Discharge
Freeze Protection Water
VII-155
-------
TABLE VII-50.
CONTAMINATED AND UNCONTAMINATED MISCELLANEOUS "NONPROCESS" WASTEWATERS
REPORTED IN THE 1983 SECTION 308 QUESTIONNAIRE
(Continued)
Contaminated "Nonprocess" Wastewaters
(therefore designated as
process wastewater)
Uncontaminated Nonprocess tfastewaters
Water Softening Backwash
Lab Drains
Closed Loop Equipment Overflow
Filter Backwash
Demineralizer Wastewater
Laboratory Offices
Demineralizer Slowdown
Utility Clarifier Slowdown
Steam Generation
RO Rejection Water
Power House Slowdown
Inert Gas Gen. Slowdown
Contaminated Groundwater
Potable Water Treatment
Unit Washes
Non-Contact Floor Cleaning
Slop Water from Dist. Facilities
Laboratory and Vacuum Truck
Ion Bed Regeneration
Tankcar Washing (HCN)
Film Wastewater
Generator Slowdown
Air Sluice Water
Research and Development
Quality Control
Steam Desuperheating
Pilot Plant
Other Company Off-site Waste
Ion Exchange Resin Rinse
H2 and CO Generation
Demineralizer Spent Regenerants
Lime Softening of Process
Miscellaneous Service Water
Recirculating Cooling System
HVAC Slowdown Lab Utility
Condenser Water Backwash
Deonfler Regenerant
Raw Water Filter Backwash
Distribution
VII-156
-------
TABLE VII-50.
CONTAMINATED AND UNCONTAMINATED MISCELLANEOUS "NONPROCESS" WASTEWATERS
REPORTED IN THE 1983 SECTION 308 QUESTIONNAIRE
(Continued)
Contaminated "Nonprocess" Wastewaters
(therefore designated as
process wastewater)
Uncontaminated Nonprocess Wastewaters
Iron Filter Backwash
Area Washdown
Vacuum Pump Wastewater
Garment Laundry
Hydraulic Leaks
Grinder Lubricant
Utility Area Process
Contact Rainwater
Alum Water Treatment
Incinerator H20
Product Wash
Backflush from Demineralizer
Water Clarifier Blowdown
Water Treatment Filter Wash
Equipment Cooling H20
Belt Filter Wash
Ejector
OCPSF Flow from Another Plant
. VII-157
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Plant-specific dilution factor calculations and adjustments are
summarized in Appendix VII-B.
BPT Performance Edits - As stated earlier in Section VII, the Agency has
chosen BPT Option I (which is based on the performance of biological treatment
only) as the technology basis for the final BPT effluent limitations. After
selecting the technology basis, the Agency developed the associated limita-
tions based on the "average-of-the-best" plants that use the BPT Option I
technology. A performance criterion was developed to segregate the better
designed and operated plants from the inadequate performers. This was done to
ensure that the plant data relied upon to develop BPT limitations reflected
the average of the best existing performers. Since the data base also
included plants that are inadequate performers, it is necessary to develop
appropriate criteria for differentiating poor from good plant performance.
The BOD5 criteria used for the March 21, 1983 Proposal, the July 17, 1985 and
the December 8, 1986 Federal Register NOAs was to include in the data base any
plants with a biological treatment system that, on the average 1) discharged
50 mg/1 or less BOD5 after treatment, or 2) removed 95 percent or more of the
BOD5 that entered the end-of-pipe treatment system.
The Agency has received two diametrically opposed sets of comments on the
proposed data editing criteria used to develop BPT limitations. EPA proposed
to select plants for analysis in developing limitations only if the plants
achieve at least a 95 percent removal efficiency for BOD5 or a long-term
average effluent BOD5 concentration below 50 mg/1. On one hand, many industry
commenters argued that these criteria were too stringent, were based upon data
collected after 1977 from plants that had already achieved compliance with BPT
permits and thus raised the standard of performance above what it would have
been had the regulation been promulgated in a timely manner, and had the
effect of excluding from the BPT data base some well-designed, well-operated
plants. An environmental interest group argued, in contrast, that the
criteria were not stringent enough, in that they resulted in the inclusion of
the majority of plants in the data base used to develop effluent limitations.
VII-158
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The data collected by EPA for the BPT regulation were indeed, as industry
commenters have noted, based largely on post-1977 data. EPA had originally
collected data in the early and mid-1970s that reflected OCPSF pollutant
control practices at that time. As a result of industry challenges to EPA's
ensuing promulgation of BPT (and other) limitations for the OCPSF industry,
EPA began a new regulatory development program, which included a new series of
data-gathering efforts (see Section I of this document). Industry commenters
are correct in noting that the data are thus taken to a large extent from
OCPSF plants that had already been issued BPT permits that required compliance
by July 1977 with BPT limitations established by the permit writers on a
case-by-case basis. It is thus fair to conclude that the performance of at
least some of these plants was better when EPA collected the data for the new
rulemaking effort than it had been in the mid-1970s when the original BPT
regulations were promulgated.
EPA does not believe that the use of post-1977 data is improper. First,
the Clean Water Act provides for the periodic revision of BPT regulations when
appropriate. Thus it is within EPA's authority to write BPT regulations after
1977 and to base them on the best information available at the time. More-
over, it is not unfair to the industry. The final BPT regulations are based
on the same technology that was used to effectively control BOD5 and TSS in
the 1970s—biological treatment preceded by appropriate process controls and
in-plant treatment to ensure effective, consistent control in the biological
system, and followed by secondary clarification as necessary to ensure
adequate control of solids. The resulting effluent limitations are not neces-
sarily more (or less) stringent than they would have been if based on pre-1977
data. Many of the plants that satisfy the final data editing criteria
discussed below, and thus are included in the BPT data base, would not have
satisfied those criteria in the mid-1970s. The improved performance wrought
by the issuance of and compliance with BPT permits in the 1970's has resulted
in EPA's ability in 1987 to use,data from a larger number of plants to develop
the BPT limitations. Approximately 72 percent of the plants for which data
were obtained pass the final BOD5 editing criteria (95 percent/40 mg/1 for
biological only treatment); the editing criteria have excluded other plants
that, despite having BPT-type technology in-place, were determined not to meet
the performance criteria used to establish the data base for support of BPT
VII-159
-------
limitations. EPA concludes that the use of post-1977 data has resulted in a
good quality but not unrealistic BPT data base.
EPA has modified the BOD5 editing criteria to make them slightly more
stringent. However, it must be noted that EPA does not consider the selection
of editing criteria to be a strict numerical exercise based upon exclusion of
data greater than a median or any other such measure. EPA specifically
disagrees with the comment that data reflecting BPT performance must
necessarily constitute performance levels better than a median. The criteria
represent in numerical terms what is essentially an exercise of the Agency's
judgment, informed in part by industry data, as to the general range of
performance that should be attained by the range of diverse OCPSF plants
operating well-designed biological systems properly. The numerical analyses
discussed below should thus be regarded as an analytical tool that assisted
EPA in exercising its judgment.
The data to which the criteria have been applied reflect the performance
of plants that have been issued BPT permits requiring compliance with BPT
permit limits. It is not unreasonable to expect, therefore, that the class of
facilities identified as the "best" performers in the industry is considerably
larger than it would have been had the data been collected in the mid-1970s.
This result is consistent with the purpose and intent of the NPDES program:
to require those plants performing below the level of the best performers to
improve their performance. Moreover, it should be noted that while the major-
ity of OCPSF plants pass the initial screening criteria, a majority of OCPSF
plants (approximately 70 percent) will nonetheless need to upgrade their
treatment systems' performance to comply with the BPT effluent limitations
guidelines, based upon the reported effluent data (for 1980), and the long-
term average targets for BOD5 and TSS. The fact that a majority of plants
will need to upgrade years after they received their initial BPT permits
indicates that the result of the adoption of the data base used to develop the
limitations is appropriately judged the best practicable treatment.
The editing criteria were applied to the "308" survey data, composed of
annual average BOD5 and TSS data from plants in the OCPSF industry. The
purpose of the editing criteria was to establish a minimum level of treatment
VII-160
-------
performance acceptable for admission of a plant's data into the data base that
would be used to determine BPT limitations. First, only data from plants with
suitable treatment (i.e., biological treatment) were considered for inclusion
in the data base. For these plants, the use of both a percent removal
criterion and an average effluent concentration criterion for BOD5 is
appropriate, since well-operated treatment can achieve either substantial
removals and/or low effluent levels. In addition, use of only a percent
removal criterion would exclude data from plants that submitted usable data
but did not report influent data. The use of an effluent level criterion
allowed the use of data from such plants in estimating the regression
equation.
Following review of the data base, EPA continues to believe that
95 percent BOD5 removal is an appropriate editing criterion. Over half the
plants in the "308" survey data that reported both influent and effluent BOD5
achieve better than 95 percent removal. The median removal for these plants
is 95.8 percent, which reflects good removal from an engineering point of
view.
The Agency also continues to believe that a cut-off for.,average effluent
BOD concentration is necessary to establish an acceptable standard of
performance in addition to percent removal. In order to establish a cutoff
value for the final regulation and respond to various .comments, the Agency
re-examined the "308" survey data. There are data from a total of 99 full
response direct discharging plants with end-of-pipe biological treatment only
(the selected BPT technology, as discussed below) that reported average
effluent BOD5 and a full range of information regarding production at the
plant. All of these data were used in the evaluation of the BOD5 cutoff, even
in cases of plants that did not report influent values and for which removal
efficiencies could therefore not be estimated. The median BOD5 average
effluent for these 99 plants is 29 mg/1. There is no engineering or statis-
tical theory that would support the use of the median effluent concentration
as a cutoff for developing a regulatory data base. In fact, there are many
plants that, in the Agency's best judgment, achieve excellent treatment and
have average effluent values greater than the overall median of 29. There are
many reasonable explanations for differences in average effluent levels at
VII-161
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well operated plants. Differences in a plant's BPT permit limitations coupled
with individual company waste management practices and wastewater treatment
system design and operation practices, in addition to the type of products and
processes at each plant, contribute to differences in average effluent levels
achieved. To obtain insight into differences in BOD5 values among different
subcategories, the data were grouped into different subsets based on
subcategory production at each plant. The results of this analysis are
summarized in Parts A and B of Table VII-51.
The Agency grouped the data two different ways for analysis. Thus, the
data were assigned by plant into two different groupings, each with different
subgroups, and the medians of the average BOD5 effluent values in each sub-
group were determined. The first grouping placed plants into three subgroups
(plastics, organics, and mixed) and the second into five subgroups (fibers/
rayon, thermoplastics, thermosets, organics, and mixed). All plants
considered in the analysis had biological treatment only in place. The
assignment of a plant to a subgroup was determined by the predominant
production at the plant (i.e., whether a plant had 95% or more of its
production in the subgroup). For instance, if a plant has 95 percent or more
plastics production, it was placed in the plastics subgroup. Those plants not
containing 95 percent or more of a subgroup production were classified as
mixed.
The largest subset median average effluent BOD5 in both groupings is
42.5 mg/1, which suggests that the proposed 50 mg/1 criterion is high.
In the absence of a theoretical engineering or statistical solution that
would determine what value should be used in a regulatory context, the Agency
examined some reasonable alternatives suggested by the results displayed in
Parts A and B of Table VII-51. The Agency considered using different editing
criteria for different product subgroups, such as those listed in Part A of
Table VII-51, but decided to use a single criterion to define the final data
base.
VII-162
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TABLE VII-51.
SUMMARY STATISTICS FOR DETERMINATION
OF BPT BOD EDITING CRITERIA BY GROUPS
Subset
Number of
Plant Averages
Median of Plant
Average Effluent
BOD (mg/1)
A. Summary of Groups for Three Groupings
Plastics 30
Organics 42
Mixed (all remaining plants) 27
All Plants 99
20.5
42.5
35
29
B. Summary of Groups for the Five Groupings
Rayon/Fibers
Thermoplastics
Thermosets
Organics
Mixed (all remaining plants)
All plants ...-..:
7
17
3
42
30
99
14
18
32
42.5
35.5
29
VII-163
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An important reason for using a single edit criterion for all subcate-
gories is that this facilitates setting an edit criterion for the group of
plants that do not fall primarily into a single subcategory. These mixed
plants comprise a significant segment of the industry; thus, regulations must
be based on data from this segment as well. Editing criteria that are
subcategory-specific cannot be applied to mixed plants. The Agency did,
however, examine BOD5 levels by subgroups to gain insight into what uniform
editing criterion would be appropriate.
For the subgroups exhibiting relatively high BOD5 levels (organics and
mixed plants), EPA determined that a 40 mg/1 BOD5 edit would be appropriate.
This value is between the median for these two subgroups. Given the fact that
plants with substantial organics production tend to have fairly high influent
BOD5 levels or complex, sometimes difficult to biodegrade wastewaters, EPA
believes that a more stringent edit would not be appropriate for these two
groups. However, EPA believes that a less stringent edit would be inappro-
priate, since many plants in these subgroups meet the 40 mg/1 criterion.
The other subgroups have median values below 40 mg/1, and EPA examined
them closely to determine whether they should be subject to more stringent
edits than the organics and mixed subgroups. EPA concluded that they should
not for the reasons discussed below.
BOD,
The thermosets subgroup contains three plants, whose average effluent
levels are approximately 15, 32, and 34 mg/1, respectively. EPA believes
all three should be retained in the data base. This is particularly important
because a major source of wastewater at the plant with the lowest value is
only melamine resin production; several other types of resins fall under the
thermoset classification. Thus, including all three plants' data provides
improved-coverage of thermoset operations in the data base. An edit of
30 mg/1 arbitrarily excludes data from the two plants whose performance
slightly exceeds 30 mg/1 and would result in melamine resin production being
the predominant thermoset production represented in the data base.
VII-164
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The average BOD5 effluent values for rayon/fibers and thermoplastics are
lower than the average values for thermosets, organics, and mixed. The Agency
evaluated the effects of these subgroups by uniformly editing the industry
data base at 30, 35, 40, and 50 mg/1, using the BPT regression approach to
calculating subcategory long-term average values. The long-term averages
calculated for rayon/fibers and thermoplastics are relatively insensitive to
the use of the 30, 35, 40, and 50 mg/1 edited data bases. That is, the
long-term averages are roughly the same regardless of which of these edits is
used.
After considering the effect of the various editing criteria on the
different subgroups discussed above, EPA has concluded that a 95 percent/
40 mg/1 BOD editing criterion is most appropriate. Moreover, in defining
BPT-level performance, this criterion results in a data base that provides
adequate coverage of the industry.
As discussed previously, the Agency also saw a need to edit the data base
for TSS performance. Some commenters recommended additional editing for TSS,
and the Agency agrees that this is justified. The Agency is using two edits
for the TSS data. The primary edit is that the data must be from a plant that
meets the BOD5 edit (i.e., achieves either 95 percent removal of BOD5 or
40 mg/1). Second is an additional requirement that the average effluent TSS
must be 100 mg/1 or less. As a result of this edit, TSS data from 61 plants
are retained for analysis.
In a well-designed, well-operated biological treatment system, achievable
effluent TSS concentration levels are related to achievable effluent BOD5
levels and, in fact, often are approximately proportional to BOD,.. This is
reflected in the OCPSF data base for those plants that meet the BOD5 perfor-
mance editing criteria (provided that they also exhibit proper clarifier
performance, as discussed below). By using TSS data only from plants that
have good BOD5 treatment, the Agency is thus establishing an effective initial
edit for TSS removal by the biological system. However, as BOD5 is treated
through biological treatment, additional TSS may be generated in the form of
biological solids. Thus, some plants may need to add post-biological
secondary clarifiers to ensure that such biological solids are appropriately
treated.
VII-165
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Thus, while the 95/40 BOD5 editing ensures good BOD5 treatment and a
basic level of TSS removal, plants meeting this BOD5 editing level will not
• necessarily meet a TSS level suitable for inclusion in the data base used to
set TSS limitations. To ensure that the TSS data base for setting limitations
reflects proper control, EPA proposed in the December 8, 1986, Notice to
include only data reflecting a long-term average TSS concentration of less
than or equal to 100 mg/1.
The December 1986 Notice requested comment on the use of the 100 mg/1 TSS
editing criterion and, as an alternative, use of 55 mg/1 TSS concentration as
the editing criterion along with setting the TSS limitations based upon the
relationship between BOD5 and TSS. Some commenters criticized both the 100
mg/1 and 55 mg/1 as overly stringent, and asserted that such additional TSS
edits were unnecessary since the BOD5 edit was sufficient to assure that TSS
was adequately controlled. These commenters, while agreeing that there was a
relationship between BOD5 and TSS, also recommended a slightly different
methodological approach for analyzing the BOD5/TSS relationship.
The Agency disagrees with the commenters who argued in effect that all
TSS data from plants that meet the BOD5 criteria be included in the data base
for setting TSS limitations. The Agency has examined the data and has
concluded that an additional TSS edit is required at a level of 100 mg/1.
Support for this is evident in the reasonably consistent BODg and TSS
relationship for plants in the data set that results from the 95/40 BOD edit,
for TSS values of 100 mg/1 or less. For TSS values above 100 mg/1, there is a
marked change in the pattern of the BOD5/TSS relationship. Below 100 mg/1
TSS, the pattern in the BOD5/TSS data shown in Figure VII-2 is characterized
by a homoscedastic or reasonably constant dispersion pattern along the range
of the data. Above the 100 mg/1 TSS value, there is a marked spread in the
dispersion pattern of the TSS data. The Agency believes that this change in
dispersion (referred to as heteroscedastic) reflects insufficient control of
TSS in some of the treatment systems. The Agency has concluded that the
100 mg/1 TSS edit provides a reasonable measure of additional control of TSS
required in good biological treatment systems that have met the BODg edit
criterion.
VII-166
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VII-167
-------
The Agency considered a more stringent TSS editing criterion of 60 mg/1,
rather than 100 mg/1. The Agency's analysis demonstrated that this is not
appropriate. Most fundamentally, this criterion would result in the exclusion
of plants that EPA believes are well-designed and well-operated plants.
Moreover, the relationship between BOD5 and TSS is well defined for plants
with TSS less than 100 mg/1 and BOD5 meeting the 952/40 mg/1 criteria.
The Agency gave serious consideration to the statistical method
recommended by a commenter for the analysis of the BOD../TSS relationship.
This commenter recommended a linear regression relationship between the
untransformed (not converted to logarithms) BOD5 and TSS data. The Agency has
retained the use of a linear regression relationship between the natural
logarithms of the BOD5 and TSS data. The logarithmic appproach is similar to
that recommended by the commenter, but resulted in a somewhat better fit to
the data.
In response to comments, the Agency also considered an editing criterion
based on secondary clarifier design criteria (i.e., clarifier overflow rates
and solids loadings rates). While the Agency agrees that using these design
criteria, if available, may have provided an appropriate editing criterion,
very little data were supplied by industry in response to the Agency's request
for data regarding these design criteria or were otherwise contained in the
record.
Daily Data Base Editing ;
Prior to the calculation of BPT variability factors, the BPT daily data
base was reviewed to determine if each plant's BOD5 and TSS data were
representative of the BPT technology performance.
The BPT daily data base contains daily data from 69 plants. The sources
of the data were the Supplemental Questionnaire, public comment data from
plants and the State of South Carolina, and data obtained during the EPA
12-Plant Study. The daily data, which included flow, BOD5, and TSS, were
entered on a computer data base. The sampling site for each parameter was
identified by a treatment code that was entered along with the data. The
VII-168
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treatment code allowed specific identification of the sampling site within the
treatment plant. For example, effluent data were identified as sampled after
the secondary clarifier, after a polishing pond, after tertiary filtration, at
final discharge, etc.
After the data base was established, the data at each sampling site
were compared with the treatment system diagrams obtained in the 1983 Section
308 Questionnaire. The comparison served to verify that the data corresponded
to the sampling sites indicated on the diagrams, and to determine if the data
were representative of the performance of OCPSF waste treatment systems. Non-
representative data were those data from effluent sampling sites where the
treatment plant effluent was diluted (>25 percent) with uncontaminated
non-process waste streams prior to sampling; treatment systems where a
significant portion of the wastewater treated by the treatment system
(>25 percent) was uncontaminated non-process or non-OCPSF wastewater;
treatment systems where side streams of wastewaters entered the treatment
system midway through the process, and no data were available for these waste
streams; and treatment systems where the influent sampling site did not
include all wastewaters entering the head of the treatment system (e.g., data
for a single process waste stream rather than all of the influent waste
streams).
Examination of the data available for each plant and the treatment system
diagrams provided the basis for exclusion of some of the plants from further
analysis. The criteria used were:
• Performance based on more than BPT Option I controls
• Data not representative of the performance of the plant's treatment
system
• Treatment systems not representative of the treatment technology
normally used in the OCPSF industry (e.g., effluent data did not
represent one wastewater treatment system, such as multiple
end-of-pipe treatment systems)
• Insufficient data due to -infrequent sampling (less than once per week
while operating) or omission of one or more parameters from testing
(BOD5, TSS, or flow)
• Treatment plant performance below that expected from the treatment
technology in operation (i.e., fail to meet the editing criteria of
95/40 for BOD. and 100 mg/1 for TSS).
VII-169
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Of the plants excluded from the data base, most were excluded for two or more
reasons. Other editing rules for plants retained in the data base included:
• Use of the most recent 12 months of all reported daily data when more
than 1 year of data was available. This allowed the Agency to use the
data from treatment systems with the most recent treatment system
improvements.
•, When historical reported long-term average and Section 308 Supplemen-
tal Questionnaire daily data were both available for a plant, the
Supplemental daily data were used to calculate the long-term average
because they provided a reproducible basis for calculating the
averages.
• When daily BOD5 or TSS values- were received or calculated
[concentration = C*(mass -f flow)] in decimal form, they were rounded
to the nearest milligram per liter.
Plots of concentration versus time and other analyses revealed that most
observations clustered around the mean with excursions far above or below the
mean. In the case of influent data, the excursions were believed to be
related to production factors such as processing unit startups and shutdowns,
accidental spills, etc. Effluent excursions, particularly those of several
days duration, were believed to be related to seasonal trends, upsets of the
treatment system, and production factors. Verification of the cause of the
excursions and of the apparent outliers in the data bases was deemed necessary
in order to supplement the analysis of the data with engineering judgment and
plant performance information. Each plant was contacted and asked to respond
to a series of questions regarding their treatment system, its performance,
and the data submitted. The plants were asked about seasonal effects on
treatment system performance and compensatory operational adjustments, winter
and summer NPDES permit limits, operation problems (slug loads, sludge
bulking, plant upsets, etc.), production changes and time of operation, plant
shutdowns, and flow metering locations. Data observations that were two
standard deviations above and below the mean were identified, and the plants
were asked to provide the cause of each excursion. The results of this effort
are described below.
VII-170
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The plant contacts and analysis of the data that were identified as being
more than two standard deviations above and below the mean revealed some of
the strengths and weaknesses of treatment in the industry. Plants within the
OCPSF.industry, regardless of products manufactured at an individual plant,
experience common treatment system problems. Daily data compiled over at
least a year show operational trends and problems, plant upsets, and seasonal
trends that would not be apparent for plants sampled less than daily.
Equalization and diversion basins are commonly used to reduce the effects of
slug loads on the treatment system and to prevent upsets. Influent data
obtained before equalization or diversion may show high strength wastes, but
the effluent may not because of equalization and diversion. Seasonal effects
tend to be more pronounced in southern climates because treatment systems
there generally may not be designed for cold weather. Operational techniques
to compensate for reduced efficiency are similar and should be practiced
industry-wide whenever needed or impossible with the existing treatment
system.
While common operational problems appear to be consistent across the
industry, responsive treatment system design and operation changes are not
fully documented within the data base. For example, some treatment systems
incorporating similar unit operations produced substantially different
effluent quality. The reasons for this may include strength and type of raw
wastes, capacity of the treatment system (under- or overloaded), knowledge and
skill of operating personnel, and design factors. While the raw waste type
can be categorized somewhat by dividing the OCPSF industry into subcategories,
the degree to which the other factors affect plant performance may not be
readily apparent in the data. For example, the daily data may not show
seasonal trends because of plant design or operational adjustments which
adequately compensate for cold weather.
Sampling and analytical techniques are another potential problem area of
the data base, particularly for the BOD5 data. The OCPSF industry manufac-
tures and uses a multitude of toxic substances that can affect a bioassay such
as the BOD5 test. Also, certain facilities sometimes collect unrefrigerated
.BOD composite samples which will affect the results of the analysis.
However, since the majority of the effluent data were collected for NPDES
VII-171
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permit compliance and approved analytical methodologies (such as standard
methods or EPA's test method) and QA/QC procedures are stipulated in each
facility's NPDES permit, it was assumed that the effluent data utilized were
collected and analyzed in an acceptable manner.
Table VII-52 presents a summary of the plants that were excluded from the
BPT daily data base and the reasons for the exclusion. Appendix VII-C
presents a plant-by-plant accounting of all 69 BPT daily data plants and
provides detailed explanations of each plant's inclusion or exclusion.
Based on the BPT daily data base editing, daily data from a total of
21 plants remain to calculate BOD5 variability factors and 20 plants remain to
calculate TSS variability factors (one plant does not meet the TSS editing
criterion). For these plants, all reported daily data from the most recent
12 months of sampling were included in the calculation of variability factors
because the Agency could not obtain sufficient information through plant
contacts and followup efforts to provide an adequate basis for deleting any
specific daily data points.
Derivation of Subcategory BOD., and TSS Long-Term Averages (LTAs)
As presented previously in Section IV, the Agency's final revised
subcategorization approach also included a methodology for calculation of BPT
BOD5 and TSS LTAs for each subcategory, which are used together with vari-
ability factors to derive facility subcategorical daily and monthly maximum
limitations. Recall from Section IV that the final subcategorization model is
given by:
= a
To estimate the average l^BOD.J corresponding to a set of the independent
variables wi;j, I4i, and Ib£, the random error term e.^ is deleted. The
estimates of the coefficients a, !.,, B, and D are used with the values of the
' independent variables to obtain the estimate.
VII-172
-------
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VII-173
-------
The LTA BOD5 for subcategory k is based on a plant that has 100 percent
of its OCPSF production in subcategory k. Therefore, to obtain the LTA BOD5
for subcategory k, set
If J=k
0,
Also, because the subcategorical LTA BOD5 is based on a plant that satisfies
the BOD5 95/40 criterion (set I41=l) and that has biological only treatment
(set Ibi-l), it follows that the BOD5 LTA for subcategory k is given by
BOD5 LTAk = exp [a + Tk + B + D],
where a, Tk, B, and D are estimates of the model parameters given in Appendix
IV-A, Exhibit 1. The estimates are derived from the data base of 157 full-
response, direct discharge OCPSF facilities that have at least biological
treatment in place, and that provided BOD5 effluent and subcategorical produc-
tion data. The parameter estimates are restated below and the subcategorical
LTAs for BOD5 are given in Table VII-53.
Parameter
a+Tl: Thermoplastics
a+T2: Thermosets
a+T3: Rayon
a+T4: Other Fibers
a+T5: Commodity Organics
a+T6: Bulk Organics
a+T7: Specialty Organics
B: Performance Shift
C: Treatment Shift
Estimate
4.27270510
5.22885710
4.32746980
4.03782486
4.49784137
4.66262711
4.92138427
-1.94453768
0.41834828
The subcategory LTAs for TSS are based on the final subcategorization
regression model for TSS, which was presented in Section IV as:
In (TSSi) = a + b [ln(BOD..)] + e. .
VII-174
-------
The estimates of the regression parameters a and b are derived from the
61 OCPSF plants that have at least biological treatment in place, meet the
95/40 editing criteria for BOD5, and have TSS effluent concentrations of at
most 100 mg/1. The estimates of parameters a and b are presented in Appendix
IV-A, Exhibit 2, and they are:
and
a = 1.84996248
b = 0.52810227.
Now, this model is used to provide subcategorical TSS LTAs corresponding to
the subcategorical BOD5 LTAs. Again, e.^ is set to zero in the model, and
TSS LTAR = exp (a + b lln(BOD5 LTAk)]
for k=l, 2, ..., 7. The calculated TSS LTA values are given in Table VII-54.
These subcategorical BOD,, and TSS LTAs allow the determination of
•* -.
plant-specific BOD5 and TSS LTAs, even for a plant that has production in more
than one subcategory. These plant-specific LTAs are then used with variability
factors to derive the effluent limitations guidelines presented in Section IX.
In particular, for a'^specific plant, let w.. be the proportion of that
plant's production in subcategory j. The plant-specific LTAs are given by:
Plant BOD,. LTA - £ w.(BOD LTA )
and
Plant TSS LTA =
w..(TSS LTA..),
where BOD LTA. and TSS LTA. are the BOD. and TSS long-term averages presented
5 ] 3 s
in Tables VII-53 and VII-54, respectively. This approach is analogous to the
building-block approach typically used by permit writers.
VII-175
-------
TABLE VII-53.
BPT SUBCATEGORY LONG-TERM AVERAGES (LTAs) FOR BOD
Subcategory
BOD LTA (mg/1)
Thermoplastics
Therraosets
Rayon
Other Fibers
Commodity Organics
Bulk Organics
Specialty Organics
16
41
16
12
20
23
30
TABLE VII-54.
BPT SUBCATEGORY LONG-TERM AVERAGES (LTAs) FOR TSS
Subcategory
TSS LTA (mg/1)
Thermoplastics
Thermosets
Rayon
Other Fibers
Commodity Organics
Bulk Organics
Specialty Organics
27
45
27
24
31
33
38
VII-176
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Calculation of BPT Variability Factors
After establishing a, final BPT daily data base, data from 21 plants for
BOD and 20 plants for TSS were retained to calculate variability factors
using the statistical methodology shown in Appendix VII-D. These statistical
methods assume a log-normal distribution; hypothesis tests investigating this
assumption are discussed in Appendix VII-E. The Agency has been using the
95th percentile average "Maximum for Monthly Average" and the 99th percentile
average "Maximum for Any One Day" variability factors for BOD5 and TSS,
regardless of the subcategory mix of each plant. However, many industry
commenters argued that effluent variability was subcategory-specific and
should be taken into account in variability factor calculations. In response
to these comments, the Agency performed an alternative variability factor
analysis which calculated production proportion-weighted variability factors
by category (plastics or organics) and subcategory for the 21 daily data
plants for BOD5 and the 20 plants for TSS. Table VII-55 presents the results
of this analysis which compares overall average variability factors with the
subcategory production proportion-weighted variability factors. This
comparison shows that subcategory-specific variability factors are not
substantially different from the overall average variability factors. This
would be expected since subcategory differences would be reflected more in the
long-term average values, while variability factors are dependent ,on treatment
system performance which is fairly consistent given that all plants use
biological treatment and perform well (i.e., after the 95/40/100 editing
rule). Based on the results of this alternative subcategory weighted
variability factor analysis, the Agency has decided to retain its approach of
calculating overall average variability factors and applying them to all OCPSF
facilities.
Individual plant variability factors are listed in Tables VII-56 and
VII-57 for BOD5 and TSS, respectively. As shown in the tables, the average
BOD Maximum for Monthly Average and Maximum for Any One Day variability
factors are 1.47 and 3.97, respectively. The average TSS Maximum for Monthly
Average and Maximum for Any One Day variability factors are 1.48 and 4.79,
respectively.
VII-177
-------
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VII-180
-------
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VII-182
-------
2. BAT Effluent Limitations
As discussed in Section VI, the Agency has decided to control 63 toxic
pollutants under BAT Subcategory One (End-of-Pipe Biological Plants) and 59
toxic pollutants under BAT Subcategory Two (non-End-of-Pipe Biological
Plants). This section discusses the data editing rules and methodology used
to derive the toxic pollutant long-term averages and variability factors that
provide the basis of the final BAT effluent limitations guidelines for both
subcategories. , .
a. BAT Data Editing Rules
The BAT toxic pollutant data base has basically two sources of data:
1) data collected during EPA sampling studies, and 2) data submitted by
industry either in response to Section 308 Questionnaire requests or as a
result of submissions during the public comment periods for ,the March 21,
1983, Proposal, the July 17, 1985. Federal Register Notice of Availability, or
the December 8, 1986, Federal Register Notice of Availability. Table VII-58
presents a summary of the BAT toxic pollutant data sources as organized into
four sets for review and editing purposes.
In general, the Agency's BAT toxic pollutant data base editing criteria
were as follows:
• Analytical methodology had to be EPA-approved (or equivalent) and have
adequate supporting QA/QC documentation.
• It was not necessary to have influent-effluent data pairs for the same
day, because many treatment systems have a wastewater retention time
of more than 24 hours.
• Since most of the effluent data have values of ND, the average
influent concentration for a compound had to be at least 10 times the
analytical minimum level ;(ML) for the difference to be meaningful and
qualify effluent concentrations for calculation of effluent limits.
For in-plant control effluent data for steam stripping and activated
carbon, the average influent concentration for a compound had to be at
least 1.0 ppm.
• Exclude data for effluent that has been diluted more than 25 percent
after treatment, but before final discharge. NPDES monitoring data
often reflects such dilution, which may be discerned by reference to
the wastewater flow diagram in a plant's response to the 1983 Section
308 Questionnaire. Appendix VII-G characterizes the problems
associated with dilution of NPDES application Form 2C data.
VII-183
-------
TABLE VII-58.
PRIORITY POLLUTANT (PRIPOL) DATA SOURCES FOR THE FINAL OCPSF RULE
EPA Sampling Programs
1.1 37 Plant Verification Study, 1978-80
1.2 Five Plant Study, 1980-81 (EPA/CMA Study)
2.0 Twelve Plant Study, 1983-84
OCPSF Proposal. 48 FR 11828 (March 21. 1983)
3.1 Data attached to 28 public comments
1983 Supplemental "308" Questionnaire*
(sent to selected plants only)
3.2 Data submitted by 74 selected plants
NOA (Proposal Revision 1), 50 FR 29068 (July 17, 1985)
4.1 Data attached to comments, or requested by EPA
as an extension of the attached data**
4.2 Requested from commenters, because the comment
implied that supporting data were available**
NOA (Proposal Revision 2). 51 FR 44082 (Dec. 8, 1986)
4.3 Data attached to comments from 5 commenters
Data Set 1
Data Set 2
Data Set 3
Data Set 4
™f r?f r?f EirV Prlori1ty Pollutant data submitted in response to
questions C13-C16 of the general questionnaire were average concentration
values instead of daily concentration values. This precluded the use of the
data for statistical calculation of effluent limitations.
**Data from a total of 21 plants were reviewed for data sets 4.1 and 4.2.
VII-184
-------
• Cyanide should be considered as having an analytical minimum level of
0.02 mg/1, and subject to the four criteria listed above.
• For data submitted by industry, exclude total phenols data, which
become meaningless with the specific measurement of phenol (priority
pollutant 65). The total phenol parameter represents a colorometric
response to the 4-Aminoantipyrine (4-AAP) reagent, which is non-
specific and characteristic of a host of both phenolic and non-
phenolic organic chemicals.
• Data not representative of BAT technology performance were eliminated
from the data base. Examples of reasons for not being representative
of BAT technology performance include process spills; treatment system
upsets; equipment malfunctions; performance not up to design specifi-
cations; past historical performance; or performance exhibited by
other plants in the data base with BAT technology in place.
• Exclude data for pollutants that could not be validated as present
based on the product/processes and the related process chemistry
associated with each product/process. Examples include phthalate
esters found because of sample contamination by the automatic sampler
tubing and methylene chloride found because of sample contamination in
the laboratory (methylene chloride is a common extraction solvent used
in GC/MS methods).
• Data for pollutants that do not satisfy the 10 times ML editing
criteria at the influent to'the end-of-pipe treatment sampling site,
because their original raw waste concentrations had been reduced
previously by an in-plant control technology, were retained when
sufficient information (i.e., verification, 12-Plant Sampling Reports,
or Section 308 Questionnaire) was available to validate the in-plant
control's presence.
In addition to the detailed editing criteria presented above, more
general editing criteria involved;
• Deletion of presampling grab samples collected prior to the EPA
12 Plant Sampling Study
• Choosing the appropriate sampling sites for the treatment system of
interest( e.g., influent to and effluent from steam stripper for BAT
Subcategory Two data base)
• Deletion of not quantifiable (NQ) values discussed above
• Averaging of replicate and duplicate samples or analyses at a sampling
site by day and, if appropriate, then across multiple laboratories.
All data points in decimal form as a result of replicate and duplicate
averaging were rounded to the nearest whole number (in ppb)
VII-185
-------
SSt I™ ? Z!r° dlscha5&ers a°d plants without appropriate BAT or
PSES treatment systems (e.g., indirect dischargers without appropriate
in-plant controls such as steam stripping, and direct dischargers
without end-of-pipe biological treatment or in-plant controls).
BAT
• Deletion of plants with more than the recommended BAT treatment
technology. [Plant 2680V from the BAT Subcategory Two data base]
• Deletion of plants without a combined raw waste sampling point, or if
430V,P1563V] r°CeSS Sampling data were collected at a plant. [Plants
tOXl P°llutant data f"m six plants for which
vere utnized- [piants
• Deletion of plant/pollutant combinations for which no effluent data
exist
™tHm* combinations when all influent values were
not detected (ND) (except for the overrides discussed above for
pollutants that do not satisfy the 10 times ML editing criteria)
• All values reported by the analytical laboratory at less than the
level minimum level were set equal to the analytical minimum
*nn °f,combined Pollutant analytical results (e.g., anthracene
and phenanthrene reported as a combined total concentration)
»na Xf ora^ory-comPosited volatile grab samples as required by
the analytical protocols instead of individual grab or automatic
composite sample analyses
• Deletion of plant/pollutant combinations based on BAT Option III
and £ni°S ^'*" ^^ Controls, end-of-pipe biological treatment,
and end-of-pipe activated carbon). [Plant 1494V, benzene]
• Deletion of plants which will be regulated under another point source
category. [Plant 1099V under the Petroleum Refining Point Source
Category] .
In addition to the editing criteria mentioned above, the Agency also
established another set of editing criteria in reviewing priority pollutant
metals data:
°!! *riori*y Poll«tant metals from non-process sources,
» non-contact cooling water blowdown and ancillary sources. An
example of an ancillary source is caustic, which commonly assays for
low levels of Cr(119), Cu(120), Ni(124), and sometimes Hg(123)
VII-186
-------
• Excluded end-of-pipe (NPDES) data, as well as data from other sampling
points, that do not represent the direct effluent from technology that
is specifically for the control of metals. In general, NPDES monitor-
ing data do not directly reflect the reduction of.priority, pollutant
'metal concentrations by such technology. Rather, the data reflect
dilution (by process wastewater and non-contact cooling water) and/or
absorption into biomass (if biological treatment of the process waste-
water is employed). Both dilution and biomass absorption of priority
pollutant metals are plant-specific factors that vary widely through-
out OCPSF wastewater collection and treatment systems. -
• Exclude complexed priority pollutant metal data, unless it is .the
direct effluent from technology that is specifically for the control
of complexed priority pollutant metals. This edit is generally appli-
cable to priority pollutant metals (e.g., chromium*3 and copper+2)
that have been very strongly complexed with organic dyes or chelating
compounds, so that the metal remains in solution and is unresponsive
to precipitation with usual reagents (lime or caustic).
• Exclude data that represent the direct effluent from technology
specifically for the control of metals, if there is no corresponding
influent data with which to evaluate the effectiveness of the
technology. .
The Agency's editing procedure differed somewhat for each data, source.
The data from the EPA sampling programs were edited using a combination of
computer analysis and manual analysis by Agency personnel. This was done
because al.l sampling data had previously been encoded. Data submitted by
industry were first reviewed to determine if the data submitted warranted,
encoding for further study, lending itself to manual editing rather than
computer analysis. However, all manual editing that could be validated by
computer analysis (e.g., the 10 x ML/1.0 ppm edit) was performed. Based on
this analysis, data from industry sources for a total of 17 plants were
retained for use in calculation of final BAT effluent limitations. Table
VI1-59 presents a summary of the data retained for each plant and how-, it was
utilized.
Table VII-60 presents a detailed explanation of the data excluded from
the limitations analysis based on the BAT performance editing criterion.
Based on this analysis, data from a total of 36 plants (plus six plant
overlaps due to resampling) for Subcategory One and 10 plants for Subcategory
Two (with nine plant overlaps with Subcategory One) from Agency studies and
public comments were retained for the limitations analysis, and, are presented
in Table VII-61 for BAT Subcategory One and Table VII-62 for BAT Subcategory
Two.
VII-187
-------
TABLE VII-59.
DATA RETAINED FROM DATA SETS 3 AND 4 FOLLOWING
BAT TOXIC POLLUTANT EDITING CRITERIA
Plant ID
63
387
500
682
1012
1650
1753
2227
1617
2445
2693
267
399
415
913
1769
1774
T, -,-, Data
Pollutants set
Zinc 3
Zinc 3
Nitrobenzene 3
Toluene 3
Zinc 3
Benzene, Naphthalene, Phenanthrene, 3
Toluene
Ethylbenzene 3
1,2-4-Trichlorobenzene, 1,2-Dichloroben- 3
zene, Nitrobenzene
Toluene 3
Methylene Chloride, Phenol 3
Chloroform, Methylene Chloride 3
Methylene Chloride 4
Zinc 4
Benzene, Toluene 4
1,2-Dichloroethane, 1,1,1-Trichloroe thane, 4
1,1,2-Trichlorethane, Chloroethane, Chloro-
form, 1,1-Dichloroe thane, 1,2-Trans-
Dichloroethylene, 1,1-Dichloroethylene,
Methylene Chloride, Tetrachloroethylene,
Trichloroethylene, Vinyl Chloride
Chlorobenzene, Chloroethane, 4
1 , 2-Dichlorobenzene, 2 , 4-Dini trotoluene ,
2,6-Dinitrotoluene, Nitrobenzene, Phenol
Zinc 4
BAT Subcategory
Data Base
One and Two
One and Two
Two Only
One Only
One and Two
One Only
One Only
One Only
One Only
One Only
One Only
One Only
One and Two
Two Only
Two Only
One Only
One and Two
VII-188
-------
TABLE VII-60.
F BAT TOXIC POLLUTANT DATA
PERFORMANCE EDITS
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This pollutant should be treated in-plant with activated carbon
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plant pretreats its phenolic wastewaters with a trickling filter
that is adequate for phenol but not for 2,4,6-trichlorophenol.
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This pollutant should be (but was not) treated in-plant with s tea
stripping prior to discharge to the end-of-ppe biological system
also, compared to data from plants retained in the data base
treating chlorobenzene with only biological treatment and having
similar raw waste concentrations, this plant's treatment system
performance for this pollutant was considered inadequate.
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This plant experienced a polyols spill during the sampling
period which saturated the end-of-pipe activated carbon
columns. These columns are used as an integral segment of
the treatment system rather than a polishing step. Th«efore,
because the listed pollutants were basically passing through the
activated carbon system untreated, this plant's treatment system
performance was considered inadequate.
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VII-190
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY ONE LIMITATIONS
Plant ID
2394
2536
725
3033
384
415
Data Set Pollutant #
1 7
25 .
27
38
57
58
59
65
86
1 3
38
65
1 6
9
12
23
44
45
52
85
88
1 10
32
34
55
65
85
1 4.
38
55
65
76
86
1 10
14
16
23
' • ' "•• - 29
30
32
44
87
Pollutant Name
Chlorobenzene
1 , 2-Dichlorobenzene
1 , 4-Dichlorobenzene
Ethylbenzene
2-Nitrophenol
4-Nitirophenol
2 , 4-Dini trophenol
Phenol
Toluene
Acrylonitrile
Ethylbenzene
Phenol
Carbon Tetrachloride
Hexachlorobenzene
Hexachloroe thane
Chloroform
Me thylene Chloride
Chloromethane
Hexachlorobu tad i ene
Tefrachloroe thylene
Vinyl Chloride
1,2-Dichloroethane
1,2-Dichloropropane
2 , 4-Dimethylphenol
Naphthalene
Phenol
Tetrachloroe thylene
Benzene
Ethylbenzene
Naphthalene
Phenol
Chrysene
Toluene
1,2-Dichloroethane
1,1, 2-Trichloroethane
Chloroe thane
Chloroform
1,1, -Dichloroethylene
1 , 2-Trans-dichloroe thylene
1 , 2-Dichloropropane
Methylene Chloride
Trichloroe thylene
VII-191
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY ONE LIMITATIONS
(Continued)
2313
2631
2481
1
4
34
39
55
65
72
73
74
75
76
77
78
80
81
84
86
8
24
25
26
31
58
81
4
10
14
16
23
29
30
32
33
38
44
86
87
4
56
59
Acenaphthene
Benzene
2,4-Dimethylphenol
Fluoranthene
Naphthalene
Phenol
Benzo(a)Anthracene
Benzo(a)Pyrene
3,4-Benzofluoranthene
Benzo(k)Fluoranthene
Chrysene
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
Pyrene
Toluene
1,2,4-Trichlorobenzene
2-Chlorophenol
1,2-Dichlorobenzene
1,3-Dichlorobenzene
2,4-Dichlorophenol
4-Nitrophenol
Phenanthrene
Benzene
1,2-Dichloroethane
1,1,2-Trichloroethane
Chloroethane
Chloroform
1,1-Dichloroethylene
1,2-Trans-dichloroethylene
1,2-Dichloropropane
1,3-Dichloropropene
Ethylbenzene
Methylene Chloride
Toluene
Trichloroethylene
Benzene
Nitrobenzene
2,4-Dini trophenol
VII-192
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY ONE LIMITATIONS
(Continued)
Plant ID
948
267
12
2221
2711
725
444
Data Set Pollutant #
2 3
4
10
29
38
65
66
68
70
71
86
2 8
25
31
65
2 1
4
34
38
55
65
86
3 38
65
86
3 65
86
3 6
10
12
23
30
52
85
88
3 4
86 ,
Pollutant Name
Acrylonitrile
Benzene
1 , 2-Dichloroe thane
1 , 1-Dichloroethylene
Ethylbenzene
Phenol
Bis-(2-Ethylhexyl)Phthalate
Di-N-Butyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
Toluene
1 , 2-4-Trichlorobenzene
1 , 2-Dichlorobenzene
2 , 4-Dichlorophenol
Phenol
Acenaphthene
Benzene
2 , 4-Dimethylphenol
Ethylbenzene
Naphthalene
Phenol
Toluene
Ethylbenzene
Phenol
Toluene
Phenol
Toluene
Carbon Tetrachloride
1 , 2-Dichloroethane
Hexachloroe thane
Chloroform
1 , 2-Trans-dichloroethylene
Hexachchlorobutadiene
Tetrachloroethylene
Vinyl Chloride
Benzene
Toluene
VII-193
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY ONE LIMITATIONS
(Continued)
Plant ID Data Set Pollutant
695 3 4
6
10
23
24
25
29
32
38
42
44
55
65
86
L650 3 4
38
55
65
77
80
81
86
•48 3 3
65
66
68
70
71
430 3 4
55
65
86
349 3 3
88
# Pollutant Name
Benzene
Carbon Tetrachloride
1 , 2-Dichloroethane
Choloroform
2-Chlorophenol
1 , 2-Dichlorobenzene
1,1-Dichloroethylene
1 , 2-Dichloropropane
Ethylbenzene
Bis-(2-Chloroisopropyl) Ether
Methylene Chloride
Naphthalene
Phenol
Toluene
Benzene
Ethylbenzene
Naphthalene
Phenol
Acenaphthylene
Fluorene
Phenanthrene
Toluene
Acrylonitrile
Phenol
Bis-(2-^Ethylhexyl) Phthalate
Di-N-Butyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
Benzene
Naphthalene
Phenol
Toluene
Acrylonitrile
Vinyl Chloride
VII-194
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT,SUBCATEGORY ONE LIMITATIONS
(Continued)
Plant ID
1494
883
659
1609
851
1890
1890*
Data Set Pollutant #
3 25
35
36
44
56
57
58
59
65
86
3 3
38
3 38
3 4
23
24
- 31
65
86
87
3 4
38
39
55
78
80
81
84
86
3 86
3 65
86
Pollutant Name
1 , 2-Dichlorobenzene
2 , 4-Dini t ro toluene
2,6-Dinitrotoluene
Methylene Chloride
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2 , 4-Dini trophenol
Phenol
Toluene
Acrylonitrile
Ethylbenzene
Ethylbenzene
Benzene
Chloroform
2-Chlorophenol
2 , 4-Dichlorophenol
Phenol
Toluene
Trichloroethylene
Benzene
Ethylbenzene
Fluoranthene
Naphthalene
Anthracene
Fluorene
Phenanthrene
Pyrene
Toluene
Toluene
Phenol
Toluene
VII-195
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY ONE LIMITATIONS
(Continued)
Plant ID
Data Set Pollutant #
Pollutant Name
2631 3 4
10
11
14
16
23
29
32
33
38
55
65
86
i051 3 4
10
32
33
86
87
196 3 4
10
11
65
86
06 3 1
4
34
39
65
72
76
77
78
81
84
86
57 4 44
'2 4 86
Benzene
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
1,1,2-Trichloroethane
Chloroethane
Chloroform
1,1-Dichloroethylene
1 , 2-Dichloropropane
1 , 3-Dichloropropene
Ethylbenzene
Naphthalene
Phenol
Toluene
Benzene
1 , 2-Dichloroethane
1, 2-Dichloropropane
1, 3-Dichloropropene
Toluene
Trichloroethylene
Benzene ,
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Phenol
Toluene
Acenaphthene
Benzene
2 , 4-Dimethylphenol
Fluoranthene
Phenol
Benzo(a)Anthracene
Chrysene
Acenaphthylene
Anthracene
Phenanthrene
Pyrene
Toluene
Methylene Chloride
Toluene
VII-196
-------
TABLE VII-61.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY ONE LIMITATIONS
(Continued)
Plant ID
Data Set Pollutant #
Pollutant Name
1617
1650
1753
4
4
86
4
55
81
86
38
Toluene
Benzene
Naphthalene
Phenanthrene
Toluene
Ethylbenzene
1769
2227
2445
2693
4 7
16
25
35
36
56
65
4 8
25
56
4 44
65
4 23
44
Chlorobenzene
Chloroe thane
1 , 2-Dichlorobenzene
2 , 4-Dini trotoluene
2 , 6-Dini trotoluene
Nitrobenzene
Phenol
1 , 2-4-Trichlorobenzene
1 , 2-Dichlorobenzene
Nitrobenzene
Methylene Chloride
Phenol
Chloroform
Methylene Cloride
Note: * denotes a plant which had tvo different treatment systems in the data
base
Data Set 1 denotes 12-Plant Study.
Data Set 2 denotes 5-Plant Study.
Data Set 3 denotes Verification Study.
Data Set 4 denotes public comments and supplemental questionnaire data.
VII-197
-------
TABLE VII-62.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY TWO LIMITATIONS
Plant ID
725
1494
415
2680
415
913
2680
500
)48
Data Set Pollutant #
1 44
45
88
1 4
1 10
14
16
23
' 29
30
44
87
1 4
3 4
86
3 10
11
13
14
16
23
29
30
44
85
87
88
1 56
57
58
59
60
3 56
2 66
68
70
71
Pollutant Name
Methylene Chloride
Chlorome thane
Vinyl Chloride
Benzene
1 , 2-Dichloroetheane
1, 12-Trichloroethane
Chloroe thane
Chloroform
1 , 1-Dichloroethylene
1 , 2-Trans-Dichloroethylene
Methylene Chloride
Trichloroethylene
Benzene
Benzene
Toluene
1 , 2-Dichloroethane
1 , 1 , 1-Trichloroethane
1 , 1-Dichloroethane
1,1, 2-Trichloroethane
Chloroe thane
Chloroform
1 , 1-Dichloroethylene
1 , 2-Trans-Dichloroethylene
Methylene Chloride
Te t rachloroe thylene
Trichloroethylene
Vinyl Chloride
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2 , 4-Dini trophenol
4 , 6-Dini tro-o-Cresol
Nitrobenzene
Bis-(2-Ethylhexyl) Phthalate
Di-n-Butyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
VII-199
-------
TABLE VII-62.
PLANT AND POLLUTANT DATA RETAINED IN BAT ORGANIC:TOXIC POLLUTANT
DATA BASE FOR BAT SUBCATEGORY TWO LIMITATIONS
(Continued)
Plant ID
Data Set
Pollutant #
Pollutant Name
2536 1 3
1293 1 1
34
39 '
55
65
72
73 "
74 , '
75
76
77
78
80
81
84
Acrylonitrile
Acenaphthene
2 , 4-Dimethylphenol
Fluoranthene
Naphthalene
Phenol
Benzo(a) Anthracene
Benzo(a)Pyrene
3 , 4-Benzof luoranthene
Benzo(k) Fluoranthene
Chrysene
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
Pyrene
Note: Data Set 1 denotes 12-Plant Study.
Data Set 2 denotes 5-Plant Study.
Data Set 3 denotes public comments and supplemental questionnaire data.
VII-200
-------
One industry commenter questioned the validity of treating pollutant data
from one plant in two different sampling projects independently. It should be
noted that the six plant overlaps occur because these plants were either
sampled in separate Agency studies or the Agency received data submitted by
commenters in addition to its sampling studies. EPA has treated these over-
lapping plant data sets separately for limitations calculations purposes
because of general changes in a plant's production levels and product mix, and
changes in a plant's treatment system or treatment system operation in the
time period between sampling studies. Using the plant data in this manner did
not significantly affect most of the pollutants being regulated.
EPA reviewed its files on these six plants relating to circumstances at
the plants during the sampling episodes. Plant 725 upgraded a steam bath to a
steam stripper by adding trays between sampling episodes. Plant 2631 had two
processes in operation during the first sampling event and three on the
second. EPA, accordingly, maintains that the 4 data sets associated with
these 2 plants be treated separately because of the referent known changes.
For the remaining four plants, EPA combined the corresponding eight data
subsets into four to yield a single data set for each of the four plants. EPA
then recomputed all of the end-of-pipe BAT toxic limitations to perform a
comparative analysis of these results to those for the EPA methodology for
calculating daily maximum limitations for all of the 55 organic pollutants
derived by this analysis.
The findings were that 11 of the 55 daily limitations changed value, but
for seven of the 11 changes the shifts were only 5 percent or less. For the
four limitations that showed larger changes, two increased and two decreased.
EPA maintains that the general rationale for treating these six plants as
12 separate entities is appropriate and that there is no bias introduced by
this approach.
VII-200
-------
b. Derivation of BAT Toxic Pollutant LTAs
Table VII-63 presents a .summary of the plants retained in the BAT toxic
pollutant data base for BAT Subcategory One and Two, and the in-plant and
end-of-pipe technologies in-place at each plant based on the 1983 Section 308
Questionnaire for industry-supplied data and on field sampling reports for,EPA
data. The table shows that the technology basis for the data to be used for
BAT Subcategory One is mainly end-of-pipe biological treatment (in the form of
activated sludge) preceded in many cases by some form of in-plant control.
These in-plant controls are sometimes in the form of highly efficient tech-
nologies such as activated carbon or steam stripping, or are a more gross form
of control used more for product recovery (e.g., distillation), but nonethe-
less contributing to a reduction.or equalization of raw waste concentrations
discharged to the end-of-pipe biological treatment system. The technology
basis for the BAT Subcategory Two toxic pollutant data base is based on
performance data from in-plant controls such as steam stripping, activated
carbon, and in-plant biological treatment.
For each pollutant at each plant from each of the four data sets, an
estimated long-term average (LTA) effluent concentration .was calculated. The
nondetected values at a plant were assigned an analytical minimum level value
using the minimum levels associated with EPA analytical methods 1624 and 1625.
The estimated long-term average was computed using a method that assigned
nondetected values a relative weight in accordance with the frequency with
which nondetected values for the pollutant were found in the daily data plants
as defined in Appendix VIII-C.
The estimated long-term average, m, for a plant-pollutant combination is
as follows: .
X.
= pD
(1 - p)
n
VII-201
-------
TABLE VII-63.
TREATMENT TECHNOLOGIES FOR PLANTS IN THE
FINAL BAT TOXIC POLLUTANT DATA BASE
Plant I.D.
Treatment Technology
2394
2536
725
3033
384
415
1293
2313
2680
2481
948
267
12
2221
2711
444
Steam stripping, distillation, chemical oxidation, thio-
sulfate waste reuse, sewer segregation, phase separation,
EQ, NEU, GRSP, ASL, SCLAR, POL, PAER
Gravity separation, EQ, NEU, SCR, CLAR, ASL, SCLAR, FILT
Steam stripping, API separator, EQ, NEU, FLOCC, CLAR, ASL,
SCLAR, FILT, CHLOR, SLDTH, SLDFILT
NEU, SCSP, NUDADD, ALA, SSIBS, SETTLING LAGOON, POL, FILT,
CAD, SSITS, POLISH BAGFILTERS
EQ, NEU, API, ASL, SCLAR, POL
Air stripping, steam stripping, carbon adsorption, distil-
lation, retention impoundment, oil separation, API
separation, EQ, NEU, CLAR, NUDADD,1 MULTISTAGE POASL, SCLAR
Primary settling, oil removal, EQ, BIOLOGICAL DIGESTION,
CLAR
Chemical precipitation, steam stripping, solvent
extraction, distillation, chemical oxidation, filtration,
equalization, EQ, NEU, CLAR, NUDADD, ASL, PACA, SCLAR
Decant sump, EQ, NEU, SS, CAD
Carbon adsorption, EQ, NE, SCR, CLAR, FLOCC, ASL, SCLAR
NEU, ASL, SCLAR, POL
Steam stripping, NEU, SCR, OLSK, OLS, CLAR, NUDADD, TF,
ASL, SCLAR, POL . ..
Solvent extraction, decantation, EQ, NEU, OLS, API, NUDADD,
ASL, SCLAR
Solvent extraction, carbon adsorption, distillation, EQ,
GR, ASL, SCLAR
EQ, ARL, ANL, SCLAR
EQ, NEU, ASL, SCLAR, DAF
VII-202
-------
TABLE VII-63.
TREATMENT TECHNOLOGIES FOR PLANTS IN THE
FINAL BAT TOXIC POLLUTANT DATA BASE
(Continued)
Plant I.D.
Treatment Technology
695
2430
1349
1494
883
659
1609
851
1890
1890*
2631
4051
« '296
306
63
387
Chemical precipitation, steam stripping, chemical
oxidation, filtration, separation, catalyst recovery, EQ,
NEU, OLSK, OLS, DAF, CLAR, FLOCC, NUDADD, ALA, SCLAR
EQ, NEU, OLS, DAF, FLOCC, NUDADD, TF, POASL, SCLAR
Steam stripping, EQ, NEU, CLAR, COAG, FLOCC, NUDADD, ASL,
SCLAR, POL
Steam stripping, solvent extraction, EQ, NEU, CLAR, ASL,
SCLAR, CAD
EQ, ASL, SCLAR, POL, FILT
EQ, NEU, SCR, DAF, COAG, FLOCC, ALA, SCLAR
EQ, NEU, CLAR, ASL, SCLAR
EQ, API, NUDADD, ASL, TF, SCLAR
Septic tank, API separator, gravity separation, ion
exchange, steam stripping, GR, API, EQ, NEU, API, NUDADD,
ALA, TF, FSA, SCLAR, FILT, CHLORINE ADDITION
Septic tank, API separator, EQ, NEU, NUDADD, ASL, SCLAR,
FILT, AERATION
Steam stripping, solvent extraction, EQ, NEU, API, CLAR,
ASL, SCLAR
API, ALA, DAF
Steam stripping, ion exchange, distillation, decantation,
org. recovery^ EQ, NEU, GR, OLSK, CLAR, ALA, POASL, SCLAR
Steam stripping, EQ, NEU, OLS, FLOCC, NUDADD, ASL, SCLAR,
FILT
Distillation, chemical precipitation, evaporation, EQ,
CLAR, ARL, ASL, SCLAR, CHLOR
Filtration, crystallization, evaporation, EQ, NEU, SCR,
CLAR, NUDADD, POLISHING BASIN, ASL, SCLAR
VII-203
-------
TABLE VII-63.
TREATMENT TECHNOLOGIES FOR PLANTS IN THE
FINAL BAT TOXIC POLLUTANT DATA BASE
(Continued)
Plant I.D.
Treatment Technology
500
682
913
1012
1617
1650
1753
1769
1774
2227
2445
2693
Steam stripping, carbon adsorption, spill containment, NEU,
CLAR, ASL, SCLAR, POL, pH ADJUSTMENT
Settling, flotation, EQ, NEU, SCR, CLAR, COAG, SETTLING,
FLOTATION, MIXING, SURFACE BAFFLES, ASL, SCLAR, DEAERATION
Steam stripping, chemical oxidation, phase separation, EQ,
NEU
EQ, SEDIM, CP, RBC, TF, SCLAR, SEDIM
Distillation, EQ, COAG, SAND BED FILTRATION, TF, SCLAR, POL
NEU, SCR, OLSK, OLS, API, ARL1, ARL2, ARL3, ARL4, ARL5,
ARL6, ANL
EQ, NEU, CLAR, NUDADD, POLADD, CP, POASL, SCLAR
Chemical precipitation, NEU, CLAR, NUDADD, FLOCC, ASL,
PACA, SCLAR, POL
EQ, NEU, CLAR, FLOCC, FILT
EQ, NEU, CLAR, FLOCC, NUDADD, ASL, SCLAR
Dissolved air flotation, EQ, NEU, SCR, API, CLAR, NUDADD,
POASL, SCLAR
Chemical precipitation, steam stripping filtration, EQ,
NEU, NUDADD, ASL, SCLAR
Note: The order in which these treatment technologies are listed does not
necessarily indicate that they are in series, since certain plants
employ multiple treatment systems to treat segregated waste streams.
*Two separate treatment systems were sampled at the same plant during the same
sampling study.
VII-204
-------
TABLE VII-63.
TREATMENT TECHNOLOGIES FOR PLANTS IN THE
FINAL BAT TOXIC POLLUTANT DATA BASE
(Continued)
Key:
CND - Cyanide Destruction
CP - Chemical Precipitation
CHRRED - Chromium Reduction
AS - Air Stripping
SS - Steam Stripping
DISTL - Distillation
EQ - Equalization
NEU - Neutralization
SCR - Screening
GR - Grit Removal
OLSK - Oil Skimming
OLS - Oil Separation
API - API Separation
DAF - Dissolved Air Flotation
CLAR - Primary Clarification
COAG - Coagulation
FLOCC - Flocculation
NUDADD - Nutrient Addition
ASL - Activated Sludge
ALA - Aerated Lagoon
ARL - Aerobic Lagoon
ANL - Anaerobic Lagoon
RBC - Rotating Biological Contractor
TF - Trickling Filters
POASL - Pure Oxygen Activated Sludge
SSIBS - Second Stage of Indicated Biological System
PACA - Powdered Activated Carbon Addition
SCLAR - Secondary Clarification
POL - Polishing Pond
FILT - Filtration
CAD - Carbon Adsorption
SSITS - Second Stage of Indicated Tertiary System
GRSP - Gravity Separation
PAER - Post Aeration
CHLOR - Chlorination
FSA - Ferrus Sulfide Addition
SLDTH - Sludge Thickening
SLDFILT - Sludge Filtering
AER - Aeration
SEDIM - Sedimentation
POLADD - Polymer Addition
Notes:
Upper Case:
Lower Case:
End-of-Pipe Treatment
In-Plant Control
VII-205
-------
where H^ is the estimated long-term average at plant j; D is the analytical
minimum level; n is the number of concentration values where Xi is detected at
or above the minimum level at plant j; and p is the proportion of nondetected
values reported from all the daily data base plants. That is, p equals the
total number of reported nondetected values from all daily data plants for a
particular pollutant divided by the total number of values reported from all
daily data plants for a particular pollutant. For plant-pollutant combina-
tions with all nondetected values, the long-term average, m, equals the
analytical minimum level. For plant-pollutant combinations where all values
are detected, the long-term average is the arithmetic mean of all values.
Pollutant group values for p were used when pollutant-specific estimates were
not available.
c. Steam Stripping Long-Term Averages
EPA is regulating 28 volatile organic pollutants based on steam stripping
technology. EPA had data on 15 of these pollutants, which were used to deter-
mine limitations using the same methodology used to determine other BAT
organic pollutant limitations. For 13 volatile organic pollutants controlled
by steam stripping, EPA lacked sufficient data to calculate estimated long-
terra averages directly from data relating to these pollutants. Instead, EPA
concluded that these pollutants may be treated to levels equivalent, based
upon Henry's Law Constants, to those achieved for the 15 pollutants for which
there were data. Dividing the 15 pollutants into "high" and "medium"
strippability subgroups, EPA developed a long-term average for each subgroup
and applied these to the 13 pollutants for which data were lacking (six
pollutants in the high subgroup and seven in the medium subgroup). The
long-term average for pollutants with no data in each subgroup was determined
by the highest of the long-term averages within each subgroup based upon the
15 pollutants for which the Agency had data. This approach tends to be
somewhat conservative but in the Agency's judgment not unreasonable in light
of the uncertainty that would be associated with achieving a lower long-term
average for the pollutants for which data are unavailable. The high
strippability long-term average thus derived is 64.5 jMg/1, while the medium
strippability long-term average is slightly higher, 64.7 ug/1.
VII-206
-------
While it may appear anomalous that the high strippable subgroup yields
just a slightly lower long-term average effluent concentration, EPA believes
that this is not the case. First, in the context of the maximum levels
entering the steam strippers within the two subgroups (12,000 ug/1 to over
23 million ug/1), the differences between these two long-term averages is
negligible and essentially reflect the same level of long-term control from an
engineering viewpoint. Second, the "high" and "medium" strippable compounds
behave comparably in steam strippers, in the sense that roughly the same low
effluent levels can be achieved with properly designed and operated steam
strippers. In other words, it is possible to mitigate small differences in
theoretical strippability among compounds in these groups with different
design and operating techniques. The small differences in long-term average
performance seen in the data reflect, in EPA's judgment, no real differences
in strippability among pollutants but rather the difference in steam stripper
operations among the plants from which the data were taken. Indeed, one could
reasonably collapse the two subgroups into one group and develop a single
long-term average for the 13 pollutants for which EPA lacks data. While such
an approach might be technically defensible, EPA decided it would be.most
reasonable to retain the distinction between "high" and "medium" subgroups,
which remains a valid and important distinction for the purpose of transfer-
ring variability factors, as discussed below.
Table VII-64 presents the long-term average values for each organic
pollutant, calculated by taking the median of the plant estimated averages for
those pollutants regulated under BAT Subcategory One and Two. The BAT
Subcategory One median of long-term average values for 1,1-dichloroethane and
4,6-dinitro-o-cresol have been transferred from BAT Subcategory Two. Since
the in-plant steam stripping and activated carbon units attain effluent levels
equal to the analytical minimum level, the addition of end-of-pipe biological
treatment for BAT Subcategory Two will not produce a measurable lower effluent
concentration.
d. Calculation of Daily Maximum and Maximum Monthly Average
Variability Factors>
After determining estimated long-term average values for each pollutant,
EPA developed two variability factors for each pollutant-^-a 99th percentile
VII-207
-------
TABLE VII-64.
BAT TOXIC POLLUTANT MEDIAN OF ESTIMATED LONG-TERM
AVERAGES FOR BAT SUBCATEGORY ONE AND TWO
Subcategory One Subcategory Two
Median of Median of
Pollutant- »• • , Estimated Estimated
MnmK^ D n „ fc „ Minimum Number Long-Term Number Long-Term
Number Pollutant Name Level of Plants Means of Plants Means
1 Acenaphthene
3 Acrylonitrile
4 Benzene
6 Carbon Tetrachloride
7 Chlorobenzene
8 1,2,4-Trichlorobenzene
9 Hexachlorobenzene
10 1,2-Dichloroe thane
11 1,1,1-Trichloroethane
12 Hexachloroe thane
13 1 , 1-Dichloroethane
14 1,1,2-Trichloroethane
16 Chloroethane
23 Chloroform
24 2-Chlorophenol
25 1 , 2-Di chlorobenzene
26 1,3-Dichlorobenzene
27 1,4-Dichlorobenzene
29 1,1-Dichloroethylene
30 Trans-l,2-Dichloroethylene
31 2,4-Dichlorophenol
32 1,2-Dichloropropane
33 1,3-Dichloropropene
34 2,4-Dimethyl Phenol
35 2, 4-Dinitro toluene
36 2,6-Dinitrotoluene
10
50
10
10
10
10
10
10
10
10
10
10
50
10
10
10
10
10
10
10
10
10
10
10
10
10
3
5
17
3
2
3
1
9
2
2
-
3
4
8
3
7
1
1
5
3
3
6
3
4
2
2
10.0 1
50.0 1
10.0 4
10.0
10.0
42.909
10.0
25.625 2
10.0 1
10.0
(10.0)** 1
10.0 2
50.0 2
12.208 2
10.0
47.946
24.80
10.0
10.0 2
10.0 2
17.429
121.50
23.00
10.794 1
58.833
132.667
10.00
50.00
28.5761
64.5000*
64.5000*
64.7218*
64.7218*
64.7218
10.0
64.7218*
10.00
10.2931
50.00
44.1081
64.7218*
64.5000*
64.5000*
10.0517
11.0517
64.7218*
64.7218*
10.00
VII-208
-------
TABLE VII-64.
BAT TOXIC POLLUTANT MEDIAN OF ESTIMATED LONG-TERM
AVERAGES FOR BAT SUBCATEGORY ONE AND TWO
(Continued)
Subcategory One Subcategory Two
Pollutant Minimum
Number Pollutant Name Level
38
39
42
44
45
52
55
56
57
58
59
60
65
66
68
70
71
72
73
74
75
76
77
78
80
81
Ethyl benzene
Fluoranthene
Bis-(2-Chloroisopropyl)
Ether
Methylene Chloride
Methyl Chloride
Hexachlorobutadiene
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2 , 4-Dini trophenol
4 , 6-Dini tro-0-Cresol
Phenol
Bis(2-Ethylhexyl)Phthalate
Di-n-Butyl Phthalate
Diethyl Phthalate
Dimethyl 'Phthalate
Benzo (a) Anthracene
Benzo(a)Pyrene
3 , 4-Benzof luoranthene
Benzo (k) . Fluoranthene
Chyrsene
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
10 i
10
10
10
50
10
10
14
20
50
50
24 ;
10
10
10
10
10
10 ,
10 ;
10 '
10
10
10
10
10
10
Median of Median ot
Estimated Estimated
Number Long-Term Number Long-Term
of Plants Means of Plants Means
14
3
1
8
1
2
10
4
2
3
3
.. -
22
2
2
2
2
2
1
1
1
3
3
-3
3
. 6
10.0
11.533
156.667
22.956
50.0
10.0
10.0
14.0
27.525
50.00
50.0
(24.0)**
10.363
47.133
17.606
42.50
10.0
10.0
10.333
10.267
10.00 '
10.0
10.0
10.0
10.0
1QJ).
-
1
-
3
1
-
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
64.5000*
11.5333
64.7218*
10.800
50.00
64.5000*
10.0
948.675
20.00
50.00
373.00
24.00
10.0
43.4545
13.0909
23.6667
10 ..00
10.00
10.333
10.2667
10.00
10.00
10.00
10.00
10.00
10.00
VII-209
-------
TABLE VII-64.
BAT TOXIC POLLUTANT MEDIAN OF ESTIMATED LONG-TERM
AVERAGES FOR BAT SUBCATEGORY ONE AND TWO
(Continued)
Subcategory One
Median of
Subcategory Two
Median of
Pollutant
Number Pollutant Name
Estimated Estimated
Minimum Number Long-Term Number Long-Term
Level of Plants Means of Plants Means
84
85
86
87
88
Pyrene
Te t rachloroe thy lene
Toluene
Trichloroethylene
Vinyl Chloride
10
10
10
10
50
3
3
24
4
3
11
10
10
10
50
.333
.4231
.00
.00
.0
1
1
2
2
2
10.
18.
12.
11.
64.
3333
4286
4177
5862
5000
Note: All units in ug/1 or ppb.
transferred median of long-term means by strippability groupings.
**Transferred from BAT Subcategory Two.
VII-210
-------
Maximum for Any One Day variability factor (VF1) and a 95th percentile Maximum
for Monthly Average variability factor ,(VF4). These .were developed by fitting
a statistical distribution to the daily data for each pollutant at each plant;
estimating a 99th percentile and a mean of the daily data distributions for
each pollutant at each plant; estimating a 95th percentile and a mean of the,
distribution of 4-day monthly averages for each pollutant at each plant;
dividing the 99th and 95th percentiles by the respective means of daily and
4-day average distributions to determine.plant-specific variability factors;
and averaging variability factors across all plants to determine a VF1-and VF4
for each pollutant. All plant-pollutant combinations for which variability -
factors were calculated have at least seven effluent concentration values
(including NDs) with at least three values at or above the minimum level.
For certain pollutants, the amount of daily data was limited and
individual pollutant variability factors could not be calculated. For such
pollutants regulated in BAT Subcategory One, variability factors were Imputed
from the variability factors for groups of pollutants expected to exhibit
comparable treatment variability based upon comparison of chemical structure
and characteristics. The priority pollutants'were^grouped, as shown in Table
VII-65, by generic classification based on a similarity of functional group or.
structure (isomers, homologs, analogs, etc.). As a consequence of these
similarities, members of each group share precursors, and/or have a common
response to generic process chemistry (7-27) and, in the Agency's judgment,
would be expected to exhibit similar characteristics in wastewater treatment
unit operations. Each pollutant in each chemical group without a variability
factor was then assigned a VF1 and VF4 equal to the average of the VFls and
VF4s of any pollutants in the same group. However, there are six pollutants
without individual variability factors that are also in pollutant variability
groups without an average variability factor. An overall average variability
factor based on all individual pollutant variability factors was transferred
to these pollutants [acrylonitrile, 2,4-dinitrotoluene, 2,6-dinitrotoluene,
~ bis(2-chloroisopropyl) ether, hexachlorobutadiene, and nitrobenzene]. In the
case of acrylonitrile and hexachlorobutadiene, the reason for not having
individual variability factors was not lack of sufficient daily data but that
all or nearly all values for these pollutants were not detected.
VII-211
-------
TABLE VII-65.
PRIORITY POLLUTANTS BY CHEMICAL GROUPS
Halogenated Methanes (Cls)
46
45
44
47
23
48
51
50
49
6
Methyl bromide
Methyl chloride
Methylene chloride (dichloromethane)
Broraoform (tribromomethane)
Chloroform (trichloromethane)
Bromod i chlorome thane
Dibromochloromethane
Dichlorodifluoromethane
Tri chlorofluorme thane
Carbon tetrachloride (tetrachloromethane)
2. Chlorinated C2s
16
88
10
13
30
29
14
11
87
85
15
12
Chloroethane (ethyl chloride)
Chloroethylene (vinyl chloride)
1,2-Dichloroethane (ethylene dichloride)
1,1-Dichloroethane
1,2-1 rans-Di chloroe thylene
1,1-Dichloroehtylene (vinylidene chloride)
1,1,2-Trichloroethane
1,1,1-Trichlorethane (methyl chloroform)
Trichloroethylene
Tetrachloroethylene
1,1,2,2-Tetrachloroethane
Hexachloroe thane
3. Chlorinated C3s
32 1,2-Dichloropropane
33 1,3-Dichloropropylene
4. Chlorinated C4
52 Hexachlorobutadiene
5. Chlorinated C5
53 Hexachlorocylopentadiene
6. Chloroalkyl Ethers
17 bis(chloromethyl)ether
18 bis(2-chloroethyl)ether
42 bis(2-chloroisopropyl)ether
19 2-chloroethylvinyl ether
43 bis(2-chloroethoxy) methane
VII-212
-------
TABLE VHr-65.
PRIORITY,POLLUTANTS BY CHEMICAL GROUPS
(Continued)
7. Metals
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
.' ' HI .1 , _ f '4. ' :
8. Pesticides
89 Aldrin
90 Dieldrin
91 Chlordane
95 alpha-Endosulfan
98 Endrin
99 Endrin aldehyde
100 Heptachlor
101 Heptachlor epoxide
102 alpha-BHC
103 beta-BHC
104 gamma-BHC (Lindane)
105 delta-BHC
92 4,4'-DDT
93 4,4'-DDE (p,p'-DDx)
94 4,4'-DDD (p,p'-TDE)
113 Toxaphene
9. Nitrosamines
61 N-Nitrosodimethyl amine
62 N-Nitrosodiphenyl amine
63 N-Nitrosodi-n-propyl amin.e
10. Miscellaneous
2 Acrolein
3 Acrylonitrile
54 Isophorone
121 Cyanide
VII-213
-------
TABLE VII-65.
PRIORITY POLLUTANTS BY CHEMICAL GROUPS
(Continued)
11. Aromatics
4 Benzene
86 Toluene
38 Ethylbenzene
12. Polyaromatics
14.
15.
16.
55
1
77
78
72
73
74
75
76
79
82
80
39
83
81
84
Naphthalene
Acenanaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene (1,2-benzantharacene)
Benzo(a)pyrene (e,4-benzopyrene)
3,4-Benzofluorantehne
Benzo(k)fluorantehene (11,12-benzofluoranthene)
Chrysene
Benzo(ghi)perylene (1,1,2-benzoperylene)
Dibenzo(a,h)anthracene (1,2,5,6-dibenzanthracene)
Fluorene
Fluoranthene
Indeno(l,2,3-cd)pyrene (2,3-o-Phenylene pyrene)
Phenanthrene
Pyrene
13. Chloroaromatics
7 Chlorobenzene
25 o-Dichlorobenzene
27 p-Dichlorobenzene
26 m-Dichlorobenzene
8 1,2,4-Trichlorobenzene
9 Hexachlorobenzene
Chlorinated Polyaromatic
20 2-Chloronaphthalene
Polychlorinated Biphenyls
106-112 Seven listed
Phthalate Esters
66
67
68
69
70
71
bis(2-Ethylhexyl)
Butylbenzyl, .,
Di-n-butyl
Di-n-octyl
Diethyl
Dimethyl
VII-214
-------
TABLE VII-65.
PRIORITY POLLUTANTS BY CHEMICAL GROUPS
(Continued)
17. Nitroaromatics
56 Nitrobenzene
35 2,4-Dinitrotoluene
36 2,6-Dinitrotoluene
18. Benzidines
5 Benzidine
28 3,3'-Dichlorobenzidine
37 1,2-Diphenylhydrazine
19. Phenols _
65 Phenol
34 2,4-Dimethylphenol
20. Nitrophenols
57 2-Nitrophenol
58 4-Nitrophenol
59 2,4-Dinitrophenol
60 4,6-Dinitro-o-cresol
21. Chlorophenols
24 2-Chlorophenol
22 4-Chloro-m-cresol
31 2,4-Dichlorophenol
21 2,4s,6-Trichlorophenol
64 Pentachlorophenol
22. 144 TCDD (2,3,7,8-Tetrachloro-dibenzo-p-dioxin)
23. Haloaryl Ethers
40 4-Chlorophenylphenyl ether
41 4-Broraophynylphynyl ether
Priority pollutant numbers refer to a published alphabetical listing of the
priority pollutants.
Source: Wise, H.E., and P.O. Fahrenthold (1981). Occurrence and
Predictability of Priority Pollutants in ffastewaters of the Organic
Chemicals and Plastics/Synthetic Fibers Industrial Categories, USEPA 1981.
VII-215
-------
For pollutants regulated in Subcategory Two (non-end-of-pipe biological),
a different methodology was employed to transfer variability factors to
pollutants without individual variability factors. In this case, transfer was
accomplished not by pollutant group, but instead by the in-plant control
technology. Therefore, variability factors were transferred among the
pollutants treated by steam stripping, activated carbon, and in-plant
biological treatment. The Agency further subdivided the pollutants controlled
by steam stripping into high and medium strippability groups (based on Henry's
Law Constants). As discussed previously in this section, Henry's Law Constant
is an important criterion in the design of steam strippers and is therefore an
appropriate factor for the transfer of variability factors. Further sub-
division of the pollutants controlled by in-plant biological treatment was not
considered necessary since all pollutants were determined to be effectively
biodegraded,- transfer of variability factors by adsorpability groups for
pollutants controlled by activated carbon was based on using the variability
factor for 2,4-dinitrophenol (low adsorpability) for the other three pollu-
tants controlled by activated carbon.
For certain pollutants controlled by in-plant biological treatment, the
transferred variability factors for in-plant biological treatment systems are
lower than the variability factors used for end-of-pipe BAT Subcategory One.
This results because BAT Subcategory One variability factors ares 1) in
general, calculated using a different data base; and 2) transferred using the
pollutant variability groups (presented in Table VII-65) rather than across
the technology (as BAT Subcategory Two variability factors are transferred).
Based on these differences, pollutants controlled by in-plant biological
systems which require transferred variability factors will receive variability
factors based on data from three phthalate esters [bis(2-ethylhexyl)
phthalate, di-n-butyl phthalate, and diethylphthalate]: this occurs because
all other pollutants controlled by in-plant biological systems have all daily
data equal to the analytical minimum level. The Agency believes that, in
addition to the reasons mentioned above, the larger end-of-pipe biological
systems have higher variability factors because they receive more commingled
waste streams with a larger number of organic pollutants; thus, they may be
more susceptible to daily fluctuations in performance.
VII-216
-------
Based on the reasons mentioned above, the Agency has decided to retain
the methodology used to transfer in-plant biological system variability
factors. EPA feels that it would be inconsistent to transfer a higher
variability factor to pollutants whose in-plant biological system reduces high
raw waste concentrations (higher than end-of-pipe biological raw waste
concentrations) to the analytical minimum level solely on the basis of
chemical structure. (It should be noted that the transferred end-of-pipe
biological system variability factor for all polynuclear aromatics would be
based on one plant-pollutant combination.)
In response to comments on the statistical aspects of the proposed
limitations development, several statistical techniques were investigated for
deriving limitations. This investigation found that a modification of the
delta-lognormal procedures provides a reasonable approximation of the under-
lying empirical toxic pollutant data. The delta-lognormal distribution
assumes that data are a mixture of positive lognormally distributed values and
zero values. Consequently, zero concentration values are modeled by a point
distribution; positive concentration values follow a lognormal distribution;
and the mixture of these values forms the delta-lognormal distribution. The
statistical methodology used for testing the assumption of lognormality is
found in Appendix VII-E, previously referenced in the BPT Section; the results
of these hypothesis tests are also included in this Appendix.
This method provides a reasonable approach for combining quantitative
concentration values with information expressed only as a nondetect, which is
more qualitative in nature. For the determination of variability factors, the
delta-lognormal procedure was modified by placing the point distribution at
the' analytical minimum level. The details of this modification of the delta
distribution are presented in Appendix VII-F. This approach, is somewhat
conservative since values reported as nondetect may actually be any value
between zero and the minimum level. The detection limit used for each pollu-
tant was the analytical minimum level in EPA analytical methods 1624 and 1625.
Assigning a minimum level to nondetected values in calculating both variability
factors and long-term averages for this data base tends to result in slightly
higher limitations than would be derived if lower values were assumed. If the
point distribution were set to a value below the analytical minimum level,
VII-217
-------
then the variability component of the limitation would increase and the
component corresponding to the mean would decrease. The net effect (mean
times variability factor) would generally result in lower limitations. In the
absence of establishing a firm estimate of the distribution of data below the
analytical minimum levels, the Agency concluded that it would be more
equitable to use the analytical minimum level to model the point distribution
in the modification to the delta-lognormal statistical procedures.
Comments were also received regarding the use of the average variability
factor for transfer to pollutants without individual variability factors for
BAT Subcategory One within each of the 23 pollutant groups. Commenters stated
that the source of data for many of the pollutants was the 3-day Verification
sampling program, and that transfer of an average variability factor to an LTA
based only on data from a 3-day sampling program did not adequately address
the effluent variability of a pollutant. To address this comment, the Agency
examined its edited BAT toxic pollutant data base and determined that the
predominant reason for a pollutant not having an individual variability factor
was not lack of sufficient daily data but that all or nearly all values for
that pollutant were not detected. Therefore, the Agency has decided to retain
the use of an overall average variability factor for each pollutant group to
transfer variability factors to all pollutants within the group without an
individual variability factor.
The Agency also notes the exclusion of two plants (2227P and 500P) from
the variability factor calculations even though they were retained for
calculation of long-term averages. For plant 2227P, EPA examined the
end-of-pipe biological treatment performance data submitted by the plant
(which consisted of data for 1,2,4-trichlorobenzene, 1,2-dichlorobenzene, and
nitrobenzene over a 1-year period) and observed a 2-month period when effluent
concentrations of these pollutants were considerably higher than the remaining
10-month period; during this period of higher effluent concentrations, the
corresponding raw waste concentrations were consistent with the remaining
10 months of raw waste concentration data. Based on this inconsistent
performance, the Agency has concluded that this plant did not have good enough
control of variability to be used to develop variability factors. Thus, the
Agency has excluded this plant from variability factor calculations. However,
VII-218
-------
the overall long-term performance is good and consistent with that achieved by
other, good performers. Therefore, this plant's data has been retained for
long-term average calculations.
For plant 500P, the Agency examined the steam stripping and carbon
adsorption performance data submitted by the plant (which consisted of data
for nitrobenzene over a 3-month period) and believes the data exhibit both
competitive adsorption effects and column breakthrough. Competitive
adsorption exists when a matrix contains adsorbable compounds in solution
which are being selectively adsorbed and desorbed. A review of the data
indicates that while the plant's long-term performance demonstrates
significant removals' of pollutants, it is not consistent, thus much more
variable than that of another plant using similar treatment and achieving
comparable long-term average concentrations. Therefore, the Agency has
excluded this plant from variability factor calculations but has retained the
data for long-term average calculations.
Table VII-66 presents the individual pollutant variability factors for
BAT Subcategory One summarized by pollutant group including the pollutants for
which the overall average variability factor has been transferred. Table
VII-67 presents the individual pollutant variability factors for BAT Sub-
category Two summarized by in-plant control technology and strippability and
adsorpability groups for steam stripping, and activated carbon, respectively.
3. BAT and PSES Metals and Cyanide Limitations
Raw wastewaters generated by certain 6.CPSF facilities contain relatively
high concentrations of.metals and total cyanide. Based on a detailed analysis
(as discussed in Sections V and VI .of this document), the Agency has. decided
to regulate the following six pollutants under BAT and PSES:
• Total chromium
• Total copper , • . .
• Total lead
• Total nickel
• Total zinc
• Total cyanide. ....-.-
VII-219
-------
TABLE VII-66.
INDIVIDUAL TOXIC POLLUTANT VARIABILITY FACTORS
FOR BAT SUBCATEGORY
-------
TABLE VII-66.
INDIVIDUAL TOXIC POLLUTANT VARIABILITY FACTORS
FOR BAT SUBCATEGORY ONE
(Continued)
Pollutant
Number Pollutant Name
Daily VF
Monthly VF
Imputed Varia-
bility Factor?
Pollutant Class = 12
1 Acenaphthene
39 Fluoranthene
55 Naphthalene
72 Benzo(a)Anthracene
73 Benzo(a)Pyrene
74 3,4-Benzofluoranthene
75 Benzo(k)Fluoranthene
76 Chrysene
77 Acenaphthylene
78 Anthracene
80 Fluorene
81 Phenanthrene
84 Pyrene
7 Chlorobenzene
8 1,2,4-Trichlorobenzene
9 Hexachlorobenzene
25 1,2-Dichlorobenzene
26 1,3-Dichlorobenzene
27 1,4-Dichlorobenzene
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
5.89125
- 5.89125
Pollutant Class = 13
2.79155
3.25317
2.79155
3.38091
1.74057
2.79155
Pollutant Class = 16
66 Bis-(2-Ethylhexyl) Phthalate 5.91768
68 Di-n-Butyl Phthalate 3.23768
70 Diethyl Phthalate 4.75961
71 Dimethyl Phthalate 4.63833
35 2,4-Dinitrotoluene
36 2,6-Dinitrotoluene
56 Nitrobenzene
Pollutant Class = 17
4.83045
4.83045
4.83045
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
2.1563
1.46787
1.58318
1.46787
1.59720
1.22323
1.46787
2.17027
1.51824
1.89895
1.86249
1.91724
1.91724
1.91724
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
•Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
VII-221
-------
TABLE VII-66.
INDIVIDUAL TOXIC POLLUTANT VARIABILITY FACTORS
FOR BAT SUBCATEGORY ONE
(Continued)
Pollutant
Number Pollutant Name
34 2,4-Dimethylphenol
65 Phenol
57 2-Nitrophenol
58 4-Nitrophenol
59 2,4-Dinitrophenol
24 2-Chlorophenol
31 2,4-Dichlorophenol
Daily VF
Imputed Varia-
Monthly VF bility Factor?
Pollutant Class =19
3.25650 1.59976
2.49705 1.40602
Pollutant Class = 20
2.49725 1.4643
2.47783 1.4331
2.45842 1.4019
Pollutant Class = 21
9.70575 3.05490
6.37097 2.22674
Yes
VII-222
-------
TABLE VII-67.
INDIVIDUAL TOXIC POLLUTANT VARIABILITY FACTORS
FOR BAT SUBCATEGORY TWO
Pollutant
Number Pollutant Name
Daily VF
Monthly VF
Imputed Varia-
bility Factor?
4
11
13
16
23
29
30
45
85
86
87
88
10
14
44
4.65485
5.88383
5.88383
5.88383
7.36230
5.88383
5.88383
5.88383
8.85657
5.88383
5.88383
2.66160
8.8604
12.2662
15.6720
1.97430
2.18759
2.18759
2.18759
2.49394
2.18759
2.18759
2.18759
2.78458
2.18759
2.18759
1.49754
2.77681
3.02524
3.27366
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Benzene
1,1,1-Trichloroe thane
1,1-Dichloroe thane
Chloroe thane
Chloroform
1,1-Dichloroe thy lene
1,2-Trans-dichloroethylene
Methyl Chloride
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride
1,2-Dichloroe thane
1,1,2-Trichloroethane
Methylene Chloride
variability factors when no variability factors available.
Pollutant
Number Pollutant Name
Daily VF
Monthly VF
Imputed Varia-
bility Factor?
56
57
58
59
60
Nitrobezene
2-Nitrophenol
4-Nitrophenol
2 , 4-Dini t rophenol
4 , 6-Dini t ro-o-Cresol
6.7477
11.5023
11.5023
11.5023
11.5023
2.35797
3.23479
3.23479
3.23479
3.23479
Yes
Yes
Yes
Note: Pollutant variability factors-variability factors for pollutant 59
used to impute variability factors for 57, 58, and 60.
VII-223
-------
TABLE VII-67.
INDIVIDUAL TOXIC POLLUTANT VARIABILITY FACTORS
FOR BAT SUBCATEGORY TWO
(Continued)
Pollutant
Number Pollutant Name
1 Acenaphthene
3 Aery lonit rile
34 2,4-Dimethylphenol
39 Fluorantehene
55 Naphthalene
65 Phenol
66 Bis-(2-Ethylhexyl) Phthalate
68 Di-n-Butyl Phthalate
70 Diethyl Phthalate
71 Dimethyl Phthalate
72 Benzo(a)Anthracene
73 Benzo(a)Pyrene
74 3,4-Benzofluoranthene
75 Benzo(k)Fluoranthene
76 Chrysene
77 Acenaphthylene
78 Anthracene
80 Fluorene
81 Phenanthrene
84 Pyrene
Daily VF
—
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
5.91768
3.23768
4.75961
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
4.63833
1 . —
Monthly VF
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
2.17027
1.51824
1.89895
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
1.86249
Imputed Varia-
bility Factor?
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
VII-224
-------
The technology basis for control of these pollutants is hydroxide precipita-
tion for the metals and alkaline chlorination for cyanide. Although sulfide
precipitation was the basis for BAT and PSES compliance cost estimates, it was
not used as the technology basis for the limitations because the Agency's
final regulation does not include control of complexed sources of these
metals. This results in a slight overestimation of costs for compliance with
the metals limits for ,BAT and PSES levels of control.
Although the concentrations of these pollutants in certain samples of
untreated OCPSF wastewater are relatively high, the metals fall within the
range of concentrations found in untreated wastewaters from metal processing
and finishing, such as those for the metal finishing and battery manufacturing
industries. Because no metals treatment performance data for OCPSF waste-
waters generated by the validated product/processes listed in Section V were
available, the Agency decided to transfer limitations from the metal finishing
point source category. Cyanide is found at levels in certain OCPSF waste
streams at higher concentrations than in metal finishing. Destruction; of
cyanide by alkaline chlorination is demonstrated in the OCPSF industry; this
technology uses .excess oxidizer (chlorine) and excess alkaline conditions, and
should be able to treat cyanide by adding sufficient detention time which has
been costed. Table VII-68 presents the long-term averages and daily and
monthly maximum variability factors for each pollutant.
The monthly maximum limitations for the metal finishing industry are
based on an assumed monitoring requirement of 10 samples per month and employ
the 99th percentile as a basis for the monthly maximum standard. For the
OCPSF standard, however, the monthly maximum standards are based on an assumed
monitoring requirement of four samples per month and they use the 95 percen-
tile as a basis. The above limitations have been adjusted accordingly to be
consistent with the other OCPSF BAT limitations by deriving 4-day variability
factors from the distributional parameters determined from the 10-day metal
finishing variability factors (see Appendix VII-F). The OCPSF daily and
monthly maximum limitations for each pollutant is the product of the respec-
tive long-term averages and respective 1-day and 4-day variability factors.
VII-225
-------
TABLE VII-68.
u °NE AND TWO LONG-TERM AVERAGES AND
VARIABILITY FACTORS FOR METALS AND TOTAL CYANIDE
Pollutant
Number
119
120
121
122
124
128
Pollutant
Name
Total Chromium
Total Copper
Total Cyanide
Total Lead
Total Nickel
Total Zinc
Long-Term
Average
(mg/1)
0.572
0.815
0.180
0.197
0.942
0.549
Maximum Monthly
Average VF
1.934
1.781
2.343
1.642
1.796
1.912
Maximum Daily
. VF
4.85
4.15
6.68
3.52
4.22
4.75
VII-226
-------
4 BAT Zinc Limitations for Plants Manufacturing Rayon by the Viscose
Process and Acrylic Fibers by the Zinc Chloride/Solvent Process
Raw wastewaters generated by the manufacture of rayon by the viscose
process and acrylic fibers by the'zinc chloride/solvent process exhibit high
concentrations of zinc with levels generally exceeding 100 mg/1. Accordingly,
the Agency has decided to control zinc in the process wastewaters from these
product/processes by establishing separate BAT effluent limitations. Since
these wastewaters do not contain-complexed sources of zinc that could inhibit
treatment by conventional methods, the Agency has selected hydroxide precipi-
tation as the basis for these process-specific BAT effluent limitations.
During the public comment periods on the March 21, 1983, proposal and
July 17, 1985, NOA, industry commenters submitted hydroxide precipitation
performance data for four rayon plants and one acrylic fibers plant. These
data sets contained influent and effluent data for four plants (three rayon,
one acrylic fiber) with over 200 influent/effluent data pairs for each data
set. One rayon plant (399) was eliminated because only effluent data were
submitted. Following a quality assurance review, the effluent concentrations
that exceeded 10 mg/1 or that exhibited less than 90 percent removal of zinc
were deleted from these three data sets. For the performance data from the
acrylic fibers plant (1012), 174-percent of the effluent zinc concentrations
were deleted, while for the three remaining rayon plants (63, 387, and 1774),
5.9, 0.8, and 63.6 percent of the respective effluent zinc concentrations were
deleted.
The Agency then investigated the data set for plant 1774 because of the
failure of 63.6 percent of the data to pass the editing criteria. Analysis of
the data revealed that the majority of the data failed the 90 percent removal
criteria. Further investigation revealed that the failure to achieve 90 per-
cent removal was not because of high effluent zinc concentrations but due to
low influent concentrations that are the result of a zinc recovery unit
upstream of the influent sampling point. Based on these findings, the entire
performance data set for plant 1774 was deleted from further limitations
calculations.
VII-227
-------
The data sets for the two remaining rayon plants and the one acrylic
fibers plant were analyzed according to the methodology for deriving BAT
effluent limitations described in Appendix VII-F. Table VII-69 presents the
resulting long-term averages and variability factors for the remaining plants.
5- PSES Effluent Limitations
As presented earlier in Section VI, the Agency has determined that
47 toxic pollutants pass through POTtfs and will be controlled by PSES effluent
limitations. For these 47 toxic pollutants, PSES effluent limitations are
equal to BAT Subcategory Two effluent limitations.
VII-228
-------
•—•
Plant
Number
63
387
1012
Long-Term
Average
(mg/1)
1.739
2.114
2.190
Maximum Monthly
VF
1.79
1.41
1.52
Maximum Daily
VF
4.19
2.50
2.95
Median of LTA 2.114
Average VF
1.572
3.214
VII-229
-------
7-1
7-2
7-3
7-4
7-5
7-6
7-7
7-8
7-9
7-10
7-11
7-12
SECTION VII
REFERENCES
Cited References
U.S. Environmental Protection Agency (USEPA). 1981 NPDF
-------
SECTION VII
REFERENCES (Continued)
Cited References (Continued)
7-13 Aire-02 News, Volume 4, No, 3, Summer 1987. Aeration Industries, Inc.,
Chaska, Minnesota.
7-14 Filtration and Chemically Assisted Clarification of Biologically Treated
Pulp and Paper Mill Industry Wastewaters. .Draft Report to the U.S.
Environmental Protection Agency, Edward C. Jordan Co., Inc., 19/y.. ,
7-15 Rice, N., A.A. Kalinske, and W.I. Arnold. 1979. A Pilot Study of;_ -
Advanced Wastewater Treatment for the Ticonderoga Mill, August 1977.
7-16 Personal Communication withsDana Dolloff, International Paper Co., June
26, 1980. ..•.••--'••
7-17 Ambere, H.R., I. Gellman, and R.H. Scott. "The Status of. Water ,-.-,•
Pollufion Control in the Soviet Union," TAPPI, Vol....58, No. 11, November
1975. .-:••••-.-•-
7-18 Scott, R.H. 1978. "Sophisticated Treatment of Baikal Pulp Mill in
USSR," Pulp and Paper, Vol. 48;, No. 4, April 1978.
7-19 Smith, O.D., R.M, Stein,,and C.E. Adams, Jr, ^975. "How Mills Cope _
With Effluent Suspended Solids," Paper Trade Journal, VoK 159, No. I/,
July 1975.
7-20 Peterson, R.R. and J.L. Graham. 1979. CH2M Hill, Inc., Post Biological
Solids Characterization and Removal from Pulp Mill Effluents.
EPA 600/2-79-037.
7-21 "Preliminary Data Base'for Review of BATEA Effluent Limitations
Guidelines, NSPS, and Pretreatment Standards for 'the Pulp, Paper,, and
Paperboard Point Source Category," Edward C. Jordan, Co., Inc., June
1979. . - • .. . , ... . ^ - • : ' ^ ' ," : "'
7-22 Ambers, H.R.. 1979. Crown Zellerbach Corp., Comments on B.C. Jordan's
Draft Report, "Preliminary Data Base for Review of BATEA Effluent
Limitations Guidelines, NSPS, ,and Pretreatment Standards for .the Pulp,
Paper, and Paperboar4 Point Source Category," September 197:9.
7-23 Cashen, R.P. 1979. St. Regis Paper Co., Comments on B.C. Jordan's
Draft Report, "Preliminary Data Base for Review of BATEA Effluent
Limitations Guidelines, NSPS, and Pretreatment Standards for the Pulp,
Paper, and Paperboard Point Source Category," September 1979.
7-24 Button, E.F. 1979. ITT Rayonier .Inc., Comments on E.G. Jordan's Draft
Report. "Preliminary Data Base for Review of BATEA Effluent Limitations
Guidelines, NSPS, and Pretreatment Standards for the Pupp, Paper, and
Paperboard Point Source Category." September 1979.
VII-231
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SECTION VII
REFERENCES (Continued)
Cited References (Continued)
7-25 Barton, Curtis A.. 1979. The Proctor & Gamble Co., Comments on B.C.
Jordan's Draft Report, "Preliminary Data Base for Review of BATEA
Effluent Limitations Guidelines, NSPS, and Pretreatment Standards for
tne Pulp, Paper, and Paperboard Point Source Category," September 1979.
7-26 National Council of the Paper Industry for Air and Stream Improvement,
of BiS^Sil ? °', I8""™"7 °f Data-chemically Assisted Clarification
SDA/ £J g S i yTTr!ated Wastewaters,» Presented in Meeting with U.S.
EPA/ Edward C. Jordan Co., Portland, Maine, February 7, 1980.
7-27 Wise, H.E. and P.O. Fahrenthold. 1981. Occurrence and Predictability
2? L /F P°llutan^ :ln tfastewaters of the Organic Chemicals and
2£3 ^y^hetic Fibers Industrial Categories, Presented at the 181st
April"? 198l! Society National Meeting, Atlanta, Georgia, March 29 -
Other References
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biological wastewater treatment. Pollution Engineering 17(12): 30.
Berger, B.B. 1983. Control of organic substances in water and
wastewater. EPA-600/8-83-011, NTIS PB86 184744/AS.
TK'S\ 19i!5i'i Contract operations: Private contracts for public
work. J. Water Poll. Control Fed. 57(7):750-755. FUUX.IC
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treatment. Chem. Eng. 92:60-74. wasiewater
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performance. J. Water Poll. Control Fed. 57(8):876-881.
Foess, G.W. and W.A. Ericson. 1980., Toxic control - the trend of the
tuture. Water & Wastes Engineering (February 1980): 21-27.
Gaudy, Jr., Anthony F. and E.T. Gaudy. 1980. Microbiology for
environmental engineers and scientists. New York: McGraw-Hill Book
Company .
Johnson, T., F. Lenzo, and K. Sullivan. 1985. Raising Stripper
Temperature Raises MEK Removal. Pollution Engineering 17(9): 34.
R'S\ 19o5< Waftevater treatment plant instrumentation
NTISPB86-108636/AS?ear Cincinnati, Ohio. EPA/600/8-85-026,
VII-232
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SECTION VII
REFERENCES (Continued)
Other References (Continued)
Metcalf & Eddy, Inc. 1979. Wastewater engineering: Treatment/
disposal/reuse. New York: McGraw-Hill Book Company.
Municipal Environmental Research Laboratory (MERL). 1980. Carbon
Adsorption Isotherms for Toxic Organics. EPA-600/8-80-023.
PB 80197320. April 1980.
Peters, R.W., Y/ Ku, and D. Bhattacharyya. Evaluation of recent
treatment techniques for removal of heavy metals from industrial
wastewaters. AIChE Symposium Series. 243:18.
Richards, S.R., C. Hastwell, and M. Davies. 1984. The comparative
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Water Poll. Control Fed, (G^B.) 83:300.
SAIC 1985. Costing documentation and notice of new information
report, Prepared for? Industrial Technology Division of the USEPA.
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Air diffuser performance in activated sludge aeration tanks. J. water
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Control and Treatment Technology for the Metal Finishing Industry:
Sulfide Precipitation. EPA 625/8-80-003.
U.S. Environmental Protection Agency (USEPA). 1980. Sources and
Treatment of Wastewater in the Nonferrous Metals Industry. EPA
600/2-80d-074.
U.S. Environmental Protection Agency (USEPA). 1982. Development
Document for Effluent Limitations, Guidelines, and Standards for the
Battery Manufacturing Point Source Category. EPA 440/l-82-067b.
U.S. Environmental Protection Agency (USEPA). ,1983a. Development
Document for Effluent Limitations Guidelines New Source Performance
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U.S. Environmental Protection Agency (USEPA). 1983c. Treatability
Manual. Office of Research and Development. EPA-600/2-82-001a.
February 1983.
VII-233
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SECTION VII
REFERENCES (Continued)
Other References (Continued)
d
of a Combined
*U,S GOVERNMENT PRINTING OFFICE:1993 -715 -i
VII-234
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