United States
Environmental Protection
Agency
Effluent Guidelines
Division (WH-552)
Washington DC 20460
EPA 440/1-84/067
August 1984
Development Final
Document for
Effluent Limitations
Guidelines and
Standards for
Battery Manufacturing
Point Source Category
Volume II
Subcateqoi
Lead
-------
VOLUME II
DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
BATTERY MANUFACTURING
POINT SOURCE CATEGORY
William D. Ruckelshaus
Administrator
Jack E. Ravan
Assistant Administrator
Office of Water
Edwin Johnson, Director
Office of Water Regulations and Standards
Jeffery D. Denit, Director
Effluent Guidelines Division
Ernst P. Hall, P.E., Chief
Metals and Machinery Branch
Mary L. Belefski
Project Officer
September, 1984
U.S. Environmental Protection Agency
Effluent Guidelines Division
Office of Water Regulations and Standards
Washington, D.C. 20460
-------
This volume is dedicated to John Allen von Hemert who worked
diligently as a member of the EPA Battery Project team, and who
suddenly passed away January 29, 1984.
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CONTENTS
SECTION TITLE
I SUMMARY AND CONCLUSIONS
II RECOMMENDATIONS
III . INTRODUCTION 31
Legal Authority 31
Guideline Development Summary 33
Industry Description 40
Industry Summary 58
Industry Outlook 61
IV INDUSTRY SUBCATEGORIZATION . 93
Subcategorization 93
Final Subcategories And Production
Normalizing Parameters 101
Operations Covered Under Other
Categories 104
V WATER USE AND WASTE CHARACTERIZATION 109
Data Collection And Analysis 109
Lead Subcategory 120
Manufacturing Process and Water
Use 122
Wastewater Characteristics 144
Wastewater Treatment Practices and
Effluent Data Analysis 156
VI SELECTION OF POLLUTANT PARAMETERS 251
Verification Parameters 251
Specific Pollutants Considered for
Regulation 289
VII CONTROL AND TREATMENT TECHNOLOGY 303
End-of-Pipe Treatment Technologies 303
Major Technologies 304
1. Chemical Reduction of Chromium 304
2. Chemical Precipitation 306
3. Cyanide Precipitation 312
4. Granular Bed Filtration 314
5. Pressure Filtration 317
6. Settling 319
7, Skimming 322
Major Technology Effectiveness 326
L & S Performance 326
iii*
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CONTENTS
SECTION TITLE PAGE
LS & F Performance 338
Minor Technologies 342
8. Carbon Adsorption 342
9. Centrifugation 344
10. Coalescing 346
11. Cyanide Oxidation By Chlorine 348
12. Cyanide Oxidation By Ozone 349
13. Cyanide Oxidation By Ozone With
UV Radiation 350
14. Cyanide Oxidation By Hydrogen
Peroxide 351
15. Evaporation 352
16. Flotation 355
17. Gravity Sludge Thickening 358
18. Insoluble Starch Xanthate 359
19. Ion Exchange 360
20. Membrane Filtration 363
21. Peat Adsorption 364
22. Reverse Osmosis 366
23. Sludge Bed Drying 369
24. Ultrafiltration 371
25. Vacuum Filtration 374
26. Permanganate Oxidation 375
In-Process Pollution Control Techniques 376
VIII COST OF WASTEWATER TREATMENT AND CONTROL 457
General Approach 457
Cost Estimation Model Bases 458
Cost Comparison: Proposal Versus
Promulgation 460
Cost Estimation Methodology: Post-
Proposal 462
Normal Plant 486
Nonwater Quality Environmental Aspects 486
IX BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE 533
Technical Approach To BPT 533
Selection of Pollutant Parameters for
Regulation 538
Production Operations and Discharge
Flows 539
Model Treatment Technology 549
Effluent Limitations 551
Pollutant Removals and Costs 551
IV
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CONTENTS
SECTION TITLE PAGE
Reasonableness of the Limitations 551
Application of Regulations in Permits 555
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE 585
Technical Approach To BAT 585
Regulated Pollutant Parameters 596
Discharge Flows
Pollutant Removals and Costs 596
Effluent Limitations 597
XI NEW SOURCE PERFORMANCE STANDARDS 621
Technical Approach to BDT 621
Pollutant Removals and Costs 623
Regulated Pollutant Parameters 623
New Source Performance Standards 623
XII PRETREATMENT STANDARDS 635
Discharge of Wastewaters to a POTW 636
Technical Approach to Pretreatment 637
PSES and PSNS Option Selection 638
Pollutant Removal Benefits and Cost 638
Pollutant Parameters for Regulation 639
Pretreatment Effluent Standards 639
XIII BEST CONVENTIONAL POLLUTANT CONTROL
TECHNOLOGY 659
XIV ACKNOWLEDGEMENTS 661
XV BIBLIOGRAPHY 663
XVI GLOSSARY . 673
CONVERSION TABLE , 690
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TABLES
Number Title Page
III-l Survey Summary . 63
II1-2 Battery General Purposes and Applications 64
III-3 Anode Half-Cell Reactions ' 65
III-4 Cathode Half-Cell Reactions 65
II1-5 Consumption of Toxic Metals in Battery Manufacture 66
II1-6 Battery Manufacturing Category Summary 67
IV-1 Lead Subcategory Elements And Production Normalizing
Parameters (PNP) 105
IV-2 Operations at Battery Plants Included in Other
Industrial Categories (Partial Listing) 106
V-l Screening and Verification Analysis Techniques 164
V-2 Screening Analysis Results - Lead Subcategory 170
V-3 Normalized Discharge Flows from Lead Subcategory Elements 174
/
V-4 Personal Hygiene Data from Industry Survey 175
V-5 Lead Subcategory Characteristics of Individual Process
Wastes 178
V-6 Pasting Wastewater Characteristics (mg/1) 183
V-7 Pasting Waste Loadings (mg/kg) 185
*
V-8 Curing Wastewater Characteristics (mg/1) 187
V-9 Curing Waste Loadings (mg/kg) 188
V-10 Double Fill and Fill & Dump Formation Waste
Characteristics (mg/1) 189
V-l1 Double Fill and Fill & Dump Formation Waste Loadings
(mg/kg) 190
V-l2 Open Formation Dehydrated Battery Waste Characteristics
(mg/1) 191
VI
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TABLES
Number Title
V-13 Open Formation Dehydrated Battery Waste Loadings
(mg/kg) 192
V-14 Battery Wash - Detergent Wastewater Characteristics
(mg/1) 193
V-15 Battery Wash - Detergent Waste Loadings (mg/kg) 194
V-16 Battery Wash - Water Only Wastewater Characteristics
(mg/1) 195
V-17 Battery Wash - Water Only Waste Loadings {mg/kg) 196
V-18 Floor Wash Wastewater Characteristics (mg/1) 197
V-19 Floor Wash Waste Loadings (mg/kg) 198
V-20 Wet Air Pollution Control Wastewater Characteristics
(mg/1) 199
V-21 Wet Air Pollution Control Waste Loadings (mg/kg) 200
V-22 Battery Repair Wastewater Characteristics (mg/1) 201
V-23 Battery Repair Waste Loadings (mg/kg) 202
V-24 Truck Wash Wastewater Characteristics (mg/1) 203
V-25 Truck V'msh Waste Loadings (mg/kg) 204
V-26 Handwash Wastewater Characteristics (mg/1) 205
V-27 Handwash Waste Loadings (mg/kg) 206
V-28 Respirator Wash Wastewater Characteristics (mg/1) 207
V-29 Respirator Wash Waste Loadings (mg/kg) 208
V-30 Laundry Wastewater Characteristics (mg/1) 209
V-31 Laundry Waste Loadings (mg/kg) 210
V-32 Reported Total Process Flow 211
Vll
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TABLES
Number Title Page
V-33 Treatment In Place at Lead Subcategory Plants 213
V-34 Total Raw Waste for Visits (mg/1) 220
V-35 Lead Subcategory Total Raw Waste Loadings (mg/kg) 223
V-36 Statistical Analysis (mg/1) of the Lead Subcategory
Total Raw Waste Concentrations 226
V-37 Statistical Analysis (mg/kg) of the Lead Subcategory
Total Raw Waste Loadings 227
V-38 Effluent Characteristics Reported in Dcp by Plants
Practicing pH Adjustment and Settling Technology 228
V-39 Effluent Characteristics Reported in Industry Survey
by Plants Practicing pH Adjustment and Settling
Technology 229
V-40 Effluent Characteristics Reported in Dcp by Plants
Practicing pH Adjustment and Filtration 230
V-41 Effluent Characteristics Reported in Industry Survey
by Plants Practicing pH Adjustment and Filter Technology 231
V-42 Effluent Characteristics Reported in Dcp by Plants
Practicing pH Adjustment Only 232
V-43 Effluent Characteristics Reported in Industry Survey
by Plants Practicing pH Adjustment Only 233
V-44 Influent to Wastewater Treatment Pollutant
Characteristics (mg/1) 234
V-45 Effluent from Sampled Plants (mg/1) 236
VI-1 Priority Pollutant Disposition 296
VI-2 Other Pollutants Considered for Regulation 301
VII-1 pH Control Effect On Metals Removal 404
VI1-2 Effectiveness Of Sodium Hydroxide For Metals
Removal 404
viii
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TABLES
Number Title
VII-3 Effectiveness Of Lime And Sodium Hydroxide For
Metals Removal 405
VII-4 Theoretical Solubilities of Hydroxides and Sulfides
of Selected Metals in Pure Water 405
VI1-5 Sampling Data From Sulfide Precipitation-
Sedimentation Systems 406
VI1-6 Sulfide Precipitation-Sedimentation Performance 407
VI1-7 Ferrite Co-Precipitation Performance 408
VI1-8 Concentration of Total Cyanide 408
VII-9 Multimedia Filter Performance 409
VII-10 Performance of Sampled Settling Systems 409
VII-11 Skimming Performance 410
VII-12 Selected Partition Coefficients 411
VI1-13 Trace Organic Removal by Skimming API Plus
Belt Skimmers 412
VII-14 Combined Metals Data Effluent Values (mg/1) 412
VII-15 L&S Performance-Additional Pollutants 413
VII-16 Combined Metals Data Set - Untreated Wastewater 413
VII-17 Maximum Pollutant Level in Untreated Wastewater-
Additional Pollutants 414
VII-18 Precipitation-Settling-Filtration (LS&F)
Performance - Plant A 415
VII-19 Precipitation-Settling-Filtration (LS&F)
Performance Plant B 416
VII-20 Precipitation-Settling-Filtration (LS&F)
Performance Plant C * 417
IX
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TABLES
Number Title
VII-21 Summary of Treatment Effectiveness
VII-22 Treatability Rating of Priority Pollutants
Utilizing Carbon Adsorption
VI1-23 Classes of Organic Compounds Adsorbed On Carbon
VI1-24 Activated Carbon Performance (Mercury)
VI1-25 Ion Exchange Performance
VII-26 Membrane Filtration System Effluent
VI1-27 Peat Adsorption Performance
VI1-28 Ultrafiltration Performance
VII-29 Process Control Technologies In Use At Battery
Manufacturing Plants
VIII-1 Battery Manufacturing Compliance Costs - Lead
Subcategory
VII1-2 In-Plant Cost Procedure Changes
VIII-3 Cost Difference Comparison •- Promulgated vs.
Proposed
VII1-4 Cost Equations for Recommended Treatment and
Control Technologies
VII1-5 Components of Total Capital Investment
VIII-6 Components of Total Annualized Costs
VII1-7 Wastewater Sampling Frequency
VII1-8 In-Plant Cost Frequency Summary
VII1-9 Nonprocess Water Disposition Among Plants
Visited After Proposal
VIII-10 Cost Program Pollutant Parameters
Page
418
419
420
421
421
422
422
423
424
489
490
493
494
500
501
502
503
504
505
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TABLES
Number Title Page
VIII-11 Example Plant Summary 506
VIII-12 Normal Plant Capital and Annual Costs 507
VIII-13 Energy Costs and Requirements 508
IX-1 Flow Basis for BPT Mass Discharge Limitations
Lead Subcategory 557
IX-2 Summary of Zero Discharge for Lead Subcategory
Process Elements . 559
IX-3 Summary of Treatment In-Place at Lead Subcategory
Plants 561
Lead Subcategory BPT Ef f1uent L imitat ions;
IX"-4 Mold Release Formulation 562
IX-5 Direct Chill Lead Casting 563
IX-6 Lead Rolling (Lead Used) 564
IX-7 Lead Rolling (Lead Rolled) 565
IX-8 Closed Formation - Double Fill, or Fill & Dump 566
IX-9 Open Formation - Dehydrated 567
IX-10 Open Formation - Wet 568
IX-11 Plate Soak 569
IX-12 Battery Wash (Detergent) 570
IX-13 Battery Wash (Water Only) 571
IX-14 Truck Wash 572
IX-15 Laundry 573
IX-16 Miscellaneous Wastewater Streams 574
IX-17 Comparison of Actual Total Flow Rates to
xi
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TABLES
Number Title
BPT Hourly Flow Rates 575
IX-18 Summary of BPT Treatment Effectiveness at
Lead Subcategory Plants 580
IX-19 Sample Derivation of the BPT 1-Day Lead
Limitation 582
X-l Process Element Flow Summary Lead Subcategory 598
X-2 Normal Plant Element Flows Lead Subcategory 599
X-3 Summary of Treatment Effectiveness Lead
Subcategory 601
X-4 Pollutant Reduction Benefits of Control Systems
Lead Subcategory - Normal Plant 602
X-5 Pollutant Reduction Benefits of Control Systems
Lead Subcategory - Normal Discharging Plant 603
X-6 Pollutant Reduction Benefits of Control Systems
Lead Subcategory - Total Dischargers 604
X-7 Pollutant Reduction Benefits of Control Systems
Lead Subcategory - Direct Dischargers 605
X-8 Battery Manufacturing Compliance Costs Lead
Subcategory 606
Lead Subcategory BAT EffluentLimitations;
X-9 Mold Release Formulation 607
X-10 Direct Chill Lead Casting 608
X-11 Open Formation - Dehydrated 609
X-l2 Open Formation - Wet 610
X-l3 Plate Soak 611
X-l4 Battery Wash (Detergent) 612
XII
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Number
X-15
X-16
X-17
XI-1
XI-2
XI-3
XI-4
XI-5
XI-6
XI-7
XI-8
XI-9
XI-10
XII-1
XII-2
XII-3
XII-4
XII-5
XII-6
TABLES
Title
Truck Mash
Laundry
Miscellaneous Wastewater Streams
Pollutant Reduction Benefits of Option 5
Lead Subcategory New Source Performance Standards:
Mold Release Formulation
Direct Chill Lead Casting
Open Formation - Dehydrated
Open Formation - Wet
Plate Soak
Battery Wash (Detergent)
Truck Wash
Laundry
Miscellaneous Wastewater Streams
Lead Subcategory Pretreatment Standards for
Existing Sources:
Pollutant Reduction Benefits of Control Systems
Lead Subcategory - Indirect Dischargers
Mold Release Formulation
Direct Chill Lead Casting
Open Formation - Dehydrated
Open Formation - Wet
Plate Soak
Pag (
613
614
615
624
625
626
627
628
629
630
631
632
633
640
641
642
643
644
645
XI11
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TABLES
Number Title Page
XI1-7 Battery Wash (Detergent) 646
XI1-8 Truck Wash ' 647
XI1-9 Laundry 648
XII-10 Miscellaneous Wastewater Streams 649
Lead Subcateqory Pretreatment Standards for
New Sources;
XII-11 Mold Release Formulation 650
XII-12 Direct Chill Lead Casting 651
XII-13 Open Fomation - Dehydrated 652
XII-14 Open Formation - Wet 653
XII-15 Plate Soak 654
XII-16 Battery Wash (Detergent) 655
XII-17 Truck Wash 656
XI1-18 Laundry 657
XI1-19 Miscellaneous Wastewater Streams 658
xiv
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FIGURES
Number Title Page
III-l Theoretical Specific Energy As a Function of
Equivalent Weight and Cell Voltage For Various
Electrolytic Couples 68
III-2 Performance Capability of Various Battery Systems 69
II1-3 Cutaway View of An Impregnated Sintered Plate
Nickel-Cadmium Cell 70
II1-4 Cutaway View of A Cylindrical Nickel-Cadmium
Battery 71
II1-5 Cutaway View of Lead Acid Storage Battery 72
III-6 Cutaway View of A Leclanche Cell . 73
II1-7 Exploded View of A Flat Leclanche Battery Used
In Film Pack 74
II1-8 Cutaway View of Two Solid Electrolyte Lithium
Cell Configurations 75
II1-9 Cutaway View of A Reserve Type Battery 76
III-l0 Cutaway View of A Carbon-Zinc-Air Cell 77
III-l1 Cutaway View of An Alkaline-Manganese Battery 78
II1-12 Cutaway View of A Mercury (Ruben) Cell 79
II1-13 Major Production Operations in Nickel-Cadmium
Battery Manufacture 80
II1-14 Simplified Diagram of Major Production Operations
In Lead Acid Battery Manufacture 81
III-15 Major Production Operations In Leclanche Dry
Battery Manufacture 82
II1-16 Major Production Operations in Lithium-Iodine
Battery Manufacture 83
III-l7 Major Production Operations In Ammonia-Activated
Magnesium Reserve Cell Manufacture 84
xv
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FIGURES
Number Title Page
111-18 Major Production Operations In Water-Activated
Carbon-Zinc-Air Cell Manufacture 85
111-19 Major Production Operations In Alkaline-Manganese
Dioxide Battery Manufacture 86
II1-20 Simplified Diagram of Major Operations In Mercury
(Ruben) Battery Manufacture 87
111-21 Value of Battery Product Shipments 1963-1977 88
111-22 Geographical-Regional Distribution of
Battery Manufacturing Plants 89
*
111-23 Distribution of Lead Subcategory Production Rates 90
II1-24 Distribution of Employment At Lemd Subcategory
Manufacturing Facilities 91
IV-1 Summary Of Category Analysis 107
V-l Generalized Lead Subcategory Manufacturing
Processes 240
V-2 Lead Subcategory Analysis 241
V-3 Percent Production Normalized Discharge From
Lead Subcategory Process Operations 243
V-4 Production Normalized Discharge From Double
and Single Fill Formation 244
V-5 Production of Closed Formation Wet Batteries 245
V-6 Production of Damp Batteries 246
V-7 Production of Dehydrated Batteries 247
V-8 Production of Batteries From Green (Unformed)
Electrodes 248
V-9 Production of Batteries from Purchased Formed
Plates 249
xvi
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FIGURES
Number Title Page
VII-1 Comparative Solubilities of Metal Hydroxides
and Sulfide as a Function of pH 427
VII-2 Lead Solubilities in Three Alkalies 428
VII-3 Effluent Zinc Concentration vs. Minimum Effluent
pH 429
VI1-4 Hydroxide Precipitation Sedimentation Effectiveness
Cadmium 430
VI1-5 Hydroxide Precipitation Sedimentation Effectiveness
Chromium 43T
VI1-6 Hydroxide Precipitation Sedimentation Effectiveness
Copper 432
VI1-7 Hydroxide Precipitation Sedimentation Effectiveness
Lead 433
VI1-8 Hydroxide Precipitation Sedimentation Effectiveness
Nickel and Aluminum 434
VI1-9 Hydroxide Precipitation Sedimentation Effectiveness
Zinc 435
VII-10 Hydroxide Precipitation Sedimentation Effectiveness
Iron % 436
VII-11 Hydroxide Precipitation Sedimentation Effectiveness
Manganese 437
VI1-12 Hydroxide Precipitation Sedimentation Effectiveness
TSS 438
VI1-13 Hexavalent Chromium Reduction with Sulfur Dioxide 439
VII-14 Granular Bed Filtration " 440
VII-15 Pressure Filtration 441
VI1-16 Representative Types of Sedimentation 442
VI1-17 Activated Carbon Adsorption Column 443
xvii
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FIGURES
Number Title
VII-18 Centrifugation
VI1-19 Treatment of Cyanide Waste by Alkaline
Chlorination
VI1-20 Typical Ozone Plant for Waste Treatment
VI1-21 UV-Ozonation
VI1-22 Types of Evaporation Equipment
VII-23 Dissolved Air Flotation
VII-24 Gravity Thickening
VII-25 Ion Exchange With Regeneration
VII-26 Simplified Reverse Osmosis Schematic
VI1-27 Reverse Osmosis Membrane Configurations
VI1-28 Sludge Drying Bed
VII-29 Simplified Ultrafiltration Flow Schematic
VII-30 Vacuum Filtration
VIII-1 Costs for Paste Mixing and Application Area Wash
Water Recycle
VII1-2 Costs for Steam Curing
VII1-3 Costs for Humidity Curing Water Recycle
VII1-4 Costs for Slow Formation
VII1-5 Costs for Countercurrent Rinsing
VII1-6 Costs for Sealant Water Recycle
VII1-7 Capital Costs for Formation Area WAPC Water
Recycle
VIII-8 Annual Costs for Formation Area WAPC Water
444
445
446
447
448
449
450
451
452
453
454
455
456
509
510
511
512
513
514
515
xviii
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FIGURES
Number Title
Recycle 516
VII1-9 Capital Costs for Reuse of Battery Rinse
Water in Acid Cutting * 517
VI11-10 Annual Costs for Reuse of Battery Rinse Water
in Acid Cutting 518
VIII-11 Costs for Power Floor Scrubber Water Settling 519
VIII-12 Costs for Segregation of Non-Process Water
Flows 520
VII1-13 General Logic Diagram of Computer Cost Model 521
VI11-14 Logic Diagram of Module, Design Procedure 522
VII1-15 Logic Diagram of the Costing Routine 523
VII1-16 Costs for Chemical Precipitation and
Sedimentation 524
VII1-17 Costs for Sulfide Precipitation and Sedimentation 525
VIII-18 Costs for Vacuum Filtration 526
\
VII1-19 Costs for Equalization 527
VIII-20 Costs for Recycling 528
VIII-21 Costs for Multimedia Filtration-Membrane Filtration 529
VII1-22 Costs for Reverse Osmosis 530
VII1-23 Costs for Oil-Water Separation 531
VIII-24 Costs for Contract Hauling 532
IX-1 Lead Subcategory BPT Treatment 583
X-l Lead Subcategory BAT Option 1 Treatment 616
X-2 Lead Subcategory BAT Option 2 Treatment 617
xix
-------
FIGURES
Number Title
X-3 Lead Subcategory BAT Option 3 Treatment 618
X-4 Lead Subcategory BAT Opt i 013 4 Treatment 619
xx
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SECTION I
SUMMARY AND CONCLUSIONS
Background
Pursuant to Sections 301, 304, 306, 307, 308, and 501 of the
Clean Water Act, and the Settlement Agreement in Natural
Resources Defense Council v. Train 8 ERC 2120 (D.D.C. 1976)
modified 12 ERC 1833 (D.D.C. 1979) by orders dated October 26,
1982, August 2, 1983, and January 6, 1984, EPA collected and
analyzed data for plants in the Battery Manufacturing Point
Source Category. There are no existing effluent limitations or
performance standards for this industry. This document and the
administrative record provide the technical bases for
promulgating effluent limitations for existing direct dischargers
using best practicable and best available technology (BPT and
BAT). Effluent standards are promulgated for existing indirect
dischargers. (PSES), and new sources, for both direct dischargers
(NSPS) and indirect dischargers (PSNS).
Battery manufacturing encompasses the production of modular
electric power sources where part or all of the fuel is contained
within the unit and electric power is generated directly from a
chemical reaction rather than indirectly through a heat cycle
engine. There are three major components of a cell — anode,
cathode, and electrolyte — plus mechanical and conducting parts
such as case, separator, or contacts. Production includes
electrode manufacture of anodes and cathodes, and associated
ancillary operations necessary to produce a battery.
This volume (Volume II) of the development document specifically
addresses the lead subcategory and Volume I addresses all other
subcategories within the battery manufacturing point source
category. Section III of both volumes provides a general
discussion of all battery manufacturing.
Subcategprigation
The category is subcategorized on the basis of anode material and
electrolyte. This subcategorization was selected because most of
the manufacturing process variations are similar within these
subcategories and the approach avoids unnecessary complexity.
The data base for this volume includes all information for the
lead subcategory.
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Within the lead subcategory manufacturing process operations (or
elements) were grouped into anode manufacture, cathode
manufacture, and ancillary operations associated with the
production . of a battery. The development of a production
normalizing parameter (pnp) for each element was necessary to
relate water use to various plant sizes and production
variations. For the lead subcategory the total (raw material)
lead use was selected as the pnp and is generally applied to all
process elements.
Data.
The data base for the lead subcategory includes 186 plants which
employed an estimated 18,745 people. Of the 186 plants, 12
discharge wastewater directly to surface waters, 117 discharge
wastewater to publicly owned treatment works (POTW), and 57 have
no discharge of process wastewater. Data collection portfolios
(dcp) were sent to all known battery companies in the U.S. and
data were requested for 1976. Data were returned by 96 percent
of the lead battery companies. The data base includes some data
for 1977, 1978, and 1982.
Water is used throughout lead battery manufacturing to clean
battery components and to transport wastes. Water is used in
paste mixing to make lead electrodes; water is also a major
component of the sulfuric acid electrolyte which is also
contained in formation baths. A total of 17 lead battery plants
were visited before proposal for engineering analysis, and
wastewater sampling was conducted at five of these plants. These
visits enabled the Agency to characterize subcategory specific
wastewater generating processes, select the pollutants for
regulation, and evaluate wastewater treatment performance in this
subcategory. Since proposal, 17 additional lead battery
manufacturing sites were visited in order to collect additional
data and to further evaluate wastewater treatment performance.
Pollutants or pollutant parameters found in significant amounts
in lead battery manufacturing wastewaters include (1) toxic
metals — copper and lead; (2) nonconventional pollutants
aluminum, iron, manganese; and (3) conventional pollutants — oil
and grease, TSS, and pH. Toxic organic pollutants generally were
not found in large quantities. Because of the amount of toxic
metals present, the sludges generated during wastewater treatment
generally contain substantial amounts of toxic metals.
Current wastewater treatment systems in the battery manufacturing
category range from no treatment to sophisticated physical
chemical treatment (although frequently not properly operated)
combined with water conservation practices. Of the 186 lead
-------
battery manufacturing plants in the data base, 23 percent of the
plants have no treatment and do not discharge, 17 percent have no
treatment and discharge, 20 percent have only pH adjust systems,
5 percent have only sedimentation or clarification devices, 29
percent have equipment for chemical precipitation and settling,
5.5 percent have equipment for chemical precipitation, settling
and filtration, and'0.5 percent have other treatment systems.
Even though treatment systems are in-place at many plants,
wastewater treatment practices in this subcategory are uniformly
inadequate. The systems in-place are generally inadequately
sized, poorly maintained, or improperly operated (systems
overloaded, solids not removed, pH not controlled, etc.).
Wastewater Treatment
The control and treatment technologies available for this
category and considered as the basis for the promulgated
regulation include both in-process and end-of-pipe treatments.
In-process treatment includes a variety of water flow reduction
steps and major process changes such as: cascade and
countercurrent rinsing (to reduce the amount of water used to
remove unwanted materials from electrodes); consumption of
cleansed wastewater in product mixes; and substitution of
nonwastewater-generating formation (charging) systems. End-of-
pipe treatment considered includes: chemical precipitation of
metals using hydroxides, carbonates, or sulfides; and removal of
precipitated metals and other materials using settling or
sedimentation; filtration; reverse osmosis; and combinations of
these technologies. While developing the final regulation, EPA
also considered the impacts of these technologies on air quality,
solid waste generation, water scarcity, and energy requirements.
The effectiveness of these treatment technologies has been
evaluated and established by examining their performance on
battery manufacturing and other similar wastewaters. The data
base for hydroxide precipitation-sedimentation (lime and settle)
technology is a composite of data drawn from EPA sampling and
analysis of copper and aluminum forming, battery manufacturing,
porcelain enameling, and coil coating effluents. A detailed
statistical analysis done on the data base showed substantial
homogeneity in the treatment effectiveness data from these five
•categories. This supports EPA's technical judgment that these
wastewaters are similar in all material respects for treatment
because they contain a range of dissolved metals which can be
removed by precipitation and solids removal. Electroplating data
were originally used in the data set, but were excluded after
further statistical analyses were performed. Following proposal,
additional battery manufacturing lime and settle technology
effluent data were obtained from battery plants primarily to
-------
evaluate treatment effectiveness for lead. Precipitation-
sedimentation and filtration technology performance is based on
the performance of full-scale commercial systems treating multi-
category wastewaters which also are essentially similar to
battery manufacturing wastewaters.
The treatment performance data is used to obtain maximum daily
and monthly average pollutant concentrations. These
concentrations (mg/1) along with the production normalized
regulatory flows (I/kg of production normalizing parameter) are
used to obtain the maximum daily and monthly average values
(mg/kg) for effluent limitations and standards. The monthly
average values are based on the average of ten consecutive
sampling days. The ten day average value was selected as the
minimum number of consecutive samples which need to be averaged
to arrive at a stable slope on a statistically based curve
relating one day and 30 day average values and it approximates
the most frequent monitoring requirement of direct discharge
permits.
Treatment Costs
The Agency estimated the costs of each control and treatment
technology using a computer program based on standard engineering
cost analysis. EPA derived unit process costs by applying plant
data and characteristics (production and flow) to each treatment
process (i.e., metals precipitation, sedimentation, mixed-media
filtration, etc.). The program also considers what treatment
equipment exists at each plant. These unit process costs were
added for each plant to yield total cost at each treatment level.
In cases where there is more than one plant at one site, costs
were calculated separately for each plant and probably overstate
the actual amount which would be spent at the site where one
combined treatment system could be used for all plants. These
costs were then used by the Agency ' to estimate the impact of
implementing the . various options on the industry. For each
control and treatment option considered the number of potential
closures, number of employees affected, and the impact on price
were estimated. These results are reported in the EPA document
entitled, Economic Impact Analysis of Effluent Limitations and
Standards forthe Battery Manufacturing Industry (EPA
440/2-84-002).
Regulation
On the basis of raw waste characteristics, in-process and end-of-
pipe treatment performance and costs, and other factors, EPA
identified and classified various control and treatment
technologies as BPT, BAT, NSPS, PSES, and PSNS. The regulation,
-------
however, does not require the installation of any particular
technology. Rather, it requires achievement of effluent
limitations equivalent to those achieved by the proper operation
of these or equivalent technologies.
Except for pH requirements, the effluent limitations for BPT,
BAT, and NSPS are expressed as mass limitations — a mass of
pollutant per unit of production (mg/kg). They were calculated
by combining three figures: (1) treated effluent concentrations
determined by analyzing control technology performance data; (2)
production-weighted wastewater flow for each manufacturing
process element of each subcategory; and (3) any relevant process
or treatment variability factor (e.g., mean versus maximum day).
This basic calculation was performed for each regulated pollutant
or pollutant parameter and for each wastewater-generating process
element of each subcategory. Pretreatment standards — PSES and
PSNS — are also expressed as mass limitations rather than
concentration limits to ensure a reduction in the total quantity
of pollutant discharges.
BPT - In general, the BPT level represents the average of the
best existing performances of plants of various ages, sizes,
processes or other common characteristics. Where existing
performance is uniformly inadequate, BPT may be transferred from
a different subcategory or category. In balancing costs in
relation to effluent reduction benefits, EPA considers the volume
and nature of existing discharges, the volume and nature of
discharges expected after application of BPT, the general
environmental effects of the pollutants, and cost and economic
impact of the required pollution control level.
EPA is promulgating BPT mass limitations for existing direct
dischargers based on model end-of-pipe treatment, which consists
of oil skimming when required and lime precipitation and
settling. The pollutant parameters selected for limitation at
BPT are: copper, lead, iron, oil and grease, total suspended
solids (TSS), and pH.
Twelve lead battery plants are direct dischargers.
Implementation of BPT limitations will remove 115,400 kilograms
(253,900 pounds) per year of toxic metals and 675,800 kilograms
(1,486,800 pounds) per year of conventional and other pollutants
from the estimated raw waste generation. The Agency estimates
that capital costs above equipment in place for these plants will
be $0.715 million ($1983) and total annual costs will be $0.499
million ($1983). The economic impact analysis concluded that
there are no potential plant closures or employment effects
associated with compliance with this regulation. If compliance
costs were passed on to consumers, price increases would be no
-------
higher than 0.3 percent for lead battery products. There are no
balance-of-trade effects. The Agency has determined that the
effluent reduction benefits associated with compliance with BPT
limitations justify the costs.
BAT - The BAT level represents the best economically achievable
performance of plants of various ages, sizes, processes or other
shared characteristics. As with BPT, where existing performance
is uniformly inadequate, BAT may be transferred from a different
subcategory or category. BAT may include feasible process
changes or internal controls, even when not common industry
practice.
In .developing BAT, EPA has given substantial weight to the
reasonableness of costs. The Agency considered the volume and
nature of discharges, the volume and nature of discharges
expected after application of BAT, the general environmental
effects of the pollutants, and the costs and economic impacts of
the required pollution control levels. Despite this
consideration of costs, the primary determinant of BAT is still
effluent reduction capability.
The direct dischargers are expected to move directly to
compliance with BAT limitations from existing treatment because
the flow reduction used to meet BAT limitations would allow the
use of smaller — and less expensive — lime and settle equipment
than would be used to meet BPT limitations without any flow
reduction. The pollutants selected for regulation at BAT are:
copper, lead, and iron.
Implementation of the BAT limitations will remove annually an
estimated 115,600 kilograms (254,000 pounds) of toxic metals and
679,000 kilograms (1,494,000 pounds) per year of other pollutants
from estimated raw waste generation at a capital cost, above
equipment in place, of $0.819 million and a total annual cost of
$0.510 million ($1983). The Agency projects no plant closures,
employment impacts, or foreign trade effects and has determined
that the BAT limitations are economically achievable.
NSPS - NSPS (new source performance standards) are based on the
best available demonstrated, technology (BDT), including process
changes, in-plant controls, and end-of-pipe treatment
technologies which reduce pollution to the maximum extent
feasible.
EPA is establishing the best available demonstrated technology
for the lead subcategory of the battery manufacturing category to
be equivalent to BAT technology with the addition of filtration
-------
prior to discharge. The pollutants regulated at NSPS are copper,
lead, iron, oil and grease, total suspended solids (TSS), and pH.
EPA estimates that a new direct discharge lead battery
manufacturing plant having the industry average annual production
level for discharging plants would generate a raw waste of 14,500
kilograms (31,800 pounds) per year of toxic pollutants. The NSPS
technology would reduce the toxic pollutant discharge levels to
4.3 kilograms (9.5 pounds) per year. The capital investment cost
for a new model lead battery manufacturing plant to install the
NSPS technology is estimated to be $0.119 million, with annual
costs of $0.069 million ($1983). EPA believes that NSPS will not
constitute a barrier to entry for new sources, prevent major
modifications to existing sources, or produce other adverse
economic effects.
PSES - PSES (pretreatment standards for existing sources) are
designed to prevent the discharge of pollutants which pass
through, interfere with, or are otherwise incompatible with the
operation of POTW. Pretreatment standards are technology-based
and analogous to the best available technology for removal of
toxic pollutants. EPA is promulgating PSES based on the
application of technology equivalent to BAT, which consists of
end-of-pipe treatment comprised of oil skimming where necessary,
and lime precipitation and settling.
The Agency has concluded that the toxic metals regulated under
these standards (copper and lead) pass through the POTW. The
nationwide average percentage of these toxic metals removed by a
well operated POTW meeting secondary treatment requirements is 58
percent for copper and 48 percent for lead, whereas the
percentage that can be removed by a lead battery manufacturing
direct discharger applying the best available technology
economically achievable is expected to be over 99 percent.
Accordingly, these pollutants pass through a POTW and are being
regulated at PSES.
Implementation of the PSES will remove annually an estimated
1,488,400 kilograms (3,274,500 pounds) of toxic pollutants, and
8,743,600 kilograms (19,235,900 pounds) of other pollutants from
estimated raw waste.
To comply with PSES, EPA estimates that total capital investment,
above equipment in place, would be $7.11 million and that annual
costs would be $4.07 million ($1983), including interest and
depreciation. The Agency has concluded that PSES is economically
achievable.
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PSNS - Like PSES, PSNS (pretreatment standards for new sources)
are established to prevent the discharge of pollutants which pass
through, interfere with, or are otherwise incompatible with the
operation of. the POTW. New indirect dischargers, like new direct
dischargers, have the opportunity to incorporate the best
available demonstrated technologies.
This regulation establishes mass-based PSNS for the lead
subcategory of the battery manufacturing category. The treatment
technology basis for the PSNS being promulgated is identical to
the treatment technology set forth as the basis for the NSPS
being promulgated. The pollutants regulated under PSNS are
copper and lead.
New source model plant costs were estimated for the lead
subcategory. The total capital investment cost for a lead
battery manufacturing plant with the industry average production
level for discharging plants to install PSNS technology is $0.119
million with corresponding total annual costs of $0.069 million
($1983). This new lead battery manufacturing plant would
generate a raw waste load of approximately 14,500 kilograms
(31,800 pounds) per year of toxic pollutants and 84,900 kilograms
(186,900 pounds) per year of other pollutants. Application of
PSNS technology would reduce the toxic pollutant discharge to 4.3
kilograms (9.5 pounds) per year and the discharge of other
pollutants to 42 kilograms (92 pounds) per year. EPA does not
believe that PSNS will pose a barrier to entry for new indirect
sources.
BCT - BCT effluent limitations for .the lead .subcategory are
deferred pending adoption of the BCT cost test.
Nonwater Quality Environmental Impacts
Eliminating or reducing one form of pollution may cause other
environmental problems. Sections 304(b) and 306 of the Act
require EPA to consider the nonwater quality environmental
impacts (including energy requirements). In compliance with
these provisions, the Agency considered the effect of this
regulation on air pollution, solid waste generation and energy
consumption. The Administrator has determined that the impacts
identified below are justified by the benefits associated with
compliance with the limitations and standards.
Imposition of BPT, BAT, NSPS, PSES, and PSNS will not create any
substantial air pollution problems because the wastewater
treatment technologies required to meet these limitations and
standards do not cause air pollution.
-------
EPA estimates that battery manufacturing plants generated 18,960
kkg (87,000 tons) of solid wastes per year from manufacturing
process operations, and an indeterminate amount of solid waste
from wastewater treatment because of the variable technologies
currently practiced. The solid wastes that would be generated at
battery manufacturing plants by lime and settle treatment
technologies are be"li.eved to be not hazardous under Section 3001
of the Resource Conservation and Recovery Act (RCRA). Only
wastewater treatment sludge generated by sulfide precipitation
technology, and wastewater treatment sludges containing mercury
are likely to be hazardous under the regulations implementing
subtitle C of RCRA.
EPA estimates that the achievement of BPT effluent limitations
for the lead subcategory will result in a net increase* in
electrical energy consumption of approximately '0.40 million
kilowatt-hours per year. The BAT effluent technology are
projected to increase electrical energy consumption by 0.30
million kilowatt hours per year, slightly less than BPT. The
energy requirements for NSPS and PSNS are estimated to be similar
to energy requirements for BAT and PSES.
-------
-------
SECTION II
RECOMMENDATIONS
1. EPA has divided the battery manufacturing category into
eight subcategories for the purpose of effluent limitations and
standards. These subcategories are:
A. Cadmium E. Lithium
B, Calcium F, Magnesium
C. Lead G. Zinc
D. Leclanche H. Nuclear
2. These subcategories have been further subdivided into
process elements specific to basic manufacturing operations
within the subcategory, and the promulgated regulations are
specific to these elements. This volume (Volume II) presents
effluent limitations and standards for the lead subcategory
(Subcategory C). Effluent limitations and standards for the
other battery subcategories of the battery manufacturing category
are presented in Volume I.
3. The following effluent limitations are promulgated for
existing sources in the lead subcategory.
A. Subcategory C - Lead
(a) BPT Limitations
(1) Subpart C - Closed Formation - Double Fill, or Fill
and Dump BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.86 0.45
Lead 0.19 0.090
Iron 0.54 0.27
Oil and Grease 9.00 5.40
TSS 18.45" 8.78
pH Within the range of 7.5 - 10.0 at all times
11
-------
(2) Subpart C - Open Formation - Dehydrated
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 20.99 11.05
Lead 4.64 2.21
Iron 16.13 6.74
Oil and Grease 221.00 132.60
TSS 453.05 215.47
pH Within the range of 7.5 - 10.0 at all times
(3) Subpart C - Open Formation - Wet
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day month 1 y average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.10 0.05
Lead 0.02 0.01
Iron 0.06 0.03
Oil and Grease 1.06 0.64
TSS 2.17 1.03
pH Within the range of 7.5 - 10.0 at all times
12
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(4) Subpart C - Plate Soak
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly aye rage
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.04 0.02
Lead 0.009 0.004
Iron 0.03 0.01
Oil and Grease 0.42 0.25
TSS 0.86 0.41
pH Within the range of 7.5 - 10.at all times
(5) Subpart C - Battery Wash (with Detergent)
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 1.71 0.90
Lead 0.38 0.18
Iron 1.08 0.55
Oil and Grease 18.00 10.80
TSS 36.90 17.55
pH Within the range of 7.5 - 10.0 at all times
13
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(6) Subpart C - Battery Wash (Water Only)
BPT Effluent Limitations
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum
monthly
for
average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS
PH
1,12
0,25
0,71
11 ,80
24.19
0.59
0.12
0.36
7,
11
08
51
Within the range of 7.5 - 10.0 at all times
(7) Subpart C - Direct Chill Lead Casting
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS.
PH
0.0004
0.00008
0.0002
0.004
0.008
Within the range of 7.5
0.0002
0.00004
0.0001
0.002
0.003
10.at all times
14
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(8) Subpart C
Mold Release Formulation
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
month1y average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.011
0.002
0.00?
0.120
0.246
Within the range of 7.5 -
0.006
0.001
0.004
0.072
0.117
10.0 at all times
(9) Subpart C - Truck Wash
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked
batteries
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.026
0.005
0.016
0.280
0.574
Within the range of 7.5
0,
0,
0,
0,
0.
014
002
008
168
273
- 10.at all times
15
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(10) Subpart C - Laundry
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS
PH
0.21
0.05
0.13
2.18
4.47
Within the range of 7.5
0.11
0.02
0.07
1 .31
2.13
10.0 at all times
(11) Subpart C - Miscellaneous Wastewater Streams
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS
PH
0.81
0. 18
0.51
8.54
17.51
0.43
0.09
26
12
0,
5,
8.33
Within the range of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
16
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(b) BAT Limitations
O) Subpart C - Open Formation - Dehydrated
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
3.19
0.71
2.02
1 .68
0.34
1 .02
(2) Subpart C - Open Formation - Wet
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Copper
Lead
Iron
mg/kg of lead used
- lb/1,000,000 Ib of lead used
0.100
0.022
0.06
0.053
0.010
0.03
(3) Subpart C -
Plate Soak
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Copper
Lead
Iron
mg/kg of lead used
- lb/1,000,000 Ib of lead used
0.039
0.008
0.030
0.021
0.004
0.010
17
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(4) Subpart C -
Battery Wash (Detergent)
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units •
English Units
Copper
Lead
Iron
mg/kg of lead used
- lb/1,000,000 Ib of lead used
0.86
0.19
0.54
0.45
0.09
0.27
(5) Subpart C -
Direct Chill Lead Casting
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Copper
Lead
Iron
mg/kg of lead used
- lb/1,000,000 Ib of lead used
0.0004
0.00008
0.0002
0.0002
0.00004
0.0001
(6) Subpart C -
Mold Release Formulation
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Copper
Lead
Iron
mg/kg of lead used
- lb/1,000,000 Ib of lead used
0.011
0.002
0.007
0.006
0.001
0.003
18
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(7) Subpart C -
Truck Wash
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Copper
Lead
Iron
mg/kg of lead in trucked batteries
- lb/1,000,000 Ib of lead in trucked
batteries
0.026
0.005
0.016
0.014
0.002
0.008
(8) Subpart C -
Laundry
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Copper
Lead
Iron
mg/kg of lead used
- lb/1,000,000 Ib of lead used
0.21
0.05
0.13
0.11
0.02
0.07
19
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(9) Subpart C - Miscellaneous Wastewater Streams
BAT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
0.58
0.13
0.37
0.31
0.06
0. 19
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
4. The following standards are promulgated for new sources.
A. Subcategory C - Lead
(1) Subpart C - Open Formation - Dehydrated - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and
TSS
pH
Grease
2,
0,
2,
16,
25,
15
47
01
80-
20
Within the limits of 7.5 -
1 .02
0.21
1 .02
16.80
20.16
10.0 at all times
20
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(2) Subpart C - Open Formation - Wet - NSPS
Pollutant or
Pollutant'
Property
Maximum for
any one day
Maximum for
monthly average
Metric Dnits - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.067
0.014
0.063
0.53
0.80
Within the limits of 7.5
used
0.032
0.006
0.032
0.53
0.64
• 10.0 at all times
(3) Subpart C - Plate Soak - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and
TSS
pH
Grease
Within the
.026
.005
.025
.21
.32
1imits
of 7.5 -
0.012
0.002
0.-012
0.21
0.25
10.0 at all times
(4) Subpart C - Battery Wash (Detergent) - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
0.576
0.126
0.540
4.50
0.274
0.058
0.274
4.50
21
-------
TSS
pH
6.75 5.40
Within the limits of 7.5 - 10.0 at all times
(5) Subpart C - Direct Chill Lead Casting - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/l,000,OQO Ib of lead
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.000256
0.000056
0.000240
0.0020
0.0030
Within the limits of 7.5
used
0
0
0
0
0
- 10.0
,000122
,000026
,000122
,0020
,0024
at all
times
(6) Subpart C - Mold Release Formulation - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.0077
0.0017
0.0072
0.060
0.090
Within the limits of 7.5
0.0037
0.0008
0.0037
0.060
0.072
10.0 at all times
22
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(7) Subpart C - Truck Wash - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked
batteries
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.006
0.001
0.006
0.050
0.075
Within the limits of 7.5
0.003
0.0007
0.003
0.050
0.060
10.0 at all times
(8) Subpart C - Laundry - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper
Lead
Iron
Oil and Grease
TSS
pH
0.14
0.03
0.13
1 .09
1 .64
07
01
07
09
31
Within the limits of 7.5 - 10.0 at all times
23
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(9) Subpart C - Miscellaneous Wastewater Streams - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0,39 0.19
Lead 0.085 0.039
Iron 0.37 0.19
Oil and Grease 3.07 3.07
TSS 4.61 3.69
pH Within the limits of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
5. The following pretreatment standards are promulgated for
existing sources,
A. Subcategory C - Lead
(1) Subpart C - Open Formation - Dehydrated - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - Ib/.l ,000,000 Ib of lead used
Copper 3.19 1.68
Lead 0.71 0.34
24
-------
(2) Subpart C - Open Formation - Wet - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.100 0.053
Lead 0.022 0.010
(3) Subpart C - Plate Soak - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.039 0.021
Lead 0.008 0.004
(4) Subpart C - Battery Wash - Detergent - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.86 0.45
Lead 0.19 0.09
25
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(5) Subpart C - Direct Chill Lead Casting - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.0004 0.0002
Lead 0.00008 0.00004
(6) Subpart C - Mold Release Formulation - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.011 0.006
Lead 0.002 0.001
(7) Subpart C - Truck Wash - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked
batteries
Copper 0.026 0.014
Lead 0.005 0.002
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(8) Subpart C - Laundry - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.21 0.11
Lead 0.05 0.02
(9) Subpart C - Miscellaneous Wastewater Streams - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.58 0.31
Lead 0.13 0.06
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed.above.
6. The following pretreatment standards are promulgated for new
sources.
A. Subcategory C - Lead
(1) Subpart C - Open Formation - Dehydrated - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 2.15 1.02
Lead 0.47 0.21
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(2) Subpart C - Open Formation - Wet - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.067 0.032
Lead 0.014 0.006
(3) Subpart C - Plate Soak - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.026 0.012
Lead 0.005 0.002
(4) Subpart C - Battery Wash - Detergent - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.576 0.274
Lead 0.126 0.058
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(5) Subpart C - Direct Chill Lead Casting - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.000256 0.000122
Lead 0.000056 0.000026
(6) Subpart C - Mold Release Formulation - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.007 0.0037
Lead 0.0017 0.0008
(7) Subpart C - Truck Wash - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked
batteries
Copper 0.006 0.003
Lead 0.001 0.0007
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(8) Subpart C - Laundry - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.14 0.07
Lead 0.03 0.01
(9) Subpart C - Miscellaneous Wastewater Streams -PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Copper 0.39 0.19
Lead 0.085 0.039
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operations other than
those battery manufacturing operations listed above.
7. Effluent limitations based on the best conventional pollutant
control technology are reserved at this time.
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SECTION III
INTRODUCTION
This section provides an overview of the legal background of the
Clean Water Act/ and of the technical background of the battery
category. Volumes I and II include general information for the
entire category in this section. Volume I also includes a brief
technical description of the cadmium, calcium, Leclanche,
lithium, magnesium, and zinc subcategories whereas only the lead
subcategory is discussed in Volume II.
LEGAL AUTHORITY
This report is a technical background document prepared to
support effluent limitations and standards under authority of
Sections 301, 304, 306, 307, 308, and 501 of the Clean Water Act
(Federal Water Pollution Control Act, as Amended, (the Clean
Water Act or the Act). These effluent limitations and standards
are in partial fulfillment of the Settlement Agreement in Natural
Resources Defense Council, Inc. v. Train, 8 ERC 2120 (D.D.C.
1976), modified 12 ERC 1833 (D.D.C. 1979), modified by orders
dated October 26, 1982, August 2, 1983 and January 6, 1984. This
document also fulfills the requirements of sections 304(b) and
(c) of the Act. These sections require the Administrator, after
consultation with appropriate Federal and State Agencies and
other interested persons, to issue information on the processes,
procedures, or operating methods which result in the elimination
or reduction of the discharge of pollutants through the
application of the best practicable control technology currently
available, the best available technology economically achievable,
and through the implementation of standards of performance under
Section 306 of the Act (New Source Performance Standards).
Background
The Clean Water Act
The Federal Water Pollution Control Act Amendments of 1972
established a comprehensive program to restore and maintain the
chemical, physical, and biological integrity of the Nation's
waters. By July 1, 1977, existing industrial dischargers were
required to achieve effluent limitations requiring the
application of the best practicable control technology currently
available (BPT), Section 301(b)(1)(A); and by July 1, 1983, these
dischargers were required to achieve effluent limitations
requiring the application of the best available technology
economically achievable which will result in reasonable
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further progress toward the national goal of eliminating the
discharge of all pollutants (BAT), Section 301(b)(2)(A). New
industrial direct dischargers were required to comply with
Section 306 new source performance standards (NSPS), based on
best available demonstrated technology; and new and existing
sources which introduce pollutants into publicly owned treatment
works (POTW) were subject to pretreatment standards under
Sections 307(b) and (c) of the Act. While the requirements for
direct dischargers were to be incorporated into National
Pollutant Discharge Elimination System (NPDES) permits issued
under Section 402 of the Act, pretreatment standards were made
enforceable directly against any owner or operator of any source
which introduces pollutants into POTW (indirect dischargers).
Although section 402(a)(l) of the 1972 Act authorized the setting
of requirements for direct dischargers on a case-by-case basis,
Congress intended that, for the most part, control requirements
would be based on regulations promulgated by the Administrator of
EPA. Section 304(b) of the Act required the Administrator to
promulgate regulations providing guidelines for effluent
limitations setting forth the degree of effluent reduction
attainable through the application of BPT and BAT. Moreover,
Section 306 of the Act requires promulgation of regulations for
NSPS. Sections 304(g), 307(b), and 307(c) required promulgation
of regulations for pretreatment standards. In addition to these
regulations for designated industry categories, Section 307(a) of
the Act required the Administrator to promulgate effluent
standards applicable to all dischargers of toxic pollutants.
Finally, Section 501(a) of the Act authorized the Administrator
to prescribe any additional regulations necessary to carry out
his functions under the Act.
The EPA was unable to promulgate many of these regulations by the
dates contained in the Act. In 1976, EPA was sued by several
environmental groups, and in settlement of this lawsuit EPA and
the plaintiffs executed a Settlement Agreement which was approved
by the Court. This Agreement required EPA to develop a program
and adhere to a schedule for promulgating for 21 major industries
BAT effluent limitations guidelines, pretreatment standards, and
new source performance standards for 65 .priority pollutants and
classes of pollutants. See Natural Resources Defense Council,
Inc. v. Train, 8 ERC 2120 (D.D.C. 1976), modified March 9, 1979.
On December 27, 1977, the President signed into law the Clean
Water Act of 1977. Although this law makes several important
changes in the Federal water pollution control program, its most
significant feature is its incorporation into the Act of several
of the basic elements of the Settlement Agreement program for
priority pollutant control. Sections 301(b)(2)(A) and
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301(b)(2)(C) of the Act now require the achievement by July 1,
1984 of effluent limitations requiring application of BAT for
"toxic" pollutants, including the 65 "priority" pollutants and
classes of pollutants which Congress declared "toxic" under
Section 307(a) of the Act. Likewise, EPA's programs for new
source performance standards and pretreatment standards are now
aimed principally at toxic pollutant controls. Moreover, to
strengthen the toxics control program, Section 304(e) of the Act
authorizes the Administrator to prescribe best management
practices (BMPs) to prevent the release of toxic and hazardous
pollutants from plant site runoff, spillage or leaks, sludge or
waste disposal, and drainage from raw material storage associated
with, or ancillary to, the manufacturing or treatment process.
In keeping with its emphasis on toxic pollutants, the Clean Water
Act of 1977 also revises the control program for non-toxic
pollutants. Instead of BAT for conventional pollutants
identified under Section 304(a)(4) (including biochemical oxygen
demand, suspended solids, fecal coliform and pH), the new Section
301(b)(2)(E) requires achievement by July 1, 1984, of effluent
limitations requiring the application of the best conventional
pollutant control technology (BCT). The factors considered in
assessing BCT for an industry include the costs of attaining a
reduction in effluents and the effluent reduction benefits
derived compared to the costs and effluent reduction benefits
from the discharge of publicly owned treatment works (Section
304(b)(4)(B). The cost methodology for BCT has not been
promulgated and BCT is presently deferred. For non-toxic,
nonconventional pollutants, Sections 301(b)(2)(A) and (b)(2)(F)
require achievement of BAT effluent limitations within three
years after their establishment or July 1, 1984, whichever is
later, but not later than July 1, 1987.
GUIDELINE DEVELOPMENT SUMMARY
The effluent guidelines for battery manufacturing were developed
from data obtained from previous EPA studies, literature sear-
ches, and a plant survey and evaluation. Initially, information
from EPA records was collected and a literature search was
conducted. This information was then catalogued in the form of
individual plant summaries describing processes performed,
production rates, raw materials utilized, wastewater treatment
practices, water uses and wastewater characteristics.
In addition to providing a quantitative description of the
battery manufacturing category, this information was used to
determine if the characteristics of the category as a whole were
uniform and thus amenable to one set of effluent limitations and
standards. Since the characteristics of the plants in the data
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base and the wastewater generation and discharge varied widely,
the establishment of subcategories was determined to be
necessary. The initial subcategorization was made by using
recognized battery type as the subcategory description:
Lead Acid . Carbon-Zinc (Air)
Nickel-Cadmium (Wet Process) . Silver Oxide-Zinc
Nickel-Cadmium (Dry Process) . Magnesium Cell
Carbon-Zinc (Paper) . Nickel-Zinc
Carbon-Zinc (Paste) . Lithium Cell
Mercury (Ruben) . Mercury (Weston)
Alkaline-Manganese . Lead Acid Reserve
Magnesium-Carbon . Miniature Alkaline
To supplement existing data, EPA sent a data collection portfolio
(dcp) under authority of Section 308 of the Federal Water
Pollution Control Act, as amended, to each known battery
manufacturing company. In addition to existing and plant
supplied information (via dcp), data were obtained through a
sampling program conducted at selected sites. Sampling consisted
of a screening program at one plant for each listed battery type
plus verification at up to 5 plants for each type. Screen
sampling was used to select pollutant parameters for analysis in
the second or verification phase of the program. The designated
priority pollutants (65 toxic pollutants) and typical battery
manufacturing pollutants formed the basic list for screening.
Verification sampling and analysis was conducted to determine the
source and quantity of the selected pollutant parameters in each
subcategory.
Conventional nomenclature of batteries provided little aid in
development of 'effluent limitations and standards. SIC groupings
are inadequate because they are based on the end use of the
product, not composition of the product, or manufacturing
processes. Based on the information provided by the literature,
dcp, and the sampling program, the initial approach to
subcategorization using battery type was reviewed. Of the
initial 16 battery types no production of mercury (Weston) cells
was found. The miniature alkaline type was dropped because it is
not a specific battery type but merely a size distinction invol-
ving several battery types (e.g., alkaline-manganese, silver
oxide-zinc, and mercury-zinc (Ruben)). In addition to the
original battery types, the dcp's disclosed seven additional
battery types (silver chloride-zinc, silver oxide-cadmium,
mercury-cadmium, mercury and silver-zinc, mercury and cadmium-
zinc, thermal, and nuclear). Nuclear batteries, however, have
not been manufactured since 1978. Since they constitute a
distinct subcategory, they have been included in the
subcategorization discussion, but have not been considered in the
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battery documents. Mercury and silver-zinc batteries have not
been manufactured since 1977, but do not constitute a single
subcategory and therefore will be discussed where appropriate.
The other five additional battery types are considered in the
battery documents.
An analysis of production methods, battery structure and electro-
lytic couple variations for each battery type revealed that there
are theoretically about 600 distinct variations that could
require further subgrouping. Based on dcp responses and plant
visits, over 200 distinct variations have been positively
identified. Because of the large number of potential subgroup-
ings associated with subcategorization by battery type, a
subcategorization basis characterizing these variations was
sought. Grouping by anode material accomplishes this objective
and results in the following subcategories:
Anode Material Designation for Battery Documents*
Cadmium Anode Cadmium
Calcium Anode Calcium
Lead Anode " Lead
Zinc Anode, Acid Electrolyte Leclanche
Lithium Anode Lithium
Magnesium Anode . Magnesium
Zinc Anode, Alkaline Electrolyte Zinc
Radioisotopes Nuclear
* All subcategories except for lead are discussed in detail in
Volume I and the lead subcategory is discussed in Volume II.
As discussed fully in Section IV, the zinc anode is divided into
two groups based on electrolyte type because of substantial
differences in manufacture and wastes generated by the two
groups. As detailed in Sections IV and V, further segmentation
using a matrix approach is necessary to fully detail each
subcategory. Specific manufacturing process elements requiring
control for each subcategory are presented in. Section IV followed
by a detailed technical discussion in Section V.
After establishing subcategorization, the available data were
analyzed to determine wastewater generation and mass discharge
rates in terms of production for each subcategory. In addition
to evaluating pollutant generation and discharges, the full range
of control and treatment technologies existing within the battery
manufacturing category was identified. This was done considering
the pollutants to be treated and the chemical, physical, and
biological characteristics of these pollutants. Special
attention was paid to in-process technologies such as the
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recovery and reuse of process solutions, the recycle of process
water, and the curtailment of water use.
The information as outlined above was then evaluated in order to
determine what levels of technology were appropriate as a basis
for effluent limitations for existing sources based on the best
practicable control technology currently available (BPT) and best
available technology economically achievable (BAT). Levels of
technology appropriate for pretreatment of wastewater introduced
into a publicly owned treatment works (POTW) from both new and
existing sources were also identified as were the new source
performance standards (NSPS) based on best demonstrated control
technology, processes, operating methods, or other alternatives
(BDT) for the control of direct discharges from new sources. In
evaluating these technologies various factors were considered.
These included treatment technologies from other industries, any
pretreatment requirements, the total cost of application of the
technology in relation to the effluent reduction benefits to be
achieved, the age of equipment and plants involved, the processes
employed, the engineering aspects of the application of various
types of control technique process changes, and non-water quality
environmental impact (including energy requirements).
Sources of Industry Data
Data on battery manufacturing were gathered from literature
studies, previous industry studies by the Agency, plant surveys
and evaluations, and inquiries to waste treatment equipment
manufacturers. These data sources are discussed below.
Literature Study - Published literature in the form of books,
reports, papers, periodicals, and promotional materials was
examined. The most informative sources are listed in Section XV.
The material research covered battery chemistry, the man-
ufacturing processes utilized in producing each battery type,
waste treatment technology, and the specific market for each
battery type.
EPA Studies - A previous preliminary and unpublished EPA study of
the battery manufacturing segment was reviewed. The information
included a summary of the industry describing: the manufacturing
processes for each battery type; the waste characteristics
associated with this manufacture; recommended pollutant
parameters requiring control; applicable end-of-pipe treatment
technologies for wastewaters from the manufacture of each battery
type; effluent characteristics resulting from this treatment; and
a background bibliography. Also included in these data were
detailed production and sampling information on approximately 20
manufacturing plants.
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Plant Survey and Evaluation - The initial collection of data
pertaining to facilities that manufacture batteries was a two-
phased operation. First, a mail survey was conducted by EPA. A
dcp was mailed to each company in the country known or believed
to manufacture batteries. This dcp included sections for general
plant data, specific production process data, waste management
process data, raw and treated wastewater data, waste treatment
cost information, and priority pollutant information based on
1976 production records. A total of 226 dcp were mailed. From
this survey, it was determined that 133 companies were battery
manufacturers, including full line manufacturers and assemblers.
Of the remaining 93 data requests that were mailed, 9 companies
were no longer manufacturing batteries, 15 were returned as
undeliverable, and 69 companies were in other business areas.
For clarification, the following terminology is used throughout
the battery manufacturing documents. Battery manufacturing sites
are physical locations where battery manufacturing processes
occur. Battery plants are locations where subcategory-specific
battery manufacturing processes occur. Battery facilities are
locations where final battery type products or their components
are produced and is primarily used for economic analysis of the
category. In the survey, some plants responded with 1977 or 1978
data, and some provided 1976 data although production has
subsequently ceased. Table III-l (page 63) summarizes the survey
responses received in terms of number of plants that provided
information in each subcategory. Another column was added to
include information obtained in the survey, by phone or by actual
plant visit, that a plant was no longer active in a subcategory.
The total number of plant responses is larger than the 133
company responses, since many companies own more than one plant
and information was requested on each site owned or operated by
the company. Also, some sites manufacture batteries in more than
one subcategory; four are active in three subcategories and nine
are active in two subcategories. Due to changes in ownership and
changes in production lines, the number of companies and the
number of plants and sites active in the category often vary.
The result is that about 230 sites are currently included in this
category. All information received was reviewed and evaluated,
and will be discussed as appropriate in subsequent sections.
The second phase of the data collection effort included visiting
selected plants, for screening and verification sampling of
wastewaters from battery manufacturing operations. The dcp
served as the major source in the selection of plants for
visitation and sampling. Specific criteria used for site
selection included:
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1. Distributing visits according to the type of battery manu-
factured.
2. Distributing visits among various manufacturers of each bat-
tery type.
3. Selecting plants whose production processes were represen-
tative of the processes performed at many plants for each
subcategory. Consideration was also given to the under-
standing of unique processes or treatment not universally
practiced but applicable to the industry in general.
4. A plant's knowledge of its production processes and waste
treatment system as indicated in the dcp.
5. The presence of wastewater treatment or water conservation
practices.
Prior to proposal forty-eight plants were visited and a
wastewater sampling program was conducted at twenty-four of these
plants. The sampling program at each plant consisted of two
activities: first, the collection of technical information, and
second, water sampling and analysis. The technical information
gathering effort centered around a review and completion of the
dcp to obtain historical data as well as specific information
pertinent to the time of the sampling. In addition to this, the
following specific technical areas were covered during these
visits.
1. Water use for each process step and waste constituents.
2. Water conservation techniques.
3. In-process waste treatment and control technologies.
4. Overall performance of the waste treatment system and future
plans or changes anticipated.
5. Particular pollutant parameters which plant personnel
thought would be found in the waste stream.
6. Any problems or situations peculiar to the plant being
visited.
All of the samples collected were kept on ice throughout each day
of sampling. At the end of each day, samples were preserved
according to EPA protocol and sent to laboratories for analysis
per EPA protocol. Details of this analysis and of the overall
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sampling program results are described in Section V of this
document.
After proposal, EPA made a second intensive study of lead battery
manufacturing (lead subcategory), and foliar battery
manufacturing (Leclanche subcategory). Seventeen additional lead
plants were visited and five were sampled. One foliar plant was
also visited. Plant supplied data from 65 lead plants was
updated using an industry survey form. This additional data is
reported in Section V, (Volume I for the Leclanche subcategory
and Volume II for the Lead subcategory).
Waste Treatment Equipment Manufacturers - Various manufacturers
of waste treatment equipment were contacted by phone or visited
to determine cost and performance data on specific technologies.
Information collected was based both on manufacturers' research
and on in-situ operation at plants that were often not battery
manufacturers but had similar wastewater characteristics
(primarily toxic metal wastes).
Utilization of Industry Data
Data collected from the previously described sources are used
throughout this report in the development of a base for BPT and
BAT limitations, and NSPS and pretreatment standards. . Previous
EPA studies and information in the literature provided the basis
for the initial battery subcategorization discussed in Section
IV. This subcategorizat'ion was further refined to an anode
grouping basis as the result of information obtained from the
plant survey and evaluation. Raw wastewater characteristics for
each subcategory presented in Section V were obtained from
screening and verification sampling because raw waste information
from other sources was so fragmented and incomplete that it was
unusable. Selection of pollutant parameters for control (Section
VI) was based on both dcp responses and plant sampling. These
provided information on both the pollutants which plant personnel
felt would be in their wastewater discharges and those pollutants
specifically found in battery manufacturing wastewaters as the
result of sampling. Based on the selection of pollutants
requiring control and their levels, applicable treatment
technologies were identified and then studied and discussed in
Section VII of this document. Actual waste treatment
technologies utilized by battery plants (as identified in dcp and
seen on plant visits) were also used to identify applicable
treatment technologies. The cost of treatment (both individual
technologies and systems) based primarily on data from equipment
manufacturers is contained in Section VIII of this document.
Finally, dcp data and sampling data are utilized in Sections IX,
X, XI, XII, and XIII (BPT, BAT, NSPS, Pretreatment, and BCT, res-
39
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pectively) for the selection of applicable treatment systems and
the presentation of achievable effluent levels and actual
effluent levels obtained for each battery subcategory discussed
in the two volumes.
INDUSTRY DESCRIPTION
Background
The industry covered by this document makes modular electric
power sources where part or all of the fuel is contained within
the unit. Electric power is generated directly from a chemical
reaction rather than indirectly through a heat cycle engine.
Batteries using a radioactive decay source where a chemical
reaction is part of the operating system were considered.
Historical - Electrochemical batteries and cells were assembled
by Alessandro Volta as early as 1798. His work establishing the
relationship between chemical and electrical energy came 12 years
after the discovery of the galvanic cell by Galvani, and 2000
years after the use of devices in the Middle East, which from
archeological evidence, appear to be galvanic cells. Volta used
silver and zinc electrodes in salt water for his cells. Soon
after Volta's experiments, Davy, and then Faraday, used galvanic
cells to carry out electrolysis studies. In 1836 Daniell
invented the cell which now bears his name. He used a copper
cathode in copper sulfate solution separated by a porous cup from
a solution of zinc sulfate in dilute sulfuric acid which
contained the amalgamated zinc anode. In 1860, Plante presented
to the French Academy of Sciences the lead acid storage battery
he had developed, and in 1868 Leclanche developed the forerunner
of the modern dry cell. Leclanche used an amalgamated zinc anode
and a carbon cathode surrounded by manganese dioxide and immersed
both in an ammonium chloride solution. The portable dry cell was
developed in the late 1880s by Gassner who prepared a paste
electrolyte of zinc oxide, ammonium chloride and water in a zinc
can, inserted the carbon rod and manganese dioxide, then sealed
the top with plaster of Paris. The cell was produced
commercially. Several other acid-electrolyte cells using
amalgamated zinc anodes and carbon or platinum cathodes saw
limited use prior to 1900.
Lalande and Chaperon developed a caustic soda primary battery
about 1880 which was used extensively for railroad signal
service. Amalgamated zinc anodes and cupric oxide cathodes were
immersed in a solution of sodium hydroxide. A layer of oil on
the surface of the electrolyte prevented evaporation of water,
and the formation of solid sodium carbonate by reaction of carbon
40
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dioxide in the air with the caustic soda electrolyte. Batteries
with capacities to 1000 ampere hours were available.
A s-torage battery of great commercial importance during the first
half of this century was the Edison cell. Although the system is
not manufactured today, a large volume of research is being
directed toward making it a workable automotive power source.
The system consists of iron anodes, potassium hydroxide
electrolyte, and nickel hydroxide cathodes. The iron powder was
packed in flat "pockets" of nickel-plated steel strips. The
nickel hydroxide, with layers of nickel flakes to improve
conductivity, was packed in tubes of nickel-plated steel strips.
The batteries were rugged and could withstand more extensive
charge-discharge cycling than lead acid storage batteries. Their
greater cost kept them from replacing lead acid batteries.
Another cell only recently displaced from the commercial market
is the Weston cell. For decades the Weston cell, consisting of
an amalgamated cadmium anode and a mercurous sulfate cathode in a
cadmium sulfate solution, was used as a voltage reference
standard in industrial instruments. Introduction of new solid
state devices and circuits has displaced the Weston cell from
most of its former industrial applications, and it is no longer
commercially available.
New battery systems are introduced even today. In the past
decade implantable lithium batteries have been developed for
heart pacemakers, tens of thousands of which are in use. Huge
development programs have been funded for electric powered
automobiles. The liquid sodium-liquid sulfur system is one of
the new "exotic" systems being studied. Advancing technology of
materials coupled with new applications requirements will result
in development of even newer systems as well as the redevelopment
of older systems for new applications. Figure III-l (page 68),
graphically illustrates the amplitude of systems in use or under
development in 1975 for rechargeable batteries. This plot of
theoretical specific energy versus equivalent weight of reactants
clearly shows the reason for present intensive developmental
efforts on lithium and sodium batteries, and the Edison battery
(Fe/NiOOH) and the zinc-nickel oxide battery.
Battery Definitions and Terminology - Batteries are named by
various systems. Classification systems include end-use, size,
shape, anode-cathode couple, inventor's name, electrolyte type,
and usage mode. Thus a flashlight battery (end-use), might also
be properly referred to as a D-Cell (size), a cylindrical cell
(shape), a zinc-manganese dioxide cell (anode-cathode couple), a
Leclanche cell (inventor), an acid cell (electrolyte type), and a
primary cell (usage mode), depending on the context. In the
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strictest sense, a cell contains only one anode-cathode pair,
whereas a battery is an assemblage of cells connected in series
to produce a greater voltage, or in parallel to produce a greater
current. Common usage has blurred the distinction between these
terms, and frequently the term battery is applied to any finished
entity sold as a single unit, whether it contains one cell, as do
most flashlight batteries, or several cells, as do automobile
batteries. In these documents the marketed end product is
usually referred to as a battery. Manufacturing flow charts and
construction diagrams reveal the actual assembly details.
In the battery documents, the terms "battery" and "cell" are used
only for self-contained galvanic devices, i.e., those devices
which convert chemical energy to electrical energy and which do
not require a separate chemical reservoir for operation of the
device. Cells where one of the reacting materials is oxygen
supplied by the atmosphere in which the cell operates are
included as well as cells which contain all of the reacting
chemicals as part of the device. In some literature, reference
is made to electrolysis cells or batteries of electrolysis cells.
Those devices are for chemical production or metal winning and
are not covered by this discussion. Fuel cells, although
functioning as galvanic devices, must be supplied with the
chemical energy from an external source, and are not considered
in this document.
The essential parts of an electrochemical cell designed as a
portable source of electrical power are the same regardless of
the size of the unit. From the smallest cell used in a watch to
the massive storage batteries used in telephone branch exchanges
there is an anode, sometimes called the negative plate, a
cathode, also called the positive plate, and electrolyte. The
anode and cathode are referred to by the general term electrodes.
One or both electrodes consist of a support or grid which serves
as a mechancial support and currentcollector, and the active
material which actually undergoes electrochemical reaction to
produce the current and voltage characteristics of the cell.
Sometimes the active material is the electrode structure itself.
The combination of an inert current collecting support and active
material is an electrode system. For convenience, in this
document as well as in many publications, the terms cathode or
anode are used to designate the cathode system or the
anodesystem.
Most practical modern batteries contain insulating porous
separators between the electrodes. The resulting assembly of
electrodes and electrolyte is contained in a protective case, and
terminals attached to the cathode and anode are held in place by
an insulating material.
42
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The operating characteristics of a battery are described by
several different parameters referred to collectively as the
battery performance. Voltage and current will vary with the
electrical load placed on the battery. In some batteries, the
voltage will remain relatively constant as the load is changed
because internal resistance and electrode polarization are not
large. Polarization is the measure of voltage decrease at an
electrode when current density is increased. Current density is
the current produced by a specified area of electrode
frequently milliamperes per square centimeter. Thus, the larger
the electrode surface the greater the current produced by the
cell unit at a given voltage.
Battery power is the instantaneous product of current and
voltage. Specific power is the power per unit weight of battery;
power density is the power per unit volume. Watts per pound and
watts per cubic foot, are common measures of these performance
characteristics. Power delivered by any battery depends on how
it is being used, but to maximize the power delivered by a
battery the operating voltage must be substantially less than the
open-circuit or no-load voltage. A power curve is sometimes used
to characterize battery performance under load, but because the
active materials are being consumed, the power curve will change
with time. Because batteries are self-contained power supplies,
additional ratings of specific energy and energy density must be
specified. These are commonly measured in units of
watthours per pound and watthours per cubic foot, respectively.
These latter measures characterize the total energy available
from the battery under specified operating conditions and allow
comparison of the ability of different battery systems to meet
the requirements of a given application. Figure III-2 (page 69)
illustrates how these measures of performance are used to compare
battery systems with each other and with alternative power
sources.
The suitability of a battery for a given application is
determined not only by its voltage and current characteristics,
and the available power and energy. In many applications,
storage characteristics and the length of time during which a
battery may be operational are also important. The temperature
dependence of battery performance is also important for some
applications. Storage characteristics of batteries are measured
by shelf-life and by self-discharge, the rate at which the
available stored energy decreases over time. Self-discharge is
generally measured in percent per unit time and is usually
dependent on temperature. In some battery types, self-discharge
differs during storage and use of the battery. For rechargeable
cells, cycle-life, the number of times a battery may be recharged
before failure, is often an important parameter.
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Battery Applications and Requirements - Batteries are used in so
many places that it would be impractical to try to name all of
them. Each application presents a unique set of battery
performance requirements which may place primary emphasis on any
specific performance parameter or combination of parameters. The
applications may be useful however, in considering groups for
which the general purpose and primary performance requirements
are similar. Such groups are shown in Table III-2 (page 64).
The requirements for a flashlight battery are: low cost, long
shelf life, suitability for intermittent use, and moderate
operating life. The household user expects to purchase
replacement cells at low cost after a reasonable operating life,
but does expect long periods before use or between uses.
An automobile battery must be rechargeable, produce large
currents to start an engine, operate both on charge and discharge
over a wide temperature range, have long life, and be relatively
inexpensive when replacement is necessary. The user looks for
high power density, rechargeability, and low cost.
Standby lighting, and life raft emergency radio beacons represent
two similar applications. For standby lighting power in
stairways and halls/ the battery is usually a storage battery
maintained in a constant state of readiness by the electrical
power system and is activated by failure of that primary system.
Such a battery system can be activated and then restored to its
original state many times and hence can be more expensive and can
have complex associated equipment. Weight is no problem/ but
reliable immediate response, high energy density and power
density are important. The emergency radio beacon in a life raft
is required to be 100 percent reliable after storage of up to
several years. It will not be tested before use, and when
activated will be expected to operate continuously until
completely discharged. Light weight may be important. Instan-
taneous response is not a requirement although a short time for
activation is expected.
Remote location operation such- as arctic meteorological stations
and orbiting spacecraft requires very high reliability and long
operating life. Cost is usually of no consequence because the
overall cost of launching a satellite or travel to a remote
location overshadows any possible battery cost. Rechargeability
is required because solar cells (solid state devices producing
small electrical power levels directly from solar illumination)
can be used to recharge the batteries during sunlight periods to
replace the energy used in brief periods of high power demand for
transmissions or satellite equipment operation. High power
density for meteorological stations and high specific power for
44
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satellites is therefore more important than high energy density
or high specific energy because the rechargeability requirement
means energy can be replaced. Additional requirements are
reliable operation over a wider range of temperatures than is
usually experienced in temperate earth regions, and sealed
operation to prevent electrolyte loss by gassing on charge
cycles.
Voltage leveling and voltage standards are similar. Voltage
leveling is a requirement for certain telephone systems. The
batteries may be maintained in a charged state, but voltage
fluctuations must be rapidly damped and some electrochemical
systems are ideally suited to this purpose. An additional
requirement is the provision of standby power at very stable
voltages. Such operation is an electrochemical analogue of a
surge tank of a very large area, maintaining a constant liquid
head despite many rapid but relatively small inflows and
outflows. The use of batteries for secondary voltage standards
requires stability of voltage over time and under fluctuating
loads. Though similar to the voltage leveling application, the
devices or instruments may be portable and are not connected to
another electrical system. Frequently power is supplied by one
battery type and controlled by a different battery type. Usually
cost is a secondary consideration, but not completely ignored.
For secondary voltage standards, wide temperature ranges can
usually be avoided, but a flat voltage-temperature response is
important over the temperature range of application. Power and
energy density as well as specific power and energy also become
secondary considerations in both of these applications.
Battery Function and Manufacture
The extremely varied requirements outlined above have led to the
design and production of many types of batteries. Because
battery chemistry is the first determiner of performance,
practically every known combination of electrode reactions has
been studied - at least on paper. Many of the possible electrode
combinations are in use in batteries today. Others are being
developed to better meet present or projected needs. Some have
become obsolete, as noted earlier. Short discussions on the
electrochemistry of batteries, battery construction, and battery
manufacturing are presented to help orient the reader.
Battery Chemistry - The essential function of the electrodes in a
battery is to convert chemical energy into electrical energy and
thereby to drive electrical current through an external load.
The driving force is measured in volts, and the current is
measured in amperes. The discrete charges carrying current in
the external circuit, or load, are electrons, which bear a
45
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negative charge. The driving force is the sum of the
electromotive force, or EMF, of the half-cell reactions occurring
at the anode and the cathode. The voltage delivered by a cell is
characteristic of the overall chemical reaction in the cell. The
theoretical open-circuit (no-load) voltage of a cell or battery
can be calculated from chemical thermodynamic data developed from
nonelectrochemical experiments. The cell voltage is related to
the Gibbs free energy of the overall chemical reaction by an
equation called the Nernst equation. The variable factors are
temperature and concentration of the reactants and products.
Voltages (or more properly the EMF) of single electrode reactions
are often used in comparing anodes of cathodes of different types
of cells. These single electrode (or half-cell) voltages are
actually the voltages of complete cells in which one electrode is
the standard hydrogen electrode having an arbitrarily assigned
value of zero. In all such calculations, equilibrium conditions
are assumed.
In this brief discussion, only the net half-cell reactions are
discussed. The very complex subject of electrode kinetics,
involving a study of exactly which ionic or solid species are
present and in what quantities, can be found in any of several
electrochemistry textbooks.
The anode supplies electrons to the external circuit - the half-
cell reaction is an oxidation. The cathode accepts electrons
from the external circuit - the reaction is a reduction. Half-
cell reactions can occur in either forward or reverse direction,
at least in theory. Some, however, cannot be reversed in a
practical cell. Tables III-3 and III-4 (page 65) show the
reactions as they are used in practical cells for delivery of
power. In those cells that are rechargeable, charging reverses
the direction of the reaction as written in the tables.
Most of the battery systems currently produced are based on
aqueous electrolytes. However, lithium and thermal batteries,
and at least one magnesium cell, have nonaqueous electrolyte.
Because lithium reacts vigorously with water, organic or non-
aqueous inorganic electrolytes are usually, but not always, used
with this very high energy anode metal. Thermal batteries are
made with the electrolyte in a solid form and are activated by
melting the electrolyte with a pyrotechnic device just prior to
use. One type of magnesium reserve cell uses a liquid ammonia
electrolyte which is injected under pressure just prior to use.
In aqueous systems, any of the anode reactions can be coupled
with any of the cathode reactions to make a working cell, as long
46
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as the electrolytes are matched and the overall cell reaction can
be balanced at electrical neutrality. As examples:
Leclanche;
anode: Zn < > Zn+2 + 2e (acid)
cathode: 2e + 2Mn02 + 2NH4C1 + Zn+z < > MN203 + H20 + Zn(NH3)2Cl2(acid)
cell: Zn + 2Mn02 + 2NH4C1 < > Mn203 + H20 + Zn(NH3)2Cl2
Alkaline Manganese;
anode: Zn + 20H- < > Zn(OH)2 + 2e (alkaline)
cathode: e + Mn02 + H20 < > MnOOH + OH~ (alkaline)
e + MnOOH- + H20 < > Mn(OH)2 + OH~ (alkaline)
cell: Zn + MnO2 + 2H20 < > Zn(OH)2 + Mn(OH)2
One essential feature of an electrochemical cell is that all
conduction within the electrolyte must be ionic. In aqueous
electrolytes the conductive ion may be H+ or OH~. In some cases
metal ions carry some of the current. Any electronic conduction
between the electrodes inside the cells constitutes a short
circuit. The driving force established between the dissimilar
electrodes will be dissipated in an unusable form through an
internal short circuit. For this reason, a great amount of
engineering and design effort is applied to prevent formation of
possible electronic conduction paths and at the same time to
achieving low internal resistance to minimize heating and power
loss.
Close spacing of electrodes and porous electrode separators leads
to low internal electrolyte resistance. But if the separator
deteriorates in the chemical environment, or breaks under
mechanical shock, it may permit electrode-electrode contact
resulting in cell destruction. Likewise, in rechargeable cells,
where high rates of charging lead to rough deposits, of the anode
metal, a porous separator may be penetrated by metal "trees" or
dendrites, causing a short circuit. The chemical compatibility
of separators and electrolytes is an important factor in battery
design.
Long shelf life is frequently a requirement for batteries. Shelf
life is limited both by deterioration of battery separators and
by corrosion (self-discharge) of electrodes which decreases the
available electrical energy and may also result in other types of
47
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cell failure. As an example, corrosion of the zinc anode in
Leclanche cells may result in perforation of the anode and
leakage of the electrolyte. Compatability of the active material
of the electrodes in contact with the electrolyte to minimize
these self-discharge reactions is an electrochemical engineering
problem. Two of the approaches to this problem are outlined
here.
Some applications require only one-time use, and the electrolyte
is injected into the cell just before use, thereby avoiding long
time contact of electrode with electrolyte. The result is a
reserve battery. One reserve battery design (now abandoned) used
a solid electrolyte and the battery was constructed in two parts
which were pressed together to activate it. The parts could be
separated to deactivate the battery. Up to 25 cycles of
activation-deactivation were reported to be possible. Reserve
batteries are usually found in critical applications where high
reliability after uncertain storage time justifies the extra
expense of the device.
In other applications, long shelf life in the activated state is
required. This allows repeated intermittent use of the battery,
but is achieved at the price of somewhat lower certainty of
operation than is provided by reserve cells. Special fabrication
methods and materials then must be used to avoid self-discharge
by corrosion of the anode. In Leclanche cells, the zinc is
protected from the acid electrolyte by amalgamating it; in some
magnesium cells a chemical reaction with the electrolyte forms a
protective film which is subsequently disrupted when current is
drained; in some lithium batteries, the very thin film formed by
chemical reaction with electrolyte conducts lithium ions at a
rate sufficiently high to be usable for power delivery. All
three types of cells require the use of specific chemicals and
special assembly techniques.
Operation of cells in the rechargeable mode places additional
constraints . on the chemical components and construction
materials. In aqueous-electrolyte cells, vented operation may be
possible, as with lead acid automotive and nickel cadmium
batteries. Or, the cells may be sealed because remote operation
prevents servicing and water replacement. Cells with liquid
organic or inorganic electrolyte also are sealed to prevent
escape of noxious vapors. Organic liquids used in cells manufac-
tured in the U. S. today include: methyl formate, acetonitrile,
methyl acetate, and dioxolane. Inorganic liquids include thionyl
chloride and ammonia.
Sealed operation of rechargable cells introduces two major
problems relating to pressure buildup that imst be accommodated
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by design and materials. Pressure changes normally occur during
discharge-charge cycling and must be accommodated by the battery
case and seal designs. Many applications also require cells to
accept overcharging. In nickel-cadmium cells, the oxygen or
hydrogen pressure would build to explosive levels in a short time
on overcharge. As a result, cells are designed with excess
uncharged negative material so that when the nickel electrode is
completely charged, the cadmium electrode will continue to
charge, and oxygen evolved at the nickel electrode will migrate
under pressure to the cadmium and be reduced before hydrogen
evolution occurs. A steady state is reached where continuous
overcharge produces no harmful effects from pressure and no net
change in the composition of electrodes or electrolytes.| The
excess uncharged negative material ensures that hydrogen is not
evolved. Oxygen recombination is used because the alternative
reaction of hydrogen recombination at an excess uncharged
positive electrode proceeds at very low rates unless expensive
special catalysts are present.
Cell reversal is the other operational phenomenon requiring
chemical and electrochemical compensation. Cell reversal occurs
when a battery of cells is discharged to a point that one cell in
the battery has delivered all of its capacity (i.e., the active
material in at least one electrode is used up) but other !cells
are still delivering power. The current then travels through the
depleted cell in the same direction but the cell becomes an
electrolytic cell.
In a nickel-cadmium battery, cell reversal results in hydrogen
generation at the nickel electrode or oxygen generation at the
cadmium electrode. Cells can be designed to avoid pressure
build-up in those instances where reversal may occur. One method
is the incorporation of an antipolar mass (APM) in the nickel
electrode. The APM is Cd(OH)2. When cell reversal occurs,' the
APM is reduced to cadmium metal. However, by using the proper
amount of APM, oxygen generated at the cell anode builds to
sufficient pressure to react with the metallic cadmium in th'e APM
before all of the Cd(OH)2 is reduced. Thus, the oxygen
generation-reduction cycle discussed above is established and
hydrogen evolution is avoided. For the oxygen cycle to fun'ction
for either overcharge or cell reversal, the separator must be
permeable to oxygen in nickel cadmium batteries. All sealed
cells also have an overpressure release to prevent violent
explosions.
Special applications may require special operating conditions.
The ability of a cell to perform its function of delivering
current is determined first of all by the kinetics of the
electrode processes for the anode-electrolyte-cathode system
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chosen. For a given electrode combination, the current per unit
area of active surface is characteristic of the system.
Temperature and pressure have an effect on the fundamental
electrode kinetics, but only in special applications is it
possible to design a battery for operation at other than ambient
temperature. For some high-power drain applications such as
prime mover power plants and central station power, it is
feasable to build a high-temperature system to take advantage of
the improved electrode kinetics and reduced electrolyte
resistance. Of course the kinetics of corrosion processes are
also enhanced, so additional materials problems must be overcome.
For the majority of cells that must be operated at a temperature
determined by the environment, the only practical way to achieve
greater power outputs is to increase the active surface area of
the electrodes. The usual approach to increasing surface area is
to subdivide the electrode material. Powdered or granular active
material is formed into an electrode with or without a structural
support. The latter may also function as a current collector.
The limitation to increasing the surface area is the fact that a
mass of. finely divided active material immersed in electrolyte
will tend to lose surface area with time, a phenomenon similar to
Ostwald ripening of silver halide photograph emulsion. The
smaller particles, which provide the large surface area, dissolve
in the electrolyte, and the larger particles grow even larger.
The nature of the electrolyte and active mass is the main
determinant of the extent of this phenomenon.
A further limitation to the power drain available from porous
electrodes results from a phenomenon called concentration
polarization. Total ampere-hours available are not affected by
this process, but the energy delivered is limited. In a thick
porous body such as a tube or pocket type electrode, the
electrolyte within the narrow, deep pores of the electrode can
become overloaded with ionic products of electrode reaction or
depleated of ions required for electrode reaction. For instance,
at the-negative plate of a lead-acid battery, sulfate ions are
required for the reaction:
Pb + S04 < > PbS04 + 2e
When an automotive battery is fully charged the concentration of
sulfuric acid, hence sulfate ions, is very high. Large currents
can be sustained for sufficient time to crank a cold engine until
it starts. However, when the battery is "low" (i.e. the sulfate
ion concentration throughout the battery is low) sufficient
sulfate ions are initially present in the pores of the negative
plate to sustain the negative plate reaction for a brief period
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of cranking the engine, then the sulfate is so drastically
depleted that the cranking current cannot be sustained. If the
battery is " allowed to "rest" a few minutes, the rather slow
process of diffusion will replenish sulfate ions in the interior
of the pores and in effect return to effective use that "deep"
surface area. The battery appears to come to "life" again.
Cranking currents will again deplete the supply of ions and the
battery is "dead." If a "light" load, such as a radio is placed
on the nearly "dead" battery the diffusion process may be able to
supply sufficient ions on a continuing basis so that the battery
appears to be functioning normally.
The above example is familiar to many people. Similar phenomena
occur in any battery with porous electrodes. In some primary
batteries the discharge products may increase in concentration to
a point of insolubility and permanently block off active material
surface. Thus a battery may deliver significantly fewer ampere-
hours to a predetermined cut-off voltage when used at the C/2
ampere rate than at the C/20 ampere rate where C is the
theoretical ampere-hour capacity of the battery and the numerical
denominator is in hours.
Concentration polarization also limits the rate at which
rechargeable batteries can be charged. Use of higher charging
voltages to shorten the recharge time can result in gassing
(e.g., production of hydrogen or oxygen in aqueous electrolyte
cells) because the electrolyte constituents required for charging
become depleted in the vicinity of the electrode and a different,
unwanted reaction begins to carry the current. This is an
inefficient mode of operation. In rechargeable cells there is an
additional consideration in preparing porous el.ectrodes. The
surface area of the electrodes must be substantially the same
after recharge as it was after the initial formation charging.
It is of little benefit to provide large surface area in the
manufacture of the cell if it cannot be sustained during a usable
number of cycles.
The steps used to manufacture batteries with stable, large-
surface-area electrodes are outlined for several types of
batteries to show similarities and differences in methods.
Further details of techniques for each specific battery type are
given in Section V.
Battery Manufacture - The details of battery construction vary
with the type of battery. For the usual liquid electrolyte
batteries the steps are: manufacture of structural components,
preparation of electrodes, and assembly into cells. Fabrication
of the structural components — cell cases or caps, terminal
fittings or fixtures, electrode support grids, separators, seals,
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and covers — are all manufacturing processes not directly
involving the electrochemistry of the cell. These components may
be fabricated by the battery producer, or they may be supplied by
other manufacturers. The steps considered to be battery
manufacturing operations are: anode and cathode fabrication, and
ancillary operations (all operations not primarily associated
with anode and cathode manufacture, or structural component
fabrication). * •
Discussion of the manufacturing operations is divided into three
parts-anodes, cathodes, and ancillary operations. In each part,
specific operations are illustrated by reference to particular
battery types. Ten battery types were chosen to illustrate a
range of materials, applications, and sizes. Figures II1-3
through 111-12 (pages 70-79) are drawings or cutaway views of
these 10 batteries. Figures 111-13 through 111-20 (pages 80-87)
are simplified manufacturing process flow diagrams for these same
batteries. Reference to the figures should help to understand
the discussion.
Anodes
Anodes are prepared by at least four basic methods depending on
the strength of the material and the application, i.e., high
current drain or low current drain. Once the electrodes are
fabricated they may require a further step, formation, to render
them active. As noted earlier, anodes are metals when they are
in their final or fully charged form in a battery. Some anodes
such as lithium anodes, and zinc anodes for some Leclanche cells,
are made directly by cutting and drawing or stamping the pure
metal sheet. Lithium, because of its flexibility, is either
alloyed with a metal such as aluminum, or is attached to a grid
of nickel or other rigid metal. Drawn sheet zinc anodes are
rigid enough to serve as a cell container.
Zinc anodes for some alkaline-manganese batteries are made from a
mixture of zinc powder, mercury, and potassium hydroxide. Zinc
is amalgamated to prevent hydrogen evolution and thus, corrosion
at the anode.
Anodes for most lead-acid batteries and some nickel-cadmium cells
are prepared from a paste of a compound of the anode metal (lead
oxides or cadmium hydroxide, respectively). Additives may be
mixed in, and then the paste is applied to a support structure
and cured.
The techniques for preparing the compounds of the anode metal may
be unique to the battery manufacturing process. For pocket-type
nickel cadmium batteries, cadmium metal is oxidized in a high
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temperature air stream, then hydrated to cadmium hydroxide.
Graphite, to increase conductivity, and iron oxide, to keep the
cadmium in a porous state during cycling, may be mixed into the
cadmium hydroxide.
Organic expanders, lampblack, and barium sulfate are added to the
paste mixture for lead-acid battery anodes. The expanders
maintain the lead in a porous state during charge-discharge
cycling. The organic expanders coat the lead particles,
preventing agglomeration. Barium sulfate holds the lead grains
apart. Lampblack aids in the formation step.
In addition to physically applying the active material to the
support structure as a metal or compound, some anode active
materials are prepared from soluble metal compounds. High-rate
nickel-cadmium battery anodes are prepared by impregnating a
porous nickel plaque with a solution of cadmium nitrate. The
plaque is transferred to an alkali solution or is made the
cathode of an electrolysis cell. Either technique precipitates
the cadmium as the hydroxide which is subsequently converted to
metallic cadmium in the forming step.
To sum up, the active mass for anodes is usually prepared as the
massive metal, finely divided metal, finely divided metal
compound, or as a soluble salt of the metal which is precipitated
onto a carrier or support structure. In most batteries, there is
an additional support structure, such as the paste for the
negative active mass of a lead-acid battery which is pressed into
a grid of lead or a lead alloy. Different types of nickel-
cadmium batteries exemplify three approaches to fabrication of
anodes. As noted above, the cadmium for pocket type anodes is
admixed with other materials then loaded into the pockets of a
perforated nickel or steel sheet. The method of precipitating an
insoluble cadmium compound from a solution of a soluble cadmium
salt in the pores of a porous powder metallurgical nickel plaque
was also described above. For some cells, highly porous cadmium
powder is mixed with cadmium compounds and pasted onto a support
structure. Chemical production of anode active materials which
are specifically used for batteries, is considered part of
battery manufacturing. This process is.usually considered as an
ancillary operation.
The final step in anode preparation for many types of batteries
is formation, or charging, of the active mass. The term
"formation" was first used to describe the process by which
Plante plates were prepared for lead-acid batteries-. In that
process, lead sheet or another form of pure lead was placed in
sulfuric acid and made anodic, generating a surface layer of lead
sulfate, then cathodic, reducing that layer to lead which
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remained in the finely divided state. Repeated cycling generated
a deep layer of finely divided lead for the anodes. Few lead-
acid anodes are made that way today, but the term "formation" has
remained to designate the final electrochemical steps in
preparation of electrodes for any type of battery.
Formation may be carried out on individual electrodes or on pairs
of electrodes in a tank of suitable electrolyte, e.g. sulfuric
acid for lead-acid battery plates, or potassium hydroxide for
nickel-cadmium battery electrodes. Formation of anodes by
themselves requires an inert, gassing, counter-electrode. More
often the electrodes for a battery are formed in pairs. The
cathodes are arranged in the tank in opposition to the anodes or
are interspaced between the anodes. Frequently, electrodes are
formed in the cell or battery after final assembly. However the
electrodes are physically arranged, current is passed through the
electrodes to charge them. For some battery types, charge-
discharge cycling up to seven times is used to form the
electrode.
Primary battery anodes are almost always prepared in the active
form, and require no formation step. Rechargeable battery anodes
almost always go through a formation step.
Cathodes
Cathode active materials are never metals despite the common
usage of the metal type to designate the cathode active material.
"Nickel" cathodes are actually nickel hydroxide; "mercury"
cathodes, are actually mercury oxide; "manganese" cathodes
(alkaline-manganese battery) are manganese oxide (pyrolusite).
Non-metals such as iodine (lithium-iodine battery) and meta-
dinitrobenzene (magnesium-ammonia reserve battery) are the other
kinds of cathode active materials used. Manufacturing of
cathodes for batteries is not necessarily more complex than that
of the anodes, however, cathode production encompasses a broader
variety of raw materials for use in different battery types.
Cathode active materials are weak electronic conductors at best,
and usually possess slight mechanical strength. Therefore, most
cathodes must have a metallic current conducting support
structure. In addition, a conducting material is frequently
incorporated into the active mass. Structural reinforcement may
be in the form of a wire mesh, a perforated metal tube, or inert
fibrous material {woven or felted). Conducting materials added
to the cathode active mass are almost invariably carbon or
nickel.
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Preparation of the cathode active material in the battery plant
is usually restricted to the metal oxides or hydroxides. Cathode
active materials for two of the ten battery types discussed here,
nickel hydroxide, and leady oxide, are specific to battery
manufacturing and are usually produped in the battery plant.
Cathode active materials for the other types are usually
purchased directly from chemical suppliers. For nickel-cadmium
pressed powder (pocket-electrode) cells nickel hydroxide is
produced by dissolution of nickel powder in sulfuric acid. The
nickel sulfate solution is reacted with sodium hydroxide. The
resulting nickel hydroxide is centrifuged, mixed with some
graphite, spray dried, compacted, and mixed with additional
graphite. For high-rate cells, nickel oxide is precipitated in
the pores of a nickel plaque immersed in nickel nitrate. A
process analogous to those described for preparation of high-rate
cadmium anodes is used. Lead-acid batteries require a specific
oxidation state of lead oxide (24 to 30 percent free lead)
referred to by industry as "leady oxide," which is produced by
the ball mill or Barton process. This leady oxide is used for
both the anode and the cathode. Chemical production of cathode
active materials which are used specifically for batteries is
considered part of battery manufacturing usually as an ancillary
operation.
Manganese dioxide for Leclanche cells and alkaline-manganese
cells is mixed with graphite to increase conductivity. For
Leclanche cells, the mixture may be compacted around the carbon
cathode rod, or is poured into the cell as a loose powder and
compacted as the carbon rod is inserted. For alkaline-manganese
cells, analagous procedures are used except that the cathode
active material takes the shape of a cylinder against the wall of
the nickel-plated steel can and no carbon rod is used. In the
foliar-cell Leclanche battery the manganese dioxide is printed
onto a conducting plastic sheet. The other side of the sheet
bears the zinc anode film to produce a bipolar electrode.
(Bipolar electrodes perform the same function as an anode and
cathode of two separate cells connected in series.)
The magnesium-ammonia reserve battery uses a different type of
cathode structure. A glass fiber pad containing the meta-
dinitrobenzene (mDNB), carbon, and ammonium thiocyanate is placed
against a stainless steel cathode current collector. Activation
of the battery causes liquid ammonia to flood the cell space,
saturate the pad, and dissolve the dry acidic salt (ammonium
thiocyanate) and the cathode active material (m-DNB). The m-DNB
functions as a dissolved cathodic depolarizer.
The cathode active material for the carbon-zinc (air) cell is
oxygen from the air. Therefore, the principal function of the
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cathode structure is to provide a large area of conductive carbon
surface in the immediate vicinity of the electrolyte-air contact
region. Air must have free access through the exposed pores of
the rigid' structure. Electrolyte in the wetted surface pores
must have a continuous path to the body of the electrolyte to
provide the ionic conduction to the anode. The porous carbon
body is wetproofed on the electrolyte surface to prevent deep
penetration and saturation or flooding of the pores by
electrolyte.
The mercury-zinc cell uses a compacted cathode active material.
Mercuric oxide mixed with graphite is pressed into pellets for
use in miniature cells, or is pressed directly into the cell
case.
In sum/ cathode fabrication almost always includes a rigid,
current-carrying structure to support the active material. The
active material may be applied to the support as a paste,
deposited in a porous structure by precipitation from a solution,
fixed to the support as a compacted pellet, or may be dissolved
in an electrolyte which has been immobilized in a porous inert
structure.
The formation step for cathodes of rechargeable batteries is much
the same as that for anodes. Nickel cathodes may be formed
outside or inside the assembled cell in a potassium hydroxide
electrolyte. Lead cathodes for lead-acid batteries are handled
in a manner similar to that used to make anodes, except they
remain in the lead peroxide state after forming. For some cell
types, chemical processes rather than electrolysis are used to
form nickel hydroxide and silver oxide cathodes or reactive
materials prior to physical application to the electrode support.
Ancillary Operations
Ancillary operations are all those operations unique to the
battery manufacturing point source category which are not
included specifically under anode or cathode fabrication. They
are operations associated mainly with cell assembly and battery
assembly. Also chemical production for anode or cathode active
materials used only for batteries (discussed above) is considered
an ancillary operations.
Cell assembly is done in several ways. The electrodes for
rectangular nickel cadmium batteries are placed in a stack with a
layer of separator material between each electrode pair and
inserted into the battery case. Almost all lead-acid batteries
are assembled in a case of hard rubber or plastic with a porous
56
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separator between electrode pairs. The cells or batteries are
filled with electrolyte after assembly.
Cylindrical cells of the Leclanche or the alkaline-manganese type
are usually assembled by insertion of the individual components
into the container. For Lecla che batteries, a paper liner which
may be impregnated with a mercury salt is inserted in the zinc
can; then depolarizer mixture, a carbon rod, and electrolyte are
added. The cell is closed and sealed, tested, aged, and tested
again. Batteries are assembled from cylindrical cells to produce
higher voltages. Several round cells can be placed in one
battery container and series connections are made internally.
Two terminals are added and the batteries are sealed.
Miniature button cells of the alkaline-manganese and mercury-zinc
types are assembled from pellets of the electrode active mass
plus separator discs, or the electrodes may be pressed directly
in the cell case to assure electrical contact and to facilitate
handling during assembly.
Leclanche foliar cell batteries are a specialty product which
illustrate the possibility of drastically modifying the
conventional battery configuration when a need exists. The
bipolar electrodes and separators are heat sealed at the edges.
After each separator is positioned, electrolyte is applied to it
before the next electrode is placed. When the battery is
completed the entire .assembly is sandwiched between two thin
aluminum sheets. Assembly is completely automated. The
resulting six-volt battery is about three inches by four inches
by three-sixteenths of an inch thick and has high specific power
and power density. Shelf life is several years and operating
lifetime depends on drain rate.
A contrasting battery is the carbon-zinc (air) cell. The cast
amalgamated zinc anodes positioned on each side of a porous
carbon air electrode are attached to the cover of the cell. Dry
potassium hydroxide and lime are placed in the bottom of the cell
case, the cover is put ir .ace and sealed, and a bag of
dessicant is placed in the fi ' -.c opening. The cell is shipped
dry and the user adds water to activate it. This cell has a very
low power density but a very long operating life.
Ancillary operations for this document, beside specific chemical
production, include some dry operations as well as cell washing,
battery washing, the washing of equipment, floors and operating
personnel. Because the degree of automation varies from plant to
plant for a given battery type, the specific method of carrying
out the ancillary operations is not as closely identifiable with
57
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a battery type as are the anode and cathode fabrication
operations.
INDUSTRY SUMMARY
The battery manufacturing industry in the United States includes
about 250 plants operated by about 130 different companies. In
all, the industry produced approximately 1.8 million tons of
batteries valued at 2.1 billion dollars in 1976, and employed
over 33 thousand workers. As Figure 111-21 (page 88) shows, the
value of industry products has increased significantly in recent
years. This growth has been accompanied by major shifts in
battery applications, and the emergence of new types of cells and
the decline and phase - out of other cell types as commercially
significant products. Present research activity in battery
technology and continuing changes in electronics and
transportation make it probable that rapid changes in battery
manufacture will continue. The rapid changes in battery
manufacturers is reflected in the age of battery manufacturing
plants. Although a few plants are more than 60 years old,
battery manufacturing plants are fairly new with over half
reported to have been built in the past twenty years. Most have
been modified even more recently. Figure II1-22 (page 89)
displays where battery plants are located throughout the U.S. and
within EPA regions.
Plants commonly manufacture a variety of cells and batteries dif-
fering in size, shape, and performance characteristics. Further,
a significant number of plants produce cells using different
reactive couples but with a common anode material, (e.g.,
mercury-zinc and alkaline manganese batteries both use a zinc
anode). Thirteen plants currently produce cells or batteries
using two or more different anode materials and therefore are
considered in two or more subcategories. Some battery
manufacturing plants purchase finished cell components and
assemble the final battery products without performing all of the
manufacturing process steps on-site. Other plants only
manufacture battery components, and perform battery manufacturing
process operations without producing finished batteries.
Finally, some battery plants have fully integrated on-site
production operations including metal forming and inorganic
chemicals manufacture which are not specific to battery
manufacturing.
The reactive materials in most modern batteries include one or
more of the following toxic metals: cadmium, lead, mercury,
nickel, and zinc. Cadmium and zinc are used as anode materials
in a variety of cells, and lead is used in both the cathode and
anode in the familiar lead-acid storage battery. Mercuric oxide
58
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is used as the cathode reactant in mercury-zinc batteries, and
mercury is also widely used to amalgamate the zinc anode to
reduce corrosion and self discharge of the cell. Nickel
hydroxide is the cathode reactant in rechargeable nickel cadmium
cells, and nickel or nickel plated steel may also serve as a
support for other reactive materials. As a result of this
widespread use, these toxic metals are found in wastewater
discharges and solid wastes from almost all battery plants.
Estimated total annual consumption of these materials in battery
manufacture is shown in Table III-5 (page 66). Since only lead-
acid batteries are reclaimed on a significant scale, essentially
all of the cadmium, mercury, nickel, and zinc consumed in battery
manufacture will eventually be found in liquid or solid wastes
either from battery manufacturers or from battery users.
Water is used in battery manufacturing plants in preparing
reactive materials and electrolytes, in depositing reactive
materials on supporting electrode structures, in charging
electrodes and removing impurities, and in washing finished
cells, production equipment and manufacturing areas. Volumes of
discharge and patterns of water use as well as the scale of
production operations, wastewater pollutants, and prevalent
treatment practices vary widely among different battery types,
but show significant similarities among batteries employing a
common anode reactant and electrolyte. Table II1-6 (page 67)
summarizes the characteristics of plants manufacturing batteries
in each of the groups discussed in the battery documents based on
anode and electrolyte. The lead subcategory is discussed below.
Lead Subcategory
The lead subcategory, encompassing lead acid reserve cells and
the more familiar lead acid storage batteries, is the largest
subcategory both in terms of number of plants and volume of
production. It also contains the largest plants and produces a
much larger total volume of wastewater.
The lead group includes 186 battery manufacturing plants of which
about 146 manufacture electrodes from basic raw materials, and
almost 40 purchase electrodes prepared off-site and assemble them
into batteries (and are therefore termed assemblers). Most
plants which manufacture electrodes also assemble them into
batteries. In 1976, plants in the lead group ranged in annual
production from 10.5 metric tons (11.5 tons) to over 40,000
metric tons (44,000 tons) of batteries with the average
production being 10,000 metric tons (11,000 tons) per year.
Total annual battery production in this subcategory is estimated
to be 1.3 million kkg (1.43 million tons) of batteries. Seven
companies owned or operated 42 percent of the plants in this sub-
category, consumed over 793,650 metric tons (875,000 tons) of
pure lead and produced over 1.1 million metric tons (1.2 million
tons) of batteries. In 1977, total lead subcategory product
shipments were valued at about 1.7 billion dollars. The number
59
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of employees reported by plants in the lead subcategory ranged
from 1 to 643 with total employment estimated to be 18,745. Most
of the plants employing fewer than 10 employees were found to be
battery assemblers who purchased charged or uncharged plates
produced in other plants. The distribution of plants in the lead
subcategory in terms of production and number of employees is
shown in Figures 111-23 and 111-24 (Page 90 and 91).
With the exception of lead-acid reserve batteries (which are
electroformed and are reported to be manufactured at only one
site), all products in this subcategory are manufactured using
similar materials and employ the same basic cell chemistry.
Products differ significantly in configuration and in
manufacturing processes, however, depending on end use. Lead-
acid battery products include cells with immobilized electrolytes
used for portable hand tools, lanterns, etc.; conventional
rectangular batteries used for automotive starting, lighting and
ignition (SLI) applications; sealed batteries for SLI use; and a
wide variety of batteries designed for industrial applications.
Manufacturers of SLI and industrial lead acid batteries have
commonly referred to batteries shipped with electrolyte as "wet-
charged" batteries and those shipped without electrolyte as "dry-
charged" batteries. The term "dry-charged" batteries which is
used to mean any battery shipped without electrolyte includes
both damp-charged batteries (damp batteries) and dehydrated plate
batteries (dehydrated batteries). Dehydrated batteries usually
are manufactured by charging of the electrodes in open tanks
(open formation), followed by rinsing and dehydration prior to
assembly in the battery case. Damp batteries are usually
manufactured by charging the electrodes in the battery case after
assembly (closed formation), and emptying the electrolyte before
final assembly and shipping. The term "wet-charged" batteries is
used to mean any battery shipped with electrolyte. Wet-charged
batteries (wet batteries) are usually manufactured by closed
formation processes, but can also be produced by open formation
processes. Details of these formation process operations are
discussed in Section V.
Dehydrated plate batteries afford significantly longer shelf-life
than wet batteries or damp batteries. In 1976, sixty plants
reported the production of 239,000 metric tons (268,000 tons) of
dehydrated plate batteries; this accounted for over 18 percent of
all lead acid batteries produced. Twenty-seven plants reported
producing damp batteries, which account for 9.3 percent of the
subcategory total, or 121,000 metric tons (136,000 tons).
Contacts with battery manufacturers have indicated a substantial
reduction in dehydrated battery manufacture since 1976 due
60
-------
largely to the introduction of sealed wet charged batteries using
calcium alloy grids which provide improved shelf-life.
Major raw materials for all of these battery types include lead,
leady oxide, lead oxide, lead alloys, sulfuric acid, battery
cases, covers, filler caps, separators and other plastic rubber
or treated paper components. Generally, additional materials
including carbon, barium sulfate, and fibrous materials are added
in the manufacture of electrodes. Many manufacturers use epoxy,
tar, or other similar materials to seal battery cases, especially
in manufacturing industrial batteries. Common alloying elements
used in the lead alloys are antimony, calcium, arsenic and tin.
Antimony may be used at levels above 7 percent while arsenic,
calcium, and tin are generally used only in small percentages (1
percent).
Patterns of water usage and wastewater discharge are found to
vary significantly among lead battery plants. Variations result
both from differences in manufacturing processes and from
differences in the degree and type of wastewater control
practiced. In general, the major points of process water use are
in the preparation and application of electrode active materials,
in the "formation" (charging) of the electrodes, and in washing
finished batteries. Process wastewater discharges may result
from wet scrubbers, floor and equipment wash water, laboratories,
casting operations, and personal hygiene where process materials
are removed by washing.
The total volume of discharge from lead subcategory battery
plants varies between 0 and 62,000 1/hr (16,400 gal/hr) with a
mean discharge rate of 6580 1/hr (1,740 gal/hr) and a median
discharge rate of 1,640 1/hr (430 gal/hr). When normalized on
the basis of the total amount of lead used in battery
manufacture, these discharge flows vary between 0 and 78 I/kg
(9.5 gal/lb) with an average of 4.280 I/kg (0.521 gal/lb). Over
60 percent of lead subcategory plants discharge wastewater to
POTW. The wastewater from these plants is characteristically
acidic as a result of contamination with sulfuric acid
electrolyte and generally contains dissolved lead and suspended
particulates which are also likely to contain lead. The
prevailing treatment practice is to treat the wastewater with an
alkaline reagent to raise its pH, and to provide settling to re-
move particulates and precipitated lead. In-process treatment
and reuse of specific waste streams is also common.
INDUSTRY OUTLOOK
The pattern of strong growth and rapid change which has
characterized the battery industry during the past decade may be
61
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expected to continue in the future. A number of technological
changes which have occurred in recent years and which are
anticipated in the near future are creating strong demand for
existing battery products and for new ones.
The advent of transistor electronics, and subsequently of
integrated circuits, light emitting diodes, and liquid crystal
devices has resulted in the development of innumerable portable
electronic devices such as radios, calculators, toys, and games,
which are powered by batteries. This has resulted in the
development of new mass markets for cells in small sizes and has
led to the rapid commercialization of new cell types. The
extremely low power drains of some digital electronic devices
have created markets for low power, high energy density, long
life cells and have resulted in the commercial development of
silver oxide-zinc and lithium batteries. Solid state technology
has also reduced or eliminated markets for some battery types,
most notably mercury (Weston) cells which were widely used as a
voltage reference in vacuum tube circuits. Continued rapid
change in electronics and growth in consumer applications are
anticipated with corresponding change and growth in battery
markets.
In transportation technology and power generation, tightening
fuel supplies and increasing costs are directing increased
attention toward electrical energy storage devices. The
development and increasing use of battery powered electric
automobiles and trucks are creating an increasing market for
large battery sizes with high energy and power densities.
Increasing application 'of batteries for peak shaving in
electrical power systems is also an anticipated development
creating higher demand for batteries in larger sizes.
In summary, while, as with Lalande, Edison and Weston cells in
the past, some battery types may become obsolete, the overall
outlook is for growth in the battery industry. Increased
production of many current products and the development of new
battery types are likely. Based on general industry patterns,
conversion of battery plants from one type of product where
demand for specific battery types is not strong to another is
more likely than plant closings.
62
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TABLE II1-1
SURVEY SUMMARY
SUBCATEGORY NUMBER OF PLANTS NUMBER OF PLANTS
(Information Received) (Currently Acti ve)
Cadmium
Calcium
Lead
Leclanche
Lithium
Magnesium
Nuclear
Zinc
13
3
186*
20
7
8
1
17
10
3
167*
19
7
8
0
16
Totals 255 228
Total Number of Plant Sites in Category - 230.
*Includes plate manufacturers and assemblers.
63
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TABLE II1-2
BATTERY GENERAL PURPOSES AND APPLICATIONS
Purpose
Portable electric power
Electric power storage
Standby or emergency
electrical power
4. Remote location electrical power
5. Voltage leveling
PBXs
6. Secondary voltage standard
Application
flashlights, toys, pocket
calculators
automobile batteries,
solar powered electrical
systems
emergency lighting for
hallways and stairways,
life raft radio beacons
spacecraft,
meteorological stations,
railway signals
telephone exchanges and
regulated power supplies
64
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TABLE II1-3
ANODE HALF-CELL REACTIONS (electrolyte)
Cd + 20H- < > Cd(OH)2 + 2e (alkaline)
Ca < > Ca+2 + 2e (nonaqueous inorganic)
Pb + H2S04 < > PbS04 + 2H+ + 2e (acidic)
Zn <—> Zn+2 + 2e (acidic)
Li < > Li+ + e (molten salt, organic, nonaqueous inorganic)
Mg < > Mg+2 + 2e (sea water)
Zn + 20H- < > Zn(OH)2 + 2e (alkaline)
TABLE II1-4
CATHODE HALF-CELL REACTIONS (electrolyte)
e + NiOOH + H20 < > Ni(OH)2 + OH~ (alkaline)
4e + Ag202 + 2H2O < > 2Ag + 40H- (alkaline)
2e + Ag20 + H20 < > 2Ag + 20H- (alkaline)
2e + HgO + H20 < > Hg + 20H- (alkaline)
2e + Pb02 + S04~2 + 4H+ < > PbS04 + 2H20 (acid)
2e + 2Mn02 + 2NH4C1 + Zn+2 < > Mn203 + H20 + Zn(NH3)2Cl2 (acid)
2e + 2AgCl + Zn+2 < > 2Ag + ZnCl2 (acid)
e + TiS2 + Li+ < > TiS2:Li (propylene carbonate)
2e + 2S02 < > S204-2 (acetonitrile)
4e + 2SOC12 + 4 Li+ < > 4 LiCl + (S0)2 (thionyl chloride)
2e + I2 + 2 Li+ < > 2 Lil [poly(2 vinyl)propylene]
2e + PbI2 + 2Li+ < > 2 Lil + Pb (nonaqueous inorganic)
2e + PbS + 2Li+ < > Li2S + Pb (nonaqueous inorganic)
e + Mn02 + HjjO < > MnOOH + OH- (alkaline)
e + MnOOH + H20 < > Mn(OH)2 + OH~ (alkaline)
8e + m-C4H4(N02)2 + 6NH4+ + Mg+2 < > m-bis-C6H4(NHOH)2
+ 6NH3 + Mg(OH)2 (ammonia)
2e + PbCl2 < > Pb + 2C1- (sea water)
e + CuCl < > Cu + Cl~ (sea water)
e + AgCl < > Ag + Cl~ (sea water)
4e + 02 + 2H2O < > 4OH- (alkaline)
65
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Table II1-5
CONSUMPTION OF TOXIC METALS IN BATTERY MANUFACTURE*
METAL ANNUAL CONSUMPTION
Metric Tons Tons
Cadmium 730 800
Lead 980,000 1,080,000
Mercury 670 ,740
Nickel 1,200 1,300
Zinc 27,000 29,000
* Based on 1976 data provided in dcp. Numbers shown are sums of
provided data. Because response to the raw materials questions was
incomplete, actual consumption will be higher by 10 to 20 percent.
66
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TABLE 111-6
BATTERY MANUFACTURING CATEGORY SUMMARY
(TOTAL DATA BASE)
Tocai
Subcategory
Cadmium
Calcium
Lead
Leclanche
Lithium
Magnesium
Batteries
Manufactured
Nickel -Cadmium
Stiver Cadmium
Mercury Cadmium
Thermal
Lead Acid
Carbon Zinc
Carbon Zinc, Air
Depolarized
Silver Chloride-
Zinc
Lithium
Thermal
Magnesium Carbon
Number of
Plants
13
3
186
20
7
8
Total Annual Production
kkg
5,250
<23
1,300,000
108,000
<23
1,220
(tons)
(5,790)
«25)
(1,430,000)
(119,000)
«25)
(1,340)
Total Nuiooer Discharges
of Employees Direct
2,500 5(4)'
240
18,745 12
4,200 0
400 1
350 1
POTW
4
2
117
8
4
3
Zero
4(5)'
1
57
12
2
4
Process tfastewater Flow
i/yr (106)
748
0.13
7, 106
16.7
0.36
3.91
[gai/yr (1
0(JU \
7O /
(0.
(1,877)
(4.
(0.
(1.
o°>i
034)
41)
095)
03)
Zinc
Magnesium
Thermal
Alkaline Manganese 17
Silver Oxide-Zinc
Mercury Zinc
Carbon Zinc-Air
Depolarized
Nickel Zinc
TOTALS • 2542
23,000
(25,000)
4,680
11
60.3
1,437,516 (1,581,180)
31,115 22(21) 149 83(84) 7,935.40
(15.9)
(2,096.469)
NOTES:
'One direct discharge plant changed to zero discharge after data was collected,
^Total does not include nuclear subcategory (1 plant).
V
-------
E
X
u
z
u
u
u
a.
w
U
p
u
a
o
u
I
H
3000
2000
1000
800
700
600
SOO
400
300
ZOO
too
•U/S
Li/Se
Li/CuS
Li/FoS
Na/S
Li/Te
LiAI/ToCU
Zn/NiOOH-
Fs/NiOOH-
TYPE OF ELECTROLYTES
© MOLTEN SALT OR CERAMIC
O AQUEOUS
O ORGANIC
O MOLTEN SALT AND AQUEOUS
Cd/NiOOH-'
Pb/PbO2'
I I
I
10
20 40 60 80 tOO
EQUIVALENT WEIGHT, G/EQUIVALENT
200
300 400
FIGURE 111-1
THEORETICAL SPECIFIC ENERGY AS A FUNCTION OF EQUIVALENT WEIGHT AND
CELL VOLTAGE FOR VARIOUS ELECTROLYTIC
COUPLES
68
-------
1000
SPECIFIC ENERGY, W-HR/KG
too
1000
100
m
j
uT
I-
5
tt
Id
u
Ul
0.
w
— TOOO
COMBUSTION
ENGINES
NiZnl I NaS
, . FUEL
VCELLS
x —
HEAVY
DUTY
LECLANCHE
ORGANIC
ELECTROLYTE
CELLS
LOW-DRAIN
LECLANCHE
0.1
0.4
6 10 20 40 60 100
SPECIFIC ENERGY WATT HOURS/LB
200
400
1000
FIGURE HI-2
PERFORMANCE CAPABILITY OF VARIOUS BATTERY SYSTEMS
69
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TERMINAL
^
BAFFLE
NEGATIVE PLATE
(CADMIUM ANODE)
SEPARATOR
POSITIVE PLATE
(NICKEL CATHODE)
CELL JAR
FIGURE HI-3
CUTAWAY VIEW OF.AN IMPREGNATED SINTERED PLATE NICKEL-CADMIUM CELL
(SIMILAR IN PHYSICAL STRUCTURE TO SOME
SILVER OXIDE-ZINC AND NICKEL-ZINC CELLS)
70
-------
NICKEL-PLATED
STEEL COVER
NICKEL-PLATED
STEEL CASE
NICKEL POSITIVE
CONTACT LUG
NYLON GASKET-
SEAL
POLYETHYLENE-
INSULATOR
POLYETHYLENE
INSULATOR
POSITIVE PLATE
(NICKEL CATHODE)
..SEPARATOR
NICKEL NEGATIVE
CONTACT LUG
NEGATIVE PLATE
(CADMIUM ANODE)
• FIGURE 111-4
CUTAWAY VIEW OF A CYLINDRICAL NICKEL-CADMIUM BATTERY (SIMILAR IN
PHYSICAL STRUCTURE TO CYLINDRICAL LEAD ACID BATTERIES)
71
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VENT PLUGS
TAPERED
TERMINAL
POSTS
CONTAINER
NEGATIVE PLATE
POST STRAP
COVER
PLATE LUGS
POSITIVE
PLATE
SEPARATORS
ELEMENT RESTS
SEDIMENT SPACE
FIGURE HI-5
CUTAWAY VIEW OF LEAD ACID STORAGE BATTERY
72
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METAL CAP
EXPANSION SPACE
ZINC CAN
(ANODE)
SEPARATOR
METAL COVER
METAL BOTTOM
BOTTOM INSULATOR
INSULATING WASHER
SUB SEAL
CARBON ELECTRODE
(CATHODE)
1-9
INCHES
MANGANESE DIOXIDE
MIX (DEPOLARIZER)
COMPLETE CELL
FIGURE 111-6
CUTAWAY VIEW OF A CYLINDRICAL LECLANCHE CELL (SIMILAR IN PHYSICAL
STRUCTURE TO SOME CARBON-ZINC-AIR AND SILVER CHLORIDE-ZINC DRY CELLS)
73
-------
NEGATIVE END (-)
MANGANESE
DIOXIDE
ZINC
CONNECTOR
(CONDUCTIVE SHEET)
ALUMINUM COVERED WITH CONDUCTIVE
PLASTIC BEARING A PATCH OF ZINC ON
THE UNDERSIDE (ALUMINUM WRAPS
AROUND ALUMINUM AT OTHER END)
DUPLEXES
(CONDUCTIVE PLASTIC-
UPPER SIDE MANGANESE
DIOXIDE, LOWER SIDE ZINC)
SEPARATOR CONTAINING
ELECTROLYTE
ADHESIVE AROUND EDGE
OF SEPARATOR
MANGANESE DIOXIDE ON
NDUCTIVE PLASTIC ON ALUMINUM
POSITIVE END
COMPLETED BATTERY
ASSEMBLED ON CARD
WITH CONTACT HOLES
THICKNESS, 1/4 INCH
FIGURE 111-7
EXPLODED VIEW OF A FOLIAR LECLANCHE BATTERY USED IN FILM PACK
74
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POLYESTER
JACKET
CATHODE CURRENT
COLLECTOR
ANODE CURRENT
COLLECTOR
DEPOLARIZER
LITHIUM ANODE
FLUOROCARBON
PLASTIC JACKET
PLASTIC LAYERS SEPARATE
DEPOLARIZER FROM CASE
LITHIUM ENVELOPE AND
FLUOROCARBON PLASTIC JACKET
SEPARATE DEPOLARIZER FROM CASE
FIGURE III-8
CUTAWAY VIEW OF TWO SOLID ELECTROLYTE
LITHIUM CELL CONFIGURATIONS
75
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GAS GENERATOR
TOP CAP
DRIVE DISK
ACTIVATOR
CUP
OUTER
CASE
BATTERY
ASSEMBLAGE
LANCE
ELECTROLYTE
RESERVOIR
BULKHEAD
QUAD RING
3 INCHES
B-C SECTION
TERMINAL PLATE
A SECTION
EXAMPLE SHOWN FOR LIQUID-AMMONIA-ACTIVATED MAGNESIUM RESERVE BATTERY:
CATHODE - CARBON DEPOLARIZED META-DINITROBENZENE
ANODE - MAGNESIUM
ELECTROLYTE - DRY AMMONIUM THIOCYANATE ACTIVATED BY LIQUID AMMONIA
FIGURE Ili-S
CUTAWAY VIEW OF A RESERVE TYPE BATTERY ("A" SECTION AND "B-C"
SECTION CONTAIN ANODE AND CATHODE)
76
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FILLER
TUBE CAP
FILLER TUBE
FOR WATER
SOLID CAUSTIC SODA
CYLINDRICAL
ZINC ANODE
CARBON CATHODE
MIXTURE OF
PELLETED LIME
AND GRANULAR
CAUSTIC SODA
FIGURE 111-10
CUTAWAY VIEW OF A CARBON-ZINC-AIR CELL
77
-------
ONE PIECE COVER
(+) PLATED STEEL
ELECTROLYTE-
POTASSIUM HYDROXIDE
CATHODE-MANGANESE
DIOXIDE MIX
SEPARATORS -
NON WOVEN FABRIC
INSULATING TUBE -
POLYETHYLENE COATED
KRAFT
METAL SPUR
INSULATOR -
PAPERBOARD
CAN -STEEL
CURRENT COLLECTOR -
BRASS
ANODE - AMALGAMATED
POWDERED ZINC
JACKET -
TIN PLATED
LITHOGRAPHED
STEEL
SEAL - NYLON
INNER CELL BOTTOM -
STEEL
PRESSURE SPRING -
PLATED SPRING STEEL
METAL WASHER | -RIVET-BRASS
OUTER BOTTOM (-)
PLATED STEEL
FIGURE IIJ-11
CUTAWAY VIEW OF AN ALKALINE-MANGANESE BATTERY
(SIMILAR IN PHYSICAL STRUCTURE TO CYLINDRICAL
MERCURY-ZINC BATTERIES)
78
-------
CELL CAN
ANODE CAP
CATHODE
(MERCURIC)
OXIDE MIX
ANODE
(AMALGAMATED
ZINC)
FIGURE ill-12
CUTAWAY VIEW OF A MERCURY-ZINC (RUBEN) CELL (SIMILAR IN PHYSICAL
STRUCTURE TO ALKALINE-MANGANESE AND SILVER OXIDE-ZINC BUTTON CELLS)
79
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POSITIVE PLATE PROCESS
NICKEL
POWDER"
RAW
MATERIALS-
a t
SINTERED
STRIP
IMPREGNATION
BRUSH
FORMATION
SEPARATOR-
NICKEL
•STRIP
POTASSIUM HYDROXIDE
SODIUM HYDROXIDE :
WATER
METAL RAW
SCREEN MATERIALS
ASSEMBLY
ELECTROLYTE
ADDITION
u
NEGATIVE
PLATE
PROCESS
•NICKEL PLATED
STEEL CASE
FIGURE 111-13
MAJOR PRODUCTION OPERATIONS IN NICKEL-CADMIUM BATTERY MANUFACTURE
80
-------
LEAD'
LEAD OXIDE.
SULFURIC •
ACID
LEADY OXIDE
PRODUCTION
MIXER
SEPARATORS
BATTERY CASE
AND COVER
PASTING
MACHINE
WITH DRYER
CURING OF
PLATES
STACKER
WELD
ASSEMBLED
ELEMENTS
PIG LEAD OR
SHEET LEAD
GRID
MANUFACTURE
PRODUCT
FIGURE 111-14
SIMPLIFIED DIAGRAM OF MAJOR PRODUCTION
OPERATIONS IN LEAD ACID BATTERY MANUFACTURE
-------
r
WATER, STARCH,
ZINCCHLOR1DE,
MERCUR'OUS CHLORIDE,
AMMONIUM CHLORIDE
ADDITION
OF PASTE
A
ncrom A 01 -rrr e — • »• ••••• • •—•• •• IIIIIIIII^IIIMII
•ZINC CANS
|
DEPOLARIZER
(MANGANESE DIOXIDE
+ CARBON BLACK)
±
MIX
ELECTROLYTE
(AMMONIUM CHLORIDE +
ZINC CHLORIDE + WATER)
CARBON ROD
DEPOLARIZER AND
ELECTROLYTE ADDED
•CARBON ROD
- PAPER LINED
ZINC CANS
SUPPORT
WASHER ADDED
PASTE
SETTING
=L_ J
CELL
SEALED
CRIMP
TEST AND
FINISH
ALTERNATE PRODUCTION STEPS
AGE AND
TEST
PRODUCT
FIGURE 111-15
MAJOR PRODUCTION OPERATIONS IN LECLANCHE BATTERY MANUFACTURE
82
-------
IODINE-
POLY-2-VINYL-PYRIDINE-
CATHODE
MIX
ELECTROLYTE
LITHIUM-
DEGREASE
ANODE
CELL CASE,
CONTACTS,
SEALS
ASSEMBLY
TEST
T
PRODUCT
FIGURE 111-16
MAJOR PRODUCTION OPERATIONS IN
LITHIUM-IODINE BATTERY MANUFACTURE
83
-------
CARBON-
DEIONIZE
WATER
SUURRY
PREPARATION
DRY
PUNCH
MAGNESIUM
STRIP
PUNCH
CATHODE
ANODE
ASSEMBLY
T
AMMONIA
-AMMONIUM-
THIOCYANATE
PRODUCT
FIGURE IH-17
MAJOR PRODUCTION OPERATIONS IN AMMONIA-ACTIVATED MAGNESIUM
RESERVE CELL MANUFACTURE
84
-------
CONTAINER
LIME .
CAUSTIC
POTASH '
DRY ELECTROLYTE
PLACED IN
CONTAINER
MANGANESE
DIOXIDE'
GRAPHITE'
CHARCOAL
POWDER•
POROUS ACTIVATED
CARBON
ELECTRODE
ELECTRODE
INSERTED
ZINC-
MERCURY-
AMALGAMATED
ZINC ELECTRODE
INSERTED
ZINC
ELECTRODE
SEALED
TEST AND
PACK
PRODUCT
FIGURE 111-18
MAJOR PRODUCTION OPERATIONS IN WATER ACTIVATED
CARBON-ZINC-AIR CELL MANUFACTURE
85
-------
BINDER,
CARBON ft
MANGANESE
DIOXIDE
ZINC ft
MERCURY
FORMED INTO
CATHODE
POTASSIUM HYDROXIDE,
WATER & BINDER
CONTAINER
PRODUCED
CATHODE
INSERTED
SEPARATOR
INSERTED
ELECTROLYTE
ANODE
ANODE
INSERTED
CURRENT
COLLECTOR
RIVET AND
SEAL INSERTED
CRIMP
00
O>
PRODUCT-
TEST AND
PACK
COVERS
ATTACHED
PRESSURE
SPRING
INSERTED
JACKET AND
PAPER
INSULATOR
ATTACHED
PRE-TEST
H
CELL WASH
FIGURE iII-19
MAJOR PRODUCTION OPERATIONS IN ALKALINE-
MANGANESE DIOXIDE BATTERY MANUFACTURE
-------
MERCURIC
.OXIDE
GRAPHITE
MANGANESE
DIOXIDE
SODIUM
HYDROXIDE-
WATER
ELECTROLYTE
PREPARED
ELECTROLYTE
ADDED
ZINC
MERCURY.
AMALGAM
ZINC ANODE
ANODE
ADDED
TOP AND
GASKET ADDED
CELL CRIMPED
AND WASHED
PRODUCT
FIGURE 111-20
SIMPLIFIED DIAGRAM OF MAJOR OPERATIONS IN MERCURY-ZINC (RUBEN)
BATTERY MANUFACTURE
87
-------
2800
00
00
400
•FROM U.S. DEPT. OF COMMERCE DATA
1 977 CENSUS OF MANUFACTURERS
FIGURE 111-21
VALUE OF BATTERY PRODUCT SHIPMENTS 1963-1977*
-------
00
vo
A 1H PLANTS
•BASED ON TOTAL OF 253 PLANTS; PLANTS
IN MULTIPLE SUBCATEGORIES COUNTED
MORE THAN ONCE.
I—X EPA REGIONS
FIGURE 111-22
GEOGRAPHICAL REGIONAL DISTRIBUTION OF BATTERY MANUFACTURING PLANTS
-------
V0
O
50
40
V)
\ 3°
J
£L
U.
0
a:
ui
m
2
3 20
Z
10
0 ' 4 ' 8 12
• REPRESENTS THE NUMBER OF PLANTS
IN INDICATED PRODUCTION RANGE
16
PRODUCTION (METRIC TONS X 10 )
FIGURE 111-23
DISTRIBUTION OF LEAD SUBCATEGORY PRODUCTION RATES
-------
so
40
W
Z
<
J
ft.
tL
0
E
U
03
5
3
Z
30
I REPRESENTS THE NUMBER OF PUANTS
HAVING THE INDICATED RANGE OF
NUMBER OF EMPLOYEES
20
10
100
200
300 " •"" ' " 400
NUMBER OF EMPLOYEES
500
700
FIGURE 111-24
DISTRIBUTION OF EMPLOYMENT AT LEAD SUBCATEGORY MANUFACTURING
PLANTS
-------
-------
SECTION IV
INDUSTRY SUBCATEGORIZATION
Subcategorization should take into account pertinent industry
characteristics, manufacturing process variations, water use,
wastewater characteristics, and other factors which are important
in determining a specific grouping of industry segments for the
purpose of regulating wastewater pollutants. Division of the
industry segment into subcategories provides a mechanism for
addressing process and product variations which result in
distinct wastewater characteristics. Effluent limitations and
standards establish mass limitations on the discharge of
pollutants and are applied, through the permit issuance process,
to specific dischargers. To allow the national standard to be
applied to a wide range of sizes of production units, the mass of
pollutant discharge must be referenced to a unit of production.
This factor is referred to as a production normalizing parameter
and is developed in conjunction with Subcategorization.
In addition to processes which are specific to battery
manufacturing, many battery plants report other process
operations. These operations, generally involve the manufacture
of battery components and raw materials and may include
operations not specific to battery manufacture. A number of
these operations are not considered in this document.
SUBCATEGORIZATION
Factors Considered
After examining the nature of the various segments of the battery
manufacturing category and the operations performed therein, the
following Subcategorization factors were selected for evaluation.
Each of these factors is discussed in the ensuing paragraphs,
followed by a description of the process leading to selection of
the anode Subcategorization.
1. Waste Characteristics
2. Battery Type
3. Manufacturing Processes
4. Water Use
5. Water Pollution Control Technology
6. Treatment Costs
7. Effluent Discharge Destination
8. Solid Waste Generation and Disposal
9. Size of Plant
10. Age of Plant
Tl. Number of Employees
93
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12. Total Energy Requirements {Manufacturing Process
and Waste Treatment and Control)
13. Non-Water Quality Characteristics
14. Unique Plant Characteristics
Waste Characteristics - While subcategorization is inherently
based on waste characteristics, these are primarily determined by
characteristics of the manufacturing process, product, raw
materials, and plant which may provide useful bases for
subcategor i zat ion.
Battery Type - Battery type as designated by reactive couples or
recognized battery types (as in the case of magnesium reserve or
thermal cells), was initially considered as a logical basis for
subcategorization. This basis has two significant shortcomings.
First, batteries of a given type are often manufactured using
several different processes with very different wastewater
generation characteristics. Second, it was found that batteries
of several types were often manufactured at a single site with
some process operations (and resultant wastewater streams) common
to the different battery types. Since modification of battery
type subcategories to reflect all process variations and product
combinations results in over 20.0 subcategories, battery type was
found to be unacceptable as the primary basis for
subcategorization. Battery type is, however, reflected to a
significant degree in manufacturing process considerations and in
anode metal.
Manufacturing Processes - The processes performed in the
manufacture of batteries are the sources of wastewater
generation, and thus are a logical basis for the establishment of
subcategories. In this category, however, similar processes may
be applied to differing raw materials in the production of
different battery types yielding different wastewater
characteristics. For example, nickel, cadmium and zinc
electrodes may all be produced by electrodeposition techniques.
Further, the number of different manufacturing process sequences
used in producing batteries is extremely large although a smaller
number of distinct process operations are used in varying com-
binations. As a result of these considerations, neither overall
process sequence nor specific process operations were found to be
suitable as primary bases for subcategorization. However,
process variations that result in significant differences in
wastewater generation are reflected in the manufacturing process
elements for which specific discharge allowances were developed
within each subcategory,
Water Use - Water use alone is not a comprehensive enough factor
upon which to subcategorize because water use is related to the
94
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various manufacturing processes used and product quality needed.
While water use is a key element in the limitations and standards
established, it is not directly related to the source or the type
and quantity of the waste. For example, water is used to rinse
electrodes and to rinse batteries. The amounts of water used for
these processes might be similar, but the quantity of pollutants
generated is significantly different.
Water Pollution Control Technology, Treatment Costs, and Effluent
Discharge Destination - The necessity for a subcategorization
factor to relate to the raw wastewater characteristics of a plant
automatically eliminates certain factors from consideration as
potential bases for subdividing the category. Water pollution
control technology, treatment costs, and effluent discharge
destination have no effect on the raw wastewater generated in a
plant. The water pollution control technology employed at a
plant and its costs are the result of a requirement to achieve a
particular effluent level for a given raw wastewater load. The
treatment technology does not affect the raw wastewater
characteristics. Likewise, the effluent discharge destination
does not affect the raw wastewater characteristics.
Solid Waste Generation and Disposal - Physical and chemical solid
waste characteristics generated by the manufacture of batteries
can be accounted for by subcategorization according to battery
type since this determines some of the resultant solid wastes
from a plant. Solid wastes resulting from the manufacture of
batteries includes process wastes (scrap and spent solutions) and
sludges resulting from wastewater treatment. The solid waste
characteristics (high metals content), as well as wastewater
characteristics, are a function of the specific battery type and
manufacturing process. However, not all solid wastes can be
related to wastewater generation and be used for developing
effluent limitations and standards. Also, solid waste disposal
techniques may be identical for a wide variety of solid wastes
but cannot be related to pollutant generation. These factors
alone do not provide a sufficient base for subcategorization.
Size of Plant - The size of a plant is not an appropriate
subcategorization factor since the wastewater characteristics per
unit of production are essentially the same for different size
plants that have similar processing sequences. However, the size
of a plant is related to its production capacity. Size is thus
indirectly used to determine the effluent limitations since these
are based on production rates. But, size alone is not an
adequate subcategorization parameter because the wastewater
characteristics of plants are also dependent on the type of
processes performed.
95
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Age of Plant - While the relative age of a plant may be important
in considering the economic impact of a regulation, it is not an
appropriate basis for subcategorization because it does not take
into consideration the significant parameters which affect the
raw wastewater characteristics. In addition, a subcategorization
based on age would have to distinguish between the age of the
plant and the age of all equipment used in the plant which is
highly variable. Plants in this industry modernize and replace
equipment relatively frequently, and changes of subcategories
would often result. Subcategorization using this factor is
therefore infeasible.
Number of Employees - The number of employees in a plant does not
directly provide a basis for subcategorizati-on since the number
of employees does not reflect the production processes used, the
production rates, or water use rates. Plants producing batteries
varied widely in terms of number of production employees. The
volume and characteristics of process wastewater was found to not
have any meaningful relationship with plant employment figures.
Total Energy Requirements - Total energy requirements were
excluded as a subcategorization parameter primarily because
energy requirements are found to vary widely within this category
and are not meaningfully related to wastewater generation and
pollutant discharge. Additionally, it is often difficult to
obtain reliable energy estimates specifically for production and
waste treatment. When available, estimates are likely to include
other energy requirements such as lighting, air conditioning, and
heating energy.
Non-Water Quality Aspects - Non-water quality aspects may have an
effect on the wastewater generated in a plant. For example, wet
scrubbers may be used to satisfy air pollution control
regulations. This could result in an additional contribution to
the plant's wastewater flow. However, it is not the primary
source of wastewater generation in the battery manufacturing
category, and therefore, not acceptable as an overall
subcategorization factor.
Unique Plant Characteristics - Unique pl-ant characteristics such
as geographical location, space availability, and water
availability do not provide a proper basis for subcategorization
since they do not affect the raw waste characteristics of the
plant. Dcp data indicate that plants in the same geographical
area do not necessarily have similar processes and, consequently
may have different wastewater characteristics. However, process
water availability may be a function of the geographic location
of a plant, and the price of water may necessitate individual
modifications to procedures employed in plants. For example, it
96
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has been generally observed that plants located in areas of
limited water supply are more likely to practice in-process
wastewater control procedures to reduce the ultimate volume of
discharge. These procedures however/ can also be implemented in
plants that have access to plentiful water supplies and thus,
constitute a basis for effluent control rather than for
subcategorization.
A limitation in the availability of land space for constructing a
waste treatment facility may in some cases affect the economic
impact of a limitation. However, in-process controls and water
conservation can be adopted to minimize the size and thus land
space required for the treatment facility. Often, a compact
treatment unit can easily handle wastewater if good in-process
techniques are utilized to conserve raw. materials and water.
Subcateqorization Development
After reviewing and evaluating data for this category, the
initial battery type subcategorization was replaced by the anode
material, electrolyte approach. This development is discussed
below in detail.
Upon initiation of the study of the battery manufacturing
category, published literature and data generated in a
preliminary study of the industry were reviewed, and a
preliminary approach to subcategorization of the industry was
defined. This approach was based on electrolytic couples (e.g.
nickel-cadmium and silver oxide-zinc) and recognized battery
types (e.g. carbon-zinc, alkaline manganese, and thermal cells).
The weight of batteries produced was chosen as the production
basis for data analysis. This approach provided the structure
within which a detailed study of the industry was conducted, and
was reflected in the data collection portfolio used to obtain
data from all battery manufacturing plants. In addition, sites
selected for on-site data collection and wastewater sampling were
chosen to provide representation of the significant electrolytic
couples and battery types identified in the data collection
portfolios.
As discussed in Section III, the preliminary review of the
category resulted in the identification of sixteen distinct
electrolytic couples and battery types requiring consideration
for effluent limitations and standards. A review of the
completed dcp returned by the industry revealed four additional
battery types requiring study but did not initially result in any
fundamental change in the approach to subcategorization.
97
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As the detailed study of the industry proceeded, however, it
became apparent that the preliminary approach to
subcategorization would not be adequate as a final framework for
the development of effluent limitations and standards. It was
determined that further breakdown of the original battery type
subcategories would be required to encompass existing and
possible process and product variations. The number of
subcategories ultimately required using this approach was likely
to approach 200. This approach was likely to result in redundant
regulations and possible confusion about applicability in some
cases.
Review of dcp responses and on-site observations at a number of
plants revealed that there was substantial process diversity
among plants producing a given battery type, and consequently
little uniformity in wastewater generation and discharge. For
most cell types, several different structures and production
processes were identified for both anode and cathode, and it was
observed that these could be combined into many variations. The
data also revealed that not all plants performed all process
operations on-site. Some battery manufacturing plants produced
cell electrodes or separators which were not assembled into
batteries within the plant, and others purchased some or all of
the components which were used in producing the finished
batteries shipped from the plant. To reflect these differences
in manufacturing processes it would have been necessary to divide
the preliminary battery type subcategories into approximately 200
subcategories to accommodate those presently existing and into
nearly 600 subcategories to encompass all of the obvious
variations possible in new sources.
The data obtained from the industry also showed that most
production operations are not separated by battery type.
Manufacture of more than one battery type at a single location is
common, and some production operations are commonly shared by
different battery types. Raw material preparation, cell washes,
and the manufacture of specific electrodes (most often the anode)
are often commonly performed for the production of different
battery types. Production schedules at some of these plants make
the association of production activity (and therefore wastewater
discharge) in these operations with specific battery types
difficult.
Many operations are intermittent and variable, and there is often
a considerable lag between the preparation of raw materials and
components, and the shipment of finished batteries. The
redundant inclusion of production operations under several
different battery types is undesirable in any case.
98
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Subcategorization of the battery category was re-evaluated and
redefined in light of the industry characteristics discussed
above. In the development of the final subcategorization
approach, objectives were to:
1. Encompass the significant variability observed in
processes and products within battery manufacturing
operations
2. Select a subcategorization basis which yielded a
manageable number of subcategories for the promulgation
of effluent limitations and standards
3. Minimize redundancy in the regulation of specific
process effluents
4. Facilitate the determination of applicability of
subcategory guidelines and standards to specific plants
5. Subcategorize so that, to the maximum extent possible,
plants fall within a single subcategory
Available data show that where multiple cell types are produced,
and especially where process operations are common to several
types, the cells frequently have the same anode material. As a
result, cell anode was considered as a subcategorization basis.
Significant differences in wastewater volume and characteristics
between plants producing zinc anode cells with alkaline
electrolytes and Leclanche cells necessitated further
subcategorization based on cell electrolyte, Subcategorization
on these bases yielded eight subcategories5 cadmium, calcium,
lead, Leclanche, lithium, magnesium, nuclear, and zinc. All
subcategories except for lead are discussed specifically in
Volume I of the Development Document for Effluent Limitations
Guidelines and Standards for the Battery Manufacturinq Point
Source Category.
These subcategories preserve most of the recognized battery types
within a single subcategory and greatly reduce the redundancy in
covering process operations. They also limit the number of
plants producing batteries under more than one subcategory to
thirteen. Recognized battery types which are split under this
approach are carbon-zinc air cells which are manufactured with
both alkaline and acidic electrolytes, and thermal batteries
which are produced with calcium, lithium, and magnesium anodes.
In both cases, however, significant variations in process water
use and discharge exist within the preliminary battery type
subcategories, and these are reflected in the breakdown resulting
from anode based'subcategorization. In most cases where process
99
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operations are common to multiple battery types, the processes
fall within a single subcategory. Where plants produce batteries
in more than one subcategory, manufacturing processes are
generally completely segregated.
Identification of these anode groups as subcategories for
effluent limitations purposes was also favored by an examination
of wastewater characteristics and waste treatment practices. In
general, plants manufacturing batteries with a common anode
reactant were observed to produce wastewater streams bearing the
same major pollutants (e.g. zinc and mercury from zinc anode
batteries, cadmium and nickel from cadmium anode batteries). As
a result, treatment practices at these plants are similar.
A battery product within a subcategory is produced from a
combination of anode manufacturing processes, cathode
manufacturing processes and various ancillary operations (such as
assembly associated operations, and chemical powder production
processes specific to battery manufacturing). Within each group
(anode, cathode, or ancillary) there are numerous manufacturing
processes or production functions. These processes or functions
may generate independent wastewater streams with significant
variations in wastewater characteristics. To obtain specific
waste characteristics for which discharge allowances could be
developed, the following approach was used (Figure IV-1, page
107). Individual process waste streams (subelements) can be
combined to obtain specific flow and waste characteristics for a
manufacturing process or function with similar production
characteristics which generates a process wastewater stream.
Some manufacturing processes are not associated with any
subelements; these are discussed in Section V. Each significant
battery manufacturing process or production function is called an
element in this document. For example, in the cadmium
subcategory, a nickel cathode can be produced for a nickel-
cadmium battery. One method of producing this cathode is by
sintering nickel paste to a support structure and impregnating
nickel salts within the pores of the sintered nickel. Several
process waste streams can be associated with this manufacturing
process such as, electrode rinse streams, spent solution streams,
and air scrubber wastewater streams. All of these subelements
are related to production of nickel impregnated cathodes, which
is the element. At the element level, flows and pollutant
characteristics can be related to ( production. Elements are
combined or can be combined in various ways at specific plants at
the subcategory level. Wastewater treatment can be related to
this level which is considered the level of regulation. The
detailed information which contributed to the adoption of the
above subcategorization approach is presented in the discussion
100
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of process wastewater sources and characteristics in Section V of
this document.
FINAL SUBCATEGORIES AND PRODUCTION NORMALIZING PARAMETERS
For lead batteries the determination was made that one
subcategory would be appropriate. The subcategory however,
needed to be divided into separate elements or process operations
to account for "various wastewater flow differences and process
mixes at different plants. Also, lead used was selected as the
most appropriate production normalizing parameter. Specific
elements within the lead subcategory are summarized in Table IV-1
(page 105). Discussion of the process elements and selection of
a production normalizing parameter is discussed below.
Lead Subcategory
All lead batteries use the lead-lead peroxide electrolytic
couple, but differences in battery type and manufacturing
processes require careful examination of production normalizing
factors. Some of the significant variations include:
Full line manufacture (plates produced on-site)
Assembly using green plates (formation on-site)
Assembly using formed plates
Leady Oxide Production
Purchased oxide
On site production
Ball Mill process
Barton process
Grid Manufacture
Grid casting
Mold Release Formulation
Direct chill casting
Lead rolling
Plate Curing
With steam
Humidity temperature controls
Stacked
Plate Formation (Charging)
101
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Closed Formation (electrodes assembled in battery case)
Single fill-single charge
Double fill - double charge
Double fill - single charge
Acid dumped after charge - no refill (damp batteries)
Open Formation
Electrodes formed, rinsed, and dried prior to assembly
(dehydrated batteries)
Plates formed prior to assembly into batteries
Plate Soak
Electrolyte
Immobilized
Liquid
Case
Sealed
Vented
Battery Wash
None
With water only
With detergent
Configuration
Cylindrical
Rectangular
Separators
Rubber
Paper-Phenoli c
Vinyl
Among these variations, the distinction between full line
manufacture and assembly, and variations in plate curing and
formation, and battery wash operations were observed to. have a
significant effect on the volume and treatability of process
wastewater. Other operations which are not specifically
associated with manufacturing operations contribute to wastewater
102
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generation: floor wash, wet air pollution control, battery
repair, laboratories, truck wash, and personal hygiene related
activities. To adequately reflect the combinations of these
variables observed within the industry, the subcategory was
subdivided on the basis of specific process operations.
The total lead weight (including the weight of alloying elements
in lead grid alloys) used in the manufacture of batteries
produced was chosen as the production normalizing parameter for
all process elements for which discharge allowances are provided
in this subcategory except truck wash. The production
normalizing parameter for truck wash is the weight of lead in
batteries moved over the highway in trucks, because this relates
more closely with what is actually washed. Total battery weight,
electrode surface area, total electrode weights, electrical
capacity of the battery, and number of employees were considered
as alternatives to the selected production normalizing parameter.
The weight of lead consumed in battery manufacture was chosen in
preference to total battery weight because total battery weight
is subject to variations resulting from differences in the ratio
of case weight to the weight of active material. Case weight is
not directly related to wastewater generation. Further, battery
weight is not applicable where plates are shipped for use at
other locations. Total electrode weights were not generally
reported by plants in this subcategory and, further, are subject
to variation due to the degree of hydration and state of charge
of the electrode. Therefore, the weight of lead was found to
provide a more available and consistent basis for effluent
limitations and standards. Since most of the wastewater
discharge volume associated with electrode production results
from depositing materials on or removing impurities from
electrode surfaces, electrode surface area was considered a
possible choice as the production normalizing parameter for lead
operations. Significant difficulty is encountered in defining
the surface area, however, and data were not always available.
The difficulty results from the fact that the electrodes
generally have significant porosity and irregular surfaces, and
it is the total wetted surface rather than the simple projected
area which determines the volume of wastewater generated. Since
this area could not be readily determined, electrode surface area
was not chosen as the production normalizing parameter for these
operations.
Electrical capacity of the battery should, in theory, correspond
closely to those characteristics of cell electrodes most closely
associated with process water use and discharge during
manufacture. The electrical capacity of cells is determined by
the mass of reactive materials present, and the processing of
reactive is often the major source of process wastewater. It was
103
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not, however, for use in this study because electrical capacity
data were not obtained.
Becuase the degree of process automation at battery manufacturing
plants was observed to vary, the number of production employees
was not found to be generally suitable as a production
normalizing parameter. Although the number of employees would be
a suitable basis for limiting discharges from employee showers
and handwashes, battery weight was chosen instead to achieve
uniformity with other ancillary wastewater sources and to
minimize the number of production normalizing parameters to be
applied.
OPERATIONS COVERED UNDER OTHER CATEGORIES
Some lead subcategory battery plants perform processes on-site
which are not unique to battery manufacturing and which are
addressed in effluent limitations and standards for other
industrial categories. These are identified in Table IV-2 (page
106) and are discussed in reference to the lead subcategory
below. Specific operations are discussed in Section V.
Plants producing batteries within the lead subcategory perform a
number of processes which may be performed in other industrial
categories. Most plants produce electrode grids on-site. These
are most often cast from lead (and lead alloys), a metal casting
operation, but may also be rolled or stamped from pure or alloy
lead in metal forming operations. For the purposes of this
battery manufacturing regulation, lead casting (die cast or
direct chill) performed at battery manufacturing plants is
regulated under the battery manufacturing category. Lead rolling
is included under the battery manufacturing category but is not
specifically regulated because there are no dischargers.
Guidance is provided for those battery manufacturing plants which
may perform this function and need to discharge wastewater. The
production of lead oxide at lead battery plants is a unique
operation yielding a "leady oxide" distinct from lead oxide
produced in inorganic chemical production. It is included under
the battery manufacturing category for the purpose of effluent
limitations and standards.
Several lead battery plants report the recovery of lead from
scrap batteries. These processes - battery cracking and
secondary lead smelting are included under the nonferrpus metals
manufacturing point source category. Some lead anode battery
plants also produce rubber or plastic battery cases on-site which
are not regulated under the battery manufacturing point source
category.
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TABLE IV-1
LEAD SUBCATEGORY ELEMENTS AND PRODUCTION NORMALIZING
PARAMETER (PNP)l/
Anodes and Cathodes
Ancillary
Personal Hygiene
Leady Oxide Production
Grid Manufacture
Grid Casting
Mold Release Formulation
Direct Chill Casting
Lead Rolling
Paste Preparation and Application
Curing
Closed Formation (in case)
Single Fill
Double Fill
Fill and Dump
Open Formation (out of case)
Wet
Dehydrated
Plate Soaking
Battery Wash
Detergent
Water Only
Floor Wash
Wet Air Pollution Control
Battery Repair
Laboratory
Truck Wash.?/
Hand Wash
Respirator Wash
Laundry
I/Production Normalizing Parameter (PNP) is the total weight of
lead used.
2./PNP is weight of lead in trucked batteries.
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TABLE IV-2
OPERATIONS AT BATTERY PLANTS INCLUDED IN OTHER
INDUSTRIAL CATEGORIES
(Partial Listing)
Plastic and Rubber Case Manufacture
Retorting, Smelting and Alloying Metals
Inorganic Chemical Production (Not Specific to Battery
Manufacturing)
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SUBCATEGORY
ANODE MANUFACTURE
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SECTION V
WATER USE AND WASTEWATER CHARACTERIZATION
This section describes the collection, analysis, and
characterization of data that form the basis for effluent
limitations and standards for the lead subcategory, and presents
the results of these efforts. Data were collected from a number
of sources including published literature, previous studies of
battery manufacturing, data collection portfolios (dcp) mailed to
all known battery manufacturers, industry surveys mailed to lead
battery manufacturers after proposal, and on-site data collection
and sampling at selected facilities. Data analysis began with an
investigation of the manufacturing processes practiced, the raw
materials used, the process water used and the wastewater
generated in the entire battery category. This analysis was the
basis for subcategorization of battery manufacturing which
resulted in a separate lead subcategory, and also was the basis
for selection of the lead subcategory production normalizing
parameter (pnp) already discussed in detail in Section IV.
Further analysis included collecting wastewater samples and
characterizing wastewater streams within the lead subcategory.
DATA COLLECTION AND ANALYSIS
The sources of data used in this study have been discussed in
detail in Section III. For the lead subcategory, data collection
and analysis were conducted in two phases, before and after
proposal. Prior to proposal data collection served to provide a
subcategorization scheme as well as characterize manufacturing
processes, water use, and treatment. After proposal, extensive
data collection and analysis was performed for the lead
subcategory in order to address issues received in comments from
the lead battery industry.
Published literature and previous studies of the battery
manufacturing category provided a basis for initial data
collection efforts and general background for the evaluation of
data from specific plants. The dcp sent -to all known battery
manufacturing companies provided the most complete and detailed
description of the category which could be obtained. Dcp were
used to develop category and lead subcategory data summaries and
were the primary basis for the selection of sites for pre-
proposal on-site sampling and data collection. Data from these
plant visits were used to characterize raw and treated wastewater
streams within the lead subcategory and provide an in-depth
evaluation of the impact of product and process variations on
wastewater characteristics and treatability.
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Prior to proposal, data analysis proceeded concurrently with data
collection and provided guidance for the initial data collection
effort. Initially, a review and evaluation of the available
information from published literature and previous studies was
used as the basis for developing the dcp format which structured
the preliminary data base for category analysis. This effort
included the definition of preliminary subcategories within the
battery manufacturing category. These subcategories were
expected to differ significantly in manufacturing processes and
wastewater discharge characteristics. Consequently on-site data
collection and wastewater sampling were performed for each
subcategory. Specific sites for sampling were selected on the
basis of data obtained from completed dcp. For each subcategory,
screening samples were collected and analyzed for all priority
pollutants and other selected parameters. The results of these
screening analyses, plus the dcp data, were evaluated to select
significant pollutant parameters within each subcategory for
verification sampling and analysis.
After proposal, additional data were collected to augment
existing data in response to a number of comments received from
lead battery manufacturers and their trade associations. A
survey was developed and distributed to lead battery
manufacturers to assess wastewater treatment system operating
characteristics, solid waste disposal, and process water use
practices. Based on industry comments and survey responses,
sites were selected for data collection and additional sample
analysis. Data from these site visits were used to further
characterize raw and treated process wastewater streams to assess
wastewater characteristics and treatability. Also, grid
manufacture operations proposed for regulation under the metal
molding and casting category were transferred to the lead
subcategory. Visit data were used to augment existing data
concerning water use and air pollution control practices in the
grid manufacturing process operations.
Data Collection Portfolio
The data collection portfolio (dcp) was used to obtain
information about production, manufacturing processes, raw
materials, water use, wastewater discharge and treatment,
effluent quality, and presence or absence of priority pollutants
in wastewaters from battery manufacturers. Because many lead
battery manufacturers operate on-site casting facilities, a dcp
addressing casting operations for the metal molding and casting
(foundry) category was included with the battery manufacturing
dcp. After collection of the data, the determination was made
that process wastewater discharges from casting were initially to
be evaluated as part of the foundry category.
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For data gathering purposes, a list of companies known to
manufacture batteries was compiled from Dun and Bradstreet Inc.
SIC code listings, battery industry trade association membership
lists (Battery Council International (BCD and Independent
Battery Manufacturers Association (IBMA) for lead batteries),
listings in the Thomas Register, and lists of battery
manufacturers compiled during previous EPA studies. These
sources included battery distributors, wholesalers, corporate
headquarters and individual plants. The lists were screened to
identify corporate headquarters for companies manufacturing
batteries and to eliminate distributors and wholesalers. As a
result, a total of 226 dcp were mailed to each corporate
headquarters, and a separate response was requested for each
battery manufacturing plant operated by the corporation.
Following dcp distribution, responses were received confirming
battery manufacture by 133 companies operating at 235
manufacturing sites. Of these, 184 lead battery manufacturing
sites were identified. Because of the dynamic nature of battery
manufacturing these numbers vary since some new sites have been
built, some sites have consolidated operations, and some have
closed. Since proposal, information was received which revealed
that 19 lead battery sites have closed, while 2 new sites have
been built.
Specific information requested in the dcp was determined on the
basis of an analysis of data available from published literature
and previous EPA studies of this category, and consideration of
data requirements for the promulgation of effluent limitations
and standards. This analysis indicated that wastewater volumes
and characteristics varied significantly among different battery
types according to the chemical reactants and electrolyte used,
and that raw materials constituted potential sources of sig-
nificant pollutants. In addition, batteries of a given type were
commonly produced in a variety of sizes, shapes, and electrical
capacities. Available data also indicated that processes could
vary significantly in wastewater discharge characteristics.
As a result of these considerations, the dcp was developed so
that specific battery types manufactured, manufacturing processes
practiced, and the raw materials used for each type could be
identified. Production information was requested in terms of
both total annual production (Ibs/yr) and production rate
(lbs/hr). The dcp requested data for the year 1976, the last
full year for which production information was expected to be
available. Some plants provided information for 1977 and 1978
rather than 1976 as requested in the dcp. All data received were
used to characterize the industry. Water discharge information
was requested in terms of gallons per hour. The dcp also
requested a complete description of the manufacturing process for
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each battery type, including flow diagrams designating points and
flow rates of water use and discharge, and type and quantity of
raw materials used. Chemical characteristics of each process
wastewater stream were also requested.
Basic information requested included the name and address of the
plant and corporate headquarters, and the names and telephone
numbers of contacts for further information. Additionally, the
dcp included a request for a description of wastewater treatment
practices, water source and use, wastewater discharge
destination, and type of discharge regulations to which each
plant was subject. Since the wast.ewaters at each plant had not
been analyzed for the priority pollutants, the dcp asked whether
each priority pollutant was known or believed to be present in,
or absent from, process wastewater from the plant.
Of the 184 confirmed lead battery manufacturing sites, all but 10
returned either a completed dcp or a letter with relevant
available information submitted in lieu of the dcp. This level
of response was achieved through follow-up telephone and written
contacts after mailing of the original data requests. Follow-up
contacts indicated that six of the 10 plants which did not
provide a written response had less than five employees and with
the other four comprised a negligible fraction of the industry.
The quality of the responses obtained varied significantly.
Although most plants could provide most of the information
requested a few indicated that available information was limited
to the plant name and location, product, and number of employees.
These plants were generally small and usually reported that they
discharged no process wastewater. Also, process descriptions
varied considerably. Plants were asked to describe all process
operations, not just those that generated process wastewater. As
a result over 50 percent of the lead subcategory plants
submitting dcp indicated that certain process operations did not
generate wastewater. In some dcp specific process flow rates
conflicted with water use and discharge rates reported elsewhere
in the dcp. Specific process flow information provided in the
dcp was sufficient to characterize flow rates for most process
elements for the lead subcategory. These data were augmented by
data from plant visits and, where appropriate, by information
gained in follow-up telephone and written contacts with selected
plants. Raw waste chemical analysis was almost universally
absent from the dcp and had to be developed almost entirely from
sampling at visited plants and data from previous EPA studies.
Upon receipt, each dcp was reviewed to determine plant products,
manufacturing processes, wastewater treatment and control
practices, and effluent quality (if available). Subsequently,
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selected data contained in each portfolio were entered into a
computer data base to provide identification of plants with
specific characteristics (e.g. specific products, process
operations, or waste treatment processes), and to retrieve basic
data for thes'e plants. The dcp data base provided quantitative
flow and production data for each plant. This information was
used to calculate production normalized flow values as well as
wastewater flow rates for each process element in the lead
subcategory. The data base was also used to identify and
evaluate wastewater treatment technologies and in-process control
techniques used.
Industry Survey
After proposal, the Agency determined that additional data were
required in order to address a number of issues in comments
received from lead battery manufacturers and trade associations.
An industry survey was developed to assess wastewater treatment
system operating characteristics including effluent quality;
solid waste disposal; process water use practices; and personal
hygiene and cleaning practices required at the plant.
The Battery Council International (BCI) played a major role in
the development of the industry survey. BCI distributed the
survey to their membership and to the Independent Battery
Manufacturing Association (IBMA). Completed forms were sent to
the EPA at the request of BCI. EPA received survey responses
from 65 plants. Two of the survey responses indicated that their
plants were closed and did not provide any new data.
The data provided in the industry surveys; along -with the dcp
data base were carefully considered in formulating the
promulgated regulation. Industry survey data were particularly
useful in evaluating personal hygiene and cleaning practices at
lead battery plants.
Plant Visits and Sampling (Pre-Proposal)
Seventeen lead subcategory plants were .visited prior to proposal.
At each plant, information was obtained about the manufacturing
processes, raw materials, process wastewater sources (if any),
and wastewater treatment and control practices. Wastewater
samples were collected at 5 lead subcategory plants.
Prior to proposal, the collection of data on priority,
conventional and nonconventional pollutants in waste streams
generated by this category was accomplished using a two-phase
sampling program. The first phase, screening, was designed to
provide samples of influent water, raw wastewater and treated
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effluent from a representative plant in each subcategory.
Samples from the screening phase were analyzed and the results
evaluated to determine the presence of pollutants in a waste
stream and their potential environmental significance. Those
pollutants found to be potentially significant in a subcategory
were selected for further study under the second, or
verification, phase »of. the program. This screening-verification
approach allowed both investigation of a large number of
pollutants and in-depth characterization of individual process
wastewater streams without incurring prohibitive costs.
Plant Visits and Sampling (Post-Proposal)
Engineering site visits were made to seventeen lead subcategory
sites after proposal. Sites were selected in order to obtain the
data necessary to accurately address the issues raised during the
comment period. During the site visits the Agency collected
information, where available, about the quality and flow rate of
raw and treated water, including treatment effectiveness data
from plants where monitoring was conducted. Additionally, the
Agency collected samples for chemical analysis for verification
at five of the sites visited. These samples were collected to
characterize pollutant loadings in raw waste streams and to
determine the effectiveness of end-of-pipe treatment. Analytical
data collected on the post-proposal sampling visits have been
combined with the data collected prior to proposal and are
included in the data base presented in this section.
Sampling and Analysis Procedures
Sampling procedures were applied for all sampling programs
including screening and verification sampling and post-proposal
sampling. For the screening effort, plants identified as being
representative of the subcategory in terms of manufacturing
processes, raw materials, products, and wastewater generation
were selected for sampling.
Screening samples were obtained to characterize the total process
wastewater before and after treatment. All screening was
performed according to EPA protocol as documented in Sampling and
Analysis Procedures for Screening of Industrial Effluents for
Priority Pollutants, April 1977. Only the combined raw waste
stream and total process effluent were sampled. At plants that
had no single combined raw waste or treated effluent, samples
were taken from discrete waste sources and a flow-proportioned
composite was used to represent the total waste stream for
screening.
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Asbestos data were collected from one lead plant as part of a
separate screening effort using self-sampling kits supplied to
the selected plant. The sampling protocol for asbestos was
developed after the initial screening efforts had been completed.
Consequently, asbestos data on plant influent, raw wastewater,
and effluent for each subcategory was not necessarily collected
from the same plants involved in the initial screening.
Plants were selected for verification sampling on the basis of
the screening results. Those plants within the subcategory that
demonstrated effective pollutant reductions were specifically
identified for sampling in order to evaluate wastewater treatment
and control practices. Plants were selected for post-proposal
sampling to obtain data to adequately address several issues
concerning process wastewater flows and effective treatment
practices that arose during the comment period.
Initially, each potential sampling site was contacted by
telephone to confirm and expand the dcp information and to
ascertain the degree of cooperation which the plant would
provide. The dcp for the plant was then reviewed to identify (a)
specific process wastewater samples needed to characterize
process raw waste streams and wastewater treatment performance
and (b) any additional data required. Each plant was usually
visited for one day to determine specific sampling locations and
collect additional information. In some cases, it was determined
during the preliminary visit that existing wastewater plumbing at
the plant would not permit meaningful characterization of battery
manufacturing process wastewater. In these cases, plans for
sampling the site were discontinued. For plants chosen for
sampling, a detailed sampling plan was developed on the basis of
the preliminary plant visit identifying sampling locations, flow
measurement techniques, sampling schedules, and additional data
to be collected during the sampling visit.
Sample points were selected at each plant to characterize a
process wastewater from each distinct process operation, the
total process waste stream, and the effluent from wastewater
treatment. Multiple wastewater streams from a single process
operation or unit, such as the individual stages of a series
rinse, were not sampled separately but combined as a flow-
proportioned composite sample. In some cases, wastewater flow
patterns at specific plants did not allow separate sampling of
certain process waste streams, and only samples of combined
wastewaters from two or more process operations were taken.
Where possible, chemical characteristics of these -individual
waste streams were determined by mass balance calculations from
the analyses of samples of other contributing waste streams and
of combined streams. In general, process wastewater samples were
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obtained belore any treatment, such as settling in sumps,
dilution, or mixing that would change its characteristics. When
samples could not be taken before treatment, sampling conditions
were carefully documented and considered in the evaluation of the
sampling results.
As a result of the pre-proposal and post-proposal sampling visits
to lead battery plants, over 100 raw waste samples were obtained
which characterize wastewater sources from 21 process elements.
In addition, samples were obtained from plant water supplies.
Samples were also taken for analysis which either characterized
wastewater streams from sources other than battery manufacturing
that were combined for treatment with battery manufacturing
wastes or characterized wastewater at intermediate points in
treatment systems that used several operations.
Samples for verification were usually collected at each site on
three successive days. Except if precluded by production or
wastewater discharge patterns, 24-hour flow proportioned
composite samples were obtained. Composite samples were prepared
either by using continuously operating automatic samplers or by
compositing grab samples obtained manually at a rate of one per
hour. For batch operations composites were prepared by combining
grab samples from each batch. Wastewater flow rates, pH, and
temperature were measured at each sampling point hourly for
continuous operations. For batch operations, these parameters
were measured at the time the sample was taken. At the end of
each sampling day, composite samples were divided into aliquots
and taken for analysis of organic priority pollutants, metals,
TSS, and oil and grease. Separate grab samples were taken for
analysis of volatile organic compounds and for total phenols
because these parameters would not remain stable during
compositing. Composite samples were kept on ice at 4°C during
handling and shipment. Analysis for metals was by plasma arc
spectrograph for screening and by atomic absorption for
verification. Metals analyses were done by both methods for
post-proposal sampling. Atomic absorption was used for analysis
of antimony and arsenic. Analysis for organic priority
pollutants was performed by gas chromatograph-mass spectrometer
for screening. For verification analysis, gas chromatograph-mass
spectrometer (GCMS) and gas chromatograph were used for organic
priority pollutant analysis as required by IPA protocol. No
organic analyses were performed for sampling done after proposal.
All sample analyses were performed in accordance with the EPA
protocol listed in Table V-l (page 164).
The sampling data provided wastewater chemical characteristics as
well as flow information for the manufacturing process elements
within the subcategory. Long-term flow and production values
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from the dcp data base or average flow and production values
obtained during sampling were used as a basis for calculating a
production normalized flow for each process element. A single
value for each plant that most accurately represented existing
plant operations was used to avoid excessively weighting visited
plants (usually three days of values) in statistical treatment of
the data.
Mean and median statistical methods were used to characterize
each process element production normalized flow and wastewater
characteristics. The mean value is the average of a set of
values, and the median of a set of values is the value below
which half of the values in the set lie. For the additional
process wastewater streams considered after proposal, a flow
weighted average was calculated using production and other
parameters from a number of plants. Production normalized flows
for the lead subcategory are described in detail later in this
section.
All data were used to determine total process element and
subcategory wastewater discharge flows. For plants that did not
supply process wastewater discharge flows, but did provide
production data, the mean of the individual production normalized
flow values was used.
Screening Analysis Results
The results of screening analysis for the lead subcategory are
presented in Table V-2 (page 170). Pollutants reported in the
dcp as known or believed to be present in process wastewater from
plants in the subcategory are also indicated on this table. In
the table, ND indicates that the pollutant was not detected and
NA indicates that the pollutant was not analyzed. For organic
pollutants other than pesticides, the symbol * is used to
indicate detection at less than or equal to 0.01 mg/1, the
quantifiable limit of detection. For pesticides (pollutants 89-
105), the symbol ** indicates detection less than or equal to the
quantifiable limit of 0.005 mg/1. For metals, the use of <
indicates that the pollutant was not detected by analysis with a
detection limit as shown. The analytical methods used for
screening analysis could not separate concentrations of certain
pollutant parameter pairs, specifically pollutants numbered 72
and 76, 78 and 81, and 74 and 75. These pollutant pairs will
have the same reported concentrations. Alkyl epoxides, and
xylenes were not analyzed in any samples because established
analytical procedures and standards were not available at the
time of analysis. 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) was
not analyzed because of the hazard in laboratory analysis
associated with handling TCDD standards. In the screening
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analysis tables dioxin is listed as not detected because analysis
was not done for this pollutant. Analysis of asbestos was
accomplished using microscopy. Results of asbestos analysis are
reported as fibers being present or absent from a sample. The
symbol + is used to indicate the presence of chrysotile fibers.
Selection Of Verification Parameters
Verification parameters were selected based on screening analysis
results, presence of the pollutants in process waste streams as
reported in dcp, and a technical evaluation of manufacturing
processes and raw materials used within the subcategory.
Criteria for selection of priority and conventional pollutants
included:
1. Occurrence of the pollutant in process wastewater from
the subcategory may be anticipated because the
pollutant is present in, or used as, a raw material or
process chemical. Also the dcp priority pollutant
segment indicated that the pollutant was known or
believed to be present in process wastewaters.
2. The pollutant was found to be present in the process
wastewater at quantifiable limits based on the results
of screening analysis. If the presence of the
pollutant was at or below .the quantifiable limit, the
other criteria were used to determine if selection of
the parameter was justified.
3. The detected concentrations were considered significant
following an analysis of the ambient water quality
criteria concentrations and an evaluation of
concentrations detected in blank, plant influent, and
effluent samples.
!
The criteria was used for the final selection of all verification
parameters, which included both toxic and conventional pollutant
parameters. An examination was made of all nonconventional
pollutants detected at screening and several were also selected
as verification parameters. Specific discussion of the selection
of verification parameters is presented in the following
paragraphs.
For the lead subcategory, the following 30 pollutant parameters
were selected for further analysisi
11 1,1,1-trichloroethane
23 chloroform
44 methylene chloride
55 naphthalene
65 phenol
118
119
120
122
123
cadmium
chromium
copper
lead
mercury
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66 bis(2-ethylhexyl)phthalate 124 nickel
67 butyl benzyl phthalate 126 silver
68 di-n-butyl phthalate 128 zinc
69 di-n-octyl phthalate aluminum
78 anthracene iron
81 phenanthrene manganese
84 pyrene phenols (4AAP)
114 antimony strontium
115 arsenic oil and grease
TSS
pH
Eighteen organic priority pollutants were detected in screening
at concentrations at or below the quantification level. These
pollutants, acenaphthene, benzene, 2,4,6,trichlorophenol, 2-
chlorophenol, 1,3-dichlorobenzene, 2,4-dichlorophenol,
ethylbenzene, fluoranthene, dichlorobromomethane,
chlorodibromomethane, 1,2-benzanthracene, 3,4-benzopyrene, 3,4-
benzofluoranthene, 11,12-benzofluoranthene, chrysene, fluorene,
trichloroethylene, and heptachlor epoxide were neither known to
be used in manufacturing within the subcategory nor reported as
present in process wastewater by any manufacturer. They were
therefore not selected for verification. Five additional organic
priority pollutants were reported as believed to be present in
process wastewater by at least one plant in the subcategory but
were not detected in screening analysis. On the basis of
screening results and the other criteria, 1,2-dichloroethane,
dichlorodifluoromethane, PCB-1242, PCB-1254, and PCB-1260, were
not selected as verification parameters for the lead subcategory.
Toluene was also indicated as believed to be present in one dcp,
but was detected in screening analysis at less than the
quantifiable limit. Therefore, it was not selected for
verification. Two organic pollutants, methylene chloride, and
naphthalene, were included in verification analysis, though
detected only at the quantifiable limit, because they were
reported to be present in process wastewater in dcp from lead
subcategory plants. Pyrene and phenol were selected as
verification parameters because they were identified as potential
pollutants resulting from oils and bituminous battery case
sealants. All other organic priority pollutants found to be
present in screening analysis for this subcategory were included
in verification.
Of the metal priority pollutant parameters, beryllium was
reported at the limit of detection. Because beryllium was not
known to be related to battery manufacture, it was not selected
for verification. Antimony, although detected at the limit of
detection, was selected for verification because of dcp
responses. All metal pollutant parameters detected in screening
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above the limits of detection were selected for verification.
Arsenic was selected as a verification parameter because it was
reported to be present in process wastewater by battery
manufacturers and was known to be used in the manufacturing
process. Another metal pollutant, mercury, was also selected for
verification because it was not analyzed in screening and was
reported as believed'to be present in process wastewaters by some
battery manufacturers. Cyanide was not selected for verification
since it was reported in all samples at the limit of detection
and was not known to be present in lead battery process
wastewaters.
A number of nonconventional pollutants were also detected in
screening, but not included in verification analysis. Iron and
total phenols were detected in screening and were consequently
included in verification analyses. Iron is present in process
wastewater as a result of corrosion of process equipment, and
total phenols may derive from oil and grease, and bituminous
materials used in manufacturing. After proposal, aluminum and
manganese were also detected and included in verification
analysis. Strontium was included in verification analysis
although it was not analyzed in screening because it is used as a
raw material in manufacturing some batteries in this subcategory.
In addition, the conventional pollutants, oil and grease, TSS,
and pH were included in verification analysis.
Presentation of_ Analytical Results. Pre-proposal and post-
proposal parameter analytical results are discussed and tabulated
by process element in the discussion which follows this section.
Pollutant concentration (mg/1) tables are shown for each sampled
process. In the tables 0.00 indicates no detection for all
organic pollutants. For organic pollutants, the symbol * is used
to indicate detection at less than or equal to 0.01 mg/1, the
quantifiable limit of detection. For the metals, total suspended
solids, and oil and grease, 0.000 indicates the pollutant was not
detected above the quantifiable limit. 'When samples were flow
proportionally combined for a process, the values shown are
calculated, and 0.0000 indicates that the pollutant was detected
in at least one sample of the combined process wastewater stream.
For chemical analysis, the *'s are calculated as positive values
which cannot be quantified, but for statistical analysis are
counted as zeroes.
LEAD SUBCATEGORY
Batteries manufactured in this subcategory use lead anodes, lead
peroxide cathodes, and acid electrolytes. Lead subcategory cells
and batteries, however, differ significantly in physical
configuration, size, and performance characteristics. They
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include small cells with immobilized electrolyte for use in
portable devices, batteries for automotive starting, lighting,
and ignition (SLI) applications, a variety of batteries designed
for industrial applications, and special reserve batteries for
military use. Lead reserve batteries are similar to dehydrated
batteries and are produced from lead electrodeposited on steel.
The SLI and industrial batteries are manufactured and shipped as
"dry-charged" and "wet-charged" units. Dry-charged batteries are
shipped without acid electrolyte and may be either "damp" or
"dehydrated plate" batteries as described in Section III. Wet-
charged batteries are shipped with acid electrolyte. Significant
differences in manufacturing processes correspond to these
product variations.
Lead subcategory battery production reported in dcp totaled over
1.3 million kkg (1.43 million tons) per year. Of this total,
72.3 percent were shipped as wet batteries, 9.3 percent were
damp, and 18.4 percent were produced as dehydrated plate
batteries. Less than 1 percent of the subcategory total
production is for lead reserve batteries. Reported annual
production of batteries at individual plants in this subcategory
ranged from 10.5 kkg (11.5 tons) to over 40,000 kkg (44,000
tons). Median annual production at lead subcategory plants was
approximately 6,000 kkg (6,600 tons). No correlation between
plant size and battery type, i.e, wet, damp, or dehydrated
batteries, was observed.
Geographically, lead acid battery plants are distributed
throughout the U.S. and are located in every EPA region. The
highest concentrations of plants in this subcategory are in EPA
Regions IV, V, and IX. Region IX in particular contains large
numbers of small manufacturers many of whom purchase battery
plates from outside suppliers.
Process water use and wastewater discharge vary widely among lead
subcategory plants because of differences in control of water
use, wastewater management practices, and manufacturing process
variations. The manufacturing process variations which most
significantly influence wastewater discharge are in electrode
formation techniques, but these variations are frequently
overshadowed by variations in plant water management practices.
Wastewater treatment practices also were observed to differ
widely, leading to significant variability in effluent quality.
Most plants in the subcategory discharge process wastewater to
POTW, and many provide little or no pretreatment.
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Manufacturing Process and Water Use
The manufacture of lead batteries is illustrated in the
generalized process flow diagram presented in Figure V-l (page
240). As shown in the figure, processes presently used in
commercial manufacture generally involve the following steps: (1)
grid or plate support structure manufacture; (2) leady oxide
production; (3) paste preparation and application to provide a
plate with a highly porous surface; (4) curing to ensure adequate
paste strength and adhesion to the plate; (5) assembly of plates
into groups or elements (semi-assembly); (6) electrolyte addition
as appropriate; (7) formation or charging (including plate
soaking) which further binds the paste to the grid and renders
the plate electrochemically active; (8) final assembly; (9)
battery testing and repair if needed; (10) battery washing; and
(11) final shipment. Each of these process steps may be
accomplished in a variety of ways and they may be combined in
different overall process sequences depending on intended use and
desired characteristics of the batteries being produced. Process
steps (1) through (7) are anode and cathode operations while
assembly, battery testing and repair, and battery washing are
ancillary operations. Additional ancillary operations involved
in the manufacture of lead batteries include floor anJ truck
washing, laboratory testing, and personal hygiene activities.
Personal hygiene activities include mandatory employee
handwashing, respirator washing, and laundering of employee work
uniforms. Each process step and ancillary operation identified
above is a process element in the lead subcategory. These
process elements, and their various combinations form the basis
for analysis of lead subcategory process wastewater generation as
shown in Figure V-2 (page 241). A general discussion summarizing
water use data collected for the lead subcategory process
elements is provided below. Following this discussion, the
process elements are discussed individually. Each process
element discussion includes a process description and a summary
of the process element water usage.
Water Use Data - Wastewater flow data for the lead subcategory
process elements were collected from the dcp, site visits, and
written responses to EPA requests for data. These flow data were
normalized with production data in order to compare flows from
different sized battery plants. The production normalizing
parameter is generally the total weight of lead used for all
processes. Lead use data were originally provided in the dcp,
however, after proposal, the Agency obtained more recent (1982)
lead use data from 41 plants. Production normalized flow values
for these 41 plants were calculated using the more recent (1982)
lead use data. Mean and median normalized discharge flows from
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all dcp, site visit, and written response data for the wastewater
production processes are summarized in Table V-3. This table
also shows the number of plants which reported flow data for each
process.
Table V-3 contains a number of wastewater sources for which
limited flow data is available. In the case of mold release
formulation, laboratory, hand wash, respirator wash, and laundry,
a flow weighted average calculation procedure was used to
calculate the mean normalized flow. This procedure varied
somewhat for the different operations due to differences in
available flow data; specific calculation procedures are provided
in each of the process element discussions. The calculation of
the average normalized flows for hand washing, respirator
washing, and laundry was determined with the aid of lead battery
manufacturers survey data regarding personal hygiene activities.
Personal hygiene activity data are summarized in Table V-4.
Normalized flow data for the major wastewater producing
manufacturing process elements are summarized in Figure V-3.
This figure shows the distribution of production normalized flows
for each process operation at those plants which produce a
wastewater discharge for the process operation. Plants which
report no process wastewater from the process are not represented
on the curves. The insert on the figure presents for each
process the median of the non-zero flows, the median of all flows
values, the total number of flow values, and the number of these
which are equal to zero. The median shown for the non-zero flows
is derived from a linear regression fit to the data and
represents the best available estimate of the median flow from
all plants discharging wastewater from each process operation.
Because of the difficulty in handling zero values in this
statistical treatment, the median shown for all values is the
classical median of the sample population (for plants supplying
specific process flow data).
As the regression lines on Figure V*-3 indicate the dispersion in
the flow data (indicated by the slopes of the lines) showed no
significant differences among the different process operations
shown on the figure. The slope for leady oxide production was
slightly less than the slope of other process element lines.
This difference is judged to be insignificant. The median flows
differed considerably. This reflects the fact that the
variability in wastewater flow from all process operations
results primarily from the same factors, i.e., plant-to-plant
variations in the degree of water conservation and flow control
practiced. No significant technical factors causing major
wastewater flow differences were identified for any of these
process elements and none are .suggested by these data.
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Consequently the data indicate that any plant active in any of
these process operations can achieve wastewater flows
demonstrated for that process by other plants without any major
process change.
Grid Manufacture. A lead or lead-alloy grid is the mechanical
framework to support active material (lead or lead peroxide) for
a battery plate or electrode. Cast or perforated grids are
designed to provide mechanical strength, paste adhesion, and
electrical conductivity while minimizing the grid weight in
relation to the weight of active material in the paste. Alloys
reported in1 dcp include lead-antimony and lead-calcium, sometimes
with the addition of tin. The literature also indicates that
lead-strontium grids may be used and that trace amounts of
arsenic, cadmium, selenium, silver and tellurium may be added to
grids.
Impurities found in lead grids include copper, silver, zinc,
bismuth, and iron. Newly developed grid structures discussed in
the literature use ABS plastic grids coated with lead or poly-
styrene interwoven with lead strands for the negative plate, but
no plant reported commercial manufacture of these grid types.
Two different operations are used to manufacture grids in the
lead subcategory: (1) grid casting (a form of die casting) of
lead and (2) perforating by punching or piercing and expanding of
lead. The latter can be preceeded by the actual manufacture of
the sheet which includes direct chill casting and lead rolling
processes. Based on dcp data, grid casting is performed at 130
lead subcategory sites and was performed at 14 of the 17 sites
visited after proposal. Grid fabrication by punching or piercing
and expanding is known to be practiced by at least 10 plants and
the practice is growing. Melting furnaces or pots are used to
produce molten lead for both grid casting and direct chill
casting methods. These melting furnaces generate fumes which are
removed by wet air pollution control devices at some sites. Wet
air pollution control is discussed later in this section. Both
of the grid manufacturing methods are discussed below.
Grid Casting - Grid casting is performed by cooling molten lead
in metal molds to produce individual grids. The molten lead is
cooled by passing noncontact cooling water through the mold.
This non-process water is recycled through cooling towers at some
sites, discharged direct 14 to the sanitary sewer at other sites,
or discharged to wastewater treatment. If the water is recycled
through cooling towers, non-process cooling tower blowdown water
is discharged to the sewer or to wastewater treatment.
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The use of molds in grid casting requires the use of a mold
release compound which prevents the molten lead from adhering to
the mold upon cooling. Mold release compounds are either cork or
silica based with either kerosene or silicon carrier fluids.
These compounds can either be purchased or formulated on-site.
Twenty-nine sites owned by two companies reported formulating
their mold release compound on-site. Process wastewater is
generated from on-site mold release formulation by cleaning
equipment after mixing batches of the release material. Flow
information for mold release formulation was obtained after
proposal from both of the companies which report this activity.
At one company approximately 50 gallons per day of water are used
at each site for equipment cleanup. At the other company, 75
gallons of water are used per day at each site.
The average production normalized flow (0.006 I/kg) for mold
release formulation was calculated as follows:
o For each company, the company mold release formulation
flow was multiplied by the number of company sites to
determine the total company mold release formulation
flow.
o The total company mold release formulation flow was
then divided by the total company production to
determine a production normalized flow for the company.
o The two production normalized company flows were then
averaged.
Perforating - In this process, grids are manufactured by
perforating sheet lead by various methods. The sheet lead can be
continuously punched and coiled or cut into individual grids.
This method does not generate wastewater and lead scrap from the
punching is reclaimed. The sheet metal can also be pierced and
expanded into grids with no wastewater discharge, although a
neglibible amount of aqueous emulsion is used for lubrication.
This method can be preceded by manufacture of the lead sheet by
direct chill casting and lead rolling.
In direct chill casting, molten lead flows by gravity through a
die. This die is sprayed with contact cooling water which causes
the lead to solidify into a continuous strip of about two inches
thick. The continuous strip is then reduced to the desired
thickness (0.05 in.) in a rolling mill. Following rolling, the
lead strip is aged for one to two weeks to increase tensile
strength prior to grid fabrication.
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Water usage data for direct chill casting and lead rolling were
collected on a post-proposal sampling visit to one site reported
to be active in these processes. At this site, direct chill
casting contact cooling water drains to a catch tank and is
continuously recirculated. The catch tank is drained to
treatment about once every four months. The average production
normalized flow of* 0.0002 I/kg was calculated for direct chill
casting as follows:
o Catch tank dimensions at the sampled site were
measured.
o The annual discharge flow from direct chill casting was
then calculated assuming three batch dumps per year.
o The annual discharge flow was divided by the site's
annual production to determine the average normalized
flow.
In lead rolling, an aqueous emulsion of 0.5 percent oil is used
to lubricate the rolling mills. This emulsion is continuously
recirculated and subsequently contract hauled once per week to
treatment and disposal off-site. Based on flow data from the
sampled site, 0.006 I/kg of spent solution are contract hauled.
Leady Oxide Production. Active materials for the positive (Pb02)
and negative (Pb) plates are derived from lead oxides in
combination with finely divided lead. Lead oxide (PbO) used in
battery plates and known as litharge exists in two crystalline
forms, the yellow orthorhombic form (yellow lead) and the red
tetrogonal form. Red lead (Pb304) is sometimes used in making
positive plates, but its use is declining. The lead oxide
mixture (PbO and Pb) called leady oxide, which is most often used
in producing electrodes, is usually produced on-site at battery
manufacturing plants by either the ball mill process or the
Barton process. Leady oxide generally contains 25-30 percent
free lead with a typical value observed to be approximately 27
percent.
In the ball, mill process, high purity lead pigs or balls tumble
in a ball mill while being subjected to a regulated flow of air.
Heat generated by friction and the exothermic oxidation reaction
causes oxidation of the eroding lead surface to form particles of
red litharge and unoxidized metallic lead. The rate of oxidation
is controlled by regulation of air flow and by non-contact
cooling of the ball mill, or bearings.
In the Barton process, molten lead is fed into a pot and vigor-
ously agitated to break lead into fine droplets by aspiration.
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Oxidation in the presence of an air stream forms a mixture of
yellow lead, red litharge, and unoxidized lead in a settling
chamber.
High purity refined lead is required to produce oxide for use on
electrodes. Recycled lead recovered by remelting scrap is
normally used in casting grids, straps, and terminals.
Water use and wastewater generation associated with leady oxide
production is dependent on the process (Barton or ball mill)
used. The Barton process uses only non-process water for cooling
screw conveyors and other mechanical parts. Shell cooling water
is the primary source of process wastewater from ball mills.
Five of the 17 sites visited after proposal used the Barton
process. None of these sites generated process wastewater. In
the ball mill process, a number of cooling configurations have
been observed in this subcategory. At some sites, noncontact
cooling water was used to cool bearings. This cooling
configuration does not generate a process wastewater stream since
the cooling water does not contact lead dust or other
contaminants. Other sites use water to cool the shell of the
ball mill. Cooling in this manner may produce a process
wastewater stream due to entrainment and dissolution of lead dust
when the ball mill is not shrouded properly. Four of the 17
sites visited after proposal operate ball mills. One of these
sites cools only bearings generating no process wastewater.
Three of the sites use shell cooling water with widely varying
cooling configurations. One site uses once-through shell
cooling. One has two ball mills with two • different cooling
configurations: in one ball mill, once through shell cooling
water is used while at the other ball mill the shell cooling
water is recirculated with minimal wastewater generation. The
third site uses a completely closed recirculating cooling
configuration with annual sump cleaning.
Twenty-nine of the 41 plants submitting data for this process
reported zero discharge of wastewater. Nine of the 12 plants
reporting discharge flows from leady oxide production are from
shell cooling. Two of 12 are discharges associated with wet
scrubbers. Wet scrubber discharges from leady oxide production
are included in the wet air pollution control process element
which is discussed later in this section. The remaining flow is
an unidentified process wastewater discharge. The average
production normalized flow is 0.37 I/kg and median is 0.00 I/kg.
Paste Preparation and Application. Lead oxides are pasted on the
grid to produce electrode plates with a porous, high area,
reactive surface. The pores provide maximum contact of the
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electrolyte with the electrode. Various mixtures of lead oxide
powder are used for the formulation of the negative and positive
pastes/ which usually are mixed separately. The positive plate
is formed from leady oxide, granular lead, or red lead with
binders such as acrylic fibers, sulfuric acid, and water. The
negative paste generally contains leady oxide, lead, sulfuric
acid, water, and expanders. Expanders are added to the negative
paste to minimize contraction and solidification of the spongy
lead. The most common expanders are lampblack, barium sulfate,
and organic materials such as lignosulfonic acid. Addition of
expanders amounting to an aggregate 1 or 2 percent of the paste
can increase the negative plate effective area by several hundred
percent.
Hardeners have been added to pastes (e.g., glycerine and carbolic
acid), but prevailing practice is to control this property by
proper oxide processing. Other additives to the paste include
ammonium hydroxide, magnesium sulfate, lead carbonate, lead
chloride, lead sulfate, potash, and zinc chloride. Where a plate
is to be placed in a dehydrated battery, mineral oil may be added
to the negative paste to protect the plate from oxidation, from
sulfation, and to reduce hydrogen evolution (depending upon the
grid alloy).
Water is added to the paste to produce proper consistency and
increase paste adhesion. During acid addition, considerable heat
is evolved. Temperature must be controlled to produce a paste
with the proper cementing action. Paste is applied to the grids
by hand or machine.
The major source of wastewater from paste preparation and
application is equipment and area cleanup. Equipment and area
cleanup is a required procedure because different paste
formulations may be used on any one pasting line, and the
equipment must be periodically cleaned. Fifty-seven of the 100
plants submitting flow data on this process report zero discharge
of wastewater from paste preparation and application. Zero
discharge is accomplished by settling and recycling paste area
water for equipment washdown. The settled paste can also be
reclaimed. The average production normalized flow for this
process is 0.49 I/kg and the median is 0.00 I/kg.
Sixteen of the 17 sites visited after proposal perform paste
formulation and application operations. Seven of these sites do
not discharge wastewater from equipment and area washdown.
Another site was planning to install a complete recirculation
washdown water system by December 1983.
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Some plants use wet scrubbers to control dust generated during
paste mixing. These wet scrubbers are discussed later in this
section under the wet air pollution control process element.
Curing. The drying and curing operations must be carefully
controlled to provide electrodes with the porosity and mechanical
strength required for adequate battery performance and service
life. The purpose of curing is to ensure proper control of
oxidation and sulfation of the plates.
Where leady oxides are present, common practice is to flash dry
the plates by passing them through a tunnel drier and then either
stacking and covering them (air curing), placing them in humidity
controlled rooms or ovens (humidity curing) for several days, or
directly applying steam in a controlled environment (steair
curing) to convert free lead particles in the plates to lead
oxide. The free lead is reduced from 24-30 percent to the
desired level (5 percent or less) during curing. Proper
conditions of temperature and humidity allow the formation of
small crystals of tribasic lead sulfate which convert easily to a
very active lead peroxide (positive plate) during formation. Toe
high a temperature (57° C) leads to the formation of coarse
crystals of tetrabasic lead which is difficult to convert to lead
peroxide and may cause shedding of active material during forma-
tion. Too little or too much moisture in the plate retards the
rate of oxidation. Steam curing increases the rate of curing by
providing controlled humidity at higher temperatures.
Multiple curing techniques are used by a number of sites in the
subcategory. For instance, at some sites plates are first cured
in humidity controlled rooms or ovens. The curing process is
then completed in covered stacks. Other sites first steam cure
plates and then finish the curing process in humidity controlled
rooms. At some sites only positive plates are steam or humidity
cured while at other sites both positive and negative plates are
steam or humidity cured. Process wastewater discharge from
curing was reported by ten of the 97 plants that supplied flow
data. The average production normalized flow for this process is
0.03 I/kg and the median is 0.00 I/kg. Discharge of wastewater
from curing is associated with humidity curing and steam curing.
Wastewater discharge from humidity curing results from
condensation in humidity controlled rooms and once-through spray
water from humidity curing ovens. Wastewater discharge from
steam curing is associated with steam condensation.
Although a few sites discharge wastewater from steam or humidity
curing, other sites have demonstrated that these operations can
be performed without the discharge of process wastewater. Eight
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of the 17 sites visited after proposal do not discharge
wastewater from positive or negative plate curing. Of these, six
use humidity controlled rooms for both types of plates; one uses
steam curing for both types of plates and one uses ambient
curing, humidity controlled rooms, or steam curing depending on
the battery and type of plate.
Semi-Assembly (Stacking, Grouping, Separator Addition)
Following curing, plates are stacked or grouped in preparation
for formation. This semi-assembly process varies depending upon
the specific formation process which is to follow and the type of
separator being used.
Separators prevent short circuiting between the anode and cathode
yet permit electrolyte conduction between the electrodes. Sepa-
rators also may serve to provide physical support to the positive
plate. The configuration and the material of separators differ
according to the specific properties desired. Materials used for
separators in lead acid storage batteries include paper, plastic,
rubber, and fiberglass.
Water use in the semi-assembly operation is limited to non-
contact cooling water associated with welding of elements and
groups. No process wastewater is generated or discharged from
the semi-assembly operation.
Electrolyte Preparation and Addition - Sulfuric acid is purchased
by battery manufacturers as concentrated acid (typically 93
percent) and must be diluted with water or "cut" to the desired
concentration(s) prior to use in forming electrodes or filling
batteries. Dilution usually proceeds in two steps. The acid is
first cut to an intermediate concentration (about 45 percent
acid) which may be used in paste preparation. Final dilutions
are made to concentrations (generally 20-35 percent) used in
battery formation and battery filling. Often two or more
different final acid concentrations are produced for use in
formation and for shipment in different battery types.
For some battery applications, sodium silicate is added to the
electrolyte prior to addition to the battery. The resulting
thixotropic gel is poured into the battery and allowed to set,
yielding a product from which liquid loss and gas escape during
operation are minimal and which may be operated in any
orientation.
Acid cutting generates heat and generally requires the use of
non-contact cooling water. Process wastewater is not generally
produced. Wet scrubbers are reported to be in use at some sites
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to control acid fumes but are used as dry mist eliminators and do
not generate process wastewater. Since water is consumed-in
"cutting" acid, some sites use this process as a sink for process
wastewater contaminated with acid and lead, thereby reducing or
eliminating'the volume requiring treatment and discharge.
The addition of electrolyte to batteries for formation and for
shipment is frequently a source of wastewater discharge in the
form of acid spillage. Electrolyte addition is accomplished by a
wide variety of techniques which result in widely varying amounts
of spillage and battery case contamination. While efficient
producers employ filling devices which sense the level of
electrolyte in the batteries and add only the proper amount with
essentially no spillage or case contamination, others continue to
regulate the amount of acid in the batteries by overfilling and
subsequently removing acid to the desired level. In some plants,
batteries are filled by immersion in tanks of acid. Overfilling
or filling by immersion results in significant contamination of
the battery case with acid and necessitates rinsing prior to
further handling or shipment, generating significant volumes of
process wastewater. Acid spills also contaminate equipment in
the formation area requiring periodic equipment washdown
(formation area washdown). Wastewater flows from formation area
washdown and battery rinsing are considered as flow values for
the formation processes.
Formation (Charging) - .Although lead peroxide is the active
material of the finished positive plate, it is not a component of
the paste applied to the plate. The formation process converts
lead oxide and sulfate to lead peroxide for the positive plate
and to lead for the negative plate by means of an electric
current. Formation starts in the region where poorly conducting
paste is in contact with the more conductive grids and proceeds
through the volume of the paste. Completion of formation is
indicated by (1) color of active materials (plates have "cleared"
and are uniform in color), (2) plates are gassing normally, (3) a
constant maximum voltage is indicated, and (4) the desired
electrolyte specific gravity is reached. Final composition for
the positive plate is 85-95 percent lead peroxide and the
negative plate is greater than 90 percent lead. Formation of
battery plates may be accomplished either within the battery case
after assembly has been completed (closed formation) or in open
tanks prior to battery assembly (open formation). Open formation
is most often practiced in the manufacture of dehydrated plate
batteries.
A number of charging techniques are used to form batteries in
this subcategory. Charging techniques used for closed formation
include (1) high rate formation, (2) low rate formation, (3)
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controlled charge rate formation, and (4) chilled acid formation.
In high rate formation, batteries are formed rapidly in one day
or less. When batteries are formed rapidly, heat generation is
so rapid that the batteries must be cooled using fine sprays of
water on the battery cases. This contact cooling water is a
significant source of wastewater. Low rate formation is a
charging technique .in which batteries are charged at a constant
rate which is low ' enough to adequately dissipate heat without
using cooling water. Low rate charging requires formation
periods of up to seven days. In controlled charging, the
charging current is varied during the course of formation to
maintain acceptable electrolyte temperatures. This eliminates
the need for contact cooling water. Current variation is
achieved manually or by the use of automatic timers or small
computer devices. Controlled charging sometimes comprises
charging slowly for a few hours initially, on the order of a few
amps; then the rate is increased for most of the formation cycle,
and then the rate is decreased again to finish charging. Other
plants charge rapidly for nine to ten hours, then let the
batteries cool for several hours and finish charging rapidly for
approximately another nine hours. Overall controlled charging
formation times have been observed to vary from nine hours to a
total of 72 hours. Another charging technique observed in this
subcategory is the use of chilled acid to reduce electrolyte
temperatures in the initial stage of charging. Reduced
electrolyte temperature in the initial stage of charging serves
to reduce the overall charging time. The initial heat of
reaction during, the charge cycle is usually greater due to the
presence of unreacted (uncured) lead oxide in the cured plate.
Instead of charging slowly at first to dissipate heat, charging
can proceed more rapidly immediately with the use of chilled
acid.
Open formation charging periods have been observed to vary from
approximately one to five days. Since batteries are formed in
open tanks heat dissipation is not a problem in open formation.
Closed Formation. Closed formation is performed in several
different ways depending upon the desired charging rate and
characteristics of the final product. The major variations in
this process may be termed: single fill-single charge, double
fill-single charge, double fill-double charge, and fill and dump
(for damp batteries). A major factor influencing the choice of
operating conditions for closed formation is the relationship
between charging rate, electrode characteristics, and electrolyte
concentration. As the electrolyte concentration increases, the
rate of formation of positive plates decreases, but durability of
the product improves. The rate of formation of negative plates
increases by increasing acid concentration.
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Single-Fill - In the single fill-single charge process, the
battery is filled with acid of a specific gravity such that,
after formation, the electrolyte will be suitable for shipment
and operation of the battery. Thirty-one of the 43 sites
reporting flow data for single fill formation achieve zero
discharge. The average production normalized flow is 0.28 I/kg
and the median is 0.00 I/kg. For sites that report a discharge,
wastewater sources include area washdown, contact cooling water,
and wet air pollution control scrubbers. Wet air pollution
control scrubbers are used to remove fumes generated during
charging and are discussed later in this section under the wet
air pollution control process element. As discussed earlier,
contact cooling water is a major source of wastewater at sites
which use high rate charging.
Eight sites visited after proposal use single fill formation.
Three of these sites use contact cooling water to dissipate heat
generated during high rate charging. One of the three sites has
two single fill operations. In one operation the cooling water
is recycled through a water softening system while the other
operation uses a once through cooling configuration which
generates the majority of wastewater discharged to treatment at
the site, about 200,000 gpd. The second site uses controlled
charging with no wastewater generation for some batteries, and
spray cooling for the remaining batteries. The third site uses
spray cooling water to dissipate heat. The remaining five sites
incorporate slow or controlled formation procedures which
eliminate the need for cooling water.
Double-Fill - Double fill formation processes use a more dilute
formation electrolyte than is used for single-fill formation.
Formation of the battery is complete in about 24 hours. The
formation electrolyte is removed for reuse, and more concentrated
fresh electrolyte suitable for battery operation is added.1.
Double fill-double charge batteries are given a boost charge
prior to shipment.
Seven of the 35 sites reporting flow data for double fill
formation achieve zero discharge. The average production
normalized flow is 0.92 I/kg and the median is 0.44 I/kg. The
sources of wastewater from double fill are essentially the same
as for single fill: cooling water, area washdown, and wet air
scrubber discharge. An additional source of wastewater
associated with double fill operations is battery rinse water.
Both filling and emptying battery cases may result in
contamination of the case with acid, necessitating subsequent
battery rinsing. The extent of this contamination depends on the
filling and emptying techniques applied. The immersion filling
method results in the most extensive battery case contamination
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and requires subsequent battery rinsing. Other filling methods
have been observed which do not require battery rinsing.
The fraction of sites using immersion filling is much greater for
double fill operations than for single fill. Based on post-
proposal site visits three of four double fill sites use at least
one filling procedure by immersion; only one of the eight sites
visited used immersion filling for single fill operations. All
sites using immersion filling were observed to rinse batteries.
Conversely, very few double fill plants practice contact cooling;
none were observed during site visits and one plant reported this
procedure based on dcp and industry survey data.
Closed formation of wet batteries (single and double fill) was
reported to produce a process wastewater discharge at 40 of 78
plants. Data specific to these two formations are summarized in
Figure V-4 (page 244). As these data show, over 70 percent of
all plants reported zero discharge from single fill formation
while 80 percent reported wastewater discharge from double fill
formation. The median flow at discharging plants was similar,
for both processes (0.28 I/kg for single fill and 0.45 I/kg for
double fill). The more frequent occurrence of discharge of
process wastewater from double fill is attributable to rinsing
batteries after immersion filling or dumping of formation
electrolyte.
Fill and Dump - The fill and dump process is used to produce damp
batteries which are a part of the group of batteries commonly
called dry-charged by manufacturers. These differ from
dehydrated plate batteries (produced by open formation) in the
degree of electrolyte removal and dehydration. The presence of
some electrolyte in the damp batteries when they are shipped
causes the degree of charge retention during long-term storage to
be less than that of the dehydrated plate type. Damp batteries
are produced by closed formation of assembled batteries and
subsequent removal of the electrolyte and draining of the battery
which is shipped without electrolyte. After the formation
electrolyte is removed from the battery, some manufacturers add
chemicals to the battery in a second acid solution which is also
dumped. These chemicals are intended to reduce the loss of
battery charge during storage. Other manufacturers centrifuge or
"spin-dry" the batteries before final assembly.
Water use and wastewater discharge in the production of damp
batteries do not differ significantly from that for double fill
wet batteries. Thirteen plants supplied flow information on this
process. One of the 13 reported zero discharge from the process.
The average production normalized flow is 1.83 I/kg and the
median is 1.49 I/kg.
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Three plants visited after proposal practice fill and dump
formation. One of these plants uses immersion filling techniques
with an associated battery rinse. All three plants reuse the
dumped acid electrolyte. At one of the plants, batteries are
filled with a chemical solution to dry the plates after the
formation electrolyte is dumped. This chemical solution is
discharged to treatment.
Open Formation - Open formation has the advantage of having
access to the battery plates during and after formation. Visual
inspection of the plates during formation allows closer control
of formation conditions than is possible during closed formation.
More significantly, however, after open formation plates can be
rinsed thoroughly to remove residual electrolyte and can then be
thoroughly dried as is required for the manufacture of dehydrated
plate batteries.
Wet - Open case formation is used in the manufacture of some wet
batteries. Because problems of inhomogeneity in the plates are
most pronounced during formation of larger plate sizes, open case
formation for the manufacture of wet batteries is frequently used
for the manufacture of industrial batteries with large
electrodes.
Ten of the 16 sites submitting flow data for open formation wet
batteries achieve zero discharge. The average production
normalized flow is 0.36 I/kg and the median is 0.00 I/kg.
Wastewater discharges from open formation for wet batteries
result from periodic replacement of spent formation electrolyte,
plate rinsing, formation area washdown, and wet air pollution
control scrubbers. Three of the six discharging sites discharge
wastewater from plate rinsing operations. Plate rinsing is done
in tanks which are periodically (about once a month) emptied to
treatment. Alternately, some sites use a light water spray to
rinse plates. The discharge flows from these plate rinsing
operations are much lower than the flows from open formation
dehydrated battery plate rinsing where single or multi staged
rinsing operations are often used to eliminate all acid from the
battery plates. Three of the six discharging sites, which
include one site which also discharges plate rinse water,
discharge spent formation electrolyte. The remaining site
discharges wastewater from • wet scrubbers and formation area
washdown. Wet scrubber discharges associated with formation are
discussed under the wet air pollution control process element.
Dehydrated - Most open case formation is for the purpose of
producing dehydrated plates. Immediately after formation, the
plates are rinsed and dehydrated. These operations are
particularly important for the (lead) negative plates which
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oxidize rapidly if acid and moisture are not eliminated* A
variety of techniques including the use of deionized water are
used to rinse the formed plates. Multi-stage rinses are
frequently used to achieve the required degree of electrolyte
removal. Drying often requires both heat and vacuum to achieve
dehydration of the plates.
The most common and significant source of wastewater from open
dehydrated formation is plate rinsing. Additional wastewater
sources are from vacuum pump seals or ejectors, wet air pollution
control scrubbers, formation area washdown, and periodic
electrolyte discharge.
Forty-two plants provided flow data . with regard to open
dehydrated formation. Two of these sites achieve zero discharge.
A wide range of flows were reported by the 40 discharge sites.
The wide range of flows is due to a number of factors. A variety
of plate rinsing techniques (single stage rinsing, multistage
series rinsing, countercurrent cascade rinsing) are practiced in
the subcategory. Water usage associated with single and multi-
stage series rinses is greater than that associated with
countercurrent cascade rinsing. At some sites, the rinse tanks
are agitated by bubbling air through sprayers or repeatedly
lifting plates in and out of the tanks. Rinse tank agitation
lowers the water usage associated with plate rinsing. The use of
flow controllers also lowers water usage. Some sites discharge
water from vacuum pump seals and ejectors used for dehydrating
plates. Vacuum pump seal or ejector water significantly
increases the flow from open dehydrated formation. The average
production normalized flow is 28.26 I/kg and the median is 11.05
I/kg.
Seven of the sites visited after proposal use open dehydrated
formation. All of these sites use plate rinses. One of the
sites uses treated water for plate rinsing. Three sites use wet
air pollution control scrubbers to remove acid fumes and mist,
while at one site electrolyte is periodically discharged to
treatment. None of the plants have a discharge associated with
vacuum pump seals or ejectors.
Plate Soak - After curing, and usually the preliminary step for
open formation, plates may be soaked in a sulfuric acid solution
to enhance sulfation and improve mechanical properties. Plate
soaking may be done in the battery case, a formation tank, or in
a separate vessel, and is usually done for plates greater than
0.25 cm (0.10 inches) thick. Wastewater results from periodic
discharge of the spent soaking acid. Wastewater flow data for
plate soaking was collected after proposal from three sites.
Assuming a monthly replacement of soaking acid, a production
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normalized flow for plate soaking was calculated for each site.
The average of the three production normalized flows is 0.026
I/kg and the median is 0.021 I/kg.
Battery Assembly - As discussed previously, assembly may be
partially accomplished prior to formation but is completed after
formation. Assembly after open formation includes interleaving
positive and negative plates and separators to create elements,
and welding connecting straps to the positive and negative lugs
on the elements to provide electrical continuity through the
battery. The battery cover is then installed and sealed in place
by heat, epoxy resin, rubber cement, or with a bituminous sealer;
vents are installed; and the battery posts are welded or "burned"
in place. Partial assembly prior to closed formation is the same
as semi-assembly. Final sealing of the case and installation of
vent covers is accomplished after formation. Wastewater
discharges from battery assembly result from using wet scrubbers
to control fumes generated from casting terminals and connector
straps (small parts casting) and welding battery posts. These
wet scrubbers are discussed later under the wet air pollution
control process element.
Battery Wash. Many plants wash batteries in preparation for
shipment. Plants which do not wash batteries generally produce
dehydrated plate batteries, or extensively use contact cooling in
formation precluding the necessity to -wash. Batteries are washed
primarily to remove sulfuric acid spilled on the outside of the
battery case. Detergent is used at some plants to remove oil and
grease. The battery wash process element is divided into two
subelements, battery wash with water only, and battery wash with
detergent.
Battery Wash with Water Only - Forty-four plants reported flow
data for water only battery washes. One of these plants achieves
zero discharge. This plant reuses battery wash water in acid
cutting. The average production normalized flow for this process
is 3.47 I/kg and the median is 0.59 I/kg. The magnitude of the
discharge flow from battery washing is related to a number of
factors. Factors which tend to reduce the discharge flow are as
follows:
o Use of a switching device (mechanical or electrical) to
stop the flow of water when batteries are not in the
battery washer.
o Use of appropriate types of spray nozzles to properly
disperse the rinsewater.
o Recycle wash water back to the battery washer.
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Seven of the sites visited since proposal operate water only
battery washes. All of these sites discharge wash water. One
site uses an electrical switching device to reduce the discharge
flow. Another site recycles the wash water with an overflow
stream to treatment.
Battery Wash with Detergent - Twenty-two plants reported flow
data for detergent battery washes. All of these plants discharge
the detergent wash water. The average production normalized flow
for this process is 1.70 I/kg and the median is 0.90 I/kg. Five
of the sites visited after proposal operate detergent battery
washes.
Floor Wash. Many battery plants use power floor scrubbers to
clean floor areas. Power floor scrubbers are sometimes not used
in areas such as (1) formation areas because acid spills tend to
corrode these machines and (2) those areas where it is not
practical to use a machine scrubber. Instead, high pressure
water hoses are used to spray equipment and floors in these
areas. Wastewater discharges associated with both power
scrubbers and hoses are considered under floor wash.
A total of 13 sites reported flow data with regard to floor
washing. Two sites reported no discharge from floorwash
operations. The average production normalized flow from floor
washing is 0.11 I/kg while the median flow is 0.13 I/kg. At some
sites, floor wash flows and formation area washdown flows are not
distinquishable. For those sites, the flow associated with
formation area washdown was included in the floor wash flow.
Floor wash information was obtained from twelve of the sites
visited after proposal. Ten sites have power floor scrubbers and
2 sites use only hoses. Five of the 10 sites use power scrubbers
to clean all floor areas including the formation area. The
remaining five sites use water hoses to washdown the formation
and other miscellaneous areas.
Wet Air Pollution Control. Wet air pollution control (WAPC)
devices are reported to be used in many lead battery plants to
varying degrees in the following process activities: leady oxide
production, grid manufacture, pasting, formation, battery
assembly, battery washing, boost charging, acid mixing, and
laboratories. From dcp, site visits, and telephone contacts with
plant personnel, 80 sites reported using scrubbers in each area
as follows: three sites for leady oxide production, 16 sites for
grid manufacturing, 53 sites for pasting, 37 sites for formation
(22 for open, 24 for closed, 15 for closed only), six sites for
battery assembly, one site for battery washing, one site for
boost charging, five sites for acid mixing, two sites for
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laboratories and one site for controlling paint fumes.
Wastewater discharges from all lead subcategory process elements
except laboratories are included in the wet air pollution control
process element. Discharges from laboratory wet scrubbers are
included in the laboratory process element.
Based on all collected data for wet air pollution control, most
plants use wet scrubbers in two or less process element
operations. Of the 80 plants which indicated the use of wet
scrubbers, 73 use scrubbers in two or less operations. Pasting
and formation represent the most common areas where wet scrubbers
are used. The use of scrubbers in other areas was found to be
rare, and site specific in nature. Grid manufacturing and
battery assembly wet scrubbing is mostly (70 percent) represented
by one company.
The scrubbers reported for battery washing and acid mixing are at
sites associated with one corporation and are now used as static
demisters without use of or generation of water. The site using
a boost charging scrubber utilizes recycle of coalescer/demister
washdown water with caustic addition, incurring infrequent low
volume blowdown to treatment. No information is availalbe
concerning the paint fume scrubber.
Based on telephone contacts and post-proposal data submittals by
lead battery companies, primarily two types of scrubbers are
used. These are as follows: (1) a static vessel of scrubber
water, or internally recirculated water, through which fumes are
sparged and (2) an acid mist or fume cpalescer with intermittent
washdown. The static vessel design typifies leady oxide
production, grid manufacture, pasting, and battery assembly
applications; the latter design typifies formation area air
scrubbing. Wastewater from the static vessel design results from
continuous overflow or periodic tank drainage. Wastewater from
the fume coalescer results from intermittent mesh washdown or the
use of a continuous water spray in the fan section of the
scrubber.
Flow rates reported by plants in the subcategory for WAPC devices
applied in pasting, grid manufacture, battery assembly, and leady
oxide production varied significantly due to widely varying
operating philosophies. The flow rates reported varied from 0
1/hr to 1,703 1/hr. After the dcp were submitted, three sites
eliminated a total of five grid manufacturing, battery assembly
and leady oxide WAPC scrubber operations and installed baghouses.
Consequently,, the current reported flow range is from 0' 1/hr to
681 1/hr. All but two of these flows are equal to or less than
227 1/hr. About 40 sites report either fcn intermittent or
unmeasureable stream which goes to wastewater treatment. The
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intermittency results from overflow or batch periodic draining to
clean the tank and reclaim any residual lead-containing material.
The measured flows connote a continuous makeup and drainage rate
for generally undefined reasons. From plant contacts with a site
which used a scrubber for grid manufacturing, it was reported
that a steady drainage was used at a time when a different mold
release compound was being used, which generated significant
loadings of soot upon application to the molds. The soot was the
desired end product to lubricate the mold. This raised the
particulate loading on their static scrubber system, purportedly
requiring continuous makeup and drainage of water. Upon
switching to cork release material, the need is negligible, and
the flow has been set back, but still remains.
Reported flow rates from formation area scrubbers varied from
negligible and intermittent to 68,130 liters per hour. This
difference is due to a number of factors. Some sites operate the
scrubber dry with intermittent washdown of the mesh. Some sites
report no mesh washdown at all. Mesh washdown frequency varies
from site to site resulting in varying wastewater flow rates.
Other sites use a continuous water spray in the fan section of
the scrubber. Based on vendor information, use of the continuous
water spray results in a wastewater discharge that 'is 20 times
greater than the discharge associated with the dry (intermittent
washdown) operating mode.
The average and median production normalized flow for wet. air
pollution control was calculated using flow data for all
scrubbers except for laboratories. Flow values for scrubbers
used for more than one process area were counted once. The flow
from one scrubber (68,130 1/hr) was not used to calculate the
average and median production normalized flow values because
water usage at this high level is considered excessive. The
average production normalized flow for WAPC is 0.26 I/kg and the
median is 0.00 I/kg, based on data from 56 scrubbers of which 32
do not discharge.
Battery Testing and Repair. Most finished batteries are tested
prior to shipment to assure correct voltage and current capacity.
Selected batteries may undergo more extensive tests including
capacity, charge rate acceptance, cycle life, over-charge, and
accelerated life tests. Batteries which are found to be faulty
in testing may be repaired on site. These repair operations
generally require disassembly of the battery and replacement of
some component(s).
The conduction of tests and subsequent disassembly, inspection,
and repair operations yield wastewater which is similar in
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character to discharges from formation operations. From industry
survey data, 30 out of 65 plants report this activity
demonstrating extensive involvement by the subcategory. The flow
data which exists for this process is primarily from the dcp and
sampling visits. Three sites reported flow values of 0.004 I/kg,
0.25 I/kg, and 0.34 I/kg. The average production normalized flow
is 0.20 I/kg and the median is 0.25 I/kg.
Laboratory Testing. A number of quality control analyses are
performed in laboratories at lead battery plants. These analyses
involve both chemical and some physical property analyses of
intermediate battery components and finished batteries. The
following parameters are commonly analyzed at battery plants in
this subcategory:
o Iron content of battery electrolyte,
o Particle size of leady oxide powder,
o Free lead content of lead oxide powder,
o Free lead content of cured plates,
o Lead sulfate content of paste,
o Lead sulfate content of formed plates
o Trace element contaminants contained in grids and lead
strip.
Fifty-seven of the 65 industry surveys reported on-site
laboratory facilities.
There are a number of wastewater sources associated with on-site
laboratory facilities. Sources of process wastewater include
instrument washing, general area cleanup, wet air pollution
control discharge, and dumped battery electrolyte. Wet air
pollution control scrubbers are used to remove lead dust and acid
mist generated from wet chemistry tests performed under a
ventilation hood. Slowdown from these scrubbers is considered
under this process element rather than with the WAPC process
element because scrubber use in the laboratory is intermittent
and the flow is minimal.
Laboratory flow data was collected on post-proposal site visits
to five sites. Flow data from four of the five sites were used
to calculate an average normalized flow for laboratories of 0.003
I/kg. One flow value reported during the site visits was more
than an order of magnitude greater than the other four values
measured or reported. This large flow is not justified in terms
of differences among sites testing and analysis procedures and
was not considered in establishing the average normalized flow.
The average normalized flow is a flow weighted average of the
four reported or measured flows. This flow was calculated by
adding the laboratory flows from the four sites and dividing by
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the total production associated with the four sites. Production
data from 1982 was used to calculate the total production.
Truck Wash. Trucks are used to transport used batteries in
connection with battery cracking {secondary lead subcategory of
the nonferrous metals category) processes and to ship new and
repairable batteries to and from battery manufacturing sites.
These trucks are periodically washed generating a wastewater
discharge. Only truck washing associated with battery
manufacturing processes is considered in the battery
manufacturing regulation. Truck washing at sites that have
battery cracking or secondary lead smelting will be considered
under nonferrous metals manufacturing.
From the industry surveys, 18 lead battery sites operate and
washdown trucks and have no associated secondary lead smelter.
Information on the number of trucks washed each day and water
usage for truck washing was not provided in the industry surveys.
However, water usage associated with truck wash operations was
measured on two postproposal site visits. One of these sites
uses about 150 liters of water per truck and the other sites uses
about 125 liters of water per truck. These sites had associated
secondary lead smelters. Although the measured flow values were
from operations associated with a secondary lead smelter, the
water usage data can also be used to estimate the use associated
with battery manufacturing truck wash operations. Using 150
liters of water per truck and the number of trucks washed, a
production normalized flow was calculated for each site. The
average normalized flow from truck washing at these sites is
0.014 I/kg.
Hand Wash. In order to control employee exposure to lead, hand
washing is a mandatory activity at most lead battery plants.
Sixty-three of the 65 plants which responded to the industry
survey reported that handwashing was a mandatory activity. No
flow data with regard to handwashing was reported in the dcp or
industry .surveys. However, on two post proposal site visits,
measurements of the volume of water used by plant personnel for
handwashing were taken. At both-plants, hand wash water usage
was measured as 1.5 liters per employee per wash. This value was
used to calculate an average normalized flow of 0.027 I/kg. The
following procedure was used to calculate the average normalized
flow:
o The number of production employees in required hand
wash activites at each site was obtained from the
industry survey (see Table V-4).
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o .Assuming 1.5 lites per employee per wash, and four
washes per day, a daily hand wash flow for each site
was calculated. This flow was converted to an annual
flow ,by assuming 250 days of operation per year.
o The hand wash flows from each of the 63 sites were then
added to determine the total annual hand wash flow for
the subcategory.
o This total flow was divided by the total production
associated with the 63 sites to determine the average
normalized flow. Site production data from 1982 was
used (when available) to calculate the .total
production. When 1982 production data was not
available for a particular site, dcp production data
was used.
Respirator Wash. At some battery plants, employees wear
respirators to prevent the inhalation of lead dust and acid
fumes. These respirators are usually cleaned and reused. Fifty-
one plants which responded to the industry survey indicated that
respirators are washed on-site. In addition, respirator wash
information was obtained from twelve of the seventeen sites
visited after proposal. The observed methods used for respirator
wash were varied. Washing techniques included rinsing in lab
sinks, laundering in conventional clothes washing machines, and
sanitizing in ultrasonic' machinery specifically used for
respirator washing.
As with handwashing, there was limited respirator wash flow data
available. No flow data were reported by plants in the dcp or
industry surveys. However, the respirator wash flow was measured
on two post proposal sampling visits and reported flow values
were obtained from four additional sites. The average respirator
wash water usage at these 6 sites is 4.6 liters per respirator.
The average normalized respirator wash flow (0.006 I/kg) was
calculated using the 4.6 liters per respirator value; 1982 (when
available) or dcp production data; and industry survey data shown
in Table V-4 on the number of respirators washed at each of the
fifty-one sites reporting a respirator wash. The procedure used
in calculating the average flow 'is identical to that used for
hand washing.
Laundry. Eleven sites in the subcategory reported on-site
laundering of work uniforms based on industry survey information
(see Table V-4). Work uniforms include clothing, towels and
other items distributed to each employee at the plant which are
laundered together. Laundry water usage data was obtained on two
post proposal sampling visits. The average water .usage for
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laundry at these two sites was 21.4 liters per uniform. The
average normalized laundry flow (0.109 I/kg) was calculated in
the same manner as the hand wash and respirator wash flows; the
number of uniforms laundered per day was used as well as 1982 or
dcp production data.
Process Integration
The different methods of carrying out each of the basic process
steps discussed above may be combined to produce a large number
of distinct process flow diagrams. Each plant will combine these
process elements in a pattern suited to its age, type of
product(s), degree of automation, and production volume. Fur-
ther, not all plants perform all process operations on-site. A
significant number of plants purchase pasted battery plates from
other plants. Conversely, some battery manufacturing plants
produce only battery plates and do not assemble finished
batteries.
When plates are formed by the plate manufacture, only assembly
and electrolyte addition are performed by the battery manu-
facturer. Alternatively, the plates may be sold "green"
(unformed) and subjected to either open or closed formation by
the battery manufacturer.
Examples of wet, damp and dehydrated battery manufacture and of
battery manufacture from purchased "green" and formed plates are
shown in the process flow diagrams of Figures V-5 through V-9
(pages 245-249). In many cases, single sites produce multiple
product types and therefore have process flows combining
operations of more than one of these figures.
Wastewater Characteristics
Wastewater samples obtained at lead subcategory sites provided
characterization of wastewater from the specific process
operations addressed in the preceding discussion. Process
wastewater samples were collected from five sites prior to
proposal. Following proposal process element wastewater samples
were obtained from three sites. These eight sites collectively
represent the production of both SLI and industrial batteries and
provide a broad view of the manufacturing processes in the lead
subcategory. They also embody a variety of in-process control
techniques including recirculation, low rate formation,
recirculation of treated process wastewater, and several
different wastewater treatment technologies. Sampling at these
sites provides the basis for characterizing wastewater resulting
from specific process operations and total lead battery
manufacturing process wastewater. Interpretation of sampling
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results was aided by reference to additional information obtained
from dcp/ industry surveys and by visits to twenty-nine
additional lead acid battery manufacturing sites at which process
wastewater samples were not obtained.
Characteristics of process element wastewater were determined as
a result of sampling performed both before and after proposal.
These wastewater characteristics are summarized in Table V-5
(page 178). The concentrations and pollutant loadings in this
table are in general, the average of all samples taken for the
process element. Wastewater characteristics of each process
element are. discussed below.
Leady Oxide Production. Process wastewater from leady oxide
production results from shell cooling of inadequately shrouded
ball mills. Shell cooling water from an inadequately shrouded
ball mill was sampled at Plant H. Pollutant concentrations and
loadings in this wastewater are shown in Table V-5 under leady
oxide production. The 0.5 mg/1 lead concentration in this
wastewater results from the entrainment and dissolution of lead
dust from the ball mill. This concentration coupled with the
large discharge flow of shell cooling water results in a
significant lead loading (3.42 mg/kg).
Grid Manufacture. Mold Release Formulation - No samples of mold
release formulation water were collected. As mold release
formulation cleanup water does not come in direct contact with
lead, pollutant concentrations should be minimal.
Direct Chill Casting - A sample of direct chill casting contact
cooling water was collected from a catch tank. No overflow was
observed from the catch tank and it was not due to be dumped when
the sample was taken. The pollutant concentrations and loadings
in the sample should adequately represent characteristics of
direct chill casting contact cooling water. These concentrations
and loadings are shown in Table V-5. As shown in Table V-5,
pollutant loadings in this wastewater are minimal.
Lead Rolling - A sample of spent rolling emulsion was collected
and pollutant concentrations and loadings are shown in Table V-5.
The spent rolling emulsion is contract hauled by all of the five
sites which roll lead in the subcategory.
Paste Preparation and Application. Wastewater samples were
collected at five sites (threeprior to proposal, two after
proposal). Table V-6 (page 183) shows the wastewater
characteristics of paste preparation and application area water
at these sites. .Pollutant loadings from the pasting wastewater
at these five sites are shown in Table V-7 (page 185).
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Wastewater samples at four of the sites (Plant D, Plant E, Plant
F and Plant H) were obtained from trenches, sumps or holding
tanks in which some settling of solids from washdown water had
occurred. A sample of the supernatant from an in-line settling
tank at Plant D was found to contain 10 mg/1 of suspended solids
and 37 mg/1 of lead indicating that significant reduction in
suspended material can be readily achieved by immediate settling.
The wastewater stream at Plant A was sampled as the washdown
water came off the equipment. This sample exemplifies the pasting
raw waste concentration. The Plant A sample was used to
characterize raw pasting water in Table V-5 and the other plant
samples were used to estimate the effects of settling the paste
stream.
Curing. Wastewater from curing was sampled during post proposal
visits to two plants. Curing wastewater at one plant results
from steam curing pasted plates while wastewater at another plant
is from a water injected humidity oven. Curing wastewater
characteristics and pollutant loads observed in sampling at these
two sites are summarized in Tables V-8, and V-9 (pages 187 and
188).
Closed Formation Single Fill. Wastewater samples from single
fill formation were obtained at Plant H. This site manufactures
both SLI and industrial batteries using single fill formation.
Contact cooling water is used to dissipate heat generated during
charging for both battery types. Wastewater samples from the
contact cooling wate(r streams of bo£h battery types were taken
and pollutant concentrations and loadings were averaged. The
average concentrations and loadings are presented in Table V-5.
Closed Formation Double Fill. Wastewater samples from double
fill formation were obtained at Plant A. These samples were from
a post-formation rinse of double fill batteries. Pollutant
concentrations and loadings in the rinse are shown in Tables V-10
and V-l1 (pages 189 and 190). No samples of double fill contact
cooling water were taken, however, this wastewater is well
represented by the single fill contact cooling water samples.
Closed Formation Fill and Dump (Damp Batteries). Wastewater
samplesfrom fill and dump formation were also taken at Plant A.
Pollutant concentrations and loadings are also displayed in
Tables V-10 and V-l1. This process replaced a conventional
dehydrated plate system in which it was necessary to remove the
cells and run them through a high-water-use, three stage washer.
The current discharge is associated with a spray rinse similar to
that used for double fill formation. Pollutant loadings in the
fill and dump spray rinse are somewhat higher than those in the
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double fill rinse, apparently as a result of case contamination
in dumping electrolyte from the batteries.
Damp batteries are also produced at Plant C, and wastewater from
formation is included in the total raw wastewater stream sampled
at the plant. Formation wastewater at that site results from
contact cooling of batteries during a high rate formation
process. Contact cooling water from fill and dump formation is
also represented by the single fill samples from Plant H which
were also from contact cooling wastewater.
Open Dehydrated Formation. Open dehydrated formation wastewater
was sampled at Plants D, G, and H. Pollutant concentrations and
loadings from these three sites are summarized in Tables V-12 and
V-13 (pages 191 and 192). At Plant D, wastewater from open
dehydrated formation results from a countercurrent cascade plate
rinse. Plant G also discharges wastewater from a countercurrent
cascade plate rinse and has an additional discharge associated
with periodically rinsing residual plate materials out of open
formation tanks (area washdown). These two wastestreams were
sampled separately and pollutant concentrations in the combined
open dehydrated formation wastewater at the site were calculated
from a mass balance. Open dehydrated formation wastewater at
Plant H results from a single stage plate rinse and an
electrolyte bleed stream which results from a partial draining of
each formation tank. The formation tanks are partially drained
each day to enable plant personnel to physically get to the
formed plates for removal. Both the electrolyte bleed and plate
rinse were sampled separately and pollutant concentrations in the
combined wastewater shown in Table V-12 were determined from a
mass balance.
No samples of vacuum pump seal "or ejector water were specifically
collected, however total raw wastewater samples from Plant B
includes vacuum ejector wastewater. Pollutant concentrations in
this wastewater should be minimal because the seal water does not
come in direct contact with lead.
Open Wet Formation. Wastewater from open wet formation was 'not.
specifically sampled. However, wastewater from this step is
primarily a result of spent electrolyte discharges and plate
rinsing. Pollutant concentrations in the electrolyte bleed
sample from Plant H should be similar to discharge from open wet
formation. This sample was used to determine the characteristics
of open wet formation wastewater which are shown in Table V-5.
Plate soaking. Plate soaking wastewater was not specifically
sampled. However, in terms of pollutant concentrations,
discharges from plate soaking should be similar to those from
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open wet formation because both of these process elements
discharge spent acid or electrolyte. Thus, the pollutant
concentrations shown in Table V-5 are the same as the
concentrations for open wet formation.
Battery Wash. Battery wash wastewater samples were collected
from Plants A, D, F, and G. Plants D and G run detergent battery
wash operations. Pollutant concentrations and loadings in the
detergent battery wash water at these sites are shown in Tables
V-14 and V-15 (pages 193 and 194). The detergent wash sample
from Plant G was collected from the battery wash tank. This tank
was being drained for cleaning and was nearly empty when the
sample was taken. As a result of this, the sample was
contaminated with sediment from the bottom of the tank and is not
representative of overflow detergent battery wash water. The
samples from Plant D included minimal flow contributions from
battery repair and area washdown. Although the Plant D samples
include these minimal flow contributions from battery repair and
area washdown, they are more representative of detergent battery
wash water than the sample from Plant G. Pollutant
concentrations in the Plant G sample are, in general, nearly ten
times greater than the concentrations in the Plant D samples.
These high concentrations most likely result from the sample
being contaminated with sediment from the bottom of the tank.
Therefore, pollutant concentrations and loadings shown in Table
V-5 for detergent battery washing are based on an average of the
samples from Plant D.
Plants A and F use water only battery washes. Pollutant
concentrations and loadings in the battery wash water are shown
in Tables V-16, and V-17 (pages 195 and 196). Pollutant
concentrations and loadings in Table V-5 for water only battery
washing are based on the average.
Floor Wash. Floor wash samples were collected at Plants A, F,
and H. Pollutant concentrations and loadings in these samples
are presented in Table V-18, and V-19 (pages 197 and 198). The
samples from Plants A and H represent wastewater from power floor
scrubbers. At Plant F, botti power floor scrubbers and water
hoses are used to clean floors. Wastewater from both of these
operations was sampled separately and a mass balance was
performed to determine the characteristics of combined floor wash
water at the site. Pollutant concentrations and loadings shown
in Tables V-18 and V-19 for Plant F represent the combined floor
wash water.
As mentioned above, the samples from Plants A and H represent
wastewater from power floor scrubbers. Many sites also use hoses
to wash certain floor areas; particularly formation area floors
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which may be space constrained or contain large amounts of acid
spillage. The average pollutant concentrations shown in Table V-
5 for floor wash water were calculated as follows:
o Using flow data and concentration data from the hose
water sample at Plant F, pollutant concentrations in
combined floor wash water at Plants A and H were
calculated (by a mass balance).
o The calculated concentrations from Plants A and H were
then averaged with the concentrations from Plant F.
Wet Air Pollution Control. Wet air pollution control water
samples were collected at Plants F and H. Both of these samples
were from formation area scrubber wastewater. Tables V-20 and V-
21 (pages 199 and 200) show pollutant concentrations and loadings
in these samples. These samples are used to characterize wet air
pollution control wastewater from all lead battery manufacturing
operations.
Battery Repair. Battery repair wastewater samples were collected
from Plants A and D. Pollutant concentrations and loadings are
shown in Tables V-22 and V-23 (pages 201 and 202).
Laboratory. A sample of laboratory wastewater was collected at
Plant H. Laboratory wastewater at this site consists of
instrument wash water, dumped battery electrolyte, and wet
scrubber water. The sample was collected from a sink where
laboratory instruments are washed and the battery electrolyte is
dumped. The wet scrubber wastewater was not sampled. Pollutant
concentrations in the combined laboratory waste stream (sink
water plus wet scrubber water) were determined from a mass
balance. The pollutant concentrations in the wet scrubber water
were estimated for the mass balance. The calculated pollutant
concentrations and waste loadings are shown in Table V-5.
Truck Wash. Truck wash samples were collected on sampling
visits to Plants G and H. Pollutant concentrations and loadings
in these samples are shown in Tables V-24 and V-25 (pages 203 and
204). The samples from these two sites were from truck wash
operations at battery manufacturing sites associated with
secondary lead smelters. Both sites haul scrap batteries to
their secondary lead smelters. These scrap batteries are often
damaged and leak electrolyte onto the floor of the trucks. The
wastewater from washing these trucks is therefore more
contaminated than the wastewater from washing trucks that are
used solely for battery manufacturing purposes. A review of
pollutant concentrations in the two samples shows that toxic
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pollutant concentrations in the sample from Plant G are generally
lower than those from Plant H. Therefore, Plant G truck wash
water is assumed to be more indicative of battery manufacturing
wastewater. The average pollutant concentrations and loadings
shown in Table V-5 for truck wash water are based on Plant G.
Hand Wash. Hand»wa.sh samples were collected from Plants G and
H. These samples were collected from the sinks where employees
wash their hands. Tables V-26 and V-27 (pages 205 and 206) show
pollutant concentrations and loadings in the two samples.
Respirator Wash. Respirator wash samples were collected from
Plants G and H. At Plant G, an ultrasonic cleaning machine is
used which rinses and sterilizes the respirators. Separate
samples of the rinse water and germicide (sterilizing solution)
were taken. Pollutant concentrations in the combined respirator
wash water were then determined from a mass balance. At Plant H,
respirators are washed first in an acetic acid bath followed by
double rinsing with water and final cleaning in an ultrasonic
machine. A composite sample from the acetic acid bath, rinse
water, and ultrasonic cleaning machine water (including the
germicide solution) was taken. Tables V-28 and V-29 (pages 207
and 208) show the pollutant concentrations and loadings in
respirator water at these sites.
Laundry. Laundry wastewater samples were also collected from
Plants G and H. Tables V-30 and V-31 (pages 209 and 210) show
the pollutant concentrations and pollutant loadings in this
wastewater.
Total Process Wastewater Discharge and Characteristics
Flow - Total plant discharge flows range from 0 to nearly 62,000
1/hr with a median value of 1,640 1/hr. Production normalized
discharge flows range from 0 to 78 I/kg with a median of 0.97
I/kg. Discharge flow from each plant in the subcategory is shown
in Table V-32 (page 211). Approximately 30 percent (57 plants)
of all plants in the subcategory reported zero process wastewater
discharge. Most of these zero discharge plants were plants which
only purchased plates and assembled batteries (17 plants) or
plants which produced only wet batteries and generally employed
single-fill formation (20 plants). Of the 57 plants, 26 plants
indicated that no process wastewater was generated. Seven others
indicated that wastewater was recycled and reused. The remaining
plants employ evaporation or holding ponds (5 plants), discharge
to dry wells, sumps, septic tanks or cesspools (13 plants),
contract removal of process wastewater (2 plants), disposal of
wastewater in a sanitary landfill (1 plant), or did not specify
the disposition of process wastes (3 plants). Among discharging
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plants, only twelve were direct dischargers. All other
discharging plants introduce process wastewater into POTW.
Raw Wastewater Characteristics - Total process wastewater
characteristics determined from the analysis of samples collected
at Plants Ar B, C, D, E, F, G, and H are presented in Table V-34
(page 220). Pollutant loads determined by sampling at each of
these sites are presented in Table V-35 (page 223). These data
represent the process wastewater stream discharged to treatment
at Plants A through F. The total process wastewater stream for
Plants G and H include both process wastewater discharged to
treatment and process wastewater that is not discharged to
treatment. Minimal amounts of process wastewater resulting from
personal hygiene activities bypass treatment at Plants A through
F. However, personal hygiene streams were not sampled at these
six sites and therefore were not included in the total process
waste stream. Pollutant loadings from personal hygiene
wastewater are minimal (as shown in Tables V-27, V-29, and V-31)
and therefore the concentrations and loadings shown in Tables V-
34, and V-35 for these six sites adequately represent the total
process waste stream. Wastewater streams which are completely
recycled such as pasting wastewater are not included in the total
waste stream.
Large differences in wastewater volume and in pollutant
concentrations among these eight sites are evident. The
differences may be understood by examining the manufacturing
process and wastewater management practices at each site.
Plant A manufactures wet and damp batteries and practices
extensive in-process control of wastewater. Pasting equipment
and area washdown at this plant is treated in a multistage
settling system and is totally reused. The clarifier supernatant
from this system is reused in equipment and area washing, and the
settled lead oxide solids are returned for use in pasting.
Batteries are formed at this site using the double-fill, double-
charge technique, filling operations are performed with equipment
designed to avoid electrolyte spillage and overfilling; and
formation is accomplished without the use of contact cooling
water. Wastewater associated with formation is limited to a
spray rinse of the battery case after the final acid fill. Wet
charged batteries are boost charged one or more times before
shipment and given a final wash just before they are shipped.
Damp batteries at this site are initially formed in the same
manner as wet batteries. The second acid fill, however, is also
dumped to reuse, and the battery is sealed and spray rinsed.
These damp batteries are given the same final wash prior to
shipment as the wet charged units. A small volume of additional
process wastewater at this site results from cleanup operations
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in a battery repair area. The total wastewater from this plant,
which is represented in Tables V-34 and V-35, includes wastewater
flowing to wastewater treatment, the battery rinses and wash
water, and the repair area cleanup wastewater, but does not
include the pasting wastewater since this stream is segregated
and totally recycled. The low pollutant concentrations and
loadings shown in the table reflect the efficiency of the in-
process controls employed by this plant. Significantly, the
wastewater treatment system includes an evaporation pond allowing
the achivement of zero pollutant discharge from this plant.
Plant B manufactures a high percentage of dehydrated plate
batteries but also practices significant in-process water use
control. Pasting equipment and area wash water is recirculated
using a system similar to that described at Plant A. Wet
batteries are produced in a single-fill formation process, which
is accomplished using low rate charging to eliminate process
contact cooling water, and filling techniques which minimize
battery case contamination. Only occasional discharges result
from the filling area and battery case washing. Open-case
formation and plate dehydration operations generate most of the
process wastewater. The wastewater sources are plate rinsing,
fume scrubbers, formation area washdown, and a vacuum ejector
used in dehydrating the formed, rinsed plates. Partially treated
wastewater is recycled from the wastewater treatment system for
use in the wet scrubbers, area washdown, and rinsing of formed
plates; but recycled water is not used in the vacuum ejectors.
As a result of the recycle practiced, the volume of the final
effluent from this plant is only 46 percent of the raw wastewater
volume shown in the table or approximately 4.0 I/kg.
The raw wastewater characterized in the table includes process
wastewater from open formation and plate dehydration, closed
formation processes, and contaminated wastewater resulting from a
cooling jacket leak on a ball mill used in producing leady oxide,
but it does not include pasting wastewater which is totally
recycled. The effect of plate rinsing operations in the open
formation process is evident in the elevated lead concentrations
and loadings at this plant. The relatively high production
normalized flow arises to a great extent from the use of large
volumes of water in ejectors to aid vacuum drying of the rinsed
plates.
Plant C produces wet and damp SLI batteries and practices only
limited in-process water use control. Pasting area wash water is
collected in a sump and pumped to central wastewater treatment at
the plant. Aside from limited settling in the sump, this
wastewater stream is neither recycled nor treated separately
prior to combining with other process wastewater streams. Wet
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and damp batteries both undergo an initial high rate formation
process in which contact cooling water is sprayed on the battery
cases and discharged to wastewater treatment. The wet batteries
are subsequently dumped (the acid is reused) and refilled with
stronger acid, boost charged, and topped off to ensure the
correct electrolyte level. Damp batteries have electrolyte
dumped after formation and are centrifuged to insure complete
electrolyte removal. Wastewater from the centrifuge, including
some formation electrolyte, also flows to wastewater treatment.
Both the wet charged and damp batteries are washed, labeled, and
tested prior to shipment. Wastewater from battery washing also
flows to treatment.
The combined raw wastewater at this plant was sampled as it
entered wastewater treatment and includes all sources discussed
above. The pasting wastewater is included in total process
wastewater for this plant. This, together with differences in
water conservation practices, appears to account for the
differences observed in pollutant concentrations and pollutant
loads between this plant and Plant A. Lead loadings, for
example, are significantly higher at Plant C as a result of the
introduction of pasting wastewater and wastewater from battery
centrifuges into wastewater treatment, but raw wastewater
concentrations are low due to the dilution afforded by the much
higher wastewater volume at this plant (approximately 8 times
greater production normalized flow).
Plant D manufactures both SLI and industrial batteries and
employs closed and open formation processes. Several in-process
water use control techniques at this plant resulted in the
generation of a relatively low volume of process wastewater.
Pasting area and equipment wash water is not recycled at this
plant, but is separately treated by settling before introduction
into the wastewater treatment system. Closed formation of SLI
batteries is accomplished in a double-fill process without the
use of contact cooling water. The final acid fill after
formation is followed by a battery rinse yielding a process
wastewater discharge. No industrial batteries (open formation
process) were formed during sampling at this plant. Open
formation is followed by a two-stage countercurrent cascade rinse
of the formed plates. They are dried in an oven without the use
of ejector or vacuum pump seal water. Finished batteries are
given a final wash prior to packaging and shipment. Additional
sources of process wastewater at this site include assembly area
washdown, battery repair operations, and wastewater from an on-
site laboratory.
Plant E manufactures only wet industrial batteries. In-process
water use control techniques at this site reduce the ultimate
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discharge volume nearly to zero. Formation is accomplished in a
single fill process using low rate charging. No contact cooling
water is used and batteries are not washed. Process wastewater
at this plant results only from washing the pasting equipment and
floor areas. This wastewater is treated and recycled for use in
washing the pasting area floors. Equipment is washed with
deionized water. This practice results in a gradual accumulation
of wastewater in the recycle system and necessitates occasional
contract removal of some wastewater. The total process waste-
water characterized in Tables V-34 and V-35 includes the waste-
water from pasting equipment and area washdown. The sample used
to characterize this wastewater was obtained from a wastewater
collection pit in which settling of paste particles occurred.
Therefore lowered lead and TSS concentrations were found. The
total process wastewater characteristics presented in Tables V-34
and V-35 were calculated from analyses of all of the individual
wastewater streams described above, including the pasting waste-
water before settling.
Plant F manufactures wet SLI batteries. Pasting equipment and
area washdown water is collected in a trench network, drains to a
sump, and is pumped to wastewater treatment. Aside from limited
settling in the trench network and sump, this wastewater is
neither recycled nor treated separately prior to combining with
other process wastewater streams. Wastewater is also generated
from curing which goes to wastewater treatment. Batteries are
formed at this site using the single fill, single charge
technique. A controlled charging procedure is used which
eliminates the need to use contact cooling water to dissipate
heat, and results in a completely formed battery in approximately
one day. The controlled charging procedure allows for a break in
the middle of formation which allows the batteries to cool.
Fumes from the formation area are vented to wet air pollution
control scrubbers. The scrubbers operate without water except
for periodic washdown of the mesh filters where acid fumes
coalesce.
At Plant F, all batteries pass .through a water only battery wash
after formation. The battery wash water is recirculated through
a small tank; an overflow stream from this tank is routed to
wastewater treatment. The overflow stream is continuously
discharged even when no batteries are being washed. Additional
process wastewater discharges at this site result from floor and
hand washing (floor washing is accomplished with both power floor
scrubbers and hoses), grid manufacturing, and laboratory testing.
All process wastewater is discharged to wastewater treatment
except one process stream which is discharged directly to the
sanitary sewer, and another process stream which is contract
hauled. Pollutant concentrations and loadings for total battery
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manufacturing process wastewater at this site are presented in
Tables V-34 and V-35.
These concentrations and loadings represent all battery
manufacturing process wastewater which is discharged to treatment
and includes the stream which is contract hauled. Hand wash
wastewater was not sampled at this site and is not included in
the total waste stream; however the contribution to the total
process waste stream from hand washing is minimal. The high
pollutant loadings in the total process waste stream are
primarily due to the discharge of pasting equipment and area
washdown water. This single wastewater source accounts for over
75% of the lead loading in the total process waste stream.
Plant G manufactures both SLI and industrial batteries and
employs closed and open formation processes. Pasting and area
washdown wastewater, which is not recycled at this site, along
with curing wastewater is discharged to treatment. Several in-
plant water use control techniques are practiced at this site.
For single fill formation, a controlled charging procedure is
used which eliminates the need for contact cooling water. The
batteries, which are charged in racks, are charged slowly for a
few hours initially; the charging rate is then increased for
several hours and then decreased for several more hours. Overall
formation time is about three days. A wet scrubber is used to
remove fumes generated during the single fill charging procedure.
Wet scrubber water is , treated with caustic and recycled. No
blowdown from the scrubber system was observed during sampling.
Both wet and dehydrated plate industrial and SLI batteries are
produced by open formation. Two stage countercurrent cascade
rinse operations are used to rinse plates prior to dehydration.
These rinse tanks are agitated to ensure proper mixing and lower
water usage. In the production of dehydrated SLI batteries,
treated water from the wastewater treatment system is used for
the countercurrent plate rinse. Thus, this plate rinse is
ultimately a zero discharge operation. Both SLI and industrial
plates are dehydrated following plate rinsing without the use of
vacuum pump seal or ejector water.
Pollutant concentrations and loadings in the total process waste
stream at this site are presented in Tables V-34, and V-35. The
concentrations and loadings in this waste stream represent both
wastewater discharged to treatment and wastewater from handwash,
respirator wash, laundry, truck wash and laboratory testing
operations which is not discharged to the central treatment
system. Pollutant loadings in the total raw waste stream are
comparable to those from Plant D, which also produces dehydrated
batteries. These loadings, although fairly low, could be reduced
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further if additional in-plant water use control practices such
as recycle of pasting area cleanup water were implemented.
Plant H manufactures both SLI and industrial batteries and
employs closed and open formation processes. Leady oxide is
produced by both the Barton and ball mill processes. In the ball
mill process/ a. large volume of process wastewater is produced
from shell cooling o'f an inadequately shrouded ball mill. Three
pasting operations are performed onsite, two of which discharge
equipment and area washdown water after limited settling. In the
third pasting operation, the equipment and area washdown water is
collected, settled, and reused in pasting area washdown. There
were plans to install a recycle system for one of the discharging.
pasting operations but this system was only partially implemented
at the time of sampling. Both SLI and industrial batteries are
produced in single fill formation operations which use contact
cooling water to dissipate heat generated during high rate
formation. Two different cooling configurations are used for the
single fill operations. In one operation, a once-through cooling
configuration is used which results in a large discharge of
process wastewater. In the second single fill operation, the
cooling water discharge is significantly reduced by recycle
through a water softening system. Dehydrated plate batteries are
also produced at this site. Wastewater discharge from the
dehydrated plate operation results from a single stage plate
rinse and bleeding electrolyte from the formation tanks. No
vacuum pump seal or ejector water is used in plate dehydration.
Additional battery manufacturing process wastewater sources at
this site result from wet air pollution control, hand and floor
washing, respirator washing, and on-site laundry facilities.
Tables V-34 and V-35 present pollutant concentrations and
loadings in the total battery manufacturing process waste stream.
These concentrations and loadings represent all battery
manufacturing process wastewater discharged at this site. As
shown in Table V-35, pollutant loadings are fairly high due to
inefficient water use in a number of processes.
A statistical summary of the total raw wastewater characteristics
observed at these sites is presented in Table V-36 (page 226).
This table shows the range, mean, and median concentrations
observed for each pollutant included in verification analyses.
Corresponding pollutant loading data are presented in Table V-37
(page 227).
Wastewater Treatment Practices and Effluent Data Analysis
Pep and Industry Survey Data - Plants in the lead subcategory
employ a variety of end-of-pipe treatment technologies shown in
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Table V-33 and in-process control techniques, and they achieve
widely varying effluent quality. End-of-pipe treatment practices
employed include pH adjustment, chemical precipitation, settling
using a variety of devices, filtration, flotation, and reverse
osmosis. In-process water use control techniques include
segregation and treatment or recycle of specific wastewater
streams arid process modifications to eliminate points of water
use and discharge. Most plants in the subcategory, which produce
a process wastewater discharge, discharge to POTW. Dcp and
industry survey response showed some significant differences
between plants discharging to POTW and direct dischargers both in
terms of treatment practices and effluent performance achieved.
Direct dischargers generally provide more extensive wastewater
treatment and control than plants discharging to POTW. Where
similar treatment equipment is in place, direct dischargers
generally operate it more effectively and achieve better effluent
quality.
The most frequently reported end-of-pipe treatment systems in
this subcategory provided pH adjustment and removal of solids.
Fifty-three plants reported the use of pH adjustment and settling
or pH adjustment and filtration for solids removal. These
filtration units generally serve as primary solids removal —
they do not function as polishing filters following settling
which are usually designed to achieve very low effluent pollutant
concentrations.
Effluent quality data provided in dcp for plants practicing pH
adjustment and settling are presented in Table V-38 (page 228).
While the dcp did not in general provide sufficient data to allow
meaningful evaluation of treatment system design and operation
parameters, some characteristics of the effluent data themselves
provide indications of the quality of treatment provided and of
the probable sources of the variability shown. First, the
limited effluent pH data provided in the dcp indicate that few
discharges are at the values (pH 8.8-9.3) appropriate for
efficient removal of lead by precipitation. In the data from
those plants reporting both lead and pH values for the effluent,
it may be observed that those plants reporting higher pH values
achieved lower effluent lead concentrations. Second, effluent
TSS values shown in Table V-38 clearly indicate that the
sedimentation systems employed by some plants are inadequate in
design or operation. Finally, plants which introduce their
wastewater into POTW produced effluents ranging from 0.5 mg/1 to
7.5 mg/1 in lead concentration with an average of 2.1 mg/1.
Plants discharging to surface waters and also practicing pH
adjustment and settling produced effluents ranging from 0.187 to
0.4 mg/1 with an average of 0.28 mg/1. The great difference in
effluent performance between direct and indirect dischargers
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corresponds to differences in the severity of regulations
presently applied to these two groups of plants. This difference
indicates that the variations in the data reflect variations in
treatment design and operating practice rather than difference in
attainable levels of pollutant reduction at plants in this
subcategory.
Effluent quality data provided in industry surveys for plants
practicing pH adjustment and settling are presented in Table V-39
(page 229). In general, the data provided in the industry
surveys corresponds closely with that provided in dcp. Less than
one third of the plants reported an effluent pH at the values
appropriate for efficient removal of lead by precipitation. The
effluent TSS values are also high indicating inadequate operation
of the settling device. Plants which introduce their wastewater
into POTW reported effluent lead concentrations ranging from 0.1
mg/1 to 6.0 mg/1; with an average of 1.8 mg/1. Plants
discharging to surface waters reported effluent lead
concentrations ranging from 0.09 mg/1 to 0.47 mg/1, with an
average of 0.23 mg/1. Effluent quality data provided in the
industry surveys support the conclusion drawn from the dcp data;
that variations in data reflect variations in treatment design
and operation rather than differences in attainable levels.
Clearly, direct dischargers are more carefully operating
treatment systems and are obtaining better lead effluent
concentrations than indirect dischargers using the same treatment
technologies.
Table V-40 {page 230) presents effluent quality data from dcp for
plants practicing pH adjustment and filtration. In general, the
indicated effluent pollutant concentrations are lower than those
shown from pH adjustment and settling, and the variability in the
data is less marked. The effluent data from these systems also
show lower lead concentrations achieved by plants practicing
direct discharge.
Effluent quality data provided in industry surveys for plants
practicing pH adjustment and filtration are presented in Table V-
41 (page 231). As was true for the dcp data, effluent lead
concentrations for plants practicing pH adjustment and filtration
are generally lower than plants practicing pH adjustment and
settling and the data exhibits less variability. Plants which
discharge wastewater directly reported lower effluent lead
concentrations (average 0.27 mg/1) than those which discharge to
a POTW (average 0.93 mg/1).
In the dcp, twenty-two plants reported the introduction of
process wastewater into POTW after pH adjustment without the
removal of suspended solids. Effluent quality data were provided
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by eleven of these indirectly discharging plants as shown in
Table V-42 (page 232). This table also shows effluent data from
one plant which reported process wastewater discharge to a POTW
without treatment. Effluent lead concentrations reported in the
dcp range from 1.0 mg/1 to 29.8 mg/1 and average 10 mg/1.
Industry survey effluent quality data for plants practicing only
pH adjustment before discharge are presented in Table V-43 (page
233). Eighteen indirect dischargers reported the use of pH
adjustment only with none of these plants reporting operation in
the desired pH range of 8.8 to 9.3. Effluent lead concentrations
range from 1.25 mg/1 to 20 mg/1, with an average 5.3 mg/1. The
effluent concentrations reported for these indirect dischargers
practicing pH adjustment only are comparable to the effluent
concentrations reported by indirect dischargers who practice pH
adjustment and settling. This clearly indicates that settling
devices are being improperly operated and controlled at lead
battery plants.
Several plants provided data in dcp indicating the use of
wastewater treatment systems other than those discussed above.
These included sulfide precipitation, flotation separation, and
reverse osmosis. One plant practicing chemical precipitation and
flotation separation of the precipitate reported an effluent lead
concentration of 0.1 mg/1.
While most plants specified end-of-pipe treatment in their dcp
responses, the in-process controls were often not clearly shown.
In many dcp in-process controls were deduced from process line
descriptions and the presence of wastewater sources similar to
those of plants which were visited for on-site data collection.
As a result, the extent to which techniques such as low-rate
charging without contact cooling water are used, cannot be
defined from the dcp. One in-process control technique which
could be identified in many dcp was segregation of process
wastewater from pasting area and equipment washdown and
subsequent settling and reuse of this wastewater stream.
Approximately 30 percent of the plants reporting wastewater
discharges indicated this practice. Those plants using this in-
process technique are identified in Tables V-38, V-40 and V-42.
The data in Tables V-38 and V-40 do not show significantly lower
effluent lead concentrations from plants recycling pasting
wastewater although raw wastewater concentrations and pollutant
loads are significantly reduced by this practice as demonstrated
by the data in Table V-42. This further substantiates the
observation that- effluent quality at existing lead subcategory
plants is primarily determined by process flow practices,
treatment system design, and operating parameters.
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Additional in-process control techniques which are indicated in
the dcp include: recirculation of wet scrubber discharge
streams; use of multistage or countercurrent rinses after open
formation; reduction or elimination of electrolyte spillage
during battery fill operations or dry cleanup of spilled
electrolyte; low-rate charging of assembled batteries without the
use of contact cooling water; and elimination or recirculation of
vacuum pump seal water or vacuum ejector streams in plate drying
operations. Recirculation of wet scrubber discharge streams is
specifically reported in some dcp and is presumed to exist at
other plants since many plants report no scrubber discharges
although acid mist and fume problems are common to most
manufacturers. Multistage or countercurrent plate rinses are
identified by approximately 25 percent of those plants which
practiced dehydrated plate manufacture and supplied process
diagrams in their dcp. The production normalized flows resulting
from these rinses are usually not significantly lower than those
resulting from single stage or unspecified rinses. Since the
spillage of electrolyte on battery cases necessitates removal of
the spilled acid prior to shipment to allow safe handling of the
battery, it may be concluded that where wet batteries are shipped
and battery wash discharges are not reported, spillage has been
eliminated, or that any spillage which has occurred has been
neutralized and cleaned up by dry techniques. Both of these
conditions have been observed, and a small but significant number
of battery manufacturers reported shipment of wet batteries and
provided complete process diagrams which did not show battery
wash wastewater production. The use of low-rate charging is
indicated at a number of battery manufacturing plants which did
not indicate contact cooling wastewater from wet-charge formation
processes. Finally, approximately 85 percent of the plants which
supplied complete process diagrams describing open case formation
and subsequent rinsing of the formed plates prior to assembly
into dehydrated plate batteries showed no wastewater from pump
seals or vacuum ejectors on plate drying and no other process
wastewater sources associated with plate drying. It is concluded
that these plants either achieve satisfactory plate drying
without the use of seal or ejector water or recirculate water
used for these purposes.
Visited and Sampled Plants - Wastewater treatment system effluent
was sampled at eight visited battery manufacturing sites (three
visited before proposal and five visited after proposal). At two
sites, Plants G and H, wastewater from on-site secondary lead
smelters is combined with battery manufacturing wastewater prior
to treatment. Pollutant concentrations in the combined influent
to wastewater treatment at these sites are shown in Table V-44.
At Plant F, wastewater is held in equalization ponds with several
days retention time prior to treatment. These ponds are not well
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agitated and thus some settling out of solids occurs. Pollutant
concentrations in the effluent from these ponds represent the
influent to wastewater treatment at Plant F. These
concentrations have also been included in Table V-44 to provide a
description of the influent to treatment at Plant F. Pollutant
concentrations in the treated effluent at each site are presented
in Table V-45. These sites all use wastewater treatment systems
based on chemical precipitation and solids removal but have
implemented a number of different solids removal techniques.
Plant B uses a tubular cloth filter from which solids are
continuously removed by the flow of the wastewater which becomes
progressively more concentrated as clarified water permeates
through the filter. This system was reported to be highly
effective in the dcp data from this site. During sampling,
however, excessive solids levels had been allowed to build up in
the system and solids were carried through the filter during
surge flows. As a result, effluent characteristics determined in
sampling do not reflect effective treatment.
Plant C employs a clarifier followed by a polishing lagoon for
wastewater treatment. As the data show, this system was
operating normally during sampling.
At Plant D, wastewater is treated by pH adjustment and subsequent
filtration through a diatomaceous earth pre-coat filter press.
During the plant visit, company personnel acknowledged that the
plant production and wastewater flow rates had increased and that
the system was therefore overloaded. This condition is reflected
in observed effluent performance which was considerably worse
than that exhibited in historical data from the plant.
plant F also employs pH adjustment (with caustic) and subsequent
filtration through a diatomaceous earth pre-coat filter press.
It was observed during the visit to this site that the
precipitation pH was 7.5 standards units. The best overall
removal of toxic metals occurs when the precipitation pH is in
the range of 8.8 to 9.3 standards units. It would appear that
plant personnel have elected to operate at this low pH not to
optimize toxic metals removals but rather to minimize the
alkaline load discharged to the POTW. Despite these practices,
however, lead was not detected in the sampled effluent from this
site. Industry survey data from this site indicate an average
lead effluent of 0.25 mg/1. This high effluent concentration is
most likely caused by the low precipitation pH.
Plant G employs a clarifier for solids removal. This site does
not practice sludge recycle to the clarifier influent or mix
tank, a practice that is widespread in the'battery manufacturing
161
-------
category as well as many others. Recycle of a portion of the
sludge is critical in floe formation in the clarifier. This
site's failure to do so limits its ability to effectively remove
toxic metals. In addition, this site was adding polyphosphates
to chelate calcium and to prevent it from precipitating in
treated wastewater which was reused. The addition of this
chemical or any other .chelating agent impedes the precipitation
and removals of metals including lead. This explains the high
lead concentrations in the effluent from two of the sampling
days.
Plant H uses two conventional clarifiers and a lamella separator
followed by a polishing lagoon to remove precipitated solids from
wastewater. As the data show, this system was operating normally
during the sampling period.
At Plant I, wastewater is treated by pH adjustment,
clarification, and filtration. Two operational problems were
observed at this site. First large solids were observed exiting
the clarifier. This is generally an indication of short
circuiting or the need of a coagulant aid (such as iron salts) to
enhance the settling properties of the precipitants. Second, the
pH of the effluent from the clarifier is lowered by the addition
of sulfuric acid prior to being introduced to the filter. This
results in redissolution of toxic metals. Despite these
operational problems, lead was not detected in the effluent from
this site. However, industry survey data indicate the average
lead concentration in the effluent from this site is 0.697 mg/1.
This high effluent value is a direct result of the operational
problems discussed above.
Plant J uses a clarifier with tube settlers to remove
precipitated solids. During the visit to this site, the
precipitation pH was observed to be 7.5. As discussed
previously, this is below the expected range for solids removal.
The tube settler used for primary solids removal was observed to
be laden with solids. This impedes the manner in which the tube
settler removes solids. In addition, the clarifier at this site
is designed for continuous operation however it was operated
intermittently during the visit.
Data from Plants B and D illustrate the importance of pH as an
operating parameter for the removal of lead by chemical
precipitation. Both Plants B and D (as well as Plant F and I)
were observed to provide treatment at pH values considerably
lower than in desirable for lead precipitation, a condition
reflected in the poor effluent performance observed by sampling.
This effect is particularly evident, on day 1 at Plant D when the
effluent pH was observed to be as low as 6, and a comparison of
162
-------
effluent lead and TSS values shows clearly that the effluent
contained considerable concentrations of dissolved lead.
After evaluating all dcp and plant visit effluent data the
conclusion is made that although plants which discharge have
treatment equipment in-place, the operation and maintenance of
most of these systems is inadequate for treating lead subcategory
pollutants.
163
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQOES
Pollutants
Screening Analysis
Methodology
Verification Analysis
Methodology
1.
2.
3.
4.
5.
6,
7.
8.
9.
10.
11.
42.
13.
1ft.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride
(fetrachloromethane)
Chlorobenzene
1,2,1 -Trichlorobenzene
Hexachlorobenzene
1 , 2-Dichloroethane
1,1,1 -Irichloroethane
Hexachl or oe thane
1,1 -Dichloroe thane
1,1 ,2-lrichloroethane
1,1,2, 2-Tetrachloroe thane
Chloroethane
Bis (Chloromethyl) Ither
Bis (2-Chloroethyl) Ether
2-Chloroethyl Vinyl Ether (Mixed)
2-Ctoloronaphthalene
2,U, 6-Trichlorophenol
Parachlorometa Cresol
Chloroform (Trichloromethane)
2-Chlorophenol
1 , 2-Dichlorobenzene
1 , 3-Dichlorobenzene
1 , ft-Dichlorobenzene
3,3-Dichlorobenzidine
1,1 -Dichloroethylene
1,2 -Trana-Dichloroethylene
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP VP: L-L Extract; GC, BCD
SP VP: L-L Extract; 3C, BCD
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP VP: L-L Extract; SC, ECD
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Screening Analysis Verification Analysis
Pollutants Methodology Methodology
31. 2,4-Da.chlorophenol SP
32. 1,2-Dichloropropane SP
33. 1,2-Dichloropropylene SP
(1»2-Dichloropropene)
34. 2,4-Dimethylphenol SP VP: GC - FID
35. 2,4-Dinitrotoluene SP
36. 2,6-Dinitrotoluene SP
37. 1,2-Diphenylhydrazine SP
38. Ethylbenzene SP
39. Fluoranthene SP SP
40. 4-Chlorophenyl Phenyl Ether SP
41. 4-Bxomophenyl Phenyl Ether SP
42. Bis(2-Chloroisopropyl) Ether SP
43. Bis(2-Chloroethoxy) Methane SP
44. Methylene Chloride (Dichloromethane) SP
45. Methyl Chloride (Chloromethane SP
46. Methyl Bromide (Bromomethane) SP
17. Bromoform {Tribrcmomethane) SP
48. Dichlorobromomethane SP
49. Trichlorofluoromethane SP
50. Dichlorodifluoromethane SP
51. chlorodibromomethane SP
52. Hexachlorobutadiene SP
53. Hexachlorocyclopentadiene SP
54. Isophorone SP SP
55. Naphthalene SP SP
56. Nitrobenzene SP
57. 2-Nitrophenol SP
58. 4-Nitrophenol SP
59. 2,4-Dinitrophenol SP
60. 4,6-Dinitro-O-Cresol SP
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Screening Analysis Verification Analysis
Pollutants Methodology Methodology
61. N-Nitrosodimethylamine SP
62. N-Nitrosodiphenylamine SP
63. N-Nitrosodi-N-Propylamine SP
64. Pentachlorophenol SP
65. Phenol SP VP: GC, ID
66. Bis(2-Ethylhexyl) Phthalate SP SP
67. Butyl Benzyl Phthalate SP SP
68. Di-N-Butyl Phthalate SP SP
69. Di-N-Octyl Phthalate SP SP
70. Diethyl Phthalate SP SP
71.. Dimethyl Phthalate SP . SP
72. 1,2-Benzanthracene SP SP
(Benzo (a) Anthracene)
73. Benzo (a) Pyrene (3,4-Benzo-Pyrene) SP SP
74. 3,4-Benzofluoranthene SP SP
75. 11,12-Benzofluoranthene SP SP
(Benzo (k) Fluoranthene}
76. Chrysene SP SP
77. Acenaphthylene SP SP
78. Anthracene SP SP
79. 1,12-Benzoperylene SP SP
{Benzo (qhi)-Perylene)
80. Fluorene SP SP
81. Phenanthrene SP SP
82. 1,2,5,6-Dibenzathracene SP SP
(Dibenzo (a,hj Anthracene)
83. Indeno (1,2,3-cd) Pyrene SP SP
(s,3-0-Phenylene Pyrene)
84. Pyrene SP^ SP
85. Tetrachloroethylene SP
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Pollutants
Screening Analysis
Methodology
Verification Analysis
Methodology
O*
-4
86. Toluene SP
87. Trichloroethylene SP
88. Vinyl Chloride (Chloroethylene) SP
89. Aldrin SP
90. Dieldrin SP
91. chlordane SP
(Technical Mixture and Metabolites)
92. 4.4-DD1 SP
93. 4,4-DDE (p,p'-DDX) SP
94. 4,4-DDD (p,p'-i:DE) SP
95. Alpha-Endosulfan SP
96. Beta-Endosulfan SP
97. Endosulfan Sulfate SP
98. Endrin SP
99. Endrin Aldehyde • SP
100. Heptachlor SP
101. Heptachlor Epoxide SP
(BHC-Hexachloroeyclohescane)
102. Alpha-BHC SP
103. Beta-BHC SP
104. Gamma-BBC (Lindane) SP
105. Delta-BHC SP
(iCB-Polychlorinated Biphenyls)
106. PCB-1242 (Aroclor 1242) SP
107. PCB-125<» (Aroclor 1254) SP
108. PCB-1221 (Aroclor 1221) SP
109. PCB-1232 (Aroclor 1232) SP
110. PCB-1248 (Aroclor 1248) SP
111. PCB-1260 (Aroclor 1260) SP
112. PCB-1016 (Aroclor 1016) SP
113. Toxaphene SP
114. Antimony SP
115. Arsenic SP
VP: L-L Extract; SC, FID
VP: L-L EKtract; SC, BCD
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Pollutants
Screening Analysis
Methodology
Verification Analysis
Methodology
ON
00
116. Asbestos
117. Beryllium
118. Cadmium
119. Chromium
Hexavalent Chromium
120. Copper
121. Cyanide 40CFR
Cyanide Amenable to Chlorination
122. Lead
123. Mercury
124. Nickel
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,4,8-Tetrachlorodibenzo-
P-Dioxin (TCDD)
Aluminum
Fluorides
Iron
Manqanese
Phenols
Phosphorous Total
Oil & Grease
TSS
IDS
pH Minimum
'pH Maximum
Temperature
I CAP
I CAP
I CAP
I CAP
136: Dist./Col. Mea.
I CAP
SP
SP
SP
SP
SP
ICAP
SP
4QCFR 136:
40CFR 136:
40CFR 136:
40CFR 136:
40CFR 136:
AA
AA
Colorimetric
AA
Dist./Col. Mea.
Mea.
4QCFR 136: Dist./Col.
4QCFR 136:AA
40CFR 136:AA
40CFR 136:AA
40CFR 136:AA
Dist./I.E.
4QCFR 136:AA
»OCFR 136:AA
40CFR 136
SM: Dig/SnC1
10CFR 136: Dist./I.E.
40CFR 136
40CFR 136
Electrochemlca1
Electrochemical
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Notes
HOCFR 136: Code of Federal Regulations, Title 40, Part 136.
SP - Samplinq_andAnalysis Procedures for Screening o§Industrial Efflaents for Priority ggllutants,
Bis. EPA, March, 1977, Revised April, Iff?.
VI> ~ Analfj:ical_Methgdj^|or the Verification Phase of BAT Review,
U.S. IPA, June, 1977.
SM - Standard Methods, 14th Edition.
ICAP - Inductively Coupled Argon Plasma.
AA - Atomic Absorption.
L-L Extract; GC, BCD - Liquid-Liquid Extraction/Gas Chromatography, Electron Capture Detection.
Diq/SnC1» - Digestion/Stannous Chloride.
Filt./Grav. - Filtration/Gravimetric
Freon Ext. - Freon Extraction
Dist./Col. Mea. - Distillation/pyridine pyrazolone colorimetric
Dist./l.l. - Distillation/Ion Electrode
GC-FID - Gas Chromatography - Flame lonizatian Detection.
SIE - Selective Ion Electrode
-------
TABLE tf-2
SCREENING ANALYSIS RESULTS
LEW)
DCP Data
KTBP, BTBP
1 . Acenaphthene
2. Aero lain
3, Aery Ion itr He
4 . Benzene
5. Benzidiae
6. Carbon letrachloride
7. Chlorobenzene
8. 1,2,1 Trichlorobenzene
9. Hexachlorobenzene
10, 1,2 Dichloroethane 0,1
11. 1,1,1 Trichloroethane 0,5
12. Hexachloroethane
13. 1,1 Dichloroethane
14. 1,1,2 Irichloroethane
15. 1,1,2,2 Tetrachloroethane
16. Chloioethane
17. Eis Chloromethyl Ether
18. Bis 2-Chloroethyl Ether
19. 2-Chloroethyl Vinyl Ether
20. 2-Chloronaphthalene
21. 2,4,6 trichlorophenol
22. Parachlorometacresol
23. Chloroform
24. 2 Chlorophenol
25. 1,2 Dichlorobenzene
26. "1,3 Dichlorobenzene
27. 1,4 Dichlorobenzene
28. 3,3 Dichlorobenzidine
29. 1,1 Dichlcroethylene
30, 1,2 Irans-Dichloroethylene
31. 2,4 Dichlorophenol
32. 1,2 Dichloropropane
33. 1,2 Dichloropropylene
34. 2,4 Diirethylphenol
35. 2,4 Dir.itrotoluene .
36. 2,6 Dir.itrotoluene
37. 1,2 Diphenylhydrazine
38. Ethylbenzene
39. Fluoranthene
40. « Chlorophenyl Phenyl Ether
41. H Brcmophenyl Phenyl Ether
42. Bis {2 Chloroisopropyl) Ether
43. Bis (2 Chloroethoxy) Methane
44. Methylene Chloride 6,0
45. Methyl Chloride
46. Methyl Bromide
SUBCATE30RX
*
Plant
Influent
Cone.
raci/1 _ _.
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.06
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.017
ND
ND
Raw •
Haste
Cone.
m
-------
TABLE V-2
SCREENING ANALYSIS RESULTS
i»7.
48.
49.
50.
51.
52.
53.
5tt.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
-70.
71.
'72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
LEAD
DCP Data
KTBP, BTBP
Brcrcoform
Dichlorobromome thane
Trichloiof luoromethane
Dichlorodifluoromethane 0,1
Chlorodibromomethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorcne
Naphthalene 0,6
Nitrobenzene
2 N it ro phenol
4 Nitrophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Nitrcsodimethylamine
B-Nit rosed iphenylamine
N-Nitrasodi-N-propylamine
Pentachlorophenol
Phenol
Bis (2-Ethylhexyl) Phthalate
Butyl Eenzyl Phthalate
Di-N-butyl Phthalate
Di-N-octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthracene
Benzo (A) Pyrene
3,4 Benzofluoranthene
11, 12-Benzofluoranthene
Chrysene
Acena ph thy lene
Anthracene
1,1 2-Benzoperylene
Fluorene
Phenanthrene
1,2,5,6 Dibenzanthracene
Indenopyrene
Pyrene
letrachloroethylene
Toluene 0,1
Trichloroethylene
Vinyl Chloride
Aldrin
Cieldrin
Chlordane
4,4 DDT
SUBCATEGORY
Plant
Influent
Cone.
mqf/1
ND
*
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
*
ND
ND
ND
ND
ND
Raw
waste
Cone.
mcj/1
ND
*
ND
ND
*
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
0.135
0.017
*
0. 140
ND
ND
*
*
*
*
*
ND
0.032
ND
*
0.032
ND
ND
*
ND
*
*
ND
ND
ND
ND
ND
Effluent
Cone .
mg/1
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
HD
*
0.016
ND
*
ND
ND
ND
*
ND
ND
ND
*
ND
0.007
ND
ND
0.007
ND
ND
*
ND
*
»
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
Nft.
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N&
NA
*
*
ND
NA
NA
NA
NA
-------
TABLE V-2
SCHEEHING ANALYSIS HESULTS
LEAD SUBCATEGORY
DCP Data Plant Raw
KTBP, BTBP Influent Haste
Cone. cone,
mq/1 mq/1
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110,
111.
112.
113.
114.
115.
116,
117.
118.
119.
120.
121.
122.
123.
121.
125.
126.
127.
128.
129.
130.
131.
4,4 DOE
4,4 ODD
Alpha-Endosulfan
Beta-Endosulfan
Endcsulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor Epoxide
Alpha-EHC
Beta-BHC
Gamaa-BHC (Lindane)
Delta-BHC
PCB-1242
PCB-12S4
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
loxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8 TCDD (Dioxin)
Xylenes
Alkyl Epoxides
Aluirinum
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
0,1
0,1
0,1
38,8
30,7
21,2
15,2
1«,32
65,9
0,6
20,8
6,0
6,5
21,7
0,3
0,2
~ i~
mm ^mm
~ f~
~~ f~
— f ~
— f —
~~ f ~
ND
NO
ND
ND
HD
ND
HD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.1
ND
ND
<0.001
0.010
0.009
0.040
ND
0.200
NA
0.010
HD
<0.001
ND
0.300
NA
NA
NA
0.060
NA
0.007
NA
11.000
<0.005
0.820
ND
ND
ND
ND
ND
ND
ND
ND
**
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.1
ND
ND
<0.001
<0.01
0.01
0.09
<0.005
14.0
NA
<0.005
RD
0.033
ND
0.40
NA
NA
NA
0.20
NA
0.03
NA
26.0
<0.005
0.8
Effluent
Cone.
mq/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.1
ND
ND
<0.001
<0.002
<0.005
<0.006
<0.005
2.0
NA
<0.005
ND
ND
ND
0.10
NA
NA
NA
<0.05
NA
<0.005
NA
45.0
<0.005
0.92
Analysis
Blank
Cone.
nqt/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
• NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
TABLE V-2
SCREENING ANALYSIS RESULTS
LEAD SUBCATEGORY
DCP Data Plant
KTBP, BTBP Influent
Cone.
mg/1
Gold ND
Iron
Maqnesim
Manqanese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttrium
<0.2
1.800
0.090
0.020
7.30
ND
,0.040
<0.015
NA
ND
0.060
0.040
<0.01
<0.02
Raw
Haste
Cone.
mq/1
ND
2.00
2.20
0.06
.0.008
36.5
0.08
0.58
100.0
NA
57.8
0.02
<0.02
<0.01
<0.02
Effluent
Cone.
mq/1
ND
<0.2
2.10
0.03
<0.005
10.0
<0.005
0.04
260.0
NA
90.6
<0.005
<0.02
<0.01
<0.02
Analysis
Blank
Cone.
mg/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
•ND
Not detected
NA Not analyzed (includes Xylenes 6 Alkyl Epoxides since laboratory analyses were
not finalized for these parameters).
KTBP .Known to be present indicated by number of plants.
BTBP Believed to be present indicated by number of plants.
-,- Not investigated in DCP survey.
* Indicates < .01 mg/1.
** Indicates < .005 mg/1.
-------
TABLE V-3
NORMALIZED DISCHARGE FLOWS FROM LEAD SUBCATE60RY ELEMENTS1/
Element
Anodes and Cathodes
%
Leady Oxide Production
Grid Manufacture
Mold Release Formulation
Direct Chill Casting
Lead Rolling
Paste Preparation and Application
Curing
Closed Formation (In Case)
Single Fill
Double Fill
Fill and Dump
Open Formation (Out of Case)
Dehydrated
Wet
Plate Soaking
Ancillary Operations
Battery Wash
Detergent
Water Only
Floor Wash
Wet Air Pollution Control2'
Battery Repair
Laboratory
Truck Wash3/
Personal Hygiene
Hand Wash
Respirator Wash
Laundry
Mean
Discharge
(I/kg)
0.37
0.006
0.0002
0.006
0.49
0.03
0.28
0.92
1.83
28.26
0.36
0.026
1.70
3.47
0.11
0.26
0.20
0.003
0.014
0.027
0.006
0.109
Median
Discharge
(I/kg)
0.00
0.0002
0.006
0.00
0.00
0.00
0.44
1.49
11.05
0.00
0.021
0.90
0.59
0.13
0.00
0.25
*
0.014
*
*
*
Number of Plants
Reporting Flow
Data
41
2
1
1
100
97
43
35
13
42
16
3
22
44
13
56
3
4
2
(29)
2 (63)
6 (51)
2 (11)
I/ - Production normalizing parameter is total weight of lead used.
2/
3/
*
- Discharge flow based on number of scrubbers froa all process areas except
laboratories.
- Production normalizing parameter is weight of lead in trucked batteries.
- Calculated as flow weighted average - no median available. (See text for
discussion on calculation.)
( ) - Number of plants used to calculate I/kg flow per unit operation.
-------
TABLE V-4
PERSONAL HYGIENE DATA FROM INDUSTRY SURVEY
Ln
Plant
ID
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Q
R
S
T
U
V
W
Production
Employees
in Required
Wash Up
180
193
75
60
125
160
148
130
256
90
130
144
350
62
225
400
100
250
300
175-230
441
•213
18
Number
of Hand
Washes
Per Day
4
4
' 4
3
4
3
3
4
4
4
4+
3
4
4
.4
3
4
4
4
4
4
4
4
Number of
Employees
Which
Shower
Per Day
65
12
75
60
30
160
148
20
256
60
20
144
225
62
150
400
50
175
60
125-185
441
213
18
Number of
Uniforms
Laundered
Per Day
120
22
75
64
85
160
148
60
256
100
100
144
250
62
150
8
50
200
95
150
441
213
18
Laundry
on Premise
(P) or at
Commercial
Laundry (C)
C
C
P
C
C
C
C
C
C
C
C
P
C
C
C
C
C
C
C
C
C
P
C
Number of
Gloves
Cleaned
Per Day
on Premise
0
0
0
0
0
0
0
0
0
0
0
0
25
0
0
0
0
0
0
0
0
0
0
Numbe'r of
Respirators
Washed
Per Day on
Premise
60
7
22
0
30
0
75
25
45
0
0*
170
80
0
60
6
20
80
0
60
127
47
0*
-------
IWBIE V-4 (Continued)
PERSONAL HYGIENE DATA FROM INDUSTRY SURVEY
Plant
ID
X
Y
Z
AA
AB
AC
AD
'AE
AF
AG
AH
AI
AJ
AK
AL
AM
AN
AO
AP
AQ
AR
Production
Bnployees
in Bequired
Wash Up
55
219
260
175
110
772
55
71
68
390
70
280
470
30
241
245
150
205
250
176
218
Number
of Hand
Washes
Per Day
4
4
4
4
3
3
3
4
3
4
4
4
3
4
4
3
4
3
4
4
3
Number of
Bnployees
Which
Shower
Per Day
30
43
180
175
20
645
55
52
68
130
70
200
470
12
241
245
75
. 205
175
90
120
Number of
Uniforms
Laundered
Per Day
55
6
220
180
110
675
55
71
68
30
70
140
470
25
241
245
100
205
215
171
120
laundry
on Premise
(P) or at
Commercial
Laundry (C)
P
C
C
C
C
P
p
C
C
C
C
C
P (72%)
C (28%)
C
P
C
C
C
C
C
P
Number of
Gloves
Cleaned
Per Day
on Premise
12
0
0
0
30
0
0
50
0
0
0
0
0
0
0
0
30
0
25
0
0
Number of
Respirators
Washed
Bar Day on
Premise
30
10
80
65
70
145
0
12
28
2
55
60
275
0
30
145
50
85
75
65
95
-------
TABLE V-4 (Continued)
PERSONAL HYGIENE MTA FRCM INDUSTRY SURVEY
Plant
ID
AS
AT
AU
AV
AW
AX
AY
AZ
BA
BB
BC
BD
BE
BF
BG
BH
BI
BJ
BK
Production
Baployees
in Required
Wash Up
75
170
250
275
275
180
112
2
145
225
250
80
325
300-350
245
98
250
243
200
Number
of Hand
Washes
Per Day
3
4
4
4
4
4
4
6
3
4 •
3
3
4
4
4
3
3-
4
4
Number of
Employees
Which
Shower
Per Day
30
46
175
175
200
100
112
2
145
190
128
80
150
225
245
74
250
132
50
Number of
Uniforms
laundered
Per Day
50
140
215
250
200
100
112
50
190
200
225
80
250
275
245
111
250
243
200
laundry
on Premise
(P) or at
Commercial
Laundry (C)
C
C
C
C
C
C
C
P
C
C
C
C
C
C
P
C
C
C
C
Number of
Gloves
Cleaned
Ber Day
on Premise
0
0
25
20
120
0
0
0
0
0
0
0~~
0
25
0
0
0
0
0
Number of
Respirators
Washed
Per Day on
Premise
8
35
75
100
80
30
60
0
145 -
50-100
0
0
80
75
35
42
200
40
12
*Disposable respirators are used.
NOTE: Two plants submitted no information on survey due to closure; total number of references
was 65.
-------
TABLE V-5
LEAD SUBCATEGORY
CHARACTERISTICS OF INDIVIDUAL PROCESS WASTES
00
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Hienol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Dt-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Ehenanthrene
84 Fyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 fereury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Rienols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
LEADY CKIDE PRODUCTION
mg/1
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
0.000
NA
0.000
0.50
NA
0.000
NA
0.000
0.000
0.25
0.062
NA
NA
1.49
0.62
7.0
7.04
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
0.000
NA
0.000
3.52
NA
0.000
NA
0.000
0.000
1.76
0.444
NA
NA
10.5
4.4
NA
7.0
rag/1
23.0
NA
NA
NA
NA
NA
NA
m
NA
NA
NA
NA
NA
NA
NA
0.012
0.009
NA
0.41
1.2
NA
0.13
NA
3.1
0.54
3.61
0.06
NA
NA
6.0
8,0
NA
8.5
IASTING
tng/kg
0.0002
23.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
NA
0.0001
0.0003
NA
0.0000
NA
0.0007
0.0001
0.0008
0.0000
NA
NA
0.0013
0.0018
NA
8.5
LEAD ROLLING
tflg/l WR/kg
27.0
*
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
NA
0.25
29.0
0.000
0.003
0.000
1.4
0.35
7.3
0.053
NA
NA
270.0
480.0
NA
7.9
0.0029
27.00
*
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
NA
0.007
0.084
0.0000
0.0000
0.000
0.0041
0.0010
0.021
0.0002
NA
NA
0.783
1.39
NA
7.9
EASTING
NA
*
*
0.00
*
*
*
#
*
0.00
*
*
*
1.223
0.000
0.060
0.000
0.000
0.261
4020.0
0.010
0.000
0.387
0.236
NA
3.56
NA
0.115
0.000
952.7
21883.3
7.7
8.4
0.326
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.386
0.000
0.019
0.000
0.000
0.083
1335.0
0.0031
0.000
0.1240
0.076
NA
1.153
NA
0.038
0.000
319.6
7035.0
7.7
8.4
a
UK/1
46.5
NA
NA
NA
NA
NA
NA
NA
m.
NA
NA
NA
NA
0.017
0.007
0.000
0.000
NA
0.045
19.675
m.
0.075
NA
0.625
4.05
4.625
0.070
NA
NA
0.000
46.5
NA
7.8
0.048
46.5
NA
.NA
NA
NA
NA
NA
NA
NA
NA
NA
KA
NA
0.0009
0.0004
0.000
0.000
NA
0.0025
1,029
NA
0.004
NA.
0.031
0.222
0.269
0.004
NA
NA
0.000
0.435
NA
7.8
NA - Not Analyzed
* - < 0.0!
-------
TABLE V-5 (Continued)
LEAD SUBCATEGORY
CHARACTERISTICS OF INDIVIDUAL PROCESS WASTES
SINGLE FILL FORMATION DOUBLE FILL FORMATION FILL & DUMP FORMATION OPEN WET FORMATION
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 ' Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Dl-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromiura, Total
Chromium, Hexavalent
120 Copper
122 Lead
123' Mercury
124 Nickel
126 Sliver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
* - < 0.01
rag/1
mg/kg
rag/1
mg/kg
n>g A
mg/kg
fflg/1
mg/kg
OPEN DEHYDRATED
FORMATION-
Blg/1
mg/kg
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.06
0.000
0.000
0.000
NA
1.5
0.275
NA
0.000
NA
0,02
0.15
4.25
0.05
NA
HA
1.5
22.5
2.0
2.0
5.717
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.34
0.000
0.000
0.000
NA
8.58
1.57
NA
0.000
NA
0.114
0.086
24.3
0.29
HA
NA
8.6
128.6
2.0
2.0
19.0
*
*
*
0.00
0.00
*
*
*
0.00
0.00
0.00
0.00
0.000
0.000
0.003
0.047
0.000
0.223
1.173
0.005
0.024
0.000
0.107
NA
5.64
NA
0.035
0.000
2.1
5.0
2.0
2.7
0.45
19.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
-0.00
0.00
0.00
0.00
0.000
0.000
0.001
0.021
0.000
0.093
0.532
0.0023
0.011
0.000
0.046
NA
2.52
NA
0.014
0.000
0.868
2.376
2.0
2.7
19.0
0.00
0.00
0.00
0.00
0.00
0.006
0.00
*
0.00
0.00
0.00
0.00
0.000
0.025
0.005
0.117
0.000
0.395
1.835
0.000
0.091
0.000
0.135
NA
6.88
NA
0.021
0;000
1.25
10.5
2.0
2.3
1.295
19.0
0.00
0.00
0.00
0.00
0.00
0.006
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.023
0.007
0.132
0.000
0.487
2.331
0.000
0.100
0.000
0.162
NA
7.967
NA
0.027
0.000
1.640
12.65
2.0
2.3
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.928
0.12
0.037
0.037
NA
0.003
2.146
NA
0.696
NA
0.557
0.278
1.078
0.000
NA
NA
0.000
148.95
NA
1.7
0.36
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.334
0.043
0.013
0.013
NA
0.001
0.773
NA
0.251
NA
0.201
0.100
0.388
0.000
NA
NA
0.000
53.6
NA
1.7
45.0
*
8.0
0.00
*
NA
0.064
0.00
*
0.00
*
*
0.00
0.141
0.004
0.002
0.022
NA
0.016
4.856
0.000
0.050
0.000
0.361
0.118
1.403
0.029
0.01
0.000
3.924
87.256
1.6
3.2
7.912
45.0
0.00
0.00
0.00
0.00
NA
0.920
0.00
0.00
0.00
0.00
0.00
0.00
0.612
0.0051
0.0187
0.2308
NA
0.208
47.635
0.000
0.5332
0.000
2.945
0.962
9.4S2
0.166
0.159
0.000
34.87
582.5
1.6
3.2
-------
TABLE V-5 (Continued)
LEAD SUBCATEGORY
CHARACTERISTICS OF INDIVIDUAL PROCESS WASTES
00
O
PLATE SOAK
BATTERY WASH DETERGENT
BATTERY WASH
WATER ONLY
FLOOR WASH
rag/1
mg/kg
mg/1
mg/kg
rag/1
mg/kg
rag/L
mg/kg
WET AIR POLLUTION
CONTROL
mg/L
rag/kg
11
23
44
55
65
.66
67
68
69
,78
81
84
114
115
118
119
120
122
123
124
126
128
Flow (I/kg)
Temperature (Deg C)
1,1,1 -Trichloroethane
Chloroform
Methylene chloride
Naphthalene
Phenol
Bis(2-ethylhexyl)phthalate
Butyl benzyl phthalate
Di-n-butyl phchalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrene
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
30.0
NA
NA
• NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.928
0.12
0.037
0.037
NA
0.003
2.146
NA
0.696
NA
0.557
0.278
1.078
0.000
NA
NA
0.000
148.95
NA
1.7
0.026
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.024
0.003
0.001
0.001
NA
0.0001
0.056
NA
0.018
NA
0.015
0.007
0.028
0.000
NA
NA
0.000
3.87
NA
1.7
28.0
*
*
*
*
NA
0,034
*
*
*
*
*
0.00
0.123
0.043
0.001
2.093
NA
1.517
12.34
0.000
1.447
0.001
3.393
NA
49.93
NA
0.021
0.000
13.13
107.8
2.0
12.0
0.61
28.0
0.00
0.00
0.00
0.00
NA
0.020
0.00
0.00
0.00
0.00
0.00
0.00
0.068
0.022
0.001
1.184
NA
0.830
7.138
0.000
0.802
0.0005
1.818
NA
28.35
NA
0.012
0.000
7.987
68.43
2.0
12.0
19.0
*
*
0.00
0.025
0.00
0.006
*
*
*
*
*
0.00
0.01
0.003
0.001
0.087
0.000
0.322
2.487
0.0247
0.060
0.000
0.632
0.17
6.707
0.085
0.017
0.013
14.5
42.0
1.5
4.6
0.439
19.0
0.00
0.00
0.00
0.011
0.00
0.002
0.00
0.00
0.00
0.00
0.00
0.00
0.003
0.0005
0.0005
0.025
0.000
0.166
1.373
0.0079
0.0178
0.000
0.1635
0.031
2.601
0.016
0.008
0.008
7.795
24.60
1.5
4.6
24.0
0.00
0.00
*
*
0.00
*
*
*
*
*
*
*
0.333
0.07
0.070
1.157
0.000
0.670
198.26
0.000
0.765
0.000
2.950
5.782
39.802
0.361
0.095
0.000
12.518
631.555
3.0
9.1
0.034
24.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.156
0.006
0.021
0.359
0.000
0.182
62.48
0.000
0.230
0.000
0.452
0.326
10.60
0.015
0.003
0.000
9.486
427.5
3.0
9.1
«
26.0
•NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.165
0.007
0.000
0.03
NA
0.075
0.225
NA
0.04
NA
0.5
0.45
6.5
0.04
NA
NA
4.7
16.5
NA
1.8
0.109
26.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.014
0.0005
0.000
0.0025
NA
0.0075
0.019
NA
0.003
NA
0.04
0.065
0.49
0.006
NA
NA
0.465
1.8
NA
1.8
NA - Not Analyzed
* - < 0.01
-------
TABLE V-5 (Continued)
LEAD SUBCATEGORY
CHARACTERISTICS OF INDIVIDUAL PROCESS WASTES
BATTERY REPAIR
LABORATORY
Flow (I/kg)
Temperature (Deg C)
11 1,1 ,i1 -Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2~ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
. 84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium'
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
«>g/1
32.0
*
*
*
*
0.00
0.012
*
0.007
*
*
0.128
0,05
0.116
0.147
0.000
3.408
13,532
0.0044
0.251
0.002
4.52
NA
169.26
HA
0.09
0.000
35.46
314.26
2.7
2,8
mg/kg
0.10
NA
0.00
0.00
0.00
0.00
0.00
0.0015
0.00
0.00
0.00
0.00
0.00
0.00
0.0004
0.005
0.0008
0.016
0.000
0.065
0.132
0.0000
0.016
0.0000
0.096
NA
0.952
NA
0.006
0.000
0.919
1.947
2.7
2.8
rag/1
25.0
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.018
0.000
HA
0.417
5.01
NA
0.000
NA
0.965
1.02
1.159
0.000
NA
NA
39.88
723.45
HA
2.0
IY
nig/kg
0.0024
25.0
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NN
NA
0.000
0.000
0.0000
0.000
HA
0.0010
0,0012
NA
0.000
NA
0.0023
0.0024
0.0028
0,000
NA
HA
0.0960
1.74
NA
2.0
TRUCK
n«/l
16.0
NA
NA
NA
NA
HA
NA
NA
NA
NA
HA
NA
NA
0.31
0.05
0.04
0.18
NA
1.2
20.9
NA
0.25
HA
1,58
37.8
1050.0
7.2
NA
NA
7.0
2500.0
NA
3.0
WASH
mg/kg
0.0027
16.0
NA
NA
NA
m.
NA
NA
NA
HA
NA
NA
HA
HA
0.0008
0.0001
0.0001
0.0005
NA
0.003
0.056
HA
0.0007
HA
0.004
0.102
2.835
0.019
NA
HA
0.019
6.75
HA
3.0
HAND
mg/1
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
0.23
0.03
0.000
0.01
NA
0.875
11.25
NA
0.025
NA
0.83
0.20
1.05
0.000
NA
NA
165.0
269.0
NA
8.0
WASH
n«/kg
0.0208
30.0
NA
NA
HA
NA
NA
HA
NA
NA
NA
NA
NA
NA
0.006
0.0007
0.000
0.0003
MA
0.019
0.221
NA
0.0004
HA
0.019
0.005
0.024
0.000
HA
NA
2.625
6.63
HA
8.0
RESPIRA'
mg/1
43.0
NA
NA
NA
NA
NA
NA
HA
NA
NA
HA
NA
NA
0.0002
0.00015
0.0002
0.31
NA
0.175
3.117
NA
0.2
NA
0.412
0.000
0.176
0.000
NA
NA
5.6
10.549
NA
7.0
mg/kg
0.0166
43.0
NA
NA
NA
NA
NA
NA
NA
KA
NA
NA
HA
NA
0.0000
0.0000
0.0000
0.0085
HA
0.008
0.081
HA
0.005
NA
0.008
0.000
0.0045
0.000
NA
NA
0.085
0.213
NA
7.0
HA - Hot Analyzed
* - < 0.01
-------
TABLE V-5 (Continued)
LEAD SUBCATEGORY
CHARACTERISTICS OF INDIVIDUAL PROCESS WASTES
LAttJDRY
00
rag/1
rag/kg
11
23
44
55
65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
Flow (I/kg)
Temperature (Deg C)
1,1,1 -Trichloroethane
Chloroform
Methylene chloride
Naphthalene
Phenol
Bis (2-ethylhexyl)phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrene
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.105
0.01
0.000
0.000
NA
0.225
13.2
NA
0.000
NA
0.58
0.25
0.95
0.000
NA
NA
49.2
135.0
NA
6.0
0.0885
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.009
0.0009
0.000
0.000
NA
0.020
1.162
NA
0.000
NA
0.050
0.022
0.083
0.000
NA
NA
4.211
12.03
NA
6.0
NA - Not Analyzed
* - < 0.01
-------
oo
CO
TABLE V-6
PASTING
WASTEWATER CHARACTERISTICS
mg/1
PLANT A
PLANT D
PLANT E
Stream Identification
11
23
44
55
65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
Temperature (Deg C)
1,1,1 -Trichloroethane
Chloroform
Methylene chloride
Naphthalene
Phenol
Bis(2-ethylhexyl)phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrene
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
MA
*
*
0.00
*
NA
*
*
*
0.00
*
*
*
0.000
0.000
0.000
0.000
0.000
0.120
2700.0
0. 0200
0.000
0.2600
0.038
NA
0.800
NA
0.085
0.000
38.0
10890.0
7.2
7.9
Clean Up Water
From
Pasting Machine
NA
0.00
0.00
0.00
*
0.00
*
0.00
*
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
0.000
0.083
6000.0
0.000
0.000
0.1900
0.160
NA
2.650
NA
0.150
0.000
1620.0
12450.0
9.8
9.8
NA
0.00
0.00
0.00
*
NA
*
0.00
*
0.00
*
*
0.00
3.670
0.000
0.180
0.000
0.000
0.580
3360.0
I
0.000
0.710
0.510
NA
7.23
NA
0.110
0.000
1200.0
42310.0
11.4
11.4
29.0
*
*
*
0.020
NA
*
0.00
*
0.00
*
*
0.00
0.000
0.000
0.007
0.033
NA
0.025
280.0
0.000
0.027
0.0100
0.780
NA
0.760
NA
0.061
0.000
9.3
6600. 0
6.1
6.1
In -Line Sump
Under Pasting
Machine
NA
*
*
0.00
0.012
NA
*
0.00
*
*
*
*
0.00
0.000
0.000
0.006
0.017
NA
0.025
208.0
0.000
0.016
0.0100
0.540
NA
0.540
NA
0.079
0,000
35.0
20900.0
NA
NA
Holding
Pitt
NA
*
*
0.00
0.016
NA
0.113
0.00
*
0.00
*
*
0.00
0.310
0.000
0.036
0.030
HA
0.190
254.0
0.000
0.024
0. 1 800
0.410
NA
2.030
NA
0.069
0.023
30.0
1 1 000. 0
NA
NA
NA
*
0.00
0.00
0.00
0.00
*
*
*
0.00
0.00
0.00
0.00
0.130
NA
0.034
NA
0.000
NA
13.40
0.0460
NA
0. 0080
3.880
NA
390.0
NA
0.020
0,000
3.0
184.0
NA
NA
I - Interference
NA - Not Analyzed
* - < 0.01
t - Includes Some Floor Wash & Deionized Water Spillage (Approximately 2 Days Residence Time Before Treatment)
-------
TABLE V-6 (Continued)
PASTING
WASTEWATER CHARACTERISTICS
rag/1
00
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Mechylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122- Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
PLANT F*
23.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0,12
0,004
0.000
0.000
NA
0.12
850.0
NA
0.000
NA
0.000
0.080
0.41
0.006
NA
NA
NA
0.2
5.5
6.0
PLANT H**
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.02
0.000
0.000
0.000
NA
0.000
384.0
NA
0.000
NA
0.02
0.000
0.15
0.000
NA
NA
160.0
730.0
NA
6.0
NA - Not Analyzed
*Composite of aliquots collected from under paste application machine conveyor belt, paste area trenches, and
belt bed under paste application machine.
**Discharge pipe from trench collection system In pasting area.
-------
TAB IE V-7
PASTING
WASTE LOADINGS
Stream Identification
Flow (I/kg)
Temperature (Deg C)
11 1,t,1-Trlchloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Dl-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
PLANT A
PLANT D
PLANT E
Clean Up Water
From
Pasting Machine
0.311
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
0.000
0.037
840.0
0.0062
0.000
0.0809
0.012
NA
0.249
NA
0.026
0.000
11.82
3388.0
7.2
7.9
0.351
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
0.000
0.029
2104.0
0.000
0.000
0.0667
0.056
NA
0.929
NA
0.053
0.000
568.2
4367.0
9.8
9.8
0.316
NA
0.00
0.00
0,00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.158
0.000
0.057
0.000
0.000
0.183
1060.0
I
0.000
0. 2244
0.161
NA
2.282
NA
0.035
0.000
378.7
13350.0
11.4
11.4
0.058
29.0
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.002
NA
0,001
16.26
0. 0006
0.002
0. 0006
0.045
NA
0.044
NA
0.004
0.000
0.540
383.3
6. 1
6.1
In -Line Sump
Under Pasting
Machine
0.063
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.001
NA
0.002
13.18
0.0006
0.001
0. 0006
0,034
NA
0.034
NA
0.005
0.000
2.205
1324.0
NA
NA
Holding
Pitt
0.064
NA
0.00
0,00
0.00
0.000
NA
0.01
0.00
0.00
0,00
0.00
0.00
0.00
0.020
0.000
0.002
0.002
NA
0.012
16.25
0.0115
0.002
0.0115
0.026
NA
0.130
NA
0.004
0.001
2.217
704.0
NA
NA
0.218
NA
0.00
0,00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.028
NA
0.007
NA
0.00
NA
2.920
0.010
NA
0.0017
0.845
NA
85.0
NA
0.004
0,000
1.919
40.09
NA
NA
I - Interference
NA - Not Analyzed
t - Includes Some
Floor Wash & Delontzed Water Spillage (Approximately 2 Days Residence Time Before Treatment),
-------
TABLE V-7 (Continued)
PASTING
WASTE LOADINGS
rag/kg
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
_^ 114 Ant imony
00 115 Arsenic
ON 118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
1.22 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
PLANT F*
0.0508
23.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.006
0.0002
0.000
0.000
NA
0.006
43.0
NA
0.000
NA
0.000
0.004
0.021
0.0003
NA
NA
NA
0.11
5.5
6.0
PLANT H**
0.0831
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.002
0.000
0.000
0.000
NA
0.000
31.9
NA
0.000
NA
0.002
0.000
0.013
0.000
NA
NA
13.3
60.7
NA
6.0
NA - Not Analyzed
*Coraposite of aliquots collected from under paste application machine conveyor belt, paste area trenches, and
belt bed under paste application machine.
**Discharge pipe from trench collection system in pasting area.
-------
00
11
23
44
55
65
66
67
68
69
7'8
81
84
114
115
118
119
120
122
123
124
126
128
Temperature (Deg C)
1 ,- 1 , 1 -Tr ichloroethane
Chloroform
Methylene chloride
Naphthalene
Phenol
Bis (2-ethylheKyl)phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrene
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Lead
• Mercury
Nickel
Silver
, Zinc
Aluminum
•- Iron .•
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-8
CURING
WASTEWATER CHARACTERISTICS
rag/1
60.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.015
0.013
0.000
0.000
NA
0.090
38.0
NA
0.15
NA
0.95
0.80
9.0
0,14
NA
NA
0.000
8.3
NA
10.11
33.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.02
0.000
0.000
0.000
NA
0.000
1.35
NA
0.000
NA
0.3
0.1
0.25
0.000
NA
NA
0.000
10.0
NA
7.5
-------
00
00
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
15 Arsenic
118 Cadmium
19 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-9
CURING
WASTE LOADINGS
rag/kg
0.0533
60.0
NA
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
0.0008
0,0007
0.000
0.000
NA
0.005
2.0
NA
0,008
NA
0.051
0.426
0.48
0.007
NA
NA
0.000
0.44
NA
10.11
0.043
33.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0009
0.000
0.000
0.000
NA
0.000
0.058
NA
.0.000
NA
0.01
0.018
0.058
0.0003
NA
NA
0.000
0.43
NA
7.5
-------
TABLE V-10
DOUBLE FILL AND FILL & DUMP FORMATION
WASTE CHARACTERISTICS
PLANT A
mg/1
00
VD
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Stront ium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
18.5
0.00
0.00
*
0.00
NA
*
*
*
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.026
0.000
0.100
0.960
0.000
0.008
0.000
0.060
NA
3.900
NA
0.016
0.000
1.0
6.0
2.0
6.8
DOUBLE FILL
20.0
*
*
*
0.00
0.00
*
*
*
0.00
0.00
0.00
0.00
0.000
0.000
0.005
0.070
0.000
0.170
1 .710
0.0150
0.044
0.000
0.083
NA
7.92
NA
0.010
0.000
1.1
8.0
2.0
FILL 6t DUMP
2.4
18.0
0.00
0.00
0.00
0.00
NA
*
0.00
*
0.00
0.00
0.00
0.00
0.000
0.000
0.006
0.045
0.000
0.400
0.850
o.ooo
0.020
0.000
0.180
NA
5.100
NA
0.078
0.000
4.2
1 .0
2.0
2.6
20.0
0.00
0.00
0.00
0.00
0.00
*
0.00
*
0.00
0.00
0.00
0.00
0.000
0.000
0.005
0.064
0.000
0.330
1 .710
0.000
0.043
0.000
0.100
NA
4.400
NA
0.020
0.000
1 .3
8.0
2.0
5.7
18.0
0.00
0.00
0.00
0.00
NA
0.012
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.050
0.005
0.170
0.000
0.460
1.960
0.000
0.140
0.000
0.170
NA
9.36
NA
0.022
0.000
1 .2
13.0
NA
2.0
NA - Not Analyzed
* - < 0.01
-------
TABLE V-11
DOUBLE FILL AND FILL & DUMP FORMATION
WASTE LOADINGS
PLANT A
o
Flow (I/kg) 0.52
Temperature (Deg C) 18.5
11 1,1,1-Trichloroethane 0.00
23 Chloroform 0.00
44 Methylene chloride 0.00
55 Naphthalene 0.00
65 Phenol NA
66 Bis(2-eehylhexyl)phthalate 0.00
67 Butyl benzyl phthalate 0.00
68 Di-n-butyl phthalate 0.00
69 Di-n-octyl phthalate 0.00
78 Anthracene 0.00
81 Phenanthrene 0.00
84 Pyrene 0.00
114 Antimony 0.000
115 Arsenic 0.000
118 Cadmium 0.000
119 Chromium, Total 0.013
Chromium, Hexavalent 0.000
120 Copper 0.052
122 Lead 0.498
123 Mercury 0.000
124 Nickel 0.004
126 Silver 0.000
128 Zinc 0.031
Aluminum NA
Iron 2.025
Manganese NA
Phenols, Total 0.008
Strontium 0.000
Oil & Grease 0.519
Total Suspended Solids 3.115
pH, Minimum 2.0
pH, Maximum 6,8
DOUBLE FILL
0.45
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.002
0.032
0.000
0.077
0.777
0.0070
0.020
0.000
0.038
NA
3.598
NA
0.005
0.000
0.500
3.634
2.0
2.4
FILL & DUMP
0.38
8.0
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.002
0.017
0.000
0.151
0.321
0.000
0.008
0.000
0.068
NA
1.926
NA
0.029
0.000
1.586
0.378
2.0
2.6
1.68
20.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.008
0.108
0.000
0.554
2.873
0.000
0.072
0.000
0.168
NA
7.393
NA
0.034
0.000
2.184
13.44
2.0
5.7
0.91
18.0 "
0.00
0.00
0.00
0.00
NA
0.011
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.046
0.005
0.155
0.000
0.420
1.789
0.000
0.128
0.000
0.155
NA
8.541
NA
0.020
0.000
1.095
11.86
NA
2.0
NA - Not Analyzed
-------
TABLE V-12
OPEN FORMATION DEHYDRATED BATTERY
WASTE CHARACTERISTICS
mg/1
PLANT D
PLANT G
PLANT H
vO
Temperature (Deg C)
11 1 ,1 ,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
1 18 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
50.0
NA
NA
NA
*
NA
0.077
0.00
*
0.00
*
+
0.00
0.000
0.000
o.uoo
0.047
NA
0.046
8.59
0.000
0.096
0.000
0.350
NA
0.930
NA
0.016
0.000
5.7
9.0
2.0
4.1
48.0
*
8.0
0.00
*
NA
0.051
0.00
*
0.00
V*
*
0.00
0.000
0.000
0.009
0.048
NA
0.036
6.72
0.000
0.130
0.000
0.330
NA
2.210
NA
0.005
0.000
2.4
0.000
2.0
5.4
47.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.18
0.0005
0.000
0.000
NA
0.006
2.9
NA
0.000
NA
0.5
0.02
0.66
0.008
NA
NA
3.0
166.0
2.0
3.0
46.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.16
0.0005
0.000
0.000
NA
0.005
5.3
NA
0.000
NA
0.5
0.02
0.52
0.10
NA
NA
0.000
60.0
2.0
3.0
47.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.18
0.004
0.000
0.000
NA
0.004
2.62
NA
0.000
NA
0.4
0.4
0.58
0.006
NA
NA
8.0
271 .0
2.0
3.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.34
0.014
0.004
0.04
NA
0.000
3.0
NA
0.08
NA
0.06
0.03
3.52
O.OOO
NA
3.52
4.7
17.0
1.5
3.0
NA - Not Analyzed
* - < 0.01
-------
TABLE V-13
OPEN FORMATION DEHYDRATED BATTERY
WASTE LOADINGS
rag/kg
PLANT D
PLANT G
PLANT H
vo
'
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH; Maximum
16.10
50.0
0.00
0.00
0.00
0.00
NA
1.240
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.757
NA
0.741
138.3
0.000
1.546
0.000
5.636
NA
14.98
NA
0.258
0.000
91.8
144.9
2.0
- 4.1
11.74
48.0
0.00
0.00
0.00
0.00
NA
0.599
0.00
0.00
0.00
0.00
0.00"
0.00
0.000
0.000
0.106
0.564
NA
0.423
78.9
0.000
1.526
0.000
3.875
NA
25.95
NA
0.059
0.000
28.18
0.000
2.0
5.4
3.1167
47.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.56
0.0016
0.000
0.000
NA
0.019
9.04
NA
0.000
NA
1.56
0.06
2.06
0.025
NA
NA
9.35
517.0
2.0
3.0
5.8707
46.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.94
0.0029
0.000
0.000
NA
0.029
31.1
NA
0.000
NA
2.9
0.12
3.05
0.59
NA
NA
0.000
352.0
2.0
3.0
9.0545
47.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.63
0.0036
0,000
0.000
NA
0.036
23.7
NA
0.000
NA
3.6
3.62
5.25
0.05
NA
NA
. 72.4
2454.0
2.0
3.0
1.59
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA'
NA
NA
NA
0.541
0.223
0.0006
0.064
NA
0.000
4.77
NA
0.127
NA
0.10
0,048
5.60
0.000
NA
NA
7.47
27.0
1.5
3.0
NA - Not Analyzed
-------
TABLE V-14
BATTERY WASH - DETERGENT
WASTEWATER CHARACTERISTICS
1 Big/L
Temperature (Deg C)
il 1,1,1-TrichLoroethane
23 Chlorofonn
44 Mechylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc ; ,
Aluminum
Iron
Manganese
,. Phenols, Total-
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
28.0
*
*
*
*
NA
0,013
*
*
*
0.00
0.000
0.000
0.000
1 .160
NA
0.290
8.42
0.000
0.630
0.000
• 0.810
NA
26.80
NA
0.018
0.000
14.0
160.0
2.0
12.0
PLANT D
28.0
*
*
NA
0.048
0.00
0.00
*
0.00
0.190
0.000
0.004
1.450
NA
PLANT G
1 .470
9.69
0.000
0.910
0.000
1.770.
NA
40.00
NA
0.021
0.000
10.4
70.4
2.0
12.0
28.0
*
*
0.0
*
NA
0.042
*
*
*
*
*
0.00
0.180
0.130
0.000
3.670
NA
2.790
18.90
0.000
2.800
0.0030
7.60
NA
83.0
NA
0.023
,0.000
= 15.0
93.0
2.0
12.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
9.1
0.000
0.000
2.2
NA
63.5
260.0
NA
2.0
NA
92.4
12.0
728.0
4.0
NA
NA
0.000
9050.0
NA
12.0
NA - -Not Analyzed
* - < 0.01
-------
TABLE V-15
BATTERY WASH - DETERGENT
WASTE LOADINGS
rag/kg
vD
Flow (L/kg) 0.730
Temperature (Deg C) 28.0
11 1,1,1-Trichloroethane 0.00
23 Chloroform 0.00
44 Mechylene chloride 0.00
55 Naphthalene 0.00
65 Phenol NA
66 Bis(2-ethylhexyl)phthalate 0.009
67 Butyl benzyl phthalate 0.00
68 Di-n-butyl phthalate 0.00
69 Di-n-octyl phthalate 0.00
78 Anthracene 0.00
81 Phenanthrene 0.00
84 Pyrene 0.00
114 Antimony 0.000
115 Arsenic 0.000
118 Cadmium 0.000
119 Chromium, Total 0.847
Chromium, Hexavalent NA
120 Copper 0.212
122 Lead 6.15
123 Mercury 0.000
t24 Nickel 0.460
126 Silver 0.000
128 'Zinc 0.591
Aluminum NA
Iron ' 19.56
Manganese NA
Phenols, Total 0.013
Strontium 0.000
Oil & Grease 10.22
Total Suspended Solids 116.8
pH, Minimum 2.0
pH, Maximum 12.0
PLANT D
0.600
28.0
0.00
0.00
0.00
0.00
NA
0.029
0.00
0.00
0.00
0.00
0.00
0.00
0.114
0.000
0.004
0.870
NA
0.882
5.814
0.000
0.546
0.000
1.062
NA
24.00
NA
0.013
0.000
6.24
42.00
2.0
12.0
PLANT G
0.500
28.0
0.00
0.00
0.00
0.00
NA
0.021
0.00
0.00
0.00
0.00
0.00
0.00
0.090
0.065
0.000
1.835
NA
1.395
9.45
0.000
1.400
0.005
3.800
NA
41.50
NA
0.011
0.000
7.50
46.50
2.0
12.0
0.2808
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.56
0.000
0.000
0.62
NA
17.8
73.0
NA
0.56
NA
25.9
3.37
204.0
1.123
NA
NA
0.000
2541.0
NA
12.0
NA - Not Analyzed
-------
TABLE V-16
BATTERY WASH - WATER ONLY
WASTEWATER CHARACTERISTICS
rag/1
Temperature (Deg C)
11 1 ,1 ,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122. Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
18.0
*
*
0.00
0.012
NA
*
*
*
0.00
*
*
0.00
0.000
0.000
0.002
0.072
0.000
0.570
6.39
0.000
0.055
0.000
0.240
NA
6.93
NA
0.016
0.039
18.0
120.0
2.0
7.7
PLANT A
18.0
0.00
0.00
0.025
0.00
*
0.00
*
*
*
*
0.00
0.000
0.000
0.000
0.000
0.000
0.280
1.200
0.0090
0.000
0.000
0.130
NA
3.900
NA
0.014
0.000
23.0
19.0
2.0
6.8
PLANT F
18.0
*
0.00
0.00
0.037
NA
0.017
*
*
*
*
*
0.00
0.000
0.000
0.004
0.017
0.000
0.330
1.370
0.0650
0.007
0.000
0.160
NA
5.000
NA
0.022
0.000
17.0
29.0
2.0
5.7
22.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.061
0.010
0.000
0.26
NA
0.11
0.99
NA
0.18
NA
2.0
0.17
11.0
0.085
NA
NA
0.000
0.000
1.0
4.0
NA - Not Analyzed
* - < 0.01
-------
TABLE V-17
BATTERY WASH - WATER ONLY
WASTE LOADINGS
mg/kg
PLANT A
Flow (I/kg) 0.651 0.639
Temperature (Deg C) 18.00 18.00
11 1,1,1-Trichioroethane 0.00 0.00
23 Chloroform 0.00 0.00
44 Methylene chloride 0.00 0.00
55 Naphthalene 0.008 0.016
65 Phenol NA 0.00
66 Bis(2-ethylhexyl)phthalate 0.00 0.00
67 Butyl benzyl phthalate 0.00 0.00
68 Di-n-butyl phthalate 0.00 0.00
69 Di-n-octyl phthalate 0.00 0.00
78 Anthracene 0.00 0.00
81 Phenanthrene . 0.00 0,00
84 Pyrene 0.00 0.00
114 Antimony 0.000 0.000
115 Arsenic 0.000 0.000
118. Cadmium 0.001 0.000
119 Chromium, Total 0.047 0.000
Chromium, Hexavaient 0.000 0.000
120 Copper 0.371 0.179
122 Lead 4.159 0.767
123 Mercury 0.000 0.0056
124 Nickel 0.036 0.000
126 Silver 0.000 0.000
128, Zinc 0.156 0.083
Aluminum NA NA
Iron 4.511 2.491
Manganese NA NA
Phenols, Total 0.010 0.009
Strontium 0.025 0.000
Oil & Grease 11.72 14.70
Total Suspended Solids 78.12 12.14
pH, Minimum 2.0 2.0
pH, Maximum 7.7 6.8
PLANT F
0.280
18.00
0.00
0.00
0.00
0.010
NA
0.005
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.001
0.005
0.000
0.093
0.384
0.0182
0.002
0.000
0.045
NA
1.402
NA
0.006
0.000
4.760
8.13
2.0
5.7
0.185
22.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.011
0.002
0.000
0.048
NA
0.020
0.18
NA
0.033
NA
0.37
0.031
2.0
0.016
NA
NA
0.000
0.000
1.0
4.0
NA - Not Analyzed
-------
TABLE V-18
FLOOR WASH
WASTEWATER CHARACTERISTICS
PLANT A
PLANT F
PLANT H
Temperature (Deg C)
11 1,1,1-Irichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bi3{2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-tmtyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phertanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
"124 Nickel
126 Silver
128 Zinc
• Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA
0.00
0.00
*
*
NA
*
*
*
*
*
*
*
0.940
0.000
0.042
0.034
0.000
0.290
251.0
0.000
0.033
0.000
0.940
NA
9.76
NA
0.153
0.000 '
HA
NA
NA
NA
22.0
0.00
0.00
*
*
0.00
*
*
*
^0.00
*
*
0,00
o.'ooo
0.000
0.035
0.019
0.000
0.210
107.0
0.000
0.023
0.000
0.710
NA
6.82
NA
0.090
0.000
25.0
1116.0
NA
10.2
NA
0.00
0.00
0.00
*
NA
*
*
*
0.00
*
*
*
0.000
0.000
0.011
0.018
0.000
0.320
51.0
0.000
0.000
0.000
0.470
NA
6.45
NA
0.161
0.000
28.0
952.0
NA
10.2
25.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.28
0.10
0.12
1.62
NA
1.27
129.0
NA
1.19
NA
3.46
11.85
57.0
0.57
NA
NA
. 4.5
318.0
3.0
8.82
23.0
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.32
0.19
0.13
1.86
NA
1.31
629.0
NA
1.21
NA
6.35
18.74
89.0
0.87
NA
NA
0.000
545.0
3.0
9.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.98
0.08
0.04
0.1
NA
0.4
120.0
NA
0.000
NA
15.2
3.9
12.4
0.15
NA
NA
42.0
450.0
NA
9.0
NA - Not Analyzed
* - < 0.01
-------
TABLE V-19
FLOOR WASH
WASTE LOADINGS
mg/kg
vo
00
PLANT A
Flow (I/kg) 0.026 0.020
Temperature (Deg C) NA 22.0
11 1,1,1-Trichloroethane 0.00 0.00
23 Chloroform 0.00 0.00
44 Methylene chloride 0.00 0.00
55 Naphthalene 0.00 0.00
65 Phenol NA 0.00
66 Bis<2-ethylhexyl)phthalate 0.00 0.00
67 Butyl benzyl phthalate 0.00 0.00
68 Di-n-butyl phthalate 0.00 0.00
69 Di-n-octyl phthalate 0.00 0.00
78 Anthracene 0.00 0.00
81 Phenanthrene 0.00 0.00
84 Pyrene 0.00 0.00
114 Antimony 0.025 0.000
115 Arsenic 0.000 0.000
118 Cadmium 0.001 0.001
119 Chromium, Total 0.001 0.000
• Chromium, Hexavalent 0.000 0.000
120 Copper 0.008 0.004
122 Lead 6.62 2.162
123 Mercury 0.000 0.000
124 Nickel 0.001 0.000
126 Silver 0.000 0.000
128 Zinc 0.025 0.014
Aluminum NA NA
Iron 0.257 0.138
Manganese NA NA
Phenols, Total 0.004 0.002
Strontium 0.000 0.000
Oil & Grease NA 0.505
Total Suspended Solids NA 22.55
pH, Minimum NA NA
pH, Maximum NA 10.2
PLANT F
PLANT H
0.026
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
0.000
0.008
1.319
0.000
0.000
0.000
0.012
NA
0.169
NA
0.004
0.000
0.724
24.62
NA
10.2
0.025
25.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0069
0.0026
0.0030
0.041
NA
0.0318
3.235
NA
0.030
NA
0.086
0.30
1.416
0.014
NA
NA
0.11
7.96
3.0
8.82
0.033
23.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0105
0.0063
0.0044
0.062
NA-
0.044
20.9
NA
0.040
NA
0.211
0.62
2.98
0.029
NA
NA
0.000
18.2
3.0
9.0
0.0148
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.015
0.001
0.0006
0.002
NA
0.006
1.78
NA
o.oop
NA
0.225
0.058
0.184
0.002
NA
NA
0.621
6.66
NA
9.0
NA - Not Analyzed
* - < 0.01
-------
Temperature (Deg C)
11 1, 1, 1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-20
WET AIR POLLUTION CONTROL
WASTEWATER CHARACTERISTICS
mg/1
PLANT F
22.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.28
0.013
0.000
0.06
NA
0.10
0.4
NA
0.08
NA
1.0
0.000
13.0
0.000
NA
NA
6.0
16.0
1.0
3.5
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.05
0.000
0.000
0.000
NA
0.05
0.05
NA
0.000
NA
0.000
0.9
0.000
0.08
NA
NA
3.4
17.0
NA
2.0
-------
NJ
O
O
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Dir-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
.Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-21
WET AIR POLLUTION CONTROL
WASTE LOADINGS
mg/kg
PLANT F
0.0757
22.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.021
0.001
0.000
0.005
NA
0.008
0.03
NA
0.006
NA
0.08
0.000
0.98
0.000
NA
NA
0.45
1.2
1 .0
3.5
PLANT H
0.142
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.007
0.000
0.000
0.000
NA
0.007
0.007
NA
0.000
NA
0.000
0.13
0.000
0.011
NA
NA
0.48
2.4
NA
2.0
-------
TABLE V-22
BATTERY REPAIR
WASTEWATER CHARACTERISTICS
rag/1
PLANT A
PLANT D
Temperature (Deg C) NA
11 1,1,1-Trichloroethane . *
23 Chloroform *
44 * Methylene chloride *
55 Naphthalene H NA
65 Phenol NA
66 Bis(2-ethylhexyl)phthalate NA
67 Butyl benzyl phthalate NA
68 Dl-n-butyl phthalate NA
69 Di-n-octyL phthalate NA
78 Anthracene NA
81 Phenanthrene NA
84 Pyrene NA
114 Antimony . 0,640
115 Arsenic 0.110
118 Cadmium 0.220
119 Chromium, Total 0.250
Chromium, HexavaLent 0.000
120 Copper 5.460
122 Lead 65,00
123 Mercury 0.0060
124 Nickel 0.430
126 Silver 0.0130
128 Zinc B.97
Aluminum NA
Iron 460.0
Manganese NA
Phenols, Total 0.039
Strontium 0.000
Oil & Grease 62.0
Total Suspended Solids 624.0
pH, Minimum 2.3
pH, Maximum 2.3
NA
*
0.00
0.00
*
0.00
0.010
*
0.012
0.00
*
*
*
0.000
0.000
0.340
0.100
0.000
9.83
0.540
0.0100
0.520
0.000
7.510
NA
370.0
NA
0.174
0.000
46.0
362,0
NA
2.0
NA
*
0.00
0.00
*
NA
0.014
*
0.014
0.00
*
*
*
0.000
0.000
0.008
0.013
0.000 '
0.280
0.270
0.0060
0.007
0.000
4.210
NA
8.05
NA
0.130
0.000
54.0
572.0
NA
NA
32.0
*
*
0.00
*
NA
0.013
0.00
~* *
*
*
*
0.00
0.000
0.150
0.013
0.250
NA
1.220
1.020
0.000
0.130
0.000
1.410
NA
5.940
NA
0.011
0.000
6.0
1.3
2.9
3.9
31 .0
*
*
*
*
NA
0.011
*
*
*
*
*
0.00
0.000
0.000
0.000
0.120
NA
0.250
0.830
0.000
0.170
0.000
0.500
NA
2.310
NA
0.091
0.000
9.3
12.0
3.4
5.6
NA - Not Analyzed
* - < 0.01
-------
TABLE V-23
1A11ERY REPAIR
WASTE LOADINGS
ng/kg
O
K>
PLANT A
Flow (I/kg) 0.003 0.004
Temperature (Deg C) NA NA
11 1,1,1-Trichloroethane 0.00 0.00
23 Chloroform 0.00 0.00
44 Methylene chloride 0.00 0.00
55 Naphthalene NA 0.00
65 Phenol NA 0.00
66 Bis(2-ethylhexyl)phthalate NA 0.00
67 Butyl benzyl phthalate NA 0.00
68 Dt-n-butyl phchalate NA 0.00
69 Di-n-octyl phthalate NA 0.00
78 Anthracene NA 0.00
81 Phenanthrene NA 0.00-
84 Pyrene NA 0.00
114 Antimony 0.002 0.000
115 Arsenic 0.000 0.000
118 Cadmium 0.001 0.001
119 Chromium, Total 0.001 0.000
Chromium, Hexavalent 0,000 0.000
120 Copper 0.0008 0.038
122 . Lead 0.218 0.002
123 -Mercury 0.000 0.000
124 Nickel 0.001 0.002
126 Silver 0.000 0.000
128 Zinc 0.033 0.029
Aluminum NA NA
Iron 1.545 1.438
Manganese " NA NA
Phenols, Total 0.000 0.001
Strontium 0.000 0.000
; Oil 8, Grease 0.208 0.179
Total Suspended Solids 2.096 ' 1.407
pH, Minimum 2.3 NA
' pH, Maximum 2.3 2.0
PLANT D
0.004
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
0.000
0.001
0.001
0.000
0.000
0.000
0.016
NA
0.030
NA
0.000
0.000
0.204
2.157
NA
NA
0.170
NA
0.00
0.00
0.00
0.00
NA
0.002
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.025
0.002
0.042
NA
0.207
0.173
0.000
0.022
0.000
0.239
NA
1 .007
NA
0.002
0.000
1.017
0.220
2.9
3.9
0.321
NA
0.00
0.00
0.00
0.00
NA
0.004
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.039
NA
0.080
0.266
0.000
0.055
0.000
0.161
NA
0.742
NA
0.029
0.000
2.986
3.853
3.4
5.6
NA - Not Analyzed
-------
to
o
Temperature (Deg C)
11 1 ,1,1-Triehloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115- Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120. Copper
122 Lead
123 Mercury
124 •• Nickel
126 Silver
128'• Zinc
Alufflinum
Iron
Manganese
. Phenols, Total
Strontium
• 011.& Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-24
TRUCK WASH
WASTEWATER .CHARACTERISTICS
rag/1
PLANT G
16.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.31
0.05
0.04
0.18
NA
1 .2
20.9
NA
0.25
NA
1.58
37.8
1050.0
7.2
NA
NA
7.0
2500.0
NA
3.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.810
0.060
0.24
0.14
NA
0.8
63.4
NA
0.15
NA
6.12
160
53.8
1.15
NA
NA
26.0
10»0.0
NA
4.0
-------
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-oetyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-25
TRUCK WASH
WASTE LOADINGS
ng/kg
PLANT G
0.0027
16.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0008
0.0001
0.0001
0.0005
NA
0.003
0.056
NA
0,0007
NA
0.004
0.102
2.835
0.019
NA
NA
0.019
6.75
NA
3.0
PLANT H
0.026
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.021
0.0016
0.006
0.0036
NA
0.02
1.65
NA
0.0039
NA
0.159
4.16
1.40
0.030
NA
NA
0.68
28.1
NA
4.0
-------
TABLE V-26
HANDWASH
MASTEWATER CHARACTERISTICS
rag/1
O
Ui
Temperature (Deg C)
11 1,1,1-Trichioroethane
23. Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Ui-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126' Silver
128..Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
. Total Suspended Solids
pH, Minimum
pH, Maximum
PLANT G
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.42
0.03
0.000
0.02
NA
1.05
8.6
NA
0.000
NA
1.3
0.30
1.45
0.000
NA
NA
0.000
490.0
NA
8.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.04
0.03
0.000
0.000
NA
0.7
13.9
NA
0.05
NA
0.36
0.10
0.65
0.000
NA
NA
330.0
8.0
NA
8.0
NA - Not Analyzed
-------
N>
O
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trlchloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antiroony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
•128 21nc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
"Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-27
HANDHASH
WASTE LOADINGS
ng/kg
PLANT G
0.0256
30.0
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.011
0,0008
0.000
0.0005
NA
0.027
0.22
NA
0.000
HA
0.0331
0.008
0.037
0.000
NA
NA
0.000
12.5
NA
8.0
PLANT H
0.0159
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0006
0.0005
0.000
0.000
NA
0.01
0.221
NA
0.0008
NA
0.0057
0.002
0.010
0.000
NA
NA
5.25
0.76
NA
8.0
-------
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 ;Di-n-butyl phthalate
69 ;Di-n-octyl phthalate
78 Anthracene
81 'Phenanthrene
•84 Pyrene
;114 'Antimony
•115 -Arsenic
. 118 Cadmium
.119 Chromium, Total
Chromium, Hexavalent
120 'Copper
122 .Lead
123 Mercury
, 124 -.Nickel
126 'Silver
128 : Zinc
Aluminum
(-Iron
• Manganese
-Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH,' Minimum
.pH, Maximum
NA - Not Analyzed
TABLE V-28
RESPIRATOR WASH
WASTEWATER CHARACTERISTICS
tog/I
PLANT G
55.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0004
0.0002
0.0003
0.000
NA
0.3
0.33
NA
0.0
NA
0.31
0.000
0.003
0.000
NA
NA
6.2
7.1
NA
7.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
0.62
NA
0.5
5.9
NA
0.4
NA
0.52
0.000
0.35
0.000
NA
NA
5.0
14.0
NA
7.0
-------
TABLE V-29
RESPIEATOR WASH
WASTE LOADINGS
-rag/kg
O
CD
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Dl-n-butyl phthalate
69 Di-n-oetyl phthalate
7.8 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
t15 Arsenic
1.18 Cadmium
1.19 Chromium, Total
Chromium, Hexavalent
120 Copper
122 . Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
- pH, Maximum
PLANT G
0.0063
55.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
0.000
NA
0.002
0.0021
NA
0.000
NA
0.002
0.000
0.000
0.000
NA
NA
0.039
0.045
NA
7.0
PLANT H
0.0269
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
0.017
NA
0.014
0.16
NA
0,01
NA
0.014
0.000
0.009
0.000
NA
NA
0.13
0.38
NA
7.0
NA - Not Analyzed
-------
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
'66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 line.
Aluminum
Iron ""'
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-30
LAUNDRY
WASTEWATER CHARACTERISTICS
rag/1
PLANT G
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
0.15
0.02
0.000
0.000
NA
0.2
14.9
NA
0.000
NA
1.06
0.30
1.35
0.000
NA
NA
90.0
110.0
NA
6.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA .
NA
NA
NA
NA
0.06
0.000
0.000
0.000
NA
0.25
11.5
NA
0.000
NA
0.1
0.20
0.55
0.000
NA
NA
8.4
160.0
' NA
6.0
-------
O
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA - Not Analyzed
TABLE V-31
LAUNDRY
WASTE LOADINGS
PLANT G
0.0850
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.013
0.002
0.000
0.000
NA
0.017
1.27
NA
0.000
NA
0.090
0.026
0. 115
0,000
NA
NA
7.65
9.35
NA
6.0
PLANT H
0.0919
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0055
0.000
0.000
0.000
NA
0.023
1.057
NA
0.000
NA
0.009
0.018
0.051
0.000
NA
NA
0.77
14.7
NA
6.0
-------
TABLE V-32
REPORTED TOTAL PROCESS FLOW
Plant Number
107
110
112
122
132
133
135
138
144
146
147
152
155
158
170
173
178
179
182
184
190
191
198
207
208
212
213
226
233
237
239
242
255
261
269
277
,278
280
Reported
Flow
Rate (1/hr)
Plant Number
Reported
Flow
Rate (l/hr)
Plant Number
1503
NA
3180
11706
NA
NA
0
NA
0
6815
0
9280
NA
0
0
0
0
7.57
NA
0
0
37325
10266
18851
NA
7041
454
9312
9375
11129
6106
NA
NA
2271
12212
NA
5770
NA
288
295
299
311
320
321
331
342
346
349
350
356
358
361
366
370
371
372
374
377
382
386
387
400
402
403
406
421
429
430
436
439
444
446
448
450
462
463
NA
0
0
20895
34450
0
2498
61920
0
7845
NA
0
7041
NA
0
NA
3390
0
3861
0
1197
7950
2006
3835
NA
NA
NA
0
0
0
0
29000
0
2063
14645
27252
2574
NA
466
467
469
472
480
486
491
493
494
495
501
503
504
513
517
520
521
522
526
529
536
543
549
553
572
575
594
620
623
634
635
640
646
652
656
668
672
677
Reported
Flow
Rate (1/hr)
0
0
15
0
30610
NA
NA
NA
3110
0
12624
0
0
1363
0
4542
0
0
18170
570
NA
0
47470
3449
2275
3634
0
NA
NA
1590
1685
25196
476
12705
NA
0
52950
0
-------
TABLE V-32 (Continued)
REPORTED TOTAL PROCESS FLOW
ro
fsi
Plane Number
680
' 681
682
683
" 685
686
690
. - 704
705
706
'708
714
716
717
- 721
, . 722
725
730
731
732
733
738
740
746
Reported
Flow
Race (1/hr)
Plant Number
1534
4542
6814
0
6359
8404
0
27125
3180
0
NA
1590
NA
6490
0
NA
0
443
2858
3607
NA
29080
NA
0
765
768
771
772
775
777
781
785
786
790
796
811
814
815
817
820
828
832
844
852
854
857
863
866
Reported
Flow
Rate (1/hr) Plant Number
11690
7881
1363
11500
4088
4325
NA
41660
5120
0
0
NA
13130
598
0
3407
40
10520
NA
16070
0
0
11055
0
877
880
883
893
901
917
920
927
936
939
942
943
947
951
963
964
968
971
972
976
978
7 982
979
990
Repotted
Flow
Rate (1/hr)
46165
0
0
2470
0
18851
NA
0
3706
NA
0
17261
18397
1135
0
0
0
0
23837
26801
1840
10540
0
3180
-------
TABLE V-33
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
Plant ID Treatment In-Place Discharge ''
107 pH adjust, settling I
110 None I
112 pH adjust I (C)
122 pH adjustment, settling, lagooning D
132 None I
133 None indicated • U
135 None Zero
138 pH adjust I
144 pH adjust, clarification, sand filtration Zero
146 Settling, pH adjust, settling I
147 Evaporation Zero
N> 152 pH adjust I
Co 155 None indicated U
158 None Zero
•170 None Zero
173 None indicated Zero
178 pH adjust, clarification, lagooning Zero
179 None I
182 None U
184 None Zero
190 None Zero
191 pH adjust . I (C)
198 pH adjust D (C)
207 pH adjust I (C)
208 pH adjust I
212 pH adjust, clarification I (C)
213 None I
226 pH adjust I (C)
233 pH adjust .• I
237 pH adjust, settling I
239 pH adjust, settling I
-------
TABLE V-33 (Continued)
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
Plant ID Treatment In-Place Discharge^/
242 None indicated U
255 None indicated U
261 pH adjust I (C)
269 pH adjust I
277 pH adjust, clarification I
278 pH adjust I
280 None indicated U
288 None indicated U
295 None indicated Zero
299 None Zero
311 pH adjust I
320 pH adjust I
321 None Zero
331 pH adjust I
342 pH adjust, lagooning I
346 None Zero
349 pH adjust, settle, filtration I
350 None indicated U
356 None indicated Zero
358 pH adjust, settle ' I
361 None I
366 None Zero
370 None indicated I
371 Clarification, filtration I
372 None Zero
374 pH adjust, filtration I
377 None Zero
382 pH adjust, clarification, sand filtration I
386 pH adjust, settling D (C)
387 pH adjust, filtration I
400 pH adjust, settling I
-------
TABLE V-33 (Continued)
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
Plant ID
402
403
406
421
429
430
436
439
444
446
448
450
462
463
466
467
469
472
480
486
491
493
494
495
501
503
504
513
517
520
Treatment In-Plaee
sand filtration
clarification, lagooning
filtration
settling, filtration
None indicated
None indicated
None indicated
None
None
None
Lagooning,
pH adjust,
None
pH adjust, coagulant addition, clarification,
filtration
pH adjust
pH adjust,
pH adjust.
None
Settling
None
pH adjust.
Settling,
pH adjust,
None
None indicated
None
pH adjust
None
pH adjust
pH adjust,
None
pH adjust,
None
pH adjust,
filtration
Discharge''
, settling
pH adjust,
pressure
clarification
filtration
coagulant addition, clarification
clarification
coagulant addition, settling,
U
U
U
Zero
Zero
Zero
Zero (C)
D
Zero
I
I
D
I
I
Zero
Zero
I
Zero
I
1
U
D
I
Zero
I
Zero
Zero
I
Zero
D (C)
-------
TABLE V-33 (Continued)
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
Plant ID
521
522
526
529
536
543
549
553
572
575
594
620
623
634
635
640
646
652
656
668
672
677
680
681
682
683
685
686
690
704
705
Treatment In-Place
None
None
pH adjust, settling
pH adjust, settling
None indicated
None
pi adjust
pH adjust
pH adjust
pH adjust
None
None indicated
None
pH adjust
adjust
pH
pH
pH
pH
clarification, filtration
settling
settling
filtration
filtration
adjust
adjust,
adjust
coagulant addition, clarification
None indicated
None
pH adjust,
None
pH adjust
adjust,
adjust,
adjust
adjust,
adjust,
Settling,
pH adjust
pH adjust,
pH
pH
pH
PH
pH
clarification
filtration
settling
settling
settle
atmospheric
settling
evaporation
Pis charge
Zero
Zero
I
I (C)
U
Zero
I
I
I
I
Zero
U
I
I
I
1
1
I
U
Zero
D
Zero
I
I
I (C)
Zero
I
I
Zero
I
1
(C)
-------
TABLE V-33 (Continued)
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
ND
Plant ID
706
708
714
716
717
721
722
725
730
731
732
733
738
740
746
765
768
771
772
775
111
781
785
786
790
796
811
814
815
817
Treatment In-Place
pH adjust
pH adjust
pH adjust
Settling
pH adjust
pH adjust
None
None
pH adjust
pH adjust
pH adjust
pH adjust
pH adjust
None indicated
None
pH adjust,
pH adjust,
pH adjusti
pH adjust,
settling
settling
settling
skimming,
aeration,
clarification
atmospheric evaporation
settling
sand filtration
clarification
settle
settling and filtration
coagulant addition, clarification,
pH adjust,
pH adjust,
pH adjust
pH adjust,
pH adjust,
None
None
Unknown
pH adjust
Zero
pH adjust,
clarification
flocculant addition,
clarification
flotation
flotation
settling
Discharge
Zero
I
1
I
I
Zero
U
Zero
D
- I
I
1
I
U
Zero
I
I
D
I
D (C)
I
1
I
I
Zero
Zero
U
I
I
Zero
-------
TABLE V-33 (Continued)
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
Ni
00
Plant ID
820
828
832
844
852
854
857
863
866
877
880
883
893
901
917
920
927
936
939
942
943
947
951
963
964
968
971
972
976
978
Treatment In-Place
Discharge^
pH adjust
None
pH adjust
pH adjust,
pH adjust,
settling
None
None
pH adjust,
None
pH adjust,
None
Settling
pH adjust
Settling
pH adjust
None
None
pH adjust,
None
None
pH adjust,
pH adjust,
Clarification
None
None
None
Settling,
pH adjust,
pH adjust
pH adjust,
settling
flocculant
addition, clarification,
clarification
clarification, filtration
settle
filtration
filtration
filtration
settling
flocculant addition, clarification
(C)
Zero
Zero
I
Zero
I
Zero
Zero
I
Zero
I
I
Zero
I
U
Zero
D
1 (C)
I (C)
Zero
Zero
Zero
Zero
I
I
I
-------
TABLE V-33 (Continued)
TREATMENT IN-PLACE AT LEAD SUBCATEGORY PLANTS
Plant ID Treatment In-Place Discharge
979 None Zero
982 pH adjust, settling I (C)
990 pH adjust I (C)
ro
I = Indirect
D = Direct
U = Unknown
C = Closed
-------
TABLE V-34
TOTAL RAW WASTE FOR VISITS
. ng/1
PLANT A
PLANT B
|S3
O
Temperature (Deg C) 18.2 18.9
11 1,1,1-Triohloroethane * *
23 Chloroform * *
44 Methylene chloride * * *
55 Naphthalene 0.006 0.013
65 Phenol NA 0.00
66 Bis(2-ethylhexyl)phthalate * *
67 Butyl benzyl phthalate * *
68 Di-n-butyl phthalate * 0.00
69 Dl-n-octyl phthalate 0.00 *
78 Anthracene * *
81 Phenanthrene * *
84 Pyrene 0.00 *
114 Antimony 0.002 0.000
115 Arsenic 0.000 0.000
118 Cadmium 0.027 0.003
119 Chromium. Total 0.120 0.032
Chromium, Hexavalent 0.000 0.000
120 -Copper 0.436 0.278
122 Lead 6.88 1.434
123 Mercury 0.0000 0.0100
124 Nickel 0.120 0.022
126 Silver 0.0000 0.000
128 Zinc ' 0.305 0.134
Aluminum NA NA
Iron 6.64 6.55
Manganese NA NA
Phenols, Total 0.015 0.014
Strontium 0.021 0.000
Oil & Grease 49.0 13.0
Total Suspended Solids 416.0 15.0
pH, Minimum 2.0 2.0
pH, MaKirauffl 11.9 6.8
18.0
*
0.00
0.00
0.015
NA
0.008
#
0.00
*
*
*
*
0.000
0.005
0.005
0.047
0.000
0.378
1.170
0,0260
0.027
0.000
0.193
NA
5.522
NA
0.050
0.000
9.2
16.4
2.0
5.7
17.0
0,025
*
*
*
*
0.135
0.017
*
0,140
0.032
0.032
*
0,000
0.000
0.008
0.009
0.000
0.083
• 13.00
% NA
0.000
0.0330
0.333
NA
2.000
NA
0.008
NA
36.5
57.8
2.2
3.6
17.0
*
0.00
*
*
NA
0,044
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.003
0.012
NA
0.090
15.40
0.000
0.000
0.0070
0.350
NA
3.800
NA
0.000
0.000
10.6
31.2
2.0
4.9
17.0
*
0.00
0.00
*
NA
0.030
0.00
0.00
0.00
0.00
0.00
*
0.000
0.000
0.012
0.017
NA
0.110
45.90
0.000
0.020
0.015C
0.380
NA
4.370
NA
0.000
0.000
5.2
52.4
1.8
3.9
NA - Not Analyzed
* - < 0.01
-------
TABLE V-34 (continued)
N>
Temperature (Deg C) 15.3
11 1,1,1-Trichloroethane *
23 Chloroform : 0.00
44 Methylene chloride 0.00
55 Naphthalene *
65 Phenol NA
66 Bis(2-ethylhexyl)phthalate *
67 Bucyl benzyl phthalate 0.00
68 Di-n-butyL phthalate 0.00
69 Di-n-octyl phthalate 0.00
78 Anthracene 0.00
81 Phenanthrene 0.00
84 Pyrene 0.00
114 Antimony 0.000
115 Arsenic 0.000
118 Cadmium 0.000
119 Chromium, Total 0.097
120 Copper 0.063
1 22 Lead 1.000
123 Mercury 0.000
124 Nickel 0.077
126 Silver 0.000
128 Zinc 0.054
Aluminum NA
Iron 9.24
Manganese NA
Phenols, Total 0.000
Strontium 0.027
Oil & Grease 3.1
Total Suspended Solids 6.0
pH, Minimum 2.1
pH, Maximum 2.9
TOTAL RAW WASTE FOR VISITS
mg/1
PLANT C
16.5
*
0.00
*
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.057
0,078
1.360
0.000
0.036
0,000
0.120
NA
15.51
NA
0.000
0.033
4.0
14.0
2.0
2.4
PLANT D
PLANT E
6.7
*
0.00
*
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.068
0.053
1.450
0.000
0.069
0.000
0.190
NA
9.41
NA
0.000
0.033
3.9
5.0
2.0
2.4
35.1
*
*
*
0.001
NA
0.032
*
*
*
*
*
*
0.000
0.019
0.002
0.670
0.324
18.29
0.000
0.384
0.0000
0.747
NA
15.45
NA
0.018
0.000
10.3
350.1
2.0
12.0
33.5
*
*
*
0.001
NA
0.037
*
' *
*
*
*
0.00
0.090
0.000
0.004
0.732
0.772
15.64
0.000
0.506
0. 0000
1.068
NA
20.14
NA
0.038
0.000
9.4
974.0
2.0
12.0
28.0
*
*
0.00
0.002
NA
0.050
*
*
*
*"
*
0.00
0.194
0.116
0.004
3.267
2.502
44.94
0.000
2.493
0.0230
6.80
NA
74.0
NA
0.028
0.003
16.7
1300.0
2.0
12.0
NA
*
o.oo
0.00
0.00
0.00
*
0.00
*
0.00
0.00
0.00
0.00
0.130
NA
0.034
NA
NA
13.40
0.046C
NA
0.008C
3.88
NA
390.0
NA
0.020
0.000
3.0
184.0
NA
NA
NA - Not Analyzed
* - < 0,01
-------
TABLE V-34 (Continued)
TOTAL RAW WASTE FOR VISITS
ng/l
PLANT F
N>
N>
11
23
44
55
65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
Temperature (Deg C)
1,1,1 -Triehloroethane
Chloroform
Methylene chloride
Naphthalene
Phenol
Bis (2-e'thylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrene,
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
27.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.114
0.014
0.0054
0.244
NA
0.155
135.4
NA
0.192
NA
1.398
1.748
12.084
0.1053
NA
NA
6.27
57.36
1.7
10.11
38.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.536
0.041
0.008
0.090
NA
0.273
36.2
NA
0.021
NA
0.871
2.80
20.1
0.42
NA
«NA
12.6
249.0
1.5
8.0
PLANT G
38.0
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
' NA
0.415
0.030
0.004
0.103
NA
0.165
13.5
NA
0.055
NA
0.736
2.12
23.6
0.34
NA
NA
10.4
257.0
2.0
8.0
38.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.226
0.010
0.0001
0.020
NA
0.122
13.2
NA
0.008
NA
0.616
0.53
6.6
0.11
NA
NA
6.3
70.0
2.0
8.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.078
0.004
0.002
0.047
NA
0.150
23.9
NA
0.027
NA
0.131
1.61
6.60
0. J1
NA
NA
32.5
93.9
1.0
8.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.054
0.004
0.004
0.060
NA
0.115
12.5
NA
0.036
NA
0.300
1.44
7.41
0.11
NA
NA
40.8
57.6
1.0
8.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.076
0.002
0.001
0.054
NA
0.074
24.1
NA
0.032
NA
0.211
1.22
4.94
0.09
NA
NA
4.77
40.4
1.0
8.0
NA - Not Analyzed
-------
TABLE V-35
LEAD SUBCATEGORY
TOTAL RAW WASTE LOADINGS
mg/kg
PLANT A
to
to
u>
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
1.207 1.196
18.2 18.9
0.00 0.00
0.00 0.00
0.00 0.00
0.008 0.016
NA 0.00
0.00 0.00
0.00 0.00
0.00 0.00
0.00 0.00
0.00 0.00
0.00 0.00
0.00 0.00
0.002 0.000
0.000 0.000
0. 033 0. 004
0.145 0.038
0.000 0.000
0.526 0.333
8.31 1.715
0.0000 0.0120
0.145 0.026
0.0000 0.0000
0.368 0.160
NA NA
8.02 7.84
NA NA
0.019 0.017
0.025 0.000
59.15 15.51
502.2 17.97
2.0 2.0
11.9 6.8
0.705
18.0
0.00
0.00
0.00
0.011
NA
0.006
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.004
0.004
0.033
0.000
0.266
0.825
0.0185
0.019
0.0000
0.136
NA
3.894
NA
0.035
0.000
6.52
11.60
2.0
5.7
8.84
17.0
0.221
0.00
0.00
0.00
0.00
1.193
0.150
0.00
1.237
0.283
0.283
0.00
0.000
0.000
0.071
0.080
0.000
0.734
114.9
NA
0.000
0.2920
2.943
NA
17.68
NA
0.071
NA
322.6
510.8
2.2
3.6
PLANT B
9.87
17.0
0.00
0.00
0.00
0.00
NA
0.434
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.030
0.118
NA
0.889
152.0
0.000
0.000
0.0690
3.455
NA
37.52
NA
0.000
0.000
104.7
308.0
2.0
4.9
10.27
17.0
0.00
0.00
0.00
0.00
NA
0.308
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.123
0.175
NA
1.130
471.4
0.000
0.205
0. 0000
3.903
NA
44.88
NA
0.000
0.000
53.41 '
538.2
1.8
3.9
NA - Not Analyzed
-------
TABLE V-35 (Continued)
LEAD SUBCATEGORY
TOTAL RAW WASTE LOADINGS
mg/kg
PLANT C
Flow (I/kg) 6,68 6.59
Temperature (Deg C) 15.3 16.5
11 1,1,1-Trichloroethane 0.00 0.00
23 Chloroform ' 0.00 0.00
44 Methylene chloride 0.00 0.00
55 Naphthalene 0.00 0.00
65 Phenol NA NA
66 Bis(2-ethylhexyl)phthalate 0.00 0.066
67 Butyl benzyl phthalate 0,00 0.00
68 Dl-n-butyl phthalate 0.00 0.00
69 Dl-n-octyl phthalate 0.00 0.00
78 Anthracene 0.00 0.00
81 Phenanthrene 0.00 0.00
84 Pyrene 0.00 0.00
114 Antimony 0.000 0.000
115 Arsenic 0.000 0.000
118 Cadmium 0.000 0.000
119 Chromium, Total 0.648 0.376
Chromium, Hexavalent NA NA
120 Copper 0.421 0.514
122 Lead ' 6.68 8.96
123 Mercury 0.0000 0.0000
124 Nickel 0.515 0.237
126 Silver 0.0000 0.0000
128 Zinc 0.361 0.791
Aluminum NA NA
Iron 61.8 102.2
Manganese NA NA
Phenols, Total 0.000 0.000
Strontium 0.180 0.218
Oil & Grease 20.72 26.37
Total Suspended Solids 40.11 92.28
pH, Minimum 2.1 2.0
pH, Maximum 2.9 2.4
PLANT D
PLANT E
6.98
16.7
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.474
NA
0.370
10.12
0. 0000
0.481
0. 0000
1.326
NA
65.7
NA
0.000
0.230
27.21
34.89
2.0
2.4
1.351
35.1
0.00
0.00
0.00
0.00
NA
0.043
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.025
0.003
0.905
NA
0.437
24.71
0. 0000
0.519
0.0010
1.009
NA
20.87
NA
0.025
0.000
13.96
472.8
2.0
12.0
1.252
33.5
0.00
0.00
0.00
0.00
NA
0.046
. 0.00
0.00
0.00
0.00
0.00
0.00
0.113
0.000
0.005
0.917
NA
0.967
19.60
0. 0000
0.634
0.0010
1.337
NA
25.21
NA
0.048
0.000
11.82
1220.0
2.0
12.0
0.562
28.0
0.00
0.00
0.00
0.00
NA
0.028
0.00
0.00
0.00
0.00
0.00
0.00
0.109
0.065
0.002
1.835
NA
1.405
25.24
0. 0000
1.400
0.0129
3.821
NA
41.58
NA
0.016
0.001
9.36
731.0
2.0
12.0
0.218
NA
0.00
0.00
0.00
0.00
0.00 -
0.000
0.00
0.00
0.00
0.00
0.00
0.00
0.028
NA
0.007
NA
0.000
NA
2.920
0.0101
NA
0. 001 8
0.845
NA
85.0
NA
0.004
0.000
0.654
40.1
NA
NA
NA - Not Analyzed
-------
TABLE V-35 (Continued)
LEAD SUBCATEGORY
TOTAL RAW WASTE LOADINGS
rag/kg
PLANT F
N>
Flow (I/kg)
Temperature (Deg C)
11 1,I,1-Triehloroethane
23 Chloroform
44 ; Methylene chloride
55 Naphthalene.
65 Phenol
66 Bia(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 " Antimony
115 Arsenic
118 .'-Cadmium
119 ,'Chromium, Total
^Chromium, Hexavalent
120 ,-Copper
122 . Lead
123 - Mercury
124 ' Nickel
126 ., Si Iver, .
128 . Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium •
•Oil &; Grease
Total Suspended Solids
pH, Minimum.
pH, Maximum
0.407
27.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.0465
0.0055
0.002
0.010
NA
0.063
55.16
NA
0.078
NA
0.570
0.711
4.92
0.043
NA
NA
2.55
23.37
1.7
10.11
1.02
38.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
' NA
0.545
0.042
0.008
0.091
NA
0.277
36.8
NA
0.021
NA
0.885
2.86
20.4
0.43
NA
NA
12.7
253.0
1.5
8.0
PLANT G
1.4
38.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.582
0.042
0.006
0.145
NA
0.232
18.9
NA
0.077
NA
1.03
2.97
33.0
0.48
NA
NA
14.6
360.0
2.0
8.0
2.10
38.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.474
0.020
0. 0002
0. 0425
NA
0.2563
27.7
NA
0.016
NA
1.29
1.11
13.9
0.23
NA
NA
13.3
146.0
2.0
8.0
3.36
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.262
0.012
0.006
0.157
NA
0.504
80.4
NA
0. 090
NA
0.439
5.41
22.2
0.37
NA
NA
109.0
315.0
1.0
8.0
PLANT H
3.17
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.172
0.011
0.013
0.190
NA
0.365
39.7
NA
0.114
NA
0.951
4.56
23.5
0.35
NA
NA
129.0
183.0
1.0
8.0
7.65
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.583
0.018
0.010
0.410
NA
0.565
185.0
NA
0.247
NA
1.617
9.33
37.8
0.69
NA
NA
36.5
309.3
1.0
8.0
NA - Not Analyzed
-------
TABLE V-36
STATISTICAL ANALYSIS (rag/1) OF THE LEAD SUBCATEGORY TOTAL
RAW WASTE CONCENTRATIONS
Minimum
Maximum
Mean
N>
to
ON
Temperature (Deg C)
11 1,1,1-TrichloroeChane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-eehylhexyl)phthalate
67 Butyl benzyl phchalate
68 Di-n-butyl phthalate
69 Di-n-oceyl phchalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Cdpper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oi1 & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
5.3
*
0.00
0.00
0.00
0.00
*
0.00
0.00
0.00
0.00
0,00
0.00
0.000
0,000
0.000
0.009
0.000
0.053
1,0
0.0000
0.000
0.0000
0.054
0.53
2,0
0.09
0.000
0.000
3.0
5.0
1.0
2.4
38.0
0.025
*
*
0.015
*
0.135
0.017
*
0.140
0.032
0.032
*
0.536
0.116
0.034
3.267
0.000
2.502
135.4
0.046
2.493
0.0330
6.8
2.80
390.0
0.42
0.050
0.033
49.0
1,300.0
2.2
11.9
25.4
0.002
*
*
0.003
*
0.029
0.001
*
0.011
0.002
0.002
*
0.096
0.013
0.006
0.301
0.000
0.327
21.93
0.0068
0.217
0.0066
0.941
1.638
32.2
0.184
0.015
0.010
14.4
212.4
1.8
7.3
Med ian
27.0
*
0.00
*
*
*
0.030
*
*
0.00
*
*
0.00
0.028
0.002
0.004
0.06
0.000
0.15
13.45
0.0000
0.036
0.0000
0.342
1.61
8.3
0.11
0.014
0.000
9.9
7
57
2.0
8.0
I
Val
19
13
6
8
10
1
13
7
8
6
7
7
5
11
10
17
19
0
19
20
4
17
8
20
7
20
7
8
5
20
20
19
19
#
Zeros
0
0
7
5
3
2
0
6
5
7
6
6
8
9
9
3
0
5
0
0
8
2
5
0
0
0
0
5
7
0
0
0
0
* - < 0.01
-------
TABLE V-37
STATISTICAL ANALYSIS (rag/kg) OF THE LEAD SUBCATEGORY
TOTAL RAW WASTE LOADINGS
Minimum
Maximum
Mean
Median
Flow (L/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
65 Phenol '
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total.
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
0.218
15.3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.01
0.000
0.063
0.825
0.0000
0. 000
0.000
0.136
0.711
3.894
0.043
0.000
0.000
0.654
11.6
1.0
2.4
10.27
38.0
0.221
0.00
0.016
0.00
1.193
0.028
0.00
1.237
0.283
0.283
0.00
0.583
0.065
0.123
1.835
0.000
1.405
471.4
0.0185
1.4
0.2920
3.903
9.33
102.2
0.69
0.071
0.230
322.6
1220.0
2.2
11.9
3.74
25.4
0.017
0.00
0.00
0.00
0.185
0.012
0.00
0.095
0.022
0.022
0.00
0.146
0.013
0.016
0.357
0.000
0.540
64.55
0.0034
0.2539
0.0291
1.362
3.850
33.89
0.370
0.018
0.055
49.48
305.5
1.8
7.3
1.75
27.0
0.00
0.00
0.00
0.00
0.043
0.00
0.00
0.00
0.00
0.00
0.00
0.015
0.004
0.0055
0.157
0.000
0.437
24.98
0.0000
0.114
0.0000
0.98
2.97
24.36
0.37'
0.016
0.000
18.12
280.5
2.0
8.0
-------
TABLE V-38
EFFLUENT CHARACTERISTICS REPORTED IN DCP BY PLANTS PRACTICING
pH ADJUSTMENT AND SETTLING TECHNOLOGY
00
ID #
Direct/
Indirect
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
D
I
I
D
I
I
I
D
I
I
D
I
I
D
I
Production
Normalized
Effluent
I/kg
5.10
1.88
3.15
8.0
4.56
9.76
2.01
6.35
13.32
51.
1.
1.
2,
5.
9
74
34
57
76
pH
6.9
7.5
6.9
7
6.65
Pollutant Parameters (mg/1)
O&G
8.2
4.5
TSS
20
1.58
5.85
26.14
3.7
3
1.4
4.6
330
257.7
Fe
2.7
0.2
Pb
1.1-4.3
7.5
0.4
0.5
1.0
0.8
0.187
1.0
0.28
1.0
0.25
Zn
Paste
Recirc
0.1
X
X
-------
TABLE V-39
EFFLUENT CHARACTERISTICS REPORTED IN INDUSTRY SURVEY BY PLANTS PRACTICING
pH ADJUSTMENT AND SETTLING TECHNOLOGY
Pollutant Parameters (mg/1)
to
NS
ID t
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Q
R
S
T
U
V
Direct/
Indirect
D
I
I
I
I
I
D
i
i
i
D
I
'1
I 1
I
1
I
I
I
I
I
I
Influent to WWT
PH
1.66
2
3-11
2.0
1.5-6.7
2.1
1.25
2.;61
1
.25-3.5
2
3-9
1.7
2
2
TSS
<100
3,580
1,203
38
100
1,500
13,470
81
Pb 304
28.8 2,250
1-15
18
8-75
450
18.5 .7,820
7.90
1-10
49-80 6,073
1-10
1-40
1,300
5.7
Average Effluent from
pH
8.0
7.41
7.93
8
7.6
8
8.2
8.76
7.8
9.0
9.0
9.0
8.8-9.2
9.2
7.9
8
7.5
TSS
4,810
3.80
29
30
7
34
50
29
150
300-500
57.1
70.0
48.3
90
Pb
0.47
3.36
2.3
1.51
0.09
0.5
0,76
2.3
0.14
0.55
1.1
3.11
0.5
1.1
3.5
1.30
6.0
2.91
0.1
0.3
WWT Permit or
804 pH
6-9
5.5-10
6.0-9.0
5.5-10
6-9.5
6.5-8.5
6-10
6-9
6-9
5.5-9.5
6.5-9.5
>6.0
6.0-9.5
6-9.5
>6.0
6-9
6-10
6.5-9
TSS
250
400
250
None
20
50
None
None
None
250
250
POTW Limit
Pb 804
0.4
10
1.0
0.5
0.6
0.05
0.14
0.5
3.0
40
3.0
0.5
40.0
5.0
< - Less Than
> - Greater Than
WWT - Wastewater treatment
-------
TABLE V-40
EFFLUENT CHARACTERISTICS REPORTED IN DCP BY PLANTS PRACTICING
pH ADJUSTMENT AND FILTRATION
K>
W
o
ID #
A
B
C-f-
D
E
F
G
Direct/
Indirect
I
D
I
I
I
D
I
Production
Normalized
Effluent
I/kg
2.78
4.41
43.1
1.56
3.46
9.9
0.70
Pollutant Parameters (mg/1)
pH
7.5
7.5
11.2
O&G
TSS
0
0.0
Fe
0.3
Pb
1.0
0.05
0.5
0.3
0.47
0.25
Past
Zn Recir
0.1
0.34
0.1
X
Filter & Settle,
-------
TABLE V-41
EFFLUENT CHARACTERISTICS REPORTED IN INDUSTRY SURVEY BY PLANTS PRACTICING
pH ADJUSTMENT AND FILTER TECHNOLOGY
Pollutant Parameters (mg/1)
Direct/ Influent to WWT
ID ff
A
B
C
D
E
F
G
H
Direct/
Indirect
I
I
0
I
I
I
1
D
Influent to WWT
2
2
<1
<2
1
pH TSS
.0
.0
.0
.0
.7
Pb S04
10
6.9
5-300
7.0
26.4
Average Effluent
pH
7.1
7.3
7.5
7.5
7.5
6.92
8.7
7.67
TSS
0
0
1
2
0
0
29 0
from WWT
Pb S04
.9
.3
.0
.0
.25
.5 1,850
.24
Permit or
PH
5-12
6-9
6-9
6-9
6-10
6-9
6-9
6-9
TSS
265
20
POTW Limit
0
0
2
0
0
Pb
.5
.07
.5
.14
S(>4
75C
< - Less Than
WWT - Wastewater Treatment
-------
TABLE V-42
EFFLUENT 'CHARACTERISTICS REPORTED IN DCP BY PLANTS PRACTICING
pH ADJUSTMENT ONLY
ID #
Direct/
Indirect
A
B
C
D
E
F
G
H
I
J+
K •
L
I
I
I
I
I
I
I
I
I
I
I
I
Production
Normalized
Effluent
I/kg pH
6.07
22.9
3.73
81.7
13.5
5.35
51.9 6.95
10.1
5.02 5.7
26.4
63.3
15.0
Pollutant Parameters (mg/1)
O&G TSS Fe Pb
1.4
33
32
0.2
29.8
10-15
2.77
6.0
27.5
1.0
3.95
10-15
3.0
26.92
Paste
Zn Recirc
0.4
0.24
- Reports no effluent treatment prior to release to
POTW.
-------
TABLE V-43
EFFLUENT CHARACTERISTICS REPORTED IN INDUSTRY SURVEY BY PLANTS PRACTICING
pH ADJUSTMENT ONLY
ID #
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Q
R
Direct/
Indirect pH
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
2-10
2-9
1-2
2
2-9
<2. 0
1-11
2
1-10
2-12
2-12
1-12
Influent
TSS
<100
50-750
346
<100
50-150 1
200-1,500
<100
<75
<100
to WWT
Polli
itant Par
rameters (
.mR/1)
Average Effluent trom WWT Permit or
Pb S04 pH
1-15
2-20
6.5
15-100
.0-10.0
7-25
2-50
1-15
2-10
7.2
7.0
7.8
7.5
6.5
8
7
-7.5
8
6.5
8
7.8
8.4
8
6.6
6.5-7.5
8.7
TSS
50
25
350
<100
47
50
5,200
100
<300
<75
68
67
<50
Pb
3.9
3.5
1.5
3.8
6.0
5
1.25
4.0
20.6
6.0
0.5
4.0
2.3
13.2
3.0
5.6
304 pH
6.0-9.0
6-9.5
6-9.5
5-10
5.5-10
5.5-9.5
5-10
6-9.5
5-10
2,000 5.5-7
6-9.0
6-9.5
5.5-10
6-9
6-9.5
6-9
TSS
275
300
350
<300
POTW Limit
Pb SO;
15.0
None
2
1.0
1.0
0.5
1.0
2.0
0.2
0.5
0.3
40
None
< - Less Than
WWT - Wastewater Treatment
-------
TABLE V-44
INFLUENT TO WASTEWATER TREATMENT
POLLUTANT CHARACTERISTICS
ng/l
PLANT F
S3
CO
Temperature (Deg C) 28.0
!1 1,1,1-Trichloroethane NA
23 Chloroform NA
44 Methylene chloride NA
55 Naphthalene NA
65 Phenol NA
66 Bis(2-ethylhexyl)phthalate NA
67 Butyl benzyl phthalate NA
68 Di-n-butyl phthalate NA
69 Di-n-octyl phthalate NA
78 Anthracene NA
81 Phenanthrene NA
84 Py-rene NA
114 Antimony 0.021
1.15 Arsenic 0.017
1,18 Cadmium 0.009
119 Chromium,' Total 0.66
Chromium, Hexavalent NA
120 Copper 0.2
122 Lead 4.8
123 Mercury NA
124 Nickel 0.47
126 Silver . NA
128 Zinc 2.8
Aluminum . 0.87
Iron 23.0
Manganese 0.000
Phenols, Total , . NA
Strontium NA
Oil & Grease 0.000
Total Suspended Solids ' 26.0
pH, Minimum 1.4
pk. Maximum 1.5
27.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.017 '
0.006
0.000
0.51
NA
0.089
4.3
NA
0.39
NA
0.34
0.54
18.0
0.23
NA
NA
0.000
26.0
1.3
1.6
28.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.26
0.04
0.04
0.06
NA
0.15
4.2
NA
0.05
NA
0.78
2.6
9.8
0.15
NA
NA
2.0-
270.0
1.5
1.5
PLANT G
28.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.28
0.02
0.000
0.08
NA
0.1
14.6
NA
0.05
NA
0.76
1.6
8.2
0.15
NA
NA
18.0
70.0
1.5
2.0
26.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.21
0.01
0.000
0.06
NA
0.05
6.6
NA
0.05
NA
0.6
1.1
5.2
0.2
NA
NA
22.0
52.0
1.5
1.7
NA - Not Analyzed
-------
TABLE V-44 (Continued)
INFLUENT TO WASTEWATER TREATMENT
POLLUTANT CHARACTERISTICS
mg/1
US
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 ^Di-n-butyl phthalate
69 'Di-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
,114 ,,Antimony
115 ,Arsenle
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
,124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
2.1
0.42
1.8
0.000
NA
0.5
25.0
NA
0.5
NA
3.2
4.0
21.0
1.0
NA
NA
2.0
22.0
1.0
6.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
3.6
0.54
1.6
0.000
NA
1.0
21.0
NA
0.5
NA
2.6
4.0
30.5
1.0
NA
NA
9.4
95.0
1.0
1.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
7.0
0.94
2.0
0.000
NA
2.5
41.0
NA
1.5
NA
10.8
8.0
54.5
2.0
NA
NA
12.0
200.0
1.0
1.0
NA - Not Analyzed
-------
PLANT B
TABLE V-45
EFFLUENT FROM SAMPLED PLANTS
ng/1
PLANT C
CO
Temperature (Deg C) 17.0 17.0
11 1,1,1-Trichloroethane * *
23 Chloroform 0.029 0.00
44 Methylene chloride * 0.00
55 Naphthalene 0.00 0.00
65 .Phenol * NA
66 Bis(2-ethylhexyl)phthalate 0.016 *
67 Butyl benzyl phthalate 0.00 *
68 Di-n-butyl phthalate * 0.00
69 Di-n-octyl phthalate 0.00 0.00
78 Anthracene * 0.00
81 Phenanthrene * 0.00
84 Pyrene * 0.00
114 Antimony 0.000 0.000
115 Arsenic 0.000 0.000
118 Cadmium 0.003 0.000
119 Chromium, Total 0.000 0.010
Chromium, Hexavalent 0.000 NA
120 Copper 0.000 0.040
122 Lead 1.350 4.050
123 Mercury NA 0.000
124 Nickel 0.000 0.000
126 Silver 0.000 0.000
128 Zinc 0.095 0.096
Aluminum NA NA
Iron 0.000 0.710
Manganese NA NA
Phenols, Total 0.000 0.000
Strontium NA 0.020
Oil & Grease 10.0 9.9
Total Suspended Solids 90.6 76.0
pH, Minimum 6.5 7.2
pH, Maximum 8.5 8.8
17.0
*
0.00
0.00
0.00
NA
*
0.00
0.00
*
0.00
0.00
0.00
0.000
0.000
0.000
0.005
NA
0.034
3.580
0.000
0.012
0.000
0.084
NA
0.590
NA
0.000
0.013
5.0
39.8
6.6
7.9
7.60
*
0.00
0.00
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.000
NA
0.018
0.110
0.000
0.011
0.000
0.000
NA
0.760
NA
0.000
0.029
1.4
13.0
9.0
9.3
7.80
*
0.00
*
0.00
NA
*
*
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.005
NA
0.014
0.130
0.000
0.009
0.000
0.000
NA
0.920
NA
0.000
027
7
0
7
0
2
11
8
9.1
8.50
*
0.00
*
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.005
NA
0.019
0.110
0.000
0.011
0.000
0.037
NA
0.950
NA
0.000
0.027
2.2
11.0
8.6
9.1
NA - Not Analyzed
* - < 0.01
-------
TABLE V-45 (continued)
EFFLUENT FROM SAMPLED PLANTS
mg/1
K>
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69. Dl-n-octyl phthalate
78 Anthracene
81 . Phenanthtene
84 -Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
• Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
1'24 Nickel
126 Silver
128 Zinc
Aluminum
Iron ,
Manganese
. Phenols,- Total
StronCiun
Oil & Crease
Tocal Suspended Solids
pH, Minimum
. pH,-Maximum
32,0
*
*
*
0.00
NA
*
*
*
0,00
*
*
0.00
0,000
0.000
0.000
0.010
NA
0.059
6.06
0.000
0.110
0.000
0.165
NA
0.420
NA
0.019
0.000
2.3
3.5
6.0
10.4
PLANT D
31.0
*
0.00
NA
0.023
0.023
0.00
0.00
*
0.00
.0,000
0.000
0.000
0.010
NA
0.050
3,880
0.000
0.068
0.000
0.000
NA
0.280
NA
0.014
0.000
7
0
7
PLANT F
1
11
7
9.2
NA
*
*
*
0.00
NA
0.00
0.00
*
0.00
*
*
o.oo'
0.000
0.000
0.000
0.059
NA
0.090
13.30
0.000
0.046
0.000
0.105
NA
3.380
NA
0.006
0.000
7.0
66.0
7.0
9.0
28.0
NA
NA
NA
NA
NA
NA
NA
NA
- ' NA
NA
NA
NA
0.044
0,043
0.007
0.000
NA
0.023
0.000
NA
0.31
NA
0.15
0.000
0.000
0.10
NA
NA
0.000
33.0
NA
NA
28.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.060
0.037
0.003
0.000-
NA
0.012
0,000
NA
0.35
NA
0.000
0.000
0.000
0.1'3
NA
NA
0.000
25.0
NA
7.11
NA - Not Analyzed
* - < 0.01
-------
TABLE V-45 (Continued)
EFFLUENT FROM SAMPLED PLANTS
ag/1
N>
U»
00
PLANT G
Temperature (Deg C) 24.0 23.0
11 1,1,1-Trichloroethane HA NA
23 Chloroform NA NA
44 Methylene chloride NA NA
55 Naphthalene NA NA
65 Phenol NA NA
66 Bis(2-ethylhexyl)phthalate NA NA
67 Butyl benzyl phthalate . NA NA
68 Di-n-butyl phthalate NA NA
69 Di-n-octyl phthalate NA NA
78 Anthracene NA NA
81 Phenanthrene NA NA
84 Pyrene NA NA
114 Antimony 0.12 0.13
115 Arsenic 0.000 0.000
118 Cadmium 0.000 0.000
119 Chromium, Total 0.000 0.000
Chromium, Hexavalent NA - NA
120 Copper 0.000 0.000
122 Lead 0.2 0.1
123 -Mercury NA NA
124 Nickel 0.000 0.000
126 Silver NA NA
128 Zinc 0.06 0.02
Aluminum 0.1 0.1
Iron 0.05 0.05
Manganese 0.1 0.1
Phenols, Total NA NA
Strontium NA NA
Oil & Grease 0.000 0.000
Total Suspended Solids 15.0 5.0
pH, Minimum 7.5 . 7.6
pH, Maximum 7.6 8.1
24.0
NA
NA
NA
•NA
NA
NA
NA
NA
NA
NA
NA
NA
0.17
0.000
0.000
0.000
NA
0.05
0.3
NA
0.000
NA
0.06
0.1
0.1
0.1
NA
NA
4.2
9.0
8.0
8.8
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.3
0.000
0.04
0.000
NA
0.05
0.1
NA
0.000
NA
0.000
0.2
0.1
0.150
NA
NA
9.0
140.0
NA
9.0
PLANT H
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.6
0.000
0.000
0.000
NA
0.000
0.07
NA
0.000
NA
0.000
0.000
0.000
0.000
NA
NA
0.000
46.0
NA
9.0
30.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.7
0.000
0.000
0.000
NA
0.000
0.19
NA
0.000
NA
0.000
0.000
0.000
0.000
NA
NA
2.0
25.0
NA
9.0
NA - Not Analyzed
* - < 0.01
-------
TABLE V-45 (Continued)
EFFLUENT FROM SAMPLED PLANTS
mg/1
LO
Temperature (Deg C)
•11 1 ,1 ,1-Trichloroethane
•23 Chloroform
44 Methylene chloride
55 Naphthalene
65 Phenol
66 Bls(2-ethylhexyl)phchalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Ot-n-octyl phthalate
78 Anthracene
81 Phenanthrene
84' Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver ' •
128 Zinc
Aluminum
Iron
Manganese
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
PLANT I
28.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N0.007
0.006
0.000
0.000
NA
0.000
0.000
NA
0.077
NA
1.4
0.000
0.29
0.066
NA
NA
0.000
0.000
NA
7.2
PLANT J
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.110
0.000
0.000
0.000
NA
0.000
0.100
NA
0.000
NA
0.080
0.200
0.200
0.000
NA
NA
NA
NA
NA
NA
NA - Not Analyzed
* - < 0.01
-------
LEAD
PbO-Pb
SULFURIC ACID
WASTEWATER
WASTEWATER
WASTEWATER
•RECYCLED TO SMELTER
FIGURE V-1
LEAD SUBCATEGORY GENERALIZED MANUFACTURING PROCESS
240
-------
FIGURE V-2
LEAD SUBCATEGORY ANALYSIS
PROCESS ELEMENTS
Anodes and Cathodes
Leady Oxide Production
Grid Manufacture
Grid Casting
Mold Release Formulation
Direct Chill Casting
Lead Rolling
Paste Preparation and Application
Curing
Closed Formation (In Case)
Single Fill
Double Fill
Fill and Dump
Open Formation (Out of Case)
Wet
SPECIFIC WASTEWATER SOURCES
Ball Mill Shell Cooling
Scrubber*
Scrubber*
Equipment Wash
Contact Cooling
Spent Emulsion Solution
Equipment and Floor Area
Cleanup
Scrubber*
Steam Curing
Humidity Curing
Contact Cooling
Formation Area Washdown
Scrubber*
Contact Cooling
Scrubber*
Product Rinse
Formation Area Washdown
Contact Cooling
Scrubber*
Product Rinse
Formation Area Washdown
• Plate Rinse
* Spent Formation Electrolyte
• Formation Area Washdown
* Scrubber*
241
-------
FIGURE V-2 (Continued)
LEAD SUBCATEGORY ANALYSIS
PROCESS ELEMENTS
Dehydrated
Plate Soak
Ancillary Operations
Assembly - Small Parts Casting
Battery Wash
With Detergent
Water Only
Floor Wash
Wet Air Pollution Control
Battery Repair
Laboratory
Truck Wash
Personal Hygiene
Hand Wash
Respirator Wash
Laundry
SPECIFIC WASTEWATER SOURCES
* Formation Area Washdown
• Plate Rinse
• Vacuum Pump Seals
* Scrubber*
• Soaking Acid
Scrubber*
* Detergent Battery Wash
• Water Only Battery Wash
* Floor Wash
* Power Floor Scrubbers
* Scrubber Slowdown From
*'d Processes
• Battery Repair Area Wash
* Laboratory Sinks
• Battery Electrolyte
* Laboratory Wash
* Scrubber Slowdown
• Truck Wash
* Hand Wash
• Respirator Wash and Rinse
• Clothing Wash and Rinse
242
-------
1OO
O
X
x
j
O
0
01
N
2
i
oc
O
O
a
O
DC
0.
Sample
Median Median Number
(Zeros (Zeros of
Excluded) Included) Values
Number
of
Zeros
Formation
Open Case:
Dehydrated
Closad Case
Damn
Leadv Oxide Production
5 10 15 20 30 40 50 60 70 80 85 90 95
98
PERCENT OF PLANTS
FIGURE V-3
PERCENT PRODUCTION NORMALIZED DISCHARGE FROM
LEAD SUBCATEGORY PROCESS OPERATIONS
243
-------
to
O
O
Q
tu
N
CC
.O
Z
Z
g
.o
3
Q
O
IT
Q.
I I I
SAMPLE NUMBER NUMBER
PROCESS MEDIAN OF OF
(L/KG) VALUES ZEROS -
SINGLE FILL FORMATION 0 43 31
DOUBLE FILL FORMATION .44 35 . 7
10
DOUBLE FILL
FORMATION,
oxo
SINGLE FILL
FORMATION
20
30 40 iO 60 70
CUMULATIVE PERCENT OF PLANTS
80
100
FIGURE V-4
PRODUCTION NORMALIZED DISCHARGE FROM DOUBLE AND SINGLE FILL FORMATION
-------
LEAD
ACID WATER
J L
LEADY
OXIDE
PREPARATION
ACID
CUTTING
DOUBLE FILL
PASTE
PREPARATION
WASTEWATER
DUMP AND
REFILL
BOOST
CHARGE
PASTING
PIG LEAD OR
SHEET LEAD
GRID
MANUFACTURE
CURING
WASTEWATER
STACKING
AND
WELDING
-SEPARATORS
ASSEMBLY
CASE, COVERS
TERMINALS
ACID FILL
CLOSED
FORMATION
WASTEWATER
SINGLE FILL
WASH
WASTEWATER
TEST
ANCILLARY
OPERATIONS
WASTEWATER
PERSONAL
HYGIENE
WASTEWATER
PRODUCT
FIGURE V-5
PRODUCTION OF CLOSED FORMATION WET BATTERIES
-------
ACID WATER
J L
LEAD
I
LEADY
OXIDE
PRODUCTION
PIG LEAD OR
SHEET LEAD
ACID
CUTTING
PASTE
PREPARATION
PASTING
WASTEWATER
GRID
MANUFACTURE
CURING
SEPARATORS.
CASE, COVERS ,
TERMINALS
WASTEWATER
STACKING
AND
WELDING
ASSEMBLY
ACID FILL
CLOSED
FORMATION
WASTEWATER
DUMP ACID
SEAL
WASH
WASTEWATER
»
TEST
ANCILLARY
OPERATIONS
WASTEWATER
PERSONAL
HYGIENE
WASTEWATER
PRODUCT
FIGURE V-6
PRODUCTION OF DAMP BATTERIES
246
-------
LEAD
ACID WATER
J I
ACID
CUTTING
LEADY
OXIDE
PRODUCTION
PASTE
PREPARATION
WASTEWATER
PIG LEAD OR
SHEET LEAD
PASTING
GRID
MANUFACTURE
CURING
WASTEWATER
WELD
GROUPS
OPEN
FORMATION
RINSING
AND
DEHYDRATION
SEPARATORS, CASES,.
COVERS, TERMINALS
WASTEWATER
ASSEMBLY
WASH
WASTEWATER
TEST
PRODUCT
ANCILLARY
OPERATIONS
WASTEWATER
PERSONAL
HYGIENE
FIGURE V-7
PRODUCTION OF DEHYDRATED BATTERIES
WASTEWATER
247
-------
PURCHASED GREEN
PLATES
ACID WATER
J 1
ACID
CUTTING
DOUBLE FILL
DUMP AND
REFILL
BOOST
CHARGE
STACKING
AND
WELDING
•SEPARATORS
ASSEMBLY
CASE, COVERS
TERMINALS
ACID FILL
CLOSED
FORMATION
WASH
TEST
PRODUCT
SINGLE FILL
WASTEWATER
WASTEWATER
ANCILLARY
OPERATIONS
WASTEWATER
PERSONAL
HYGIENE
WASTEWATER
FIGURE V-8
PRODUCTION OF BATTERIES FROM GREEN (UNFORMED) ELECTRODES
248
-------
FORMED PLATE
GROUPS
ACID WATER
1 1
ACID
CUTTING
ASSEMBLY
1
ACJD Fitt
i
WASH
i
TEST
1
PRODUCT
SEPARATORS, CASES
COVERS, TERMINALS
» W A STEW ATE R
ANCILLARY
OPERATIONS
1
WASTEWATER
PERSONAL
HYGIENE
WASTEWATER
FIGURE V-9
PRODUCTION OF BATTERIES FROM PURCHASED FORMED PLATES
249
-------
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The priority, nonconventional, and conventional pollutant
parameters that are to be examined for possible regulation were
presented in Section V. Data from plant sampling visits, and
results of subsequent chemical analysis were presented and
discussed. Pollutant parameters were selected for verification
according to a specified rationale.
Each of the pollutant parameters selected for verification
analysis is discussed in detail in this section. The selected
priority pollutants are presented in numerical order and are
followed by nonconventional pollutants and then conventional
pollutants, both in alphabetical order. The final part of this
section sets forth the pollutants which are to be considered for
regulation in the lead subcategory. The rationale for that final
selection is included.
VERIFICATION PARAMETERS
Pollutant parameters selected for verification sampling and
analysis for the lead subcategory are listed in Section V (page
118). The subsequent discussion is designed to provide
information about: where the pollutant comes from - whether it
is a naturally occurring element, processed metal, or
manufactured compound; general physical properties and the
physical form of the pollutant; toxic effects of the pollutant in
humans and other animals; and behavior of the pollutant in POTW
at the concentrations that might be expected from industrial
dischargers.
1,1,l-Trichloroethane(11). 1,1,1-Trichloroethane is one of the
two possible trichlorethanes. It is manufactured by
hydrochlorinating vinyl chloride to 1,1-dichloroethane which is
then chlorinated to the desired product. 1,1,1-Trichloroethane
is a liquid at room temperature with a vapor pressure of 96 mm Hg
at 20°C and a boiling point of 74°C. Its formula is CC13CH3. It
is slightly soluble in water (0.48 g/1) and is very soluble in
organic solvents. U.S. annual production is greater than one-
third of a million tons. 1,1,1-Trichlbroethane is used as an
industrial solvent and degreasing agent.
Most human toxicity data for 1,1,1-trichloroethane relates to
inhalation and dermal exposure routes. Limited data are
available for determining toxicity of ingested 1,1,1-
trichloroethane, and those data are all for the compound itself
251
-------
not solutions in water. No data are available regarding its
toxicity to fish and aquatic organisms. For the protection of
human health from the toxic properties of 1,1,1-trichloroethane
ingested through the consumption of water and fish, the ambient
water criterion is 18.4 mg/1. The criterion is based on bioassy
for possible carcinogenicity.
No detailed study of 1,1,1-trichloroethane behavior in POTW is
available. However, it has been demonstrated that none of the
organic priority pollutants of this type can be broken down by
biological treatment processes . as readily as fatty acids,
carbohydrates, or proteins.
Biochemical oxidation of many of the organic priority pollutants
has been investigated, at least in laboratory scale studies, at
concentrations higher than commonly expected in municipal
wastewater. General observations relating molecular structure to
ease of degradation have been developed for all of these
pollutants. The conclusion reached by study of the limited data
is that 'biological treatment produces a moderate degree of
degradation of 1,1,1-trichloroethane. No evidence is available
for drawing conclusions about its possible toxic or inhibitory
effect on POTW operation. However, for degradation to occur a
fairly constant input of the compound would be necessary.
Its water solubility would allow 1,1,1-trichloroethane, present
in the influent and not biodegradable, to pass through a POTW
into the effluent. One fac'tor which has received some attention,
but no detailed study, is the volatilization of the lower
molecular weight organics from POTW. If 1,1,1-trichloroethane is
not biodegraded, it will volatilize during aeration processes in
the POTW.
*
Chloroform(23). Chloroform is a colorless liquid manufactured
commercially by chlorination of methane. Careful control of
conditions maximizes chloroform production, but other products
must be separated. Chloroform boils at 61°C and has a vapor
pressure of 200 mm Hg at 25°C. It is slightly soluble in water
(8.22 g/1 at 20°C) and readily soluble in organic solvents.
Chloroform is used as a solvent and to manufacture refrigerents,
Pharmaceuticals, plastics, and anesthetics. It is seldom used as
an anesthetic.
Toxic effects of chloroform on humans include central nervous
system depression, gastrointestinal irritation, liver and kidney
damage and possible cardiac sensitization to adrenalin.
Carcinogenicity has been demonstrated for chloroform on
laboratory animals.
252
-------
For the maximum protection of human health from the potential
carcinogenic effects of exposure to chloroform through ingestion
of water and contaminated aquatic organisms, the ambient water
concentration is zero based on the non-threshold assumption for
this chemical. However, zero level may not be attainable at the
present time. Therefore, the levels which may result in
incremental increase of cancer risk over the lifetime are
estimated at 10~7, 10~'*, and 10~5. The corresponding recommended
criteria are 0.000019 mg/1, 0.00019 mg/1, and 0.0019 mg/1.
No data are available regarding the behavior of chloroform in a
POTW. However, the biochemical oxidation of this compound was
studied in one laboratory scale study at concentrations higher
than these expected to be contained by most municipal
wastewaters. After 5, 10, and 20 days no degradation of
chloroform was observed. The conclusion reached is that
biological treatment produces little or no removal by degradation
of chloroform in POTW.
The high vapor pressure of chloroform is expected to result in
volatilization of the compound from aerobic treatment steps in
POTW. Remaining chloroform is expected to pass through into the
POTW effluent.
Methylene Chloride(44). Methylene chloride, also called
dichloromethane (CH2C12), is a colorless liquid manufactured by
chlorination of methane or methyl chloride followed by separation
from the higher chlorinated methanes formed as coproducts.
Methylene chloride boils at 40°C, and has a vapor pressure of
362 mm Hg at 20°C. It is slightly soluble in water (20 g/1 at
20°C), and very soluble in organic solvents. U.S. annual
production is about 250,000 tons.
Methylene chloride is a common industrial solvent found in
insecticides, metal cleaners, paint, and paint and varnish
removers.
Methylene chloride is not generally regarded as highly toxic to
humans. Most human toxicity data are for exposure by inhalation.
Inhaled methylene chloride acts as a central nervous system
depressant. There is also evidence that the compound causes
heart failure when large amounts are inhaled.
Methylene chloride does produce mutation in tests for this
effect. In addition a bioassay recognized for its extremely high
sensitivity to strong and weak carcinogens produced results which
were marginally significant. Thus potential carcinogenic effects
of methylene chloride are not confirmed or denied, but are under
continuous study. Difficulty in conducting and interpreting the
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test results from the low boiling point (40°C) of methylene
chloride which increases the difficulty of maintaining the
compound in growth media during incubation at 37°C; and from the
difficulty of removing all impurities, some of which might
themselves be carcinogenic.
For the protection of human health from the potential
concinogenic effects due to exposure to methylene chloride
through ingestion of contaminated water and contaiminated aquatic
organisms, the ambient water concentration should be zero based
on the non-threshold assumption for this chemical. However, zero
level may not be attainable at the present time. Therefore, the
levels which may result in incremental increase of cancer risk
over the lifetime are estimated at 10-5, 10~« and 10~7. The
corresponding recommended criteria are 0.0019 mg/1, 0.00019 mg/1,
and 0.000019 mg/1.
The behavior of methylene chloride in POTW has not been studied
in any detail. However, the biochemical oxidation of this
compound was studied in one laboratory scale study at
concentrations higher than those expected to be contained by most
municipal wastewaters. After five days no degradation of
methylene chloride was observed. The conclusion reached is that
biological treatment produces litte or no removal by degradation
of methylene chloride in POTW.
The high vapor pressure of methylene chloride is expected to
result in volatilization of the compound from aerobic treatment
steps in POTW. It has been reported that methylene chloride
inhibits anaerobic processes in POTW. Methylene chloride that is
not volatilized in the POTW is expected to pass through into the
effluent.
Naphthalene(55). Naphthalene is an aromatic hydrocarbon with two
orthocondensed benzene rings and a molecular formula of C10H8.
As such it is properly classed as a polynuclear aromatic
hydrocarbon (PAH). Pure naphthalene is a white crystalline solid
melting at 80°C. For a solid, it has a relatively high vapor
pressure (0.05 mm Hg at 20°C), and moderate water solubility (19
mg/1 at 20°C). Naphthalene is the most abundant single component
of coal tar. Production is more than a third of a million tons
annually in the U.S. About three fourths of the production is
used as feedstock for phthalic anhydride manufacture. Most of
the remaining production goes into manufacture of insecticide,
dyestuffs, pigments, and Pharmaceuticals. Chlorinated and
partially hydrogenated naphthalenes are used in some' solvent
mixtures. Naphthalene is also used as a moth repellent.
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Napthalene, ingested by humans, has reportedly caused vision loss
(cataracts), hemolytic anemia, and occasionally, renal disease.
These effects of naphthalene ingestion are confirmed by studies
on laboratory animals. No carcinogenicity studies are available
which can be used to demonstrate carcinogenic activity for
naphthalene. Naphthalene does bioconcentrate in aquatic
organisms.
There are insufficient data on which to base any ambient water
criterion.
Only a limited number of studies have been conducted to determine
the effects of naphthalene on aquatic organisms. The data from
those studies show only moderate toxicity.
Naphthalene has been detected in sewage plant effluents at
concentrations up to 0.022 mg/1 in studies carried out by the
U.S. EPA. Influent levels were not reported. The behavior of
naphthalene in POTW has not been studied. However, recent
studies have determined that naphthalene will accumulate in
sediments at 100 times the concentration in overlying water.
These results suggest that naphthalene will be readily removed by
primary and secondary settling in POTW, if it is not biologically
degraded.
Biochemical oxidation of many of the organic priority pollutants
has been investigated in laborat.ory-scale studies at
concentrations higher than would normally be expected in
municipal wastewater. General observations relating molecular
structure to ease of degradation have been developed for all of
these pollutants. The conclusion reached by study of the limited
data is that biological treatment produces a high removal by
degradation of naphthalene. One recent study has shown that
microorganisms can degrade naphthalene, first to a dihydro
compound, and ultimately to carbon dioxide and water.
Phenol(65). Phenol, also called hydroxybenzene and carbolic
acid, is a clear, colorless, hygroscopic, deliquescent,
crystalline solid at room temperature. Its melting point is 43°C
and its vapor pressure at room temperature is 0.35 mm Hg. It is
very soluble in water (67 gm/1 at 16°C) and can be dissolved in
benzene, oils, and petroleum solids. Its formula is C«H5OH.
Although a small percent of the annual production of phenol is
derived from coal tar as a naturally occuring product, most of
the phenol is synthesized. Two of the methods are fusion of
benzene sulfonate with sodium hydroxide, and oxidation of cumene
followed by clevage with a catalyst. Annual production in the
U.S. is in excess of one million tons* Phenol is generated
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during distillation of wood and the microbiological decomposition
of organic matter in the mammalian intestinal tract.
Phenol is used as a disinfectant, in the manufacture of resins,
dyestuffs, and Pharmaceuticals, and in the photo processing
industry. In this discussion, phenol is the specific compound
which is separated by methylene chloride extraction of an
acidified sample and identified and quantified by GC/MS. Phenol
also contributes to the "Total Phenols", discussed elsewhere
which are determined by the 4-AAP colorinmetric method.
Phenol exhibits acute and sub-acute toxicity in humans and
laboratory animals. Acute oral doses of phenol in humans cause
sudden collapse and unconsciousness by its action on the central
nervous system. Death occurs by respiratory arrest. Sub-acute
oral doses in mammals are rapidly absorbed then quickly
distributed to various organs, then cleared from the body by
urinary excretion and metabolism. Long term exposure by drinking
phenol contaminated water has resulted in statistically
significant increase in reported cases of diarrhea, mouth sores,
and burning of the mouth. In laboratory animals long term oral
administration at low levels produced slight liver and kidney
damage. No reports were found regarding carcinogenicity of
phenol administered orally - all carcinogenicity studies were
skin tests.
For the protection of human health from phenol ingested through
water and through contaminated aquatic organisms the
concentration in water should not exceed 3.5 mg/1.
Fish and other aquatic organisms demonstrated a wide range of
sensitivities to phenol concentration. However, acute toxicity
values were at moderate levels when compared to other organic
priority pollutants.
Data have been developed on the behavior of phenol in POTW.
Phenol is biodegradable by biota present in POTW. The ability of
a POTW to treat phenol-bearing influents depends upon acclimation
of the biota and the constancy of the phenol concentration. It
appears that an induction period is required to build up the
population of organisms which can degrade phenol. Too large a
concentration will result in upset or pass through in the POTW,
but the specific level causing upset depends on the immediate
past history of phenol concentrations in the influent. Phenol
levels as high as 200 mg/1 have been treated with 95 percent
removal in POTW, but more or less continuous presence of phenol
is necessary to maintain the population of microorganisms that
degrade phenol.
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Phenol which is not degraded is expected to pass thorugh the POTW
because of its very high water solubility. However, in POTW
where chlorination is practiced for disinfection of the POTW
effluent, chlorination of phenol may occur. The products of that
reaction may be priority pollutants.
The EPA has developed data on influent and effluent
concentrations of total phenols in a study of 103 POTW. However,
the analytical procedure was the 4-AAP method mentioned earlier
and not the GC/MS method specifically for phenol. Discussion of
the study, which of course includes phenol, is presented under
the pollutant heading "Total Phenols."
Phthalate Esters (66-71). Phthalic acid, or 1,2-
benzenedicarboxylic acid, is one of three isomeric
benzenedicarboxylic acids produced by the chemical industry.
The other two isomeric forms are called isophthalic and
terephthalic acids. The formula for all three acids is
C6H4(COOH)2. Some esters of phthalic acid are designated as
priority pollutants. They will be discussed as a group here, and
specific properties of individual phthalate .esters will be
discussed afterwards.
Phthalic acid esters are manufactured in the U.S. at an annual
rate in excess of 1 billion pounds. They are used as
plasticizers - primarily in the production of polyvinyl chloride
(PVC) resins. The most widely used phthalate plasticizer is bis
(2-ethylhexyl) phthalate (66) which accounts for nearly one third
of the phthalate esters produced. This particular ester is
commonly referred to as dioctyl phthalate (DOP) and should not be
confused with one of the less used esters, di-n-octyl phthalate
(69), which is also used as a plasticizer. In addition to these
two isomeric dioctyl phthalates, four other esters, also used
primarily as plasticizers, are designated as priority pollutants.
They are: butyl benzyl phthalate (67), di-n-butyl phthalate (68),
diethyl phthalate (70), and dimethyl phthalate (71).
Industrially, phthalate esters are prepared from phthalic
anhydride and the specific alcohol to form the ester. Some
evidence is. available suggesting that phthalic acid esters also
may be synthesized by certain plant and animal tissues. The
extent to which this occurs in nature is not known.
Phthalate esters used as plasticizers can be present in
concentrations up to 60 percent of the total weight of the PVC
plastic. The plasticizer is not linked by primary chemical bonds
to the PVC resin. Rather, it is locked' into the structure of
intermeshing polymer molecules and held by van der Waals forces.
The result is that the plasticizer is easily extracted.
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Plasticizers are responsible for the odor associated with new
plastic toys or flexible sheet that has been contained in a
sealed package.
Although the phthalate esters are not soluble or are only very
slightly soluble in water, they do migrate into aqueous solutions
placed in contact with the plastic. Thus industrial facilities
with tank linings, wire and cable coverings, tubing, and sheet
flooring of PVC are expected to discharge some phthalate esters
in their raw waste. In addition to their use as plasticizers,
phthalate esters are used in lubricating oils and pesticide
carriers. These also can contribute to industrial discharge of
phthalate esters.
From the accumulated data on acute toxicity in animals, phthalate
esters may be considered as having a rather low order of
toxicity. Human toxicity data are limited. It is thought that
the toxic effects of the esters is most likely due to one of the
metabolic • products, in particular the monoester. Oral acute
toxicity in animals is greater for the lower molecular weight
esters than for the higher molecular weight esters.
Orally administered phthalate esters generally produced
enlargeing of liver and kidney, and atrophy of testes in
laboratory animals. Specific esters produced enlargement of
heart and brain, spleenitis, and degeneration of central nervous
system tissue.
Subacute doses administered orally to laboratory animals produced
some decrease in growth and degeneration of the testes. Chronic
studies in animals showed similar effects to those found in acute
and subacute studies, but to a much lower degree. The same
organs were enlarged, but pathological changes were not usually
detected.
A recent study of several phthalic esters produced suggestive but
not conclusive evidence that dimethyl and diethyl phthalates have
a cancer liability. Only four of the six priority pollutant
esters were included in the study. Phthalate esters do
bioconcentrate in fish. The factors, weighted for relative
consumption of various aquatic and marine food groups, are used
to calculate ambient water quality criteria for four phthalate
esters. The values are included in the discussion of the
specific esters.
Studies of toxicity of phthalate esters in freshwater and salt
water organisms are scarce. Available data show that adverse
effects on freshwater aquatic life occur at phthalate ester
concentrations as low as 0.003 mg/1.
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The behavior of phthalate esters in POTW has not been studied.
However, the biochemical oxidation of many of the organic
priority pollutants has been investigated in laboratory-scale
studies at concentrations higher than would normally be expected
in municipal wastewater. Three of the phthalate esters were
studied. Bis(2-ethylhexyl) phthalate was found to be degraded
slightly or not at ail.and its removal by biological treatment in
a POTW is expected to be slight or zero. Di-n-butyl phthalate
and diethyl phthalate were degraded to a moderate degree and it
is expected that they will be biochemically oxidized to a lesser
extent than domestic sewage by biological treatment in POTW. On
the same basis it is expected that di-n-octyl phthalate will not
be biochemically oxidized to a significant extent by biological
treatment in a POTW. An EPA study of seven POTWs revealed that
for all but di-n-octyl phthalate, which was not studied, removals
ranged from 62 to 87 percent.
No information was found on possible interference with POTW
operation or the possible effects on sludge by the phthalate
esters. The water insoluble phthalate esters - butylbenzyl and
di-n-octyl phthalate - would tend to remain in sludge, whereas
the other four priority pollutant phthalate esters with water
solubilities ranging from 50 mg/1 to 4.5 mg/1 would probably pass
through into the POTW effluent.
Phthalate esters selected for verification analysis in the lead
subcategory - are discussed individually below.
Bis (2-ethylhexyl) phthalate(66). In addition to the general
remarks and discussion on phthalate esters, specific information
on bis(2-ethylhexyl) phthalate is provided. Little information
is available about the physical properties of bis(2-ethylhexyl)
phthalate. It is a liquid boiling at 387°C at 5mm Hg and is
insoluble in water. Its formula is C«H4(COOC8H17)Z. This
priority pollutant constitutes about one third of the phthalate
ester production in the U.S. It is commonly referred to as
dioctyl phthalate, or DOP, in the plastics industry where it is
the most extensively used compound for the plasticization of
polyvinyl chloride (PVC). Bis(2-ethylhexyl) phthalate has been
approved by the FDA for use in plastics in contact with food.
Therefore, it may be found in wastewaters coming in contact with
discarded plastic food wrappers as well.as the PVC films and
shapes normally found in industrial plants. This priority
pollutant is also a commonly used organic diffusion pump oil
where its low vapor pressure is an advantage.
For the protection of human health from the toxic properties of
bis(2-ethylhexyl) phthalate ingested through water and through
contaminated aquatic organisms, the ambient water quality
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criterion is determined to be 15 mg/1. If contaminated aquatic
organisms alone are consumed, excluding the consumption of water,
the ambient water criteria is determined to be 50 mg/1.
Although the behavior of bis(2-ethylhexyl) phthalate in POTW has
not been studied, biochemical oxidation of this priority
pollutant has been studied on a laboratory scale at
concentrations higher than would normally be expected in
municipal wastewater. In fresh water with a non-acclimated seed
culture no biochemical oxidation was observed after 5, 10, and 20
days. However, with an acclimated seed culture, biological
oxidation occurred to the extents of 13, 0, 6, and 23 of
theoretical after 5, 10, 15 and 20 days, respectively. Bis(2-
ethylhexyl) phthalate concentrations were 3 to 10 mg/1. Little
or no removal of bis(2-ethylhexyl) phthalate by biological
treatment in POTW is expected.
Butyl benzyl phthalate(67). In addition to the general remarks
and discussion on phthalate esters, specific information on butyl
rbenzyl phthalate is provided. No information was found on the
physical properties of this compound.
Butyl benzyl phthalate is used as a plasticizer for PVC. Two
special applications differentiate it from other phthalate
esters. It is approved by the U.S. FDA for food contact in
wrappers and containers; and it is the industry standard for
plasticization of vinyl flooring because it provides stain
resistance.
No ambient water quality criterion is proposed for butyl benzyl
phthalate.
Butylbenzylphthalate removal in POTW by biological treatment in a
POTW is discussed in the general discussion of phthalate esters.
Di-n-butyl phthalate (68). In addition to the general remarks
and discussion on phthalate esters, specific information on di-n-
butyl phthalate (DBP) is provided. DBP is a colorless, oily
liquid, boiling at 340°C. Its water solubility at room
temperature is reported to be 0.4 g/1 and.4.5g/l in two different
chemistry handbooks. The formula for DBP, C6H4(COOC4H,)2 is the
same as for its isomer, di-isobutyl phthalate. DBP production is
one to two percent of total U.S. phthalate ester production.
Dibutyl phthalate is used to a limited extent as a plasticizer
for polyvinylchloride (PVC). It is not approved for contact with
food. It is used in liquid lipsticks and as a diluent for
polysulfide dental impression materials. DBP is used as a
plasticizer for nitrocellulose in making gun powder, and as a
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fuel in solid propellants for rockets. Further uses are
insecticides, safety glass manufacture, textile lubricating
agents, printing inks, adhesives, paper coatings and resin
solvents.
For protection of human health from the toxic properties of
dibutyl phthalate ingested through water and through contaminated
aquatic organisms, the ambient water quality criterion is
determined to be 34 mg/1. If contaminated aquatic organisms are
consumed, excluding the consumption of water, the ambient water
criterion is 154 mg/1.
Although the behavior of di-n-butyl phthalate in POTW has not
been studied, biochemical oxidation of this priority pollutant
has been studied on a laboratory scale at concentrations higher
than would normally be expected in municipal wastewater.
Biochemical oxidation of 35, 43, and 45 percent of theoretical
oxidation were obtained after 5, 10, and 20 days, respectively,
using sewage microorganisms as an unacclimated seed culture.
Based on these data it is expected that di-n-butyl phthalate will
be biochemically oxidized to a lesser extent than domestic sewage
by biological treatment in POTW.
Di-n-octyl phthalate(69). In addition to the general remarks and
discussion on phthalate esters, specific information on di-n-
octyl phthalate is provided. Di-n-octyl phthalate is not to be
confused with the isomeric bis(2-ethylhexyl) phthalate which is
commonly referred to in the plastics industry as OOP. Di-n-octyl
phthalate is a liquid which boils at 220°C at 5 mm Hg. It is
insoluble in water. Its molecular formula is C«H4(COOC8H,7)2.
Its production constitutes about one percent of all phthalate
ester production in the U.S.
Industrially, di-n-octyl phthalate is used to plasticize
polyvinyl chloride (PVC) resins.
No ambient water quality criterion is proposed for di-n-octyl
phthalate.
Biological treatment in POTW is expected to lead to little or no
removal of di-n-octyl phthalate.
Polynuclear Aromatic Hydrocarbons(72-84). The polynuclear
aromatic hydrocarbons (PAH) selected as priority pollutants are a
group of 13 compounds consisting of substituted and unsubstituted
polycyclic aromatic rings. The general class of PAH includes
hetrocyclics, but none of those were selected as priority
pollutants. PAH are formed as the result of incomplete
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combustion when organic compounds are burned with insufficient
oxygen. PAH are found in coke oven emissions, vehicular
emissions, and volatile products of oil and gas burning. The
compounds chosen as priority pollutants are listed with their
structural formula and melting point (m.p.). All are insoluble
in water.
72 Benzo(a)anthrancene (1,2-benzanthracene)
m.p. 162°C
73 Benzo(a)pyrene (3,4-benzopyrene)
m.p. 176°C
74 3,4-Benzofluoranthene
m.p. 168°C
75 Benzo(k)fluoranthene (11,12-benzofluoranthene)
m.p. 217°C
76 Chrysene {1,2-benzphenanthrene)
m.p. 255°c
77 Acenaphthylene
HC=Ch
m.p. 92°C
78 Anthracene
m.p. 216°C
79 Benzo(ghi)perylene (1,12-benzoperylene)
m.p. not reported
80 Fluorene (alpha-diphenylenemethane)
m.p. 116°C
81 Phenanthrene
m.p. 101°C
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82 Dibenzo(a,h)anthracene (1,2,5,6-dibenzoanthracene)
m.p. 269°C
83 Indeno(1,2,3-cd)pyrene (2,3-o-phenyleneperylene)
m.p. not available
84 Pyrene
m.p. 156<>C
Some of these priority pollutants have commercial or industrial
uses. Benzo(a)anthracene, benzo(a)pyrene/ chrysene, anthracene,
dibenzo(a,h)anthracene, and pyrene are all used as antioxidants.
Chrysene, acenaphthylene, anthracene, fluorene, phenanthrene, and
pyrene are all used for synthesis of dyestuffs or other organic
chemicals. 3,4-Benzofluoranthrene, benzo(k)fluoranthene,
benzo(ghi)perylene, and indeno (1,2,3-cd)pyrene have no known
industrial uses, according to the results of a recent literature
search.
Several of the PAH priority pollutants are found in smoked meats,
in smoke flavoring mixtures, in vegetable oils, and in coffee.
They are found in soils and sediments in river beds.
Consequently, they are also found in many drinking water
supplies. The wide distribution of these pollutants in complex
.mixtures with the many other PAHs which have not been designated
as priority pollutants results in exposures by humans that cannot
be associated with specific individual compounds.
The screening and verification analysis procedures used for the
organic priority pollutants are based on gas chromatography mass
spectrometry (GCMS). Three pairs of the PAH have identical
elution times on the column specified in the protocol, which
means that the parameters of the pair are not differentiated.
For these three pairs [anthracene (78) - phenanthrene (81); 3,4-
benzofluoranthene (74) - benzo(k)fluoranthene (75); and
benzo(a)anthracene (72) - chrysene (76)] results are obtained and
reported as "either-or." Either both are present in the combined
concentration reported, or one is present in the concentration
reported. When detections below reportable limits are recorded
no further analysis is required. For samples where the
concentrations of coeluting pairs have a significant value,
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additional analyses are conducted, using different procedures
that resolve the particular pair.
There are no studies to document the possible carcinogenic risks
to humans by direct ingestion. Air pollution studies indicate an
excess of lung cancer mortality among workers exposed to large
amounts of PAH containing materials such as coal gas, tars, and
coke-oven emissions. However, no definite proof exists that the
PAH present in these materials are responsible for the cancers
observed.
Animal studies have demonstrated the toxicity of PAH by oral and
dermal administration. The carcinogenicity of PAH has been
traced to formation of PAH metabolites which, in turn, lead to
tumor formation. Because the levels of PAH which induce cancer
are very low, little work has been done on other health hazards
resulting from exposure. It has been established in animal
studies that tissue damage and systemic toxicity can result from
exposure to non-carcinogenic PAH compounds.
Because there were no studies available regarding chronic oral
exposures to PAH mixtures, proposed water quality criteria were
derived using data on exposure to a single compound. Two studies
were selected, one involving benzo{a)pyrene ingestion and one
involving dibenzo(a,h)anthracene ingestion. Both are known
animal carcinogens.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to polynuclear aromatic hydro-
carbons (PAH) through ingestion of water and contaminated aquatic
organisms, the ambient water concentration should be zero based
on the non-threshold assumption for these chemicals. However,
zero level may not be attainable at the present time. Therefore,
the levels which may result in incremental increase of cancer
risk over the life time are estimated at 10~5, 10-*, and 10~7
with corresponding recommended criteria of 0.000028 mg/1,
0.0000028 mg/1, and 0.00000028 mg/1, respectively.
No standard toxicity tests have been reported for freshwater or
saltwater organisms and any of the 13 PAH discussed here.
The behavior of PAH in POTW has received only a limited amount of
study. It is reported that up to 90 percent of PAH entering a
POTW will be retained in the sludge generated by conventional
sewage treatment processes. Some of the PAH can inhibit
bacterial- growth when they are present at concentrations as low
as 0.018 mg/1. Biological treatment in activated sludge units
has been shown to reduce the concentration of phenanthrene and
anthracene to some extent. However, a study of biochemcial
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oxidation of fluorene on a laboratory scale showed no degradation
after 5, 10, and 20 days. On the basis of that study and studies
of other organic priority pollutants, some general observations
were made relating molecular structure to ease of degradation.
Those observations lead to the conclusion that the 13 PAH
selected to represent that group as priority pollutants will be
removed only slightly or not at all by biological treatment
methods in POTW. Based on their water insolubility and tendency
to attach to sediment particles very little pass through of PAH
to POTW effluent is expected.
No data are available at this time to support any conclusions
about contamination of land by PAH on which sewage sludge
containing PAH is spread.
Antimony(114). Antimony (chemical name - stibium, symbol Sb)
classified as a non-metal or metalloid, is a silvery white ,
brittle, crystalline solid. Antimony is found in small ore
bodies throughout the world. Principal ores are oxides of mixed
antimony valences, and an oxysulfide ore. Complex ores with
metals are important because the antimony is recovered as a by-
product. Antimony melts at 631°C, and is a poor conductor of
electricity and heat.
Annual U.S. consumption of primary antimony ranges from 10,000 to
20,000 tons. About half is consumed in metal products - mostly
antimonial lead for lead acid storage batteries, and about half
in nonmetal products. A principal compound is antimony trioxide
which is used as a flame retardant in fabrics, and as an
opacifier in glass, ceramincs, and enamels. Several antimony
compounds are used as catalysts in organic chemicals synthesis,
as fluorinating agents (the antimony fluoride), as pigments, and
in fireworks. Semiconductor applications are economically
significant.
Essentially no information on antimony - induced human health
effects has been derived from community epidemiology studies.
The available data are in literature relating effects observed
with therapeutic or medicinal uses of antimony compounds and
industrial exposure studies. Large therapeutic doses of
antimonial compounds, usually used to treat schistisomiasis, have
caused severe nausea, vomiting, convulsions, irregular heart
action, liver damage, and skin rashes. Studies of acute
industrial antimony poisoning have revealed loss of appetite,
diarrhea, headache, and dizziness in addition to the symptoms
found in studies of therapeutic doses of antimony.
For the protection of human health from the toxic properties of
antimony ingested.through water and through contaminated aquatic
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organisms the ambient water criterion is determined to be 0.146
mg/1. If contaminated aquatic organisms alone are consumed,
excluding the consumption of water, the ambient water criterion
is determined to be 45 mg/1. Available data show that adverse
effects on aquatic life occur at concentrations higher than those
cited for human health risks.
f
Very little information is available regarding the behavior of
antimony in POTW. The limited solubility of most antimony
compounds expected in POTW, i.e. the oxides and sulfides,
suggests that at least part of the antimony entering a POTW will
be precipitated and incorporated into the sludge. However, some
antimony is expected to remain dissolved and pass through the
POTW into the effluent. Antimony compounds remaining in the
sludge under anaerobic conditions may be connected to stibine
(SbH3), a very soluble and very toxic compound. There are no
data to show antimony inhibits any POTW processes. Antimony is
not known to be essential to the growth of plants, and has been
reported to be moderately toxic. Therefore, sludge containing
large amounts of antimony could be detrimental to plants If it is
applied in large amounts to cropland.
Arsenic(115). Arsenic (chemical symbol As), is classified as a
non-metal or metalloid. Elemental arsenic normally exists in the
alpha-crystalline metallic form which is steel gray and brittle,
and in the beta form which is dark gray and amorphous. Arsenic
sublimes at 615°C. Arsenic is widely distributed throughout the
world in a large number of minerals. The most important
commercial source of arsenic is as a by-product from treatment of
copper, lead, cobalt, and gold ores. Arsenic is usually marketed
as the trioxide (As203). Annual U.S. production of the trioxide
approaches 40,000 tons.
The principal use of arsenic is in agricultural chemicals
(herbicides) for controlling weeds in cotton fields. Arsenicals
have various applications in medicinal and veterinary use, as
wood preservatives, and in semiconductors.
The effects of arsenic in humans were known by the ancient Greeks
and Romans. The principal toxic effects are gastrointestinal
disturbances. Breakdown of red blood cells occurs. Symptoms of
acute poisoning include vomiting, diarrhea, abdominal pain,
lassitude, dizziness, and headache. Longer exposure produced
dry, falling hair, brittle, loose nails, eczema, and exfoliation.
Arsenicals also exhibit teratogenic and mutagenic effects in
humans. Oral administration of arsenic compounds has been
associated clinically with skin cancer for nearly a hundred
years. Since 1888 numerous studies have linked occupational
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exposure to, and therapeutic administration of arsenic compounds
to increased incidence of respiratory and skin cancer.
For the maximum protection of human health from the potential
carcinogenic effects due to exposure to arsenic through ingestion
of water and contaminated aquatic organisms, the ambient water
concentration should be zero based on the non-threshold
assumption of this chemical. However, zero level may not be
attainable at the present time. Therefore, the levels which may
result in incremental increase of cancer risk over the lifetime
are estimated at 10~5, 10~* and 10~7. The corresponding
recommended criteria are 2.2 x 1O-7 mg/1, 2.2 x 10-« mg/1, and
2.2 x 10-* mg/1. If contaminated aquatic organisms alone are
consumed, excluding the consumption of water, the water
concentration should be less than 1.75 x 10-4 mg/1 to keep the
increased lifetime ' cancer risk below 10-5. Available data show
that adverse effects on aquatic life occur at concentrations
higher than those cited for human health risks.
A few studies have been made regarding the behavior of arsenic in
POTW. One EPA survey of 9 POTW reported influent concentrations
ranging from 0.0005 to 0.693 mg/1; effluents from 3 POTW having
biological treatment contained 0.0004 - 0.01 mg/1; 2 POTW showed
arsenic removal efficiencies of 50 and 71 percent in biological
treatment. Inhibition of treatment processes by sodium arsenate
is reported to occur at 0.1 mg/1 in activated sludge, and
1.6 mg/1 in anaerobic digestion processes. In another study
based on data from 60 POTW, arsenic in sludge ranged from 1.6 to
65.6 mg/kg and the median value was 7.8 mg/kg. Arsenic in sludge
spread on cropland may be taken up by plants grown on that land.
Edible plants can take up arsenic, but normally their growth is
inhibited before the plants are ready for harvest.
Cadmium(118). Cadmium is a relatively rare metallic element that
is seldom found in sufficient quantities in a pure state to
warrant mining or extraction from the earth's surface. It is
found in trace amounts of about 1 ppm throughout the earth's
crust. Cadmium is, however, a valuable by-product of zinc
production.
Cadmium is used primarily as an electroplated metal, and is found
as an impurity in the secondary refining of zinc, lead, and
copper.
Cadmium is an extremely dangerous cumulative toxicant, causing
progressive chronic poisoning in mammals, fish, and probably
other organisms.
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Toxic effects of cadmium on man have been reported from
throughout the world. Cadmium may be a factor in the development
of such human pathological conditions as kidney disease,
testicular tumors, hypertension, arteriosclerosis, growth
inhibition, chronic disease of old age, and cancer. Cadmium is
normally ingested by humans through food and water as well as by
breathing air contaminated by cadmium dust. Cadmium is
cumulative in the liver, kidney, pancreas, and thyroid of humans
and other animals. A severe bone and kidney syndrome known as
itai-itai disease has been documented in Japan as caused by
cadmium ingestion via drinking water and contaminated irrigation
water. Ingestion of as little as 0.6 mg/day has produced the
disease. Cadmium acts synergistically with other metals. Copper
and zinc substantially increase its toxicity.
Cadmium is concentrated by marine organisms, particularly
molluscs, which accumulate cadmium in calcareous tissues and in
the viscera. A concentration factor of 1000 for cadmium in fish
muscle has been reported, as have concentration factors of 3000
in marine plants and up to 29,600 in certain marine animals. The
eggs and larvae of fish are apparently more sensitive than adult
fish to poisoning by cadmium, and crustaceans appear to be more
sensitive than fish eggs and larvae.
For the protection of human health from the toxic properties of
cadmium ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 0.010
mg/1.
Cadmium is not destroyed when it is introduced into a POTW, and
will either pass through to the POTW effluent or be incorporated
into the POTW sludge. In addition, it can interfere with the
POTW treatment process.
In a study of 189 POTW, 75 percent of the primary plants, 57
percent of the trickling filter plants, 66 percent of the
activated sludge plants and 62 percent of the biological plants
allowed over 90 percent of the influent cadmium to pass thorugh
to the POTW effluent. Only 2 of the 189 POTW allowed less than
20 percent pass-through, and none less than 10 percent pass-
through. POTW effluent 'concentrations ranged from 0.001 to
1.97 mg/1 (mean 0.028 mg/1, standard deviation 0.167 mg/1).
Cadmium not passed through the POTW will be retained in the
sludge where it is likely to build up in concentration. Cadmium
contamination of sewage sludge limits its use on land since it
increases the level of cadmium in the soil. Data show that
cadmium can be incorporated into crops, including vegetables and
grains, from contaminated soils. Since the crops themselves show
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no adverse effects from soils with levels up to 100 mg/kg
cadmium, these contaminated crops could have a significant impact
on human health. Two Federal agancies have already recognized
the potential adverse human health effects posed by the use of
sludge on cropland. The FDA recommends that sludge containing
over 30 mg/kg of cadmium should not be used on agricultured land.
Sewage sludge contains 3 to 300 mg/kg (dry basis) of cadmium
(mean = 10 mg/kg). The USDA also recommends placing limits on
the total cadmium from sludge that may be applied to land.
Chromium(119). Chromium is an elemental metal usually found as a
chromite (FeO«Cr20,). The metal is normally produced by reducing
the oxide with aluminum. A significant proportion of the
chromium used is in the form of compounds such as sodium
dichromate (Na2Cr04), and chromic acid (Cr03) - both are
hexavalent chromium compounds.
Chromium is found as an alloying component of many steels and its
compounds are used in electroplating baths, and as corrosion
inhibitors for closed water circulation systems.
The two chromium forms most frequently found in industry
wastewaters are hexavalent and trivalent chromium. Hexavalent
chromium is the form used for metal treatments. Some of it is
reduced to trivalent chromium as part of the process reaction.
The raw wastewater containing both valence states is usually
treated first to reduce remaining hexavalent to trivalent
chromium, and second to precipitate the trivalent form as the
hydroxide. The hexavalent form is not removed by lime treatment.
Chromium, in its various valence states, is hazardous to man. It
can produce lung tumors when inhaled, and induces skin
sensitizations. Large doses of chromates have corrosive effects
on the intestinal tract and can cause inflammation of the
kidneys. Hexavalent chromium is a known . human carcinogen.
Levels of chromate ions that show no effect in man appear to be
so low as to prohibit determination, to date.
The toxicity of chromium salts to fish and other aquatic life
varies widely with the species, temperature, pH, valence of the
chromium, and synergistic or antagonistic effects, especially the
effect of water hardness. Studies have shown that trivalent
chromium is more toxic to fish of some types than is hexavalent
chromium. Hexavalent chromium retards growth of one fish species
at 0.0002 mg/1. Fish food organisms and other lower forms of
aquatic life are extremely sensitive to chromium. Therefore,
both hexavalent and trivalent chromium must be considered harmful
to particular fish or organisms.
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For the .protection of human health from the toxic properties of
chromium (trivalent) ingested through water and contaminated
aquatic organisms, the recommended water qualtiy criterion is 170
mg/1. If contaminated aquatic organisms alone are consumed,
excluding the consumption of water, the water criterion for
trivalent chromium is 3,443 mg/1. The ambient water quality
criterion for hexavalent chromium is recommended to be identical
to the existing drinking water standard for total chromium which
is 0.050 mg/1.
Chromium is not destroyed when treated by POTW (although the
oxidation state may change), and will either pass through to the
POTW effluent or be incorporated into the POTW sludge. Both
oxidation states can cause POTW treatment inhibition and can also
limit the usefuleness of municipal sludge.
Influent concentrations of chromium to POTW facilities have been
observed by EPA to range from 0.005 to 14.0 mg/1, with a median
concentration of 0.1 mg/1. The efficiencies for removal of
chromium by the activated sludge process can vary greatly,
depending on chromium concentration in the influent, and other
operating conditions at the POTW. Chelation of chromium by
organic matter and dissolution due to the presence of carbonates
can cause deviations from the predicted behavior in treatment
systems.
The systematic presence of chromium compounds will halt
nitrification in a POTW for short periods, and most of the
chromium will be retained in the sludge solids, Hexavalent
chromium has been reported to severely affect the nitrification
process, but trivalent chromium has litte or no toxicity to
activated sludge, except at high concentrations. The presence of
iron, copper, and low pH will increase the toxicity of chromium
in a POTW by releasing the chromium into solution to be ingested
by microorganisms in the POTW.
The amount of chromium which passes through to the POTW effluent
depends on the type of treatment processes used by the POTW. In
a study of 240 POTW 5.6 percent of the primary plants allowed more
than 80 percent pass through to POTW effluent. More advanced
treatment 'results in less pass-through. POTW effluent
concentrations ranged from 0.003 to 3.2 mg/1 total chromium (mean
« 0.197, standard deviation * 0.48), and from 0.002 to 0.1 mg/1
hexavalent chromium (mean = 0.017, standard deviation = 0.020).
Chromium not passed through the POTW will be retained in the
sludge, where it is likely to build up in concentration. Sludge
concentrations of total chromium of over 20,000 mg/kg (dry basis)
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have been observed. Disposal of sludges containing very high
concentrations of trivalent chromium can potentially cause
problems in uncontrollable landfills. Incineration, or similar
destructive oxidation processes can produce hexavalent chromium
from lower valance states. Hexavalent chromium is potentially
more toxic than trivalent chromium. In cases where high rates of
chrome sludge application on land are used, distinct growth
inhibition and plant tissue uptake have been noted.
Pretreatment of discharges substantially reduces the
concentration of chromium in sludge. In Buffalo, New York,
pretreatment of electroplating 'waste resulted in a decrease in
chromium concentrations in POTW sludge from 2,510 to 1,040 mg/kg.
A similar reduction occurred in Grand Rapids, Michigan, POTW
where the chromium concentration in sludge decreased from 11,000
to 2,700 mg/kg when pretreatment was made a requirement.
Copper(120). Copper is a metallic element that sometimes is
found free, as the native metal, and is also found in minerals
such as cuprite (Cu20), malechite [CuCO3»Cu(OH)2], azurite
[2CuC03»Cu(OH)2], chalcopyrite (CuFeS2), and bornite (Cu5FeS4).
Copper is obtained from these ores by smelting, leaching, and
electrolysis. It is used in the plating, electrical, plumbing,
and heating equipment industries, as well as in insecticides and
fungicides.
Traces of copper are found in all forms of plant and animal life,
and the metal is an essential trace element for nutrition.
Copper is not considered to be a cumulative systemic poison for
humans as it is readily excreted by the body, but it can cause
symptoms of gastroenteritis, with nausea and intestinal
irritations, at relatively low dosages. The limiting factor in
domestic water supplies is taste. To prevent this adverse
organoleptic effect of copper in water, a criterion of 1 mg/1 has
been established.
The toxicity of copper to aquatic organisms varies significantly,
not only with the species, but also with the physical and
chemical characteristics of the water, including temperature,
hardness, turbidity, and carbon dioxide content. In hard water,
the toxicity of copper salts may be reduced by the precipitation
of copper carbonate or other insoluble compounds. The sulfates
of copper and zinc, and of copper and calcium are synergistic in
their toxic effect on fish.
Relatively high concentrations of copper may be tolerated by
adult fish for short periods of time; the critical effect of
copper appears to be its higher toxicity to young or juvenile
fish. Concentrations of 0.02 to 0.031 mg/1 have proved fatal to
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some common fish species. In general the salmonoids are very
sensitive and the sunfishes are less sensitive to copper.
The recommended criterion to protect freshwater aquatic life is
0.0056 mg/1 as a 24-hour average, and 0.012 mg/1 maximum
concentration at a hardness of 50 mg/1 CaC03. For total
recoverable copper the criterion to protect freshwater aquatic
life is 5.6 x TO-3 mg/1 as a 24-hour average.
Copper salts cause undesirable color reactions in the food
industry and cause pitting when deposited on some other metals
such as aluminum and galvanized steel.
Irrigation water containing more than minute quantities of copper
can be detrimental to certain crops. Copper appears in all
soils, and its concentration ranges from 10 to 80 ppm. In soils,
copper occurs in association with hydrous oxides of manganese and
iron, and also as soluble and insoluble complexes with organic
matter. Copper is essential to the life of plants, and the
normal range of concentration in plant tissue is from 5 to
20 ppm. Copper concentrations in plants normally do not build up
to high levels when toxicity occurs. For example, the
concentrations of copper in snapbean leaves and pods was less
than 50 and 20 mg/kg, respectively, under conditions of severe
copper toxicity. Even under conditions of copper toxicity, most
of the excess copper accumulates in the roots; very little is
moved to the aerial part of the plant.
Copper is not destroyed when treated by a POTW, and will either
pass through to the POTW effluent or be retained in the POTW
sludge. It can interfere with the POTW treatment processes and
can limit the usefulness of municipal sludge.
The influent concentration of copper to POTW facilities has been
observed by the EPA to range from 0.01 to 1.97 mg/1, with a
median concentration of 0.12 mg/1. The copper that is removed
from the influent stream of a POTW is adsorbed on the sludge or
appears in the sludge as the hydroxide of the metal. Bench scale
pilot studies have shown that from about 25 percent to 75 percent
of the copper passing through the activated sludge process
remains in solution in the final effluent. Four-hour slug
dosages of copper sulfate in concentrations exceeding 50 mg/1
were reported to have severe effects on the removal efficiency of
an unacclimated system, with the system returning,to normal in
about 100 hours. Slug dosages of copper in the form of copper
cyanide were observed to have much more severe effects on the
activated sludge system, but the total system returned to normal
in 24 hours.
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In a recent study of 268 POTW, the median pass-through was over
80 percent for primary plants and 40 to 50 percent for trickling
filter, activated sludge, and biological treatment plants. POTW
effluent concentrations of copper ranged from 0.003 to 1.8 mg/1
(mean 0.126, standard deviation 0.242).
Copper which does not pass through the POTW will be retained in
the sludge where it will build up in concentration. The presence
of excessive levels of copper in sludge may limit its use on
cropland. Sewage sludge contains up to 16,000 mg/kg of copper,
with 730 mg/kg as the mean value. These concentrations are
significantly greater than those normally found in soil, which
usually range from 18 to 80 mg/kg. Experimental __data indicate
that when dried sludge is spread over tillable land, the copper.
tends to remain in place down to the depth of tillage, except for
copper which is taken up by plants grown in the soil. Recent
investigation has shown that the extractable copper content of
sludge-treated soil decreased with time, which suggests a
reversion of copper to less soluble forms was occurring.
Lead (122). Lead is a soft, malleabLe-r-ductible, blueish-gray,
metallic element, usually obtained fronriEe-mineral galena (lead
sulfide, PbS), anglesite (lead sulfate, PbS04), or cerussite
(lead carbonate, PbC03). Because it is usually associated with
minerals of zinc, silver, copper, gold, cadmium, antimony,'and
arsenic, special purification methods are frequently used before
and after extraction of the metal from the ore concentrate by
smelting.
Lead is widely used for its corrosion resistance, sound and
vibration absorption, low melting point (solders), and relatively
high imperviousness to various forms of radiation. Small amounts
of copper, antimony and other metals can be alloyed with lead to
achieve greater hardness, stiffness, or corrosion resistance than
is afforded by the pure metal. Lead compounds are used in glazes
and paints. About one third of U.S. lead consumption goes into
storage batteries. About half of U.S., lead"consumption is from
secondary lead recovery. U.S. consumption of ^Cead is in the
range of-one million-tons annually.
Lead "ingested by humans produces a variety of toxic effects
including impaired reproductive ability, disturbances in blood
chemistry, neurological disorders, kidney damage, and adverse
cardiovascular effects. Exposure to lead in the diet results in
permanent increase in lead levels in the body. Most of the lead
entering the body eventually becomes localized in the bones where
it accumulates. Lead is a carcinogen or co-carcinogen in some
species of experimental animals. Lead is teratogenic in
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experimental animals. Mutagenicity data are not available for
lead.
For the protection of human health from the toxic properties of
lead ingested through water and through contaminated aquatic
organisms the ambient water criterion is 0.050 mg/1. Available
data show that adverse effects on aquatic life occur at
concentrations as low as 7.5 x 10-4 mg/1 of total recoverable
lead as a 24-hour average with a water hardness of 50 mg/1 as
CaCO,.
Lead is not destroyed in POTW, but is passed through to the
effluent or retained in the POTW sludge; it can interfere with
POTW treatment processes and can limit the usefulness of POTW
sludge for application to agricultural croplands. Threshold
concentration for inhibition of the activated sludge process is
0.1 mg/1, and for the nitrification process is 0.5 mg/1. In a
study of 214 POTW, median pass through values were over 80
percent for primary plants and over 60 percent for trickling
filter, activated sludge, and biological process plants. Lead
concentration in POTW effluents ranged from 0.003 to 1.8 mg/1
(means * 0.106 mg/1, standard deviation » 0.222).
Application of lead-containing sludge to cropland should not lead
to uptake by crops under most conditions because normally lead is
strongly bound by soil. However, under the unusual conditions of
low pH (less than 5.5) and low concentrations of labile
phosphorus, lead solubility is increased and plants can
accumulate lead.
Mercury. Mercury (123) is an elemental metal rarely found in
nature as the free metal. Mercury is unique among metals as it
remains a liquid down to about 39 degrees below zero. It is
relatively inert chemically and is insoluble in water. The
-principal ore is cinnabar (HgjS).
Mercury is used industrially as the metal and as mercurous and
mercuric salts and compounds. Mercury is used in several types
of batteries. Mercury released to the aqueous environment is
subject to biomethylation - conversion to the extremely toxic
methyl mercury.
Mercury "can—be^Jjitjoduced into the body through the skin and the
respiratory~system as_the elemental vapor. Mercuric salts are
highly toxic to humans and can be absorbed through the
gastrointestinal tract. Fatal doses can vary from 1 to 30 grams.
Chronic toxicity of methyl mercury is evidenced primarily by
neurological symptoms. Some mercuric salts cause death by kidney
failure.
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Mercuric salts are extremely toxic to fish and other aquatic
life. Mercuric chloride is more lethal than copper, hexavalent
chromium, zinc, nickel, and lead towards fish and aquatic life.
In the food cycle, algae containing mercury up to TOO times the
concentration in the surrounding sea water are eaten by fish
which further concentrate the mercury. Predators that eat the
fish in turn concentrate the mercury even further.
For the protection of human health from the toxic properties of
mercury ingested through water and through contaminated aquatic
organisms the ambient water criterion is determined to be
0.000144 mg/1.
Mercury is not destroyed when treated by a POTW, and will either
pass through to the POTW effluent or be incorporated into the
POTW sludge. At low concentrations it may reduce POTW removal
efficiencies, and at high concentrations it may upset the POTW
operation.
The influent concentrations of mercury to POTW have been observed
by the EPA to range from 0.0002 to 0.24 mg/1, with a median
concentration of 0.001 mg/1. Mercury has been reported in the
literature to have inhibiting effects upon an activated sludge
POTW at levels as low as 0.1 mg/1. At 5 mg/1 of mercury, losses
of COD removal efficiency of 14 to 40 percent have been reported,
while at 10 mg/1 loss of removal of 59 percent has been reported.
Upset of an activated sludge POTW is reported in the literature
to occur near 200 mg/1. The anaerobic digestion process is much
less affected by the presence of mercury, with inhibitory effects
being reported at 1365 mg/1.
In a study of 22 POTW having secondary treatment, the range of
removal of mercury from the influent to the POTW ranged from 4 to
99 percent with median removal of 41 percent. Thus significant
pass through of mercury may occur.
In sludges, mercury content may be high if industrial sources of
mercury contamination are present. Little is known about the
form in which mercury occurs 'in sludge. Mercury may undergo
biological methylation in sediments, but no methylation has been
observed in soils, mud, or sewage sludge.
The mercury content of soils not receiving additions of POTW
sewage sludge lie in the range from 0.01 to 0.5 mg/kg. In soils
receiving POTW sludges for protracted periods, the concentration
of mercury has been observed to approach 1.0 mg/kg. In the soil,
mercury enters into reactions with the exchange complex of clay
and organic fractions, forming both ionic and covalent bonds.
Chemical and microbiological degradation of mercurials can take
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place side by side in the soil, and the products - ionic or
molecular - are retained by organic matter and clay or may be
volatilized if gaseous. Because of the high affinity between
mercury and 'the solid soil surfaces, mercury persists in the
upper layer of soil.
Mercury can enter plants through the roots, it can readily move
to other parts of the plant, and it has been reported to cause
injury to plants. In many plants mercury concentrations range
from 0.01 to 0.20 mg/kg, but when plants are supplied with high
levels of mercury, these concentrations can exceed 0.5 mg/kg.
Bioconcentration occurs in animals ingesting mercury in food.
Nickel(124). Nickel is seldom found in- nature as the pure
elemental metal. It is a relatively plentiful element and is
widely distributed throughout the earth's crust. It occurs in
marine organisms and is found in the oceans. The chief
commercial ores for nickel are pentlandite [(Fe,Ni),S8], and a
lateritic ' ore consisting of hydrated nickel-iron-magnesium
silicate.
Nickel has many and varied uses. . It is used in alloys and as the
pure metal. Nickel salts are used for electroplating baths.
The toxicity of nickel to man is thought to be very low, and
systemic poisoning of human beings by nickel or nickel salts is
almost unknown. In non-human mammals nickel acts to inhibit
insulin release, depress growth, and reduce cholesterol. A high
incidence of cancer of the lung and nose has been reported in
humans engaged in the refining of nickel.
Nickel salts can kill fish at very low concentrations. However,
nickel has been found to be less toxic to some fish than copper,
zinc, and iron. Nickel is present in coastal and open ocean
water at concentrations in the range of 0.0001 to 0.006 mg/1
although the most common values are 0.002 ~ 0.003 mg/1. Marine
animals contain up to 0.4 mg/1 and marine plants contain up to
3 mg/1. Higher nickel concentrations have been reported to cause
reduction in photosynthetic activity of the giant kelp. A low
concentration was found to kill oyster eggs.
For the protection of human health based on the toxic properties
of nickel ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 0.0134
mg/1. If contaminated aquatic organisms are consumed, excluding
consumption of water, the ambient water criterion is determined
to be 0.100 mg/1. Available data show that adverse .effects on
aquatic life occur for total recoverable nickel concentrations as
low as 0.0071 mg/1 as a 24-hour average.
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Nickel is not destroyed when treated in a POTW, but will either
pass through to the POTW effluent or be retained in the POTW
sludge. It can interfere with POTW treatment processes and can
also limit the usefulness of municipal sludge.
Nickel salts have caused inhibition of the biochemical oxidation
of sewage in a £OTW. In a pilot plant, slug doses of nickel
significantly reduced normal treatment efficiencies for a few
hours, but the plant acclimated itself somewhat to the slug
dosage and appeared to achieve normal treatment efficiencies
within 40 hours. It has been reported that the anaerobic
digestion process is inhibited only by high concentrations of
nickel, while a low concentration of nickel inhibits the
nitrification process.
The influent concentration of nickel to POTW facilities has been
observed by the EPA to range from 0.01 to 3.19 mg/1, with a
median of 0.33 mg/1. In a study of 190 POTW, nickel pass-through
was greater than 90 percent for 82 percent of the primary plants.
Median pass-through for trickling filter, activated sludge, and
biological process, plants was greater than 80 percent. POTW
effuent concentrations ranged from 0.002 to 40 mg/1
(mean = 0.410, standard deviation = 3.279).
Nickel not passed through the POTW will be incorporated into the
sludge. In a recent two-year study of eight cities, four of the
cities had median nickel concentrations of over 350 mg/kg, and
two were over 1,000 mg/kg. The maximum nickel concentration
observed was 4,010 mg/kg.
Nickel is found in nearly all soils, plants, and waters. Nickel
has no known essential function in plants. In soils, nickel
typically is found in the range from 10 to 100 mg/kg. Various
environmental exposures to nickel appear to correlate with
increased incidence of tumors in man. For example, cancer in the
maxillary antrum of snuff users may result from using plant
material grown on soil high in nickel.
Nickel toxicity may develop in plants from application of sewage
sludge on acid soils. Nickel has caused reduction of yields for
a variety of crops including oats, mustard, turnips, and cabbage.
In one study nickel decreased the yields of oats significantly at
100 mg/kg.
Whether nickel exerts a toxic effect on plants depends on several
soil factors, the amount of nickel applied, and the contents of
other metals in the sludge. Unlike copper and zinc, which are
more available from inorganic sources than from sludge, nickel
uptake by plants seems to be promoted by the presence of the
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organic matter in sludge. Soil treatments, such as liming reduce
the solubility of nickel. Toxicity of nickel to plants is
enhanced in acidic soils.
Silver(126). Silver is a soft, lustrous, white metal that is
insoluble in water and alkali. In nature, silver is found in the
elemental state (native silver) and combined in ores such as
argentite (Ag2S), horn silver (AgCl), proustite (Ag3AsS3), and
pyrargyrite (Ag3SbS3). Silver is used extensively in several
industries, among them electroplating.
Metallic silver is not considered to be toxic, but most of its
salts are toxic to a large number of organisms. Upon ingestion
by humans, many silver salts are absorbed in the circulatory
system and deposited in various body tissues, resulting in
generalized or sometimes localized gray pigmentation of the skin
and mucous membranes know as argyria. There is no known method
for removing silver from the tissues once it is deposited, and
the effect is cumulative.
Silver is recognized as a bactericide and doses from 0.000001 to
0.0005 mg/1 have been reported as sufficient to sterilize water.
The criterion for ambient water to protect human health from the
toxic properties of silver ingested through water and through
contaminated aquatic organisms is 0.050 mg/1.
The chronic toxic effects of silver on the aquatic environment
have not been given as much attention as many other heavy metals.
Data from existing literature support the fact that silver is
very toxic to aquatic organisms. Despite the fact that silver is
nearly the most toxic of the heavy metals, there are insufficient
data to adequately evaluate even the effects of hardness on
silver toxicity. There are no data available on the toxicity of
different forms of silver.
There is no available literature on the incidental removal of
silver by POTW. An incidental removal of about 50 percent is
assumed as being representative. This is the highest average
incidental removal of any metal for which data are available.
(Copper has been indicated to have a median incidental removal
rate of 49 percent).
Bioaccumulation and concentration of silver from sewage sludge
has not been studied to any great degree. There is some
indication that silver could be bioaccumulated in mushrooms to
the extent that there could be adverse physiological effects on
humans if they consumed large quantites of mushrooms grown in
silver enriched soil. The effect, however, would tend to be
unpleasant rather than fatal.
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There is little summary data available on the quantity of silver
discharged to POTW. Presumably there would be a tendency to
limit its discharge from a manufacturing facility because of its
high intrinsic value.
Zinc(1281. Zinc occurs abundantly in the earth's crust,
concentrated in ores. It is readily refined into the pure,
stable, silvery-white metal. In addition to its use in alloys,
zinc is used as a protective coating on steel. It is applied by
hot dipping (i.e. dipping the steel in molten zinc) or by
electroplating.
Zinc can have an adverse effect on man and animals at high con-
centrations. Zinc at concentrations in excess of 5 mg/1 causes
an undesirable taste which persists through conventional
treatment. For the prevention of adverse effects due to these
organoleptic properties of zinc, concentrations in ambient water
should not exceed 5 mg/1. Available data show that adverse
effects on aquatic life occur at concentrations as low as 0.047
mg/1 as a 24-hour average.
Toxic concentrations of zinc compounds cause adverse changes in
the morphology and physiology of fish. Lethal concentrations in
the range of 0.1 mg/1 have been reported. Acutely toxic
concentrations induce cellular breakdown of the gills, and
possibly the clogging of the gills with mucous. Chronically
toxic concentrations of zinc compounds cause general enfeeblement
and widespread histological changes to many organs, but not to
gills. Abnormal swimming behavior has been reported at
0.04 mg/1. Growth and maturation are retarded by zinc. It has
been observed that the effects of zinc poisoning may not become
apparent immediately, so that fish removed from zinc-contaminated
water may die as long as 48 hours after removal.
In general, salmonoids are most sensitive to elemental zinc in
soft water; the rainbow trout is the most sensitive in hard
waters. A complex relationship exists between zinc
concentration, dissolved zinc concentration, pH, temperature, and
calcium and magnesium concentration. Prediction of harmful
effects has been less than reliable and controlled studies have
not been extensively documented.
The major concern with zinc compounds in marine waters is not
with acute lethal effects, but rather with the long-term
sublethal effects of the metallic compounds and complexes. Zinc
accumulates in some marine species, and marine animals contain
zinc in the range of 6 to 1500 mg/kg. From the point of view of
acute lethal effects, invertebrate marine animals seem to be the
most sensitive organism tested.
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Toxicities of zinc in nutrient solutions have been demonstrated
for a number of plants. A variety of fresh water plants tested
manifested harmful symptoms at concentrations of 10 mg/1. Zinc
sulfate has also been found to be lethal to many plants and it
could impair agricultural uses of the water.
Zinc is not destroyed when treated by POTW, but will either pass
through to the POTW effluent or be retained in the POTW sludge.
It can interfere with treatment processes in the POTW and can
also limit the usefuleness of municipal sludge.
In slug doses, and particularly in the presence of copper,
dissolved zinc can interfere with or seriously disrupt the
operation of POTW biological processes by reducing overall
removal efficiencies, largely as a result of the toxicity of the
metal to biological organisms. However, zinc solids in the form
of hydroxides or sulfides do not appear to interfere with
biological treatment processes, on the basis of available data.
Such solids accumulate in the sludge.
The influent concentrations of zinc to POTW facilities has been
observed by the EPA to range from 0.017 to 3.91 mg/1, with a
median concentration of 0.33 mg/1. Primary treatment is not
efficient in removing zinc; however, the microbial floe of
secondary treatment readily adsorbs zinc.
In a study of 258 POTW, the median pass-through values were 70 to
88 percent for primary plants, 50 to 60 percent for trickling
filter and biological process plants, and 30-40 percent for
activated process plants. POTW effluent concentrations of zinc
ranged from 0.003 to 3.6 mg/1 (mean «= 0.330, standard deviation =
0.464).
The zinc which does not pass through the POTW is retained in the
sludge. The presence of zinc in sludge may limit its use on
cropland. Sewage sludge contains 72 to over 30,000 mg/kg of
zinc, with 3,366 mg/kg as the mean value. These concentrations
are significantly greater than those normally found in soil,
which range from 0 to 195 mg/kg, with 94 mg/kg being a common
level. Therefore, application of sewage sludge to soil will
generally increase the concentration of zinc in the soil. Zinc
can be toxic to plants, depending upon soil pH. Lettuce,
tomatoes, turnips, mustard, kale, and beets are especially
sensitive to zinc contamination.
Aluminum. Aluminum is a nonconventional pollutant. It is a
silvery white metal, very abundant in the earths crust (8.1
percent), but never found free in nature. Its principal ore is
bauxite. Alumina (A1203) is extracted from the bauxite and
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dissolved in molten cryolite. Aluminum is produced by
electrolysis of this melt.
Aluminum is light, malleable, ductile, possesses high thermal and
electrical conductivity, and is non-magnetic. It can be formed,
machined or cast. Although aluminum is very reactive, it forms a
protective oxide film on 'the surface which prevents corrosion
under many conditions. In contact with other metals in presence
of moisture the protective film is destroyed and voluminous white
corrosion products form. Strong acids and strong alkali also
break down the protective film.
There is increasing evidence that dissolved aluminum has
substantial adverse effects on human health. Aluminum has been
implicated by several studies in the development of Alzheimer's
disease (progressive senile dementia). This disease is
associated with the formation of tangled bunches of nerve fibers
or "neurofibrillary tangles" (NFT). Autopsy studies have shown
that aluminum is present in 90 percent of the nuclei of NFT
neurons. It is present in less than 6 percent of the nuclei of
normal neurons. This trend is also apparent in the cytoplasm of
NFT neurons, although less prominent than in the nuclei: aluminum
was found in 29.4 percent of the cytoplasms of NFT neurons and
11.1 percent of the cytoplasms of normal neurons.
Brains of individuals suffering from several other neurological
diseases have also displayed elevated concentrations of aluminum.
These diseases include Huntington's disease, Parkinsons' disease,
progressive supranuclear palsy, acoustic neuroma, and Guamanian
amyotrophic lateral sclerosis (ALS).
These increased concentrations of aluminum may be a result of the
development of the disease, rather than a contributing cause;
however, this possibility seems less likely in light of several
recent studies correlating high concentrations of aluminum in the
environment to a high incidence of several of these neurological
disorders. These and other studies are discussed in greater
detail in the report "Aluminum.: An Environmental and Health
Effects Assessment," cited as a reference in this document.
Although much work remains to be done on this subject, the Agency
believes that the evidence points to a much broader neurotoxic
role for aluminum than had previously been assumed.
In addition, mildly alkaline conditions can cause precipitation
of aluminum as the hydroxide. When aluminum hydroxide
precipitates in waterways or bodies of water, it can blanket the
bottom, having an adverse effect on the benthos and on aquatic
plant life rooted on the bottom. Aluminum hydroxide, like many
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precipitates, can also impair the gill action of fish when
present in large amounts.
Alum, an aluminum salt with the chemical formula Alj,(S04)3»14 HjO
is used as a coagulant in municipal and industrial wastewater
treatment. This form is different from dissolved aluminum and
aluminum hydroxide, which are both harmful pollutants. The
amount of dissolved aluminum in finished water does not generally
depend upon the amount of alum used as a coagulant, unless a
large excess is used. The alum is contained in the treatment
sludge; very little passes through into the effluent.
Similarly, the amount of aluminum hydroxide in finished water
does not depend on the amount of alum used in coagulation, but
rather on the pH and the concentration of dissolved aluminum.
Therefore, the use of alum as a coagulant does not result in
large amounts of either aluminum or aluminum hydroxide in
finished water. There are no data available on the POTW removal
efficiency for the pollutant aluminum.
Iron. Iron is a nonconventional polluant. It is an abundant
metal found at many places in the earth's crust. The most common
iron ore is hematite (Fej,O,) from which iron is obtained by
reduction with carbon. Other forms of commercial ores are
magnetite (Fe304) and taconite (FeSiO). Pure iron is not often
found in commercial use, but it is usually alloyed with other
metals and minerals. The,most common of these is carbon.
Iron is the basic element in the production of steel. Iron with
carbon is used for casting of major parts of machines and it can
be machined, cast, formed, and welded. Ferrous iron is used in
paints, while powdered iron can be sintered and used in powder
metallurgy. Iron compounds are also used to precipitate other
metals and undesirable minerals from industrial wastewater
streams.
Corrosion products of iron in water cause staining of porcelain
fixtures, and ferric iron combines with tannin to produce a dark
violet color. The presence of excessive iron in water
discourages cows from drinking and thus reduces milk production.
High concentrations of ferric and ferrous ions in water kill most
fish introduced to the solution within a few hours. The killing
action is attributed to coatings of iron hydroxide precipitates
on the gills. Iron oxidizing bacteria are dependent on iron in
water for growth. These bacteria form slimes that can affect the
aesthetic values of bodies of water and cause stoppage of flows
in pipes.
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Iron is an essential nutrient and micro-nutrient for all forms of
growth. Drinking water standards in the U.S. set a limit of 0.3
mg/1 of iron in domestic water supplies based on aesthetic and
organoleptic properties of iron in water.
High concentrations of iron do not pass through a POTW into the
effluent. In some .POTW iron salts are added to coagulate
precipitates and suspended sediments into a sludge. In an EPA
study of POTW the concentration of iron in the effluent of 22
biological POTW meeting secondary treatment performance levels
ranged from 0.048 to 0.569 mg/1 with a median value of 0.25 mg/1.
This represented removals of 76 to 97 percent with a median of 87
percent removal.
Iron in sewage sludge spread on land used for agricultural
purposes is not expcected to have a detrimental effect on crops
grown on the land.
Manganese. Manganese is a nonconventional pollutant. It is a
gray-white metal resembling iron, but more brittle. The pure
metal does not occur in nature, but must be produced by reduction
of the oxide with sodium, magnesium, or aluminum, or by
electrolysis. The principal ores are pyrolusite (MnOz) and
psilomelane (a complex mixture of Mn02 and oxides of potassium,
barium and other alkali and alkaline earth metals). The largest
percentage of manganese used in the U.S. is in ferro-manganese
alloys. A small amount goes into dry batteries and chemicals.
Manganese is not often present in natural surface waters because
its hydroxides and carbonates are only sparingly soluble.
Manganese is undesirable in domestic water supplies because it
causes unpleasant tastes, deposits on food during cooking, stains
and discolors laundry and. plumbing fixtures, and fosters the
growth of some microorganisms in reservoirs, filters, and
distribution systems.
Small concentratons of 0.2 to 0.3 mg/1 manganese may cause
building of heavy encrustations in piping. Excessive manganese
is also undesirable in water for use in many industries,
including textiles, dying, food processing, distilling, brewing,
ice, and paper.
The recommended limitations for manganese in drinking water in
the U.S. is 0.05 mg/1. The limit appears to be based on
aesthetic and economic factors rather than physiological hazards.
Most investigators regard manganese to be of no toxicological
significance in drinking water at concentrations not causing
unpleasant tastes. However, cases of manganese poisoning have
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been reported in the literature. A small outbreak of
encephalitis - like disease, with early symptoms of 1ethergy and
edema, was traced to manganese in the drinking water in a village
near Tokyo. Three persons died as a result of poisoning by well
water contaminated by manganese derived from dry-cell batteries
buried nearby. Excess manganese in the drinking water is also
believed to be the cause of a rare disease endemic in
Northeastern China.
No data were found regarding the behavior of manganese in POTW.
However, one source reports that typical mineral pickup from
domestic water use results in an increase in manganese
concentration of 0.2 to 0.4 mg/1 in a municipal sewage system.
Therefore, it is expected that interference in POTW, if it
occurs, would not be noted until manganese concentrations
exceeded 0.4 mg/1.
Phenols(Total). "Total Phenols" is a nonconventional pollutant
parameter. Total phenols is the result of analysis using the 4-
AAP (4-aminoantipyrene) method. This analytical procedure
measures the color development of reaction products between 4-AAP
and some phenols. The results are reported as phenol. Thus
"total phenol" is not total phenols because many phenols (notably
nitrophenols) do not react. Also, since each reacting phenol
contributes to the color development to a different degree, and
each phenol has a molecular weight different from others and from
phenol itself, analyses of several mixtures containing the same
total concentration in mg/1 of several phenols will give
different numbers depending on the proportions in the particular
mixture.
Despite these limitations of the analytical method, total phenols
is a useful parameter when the mix of phenols is relatively
constant and an inexpensive monitoring method is desired. In any
given plant or even in an industry subcategory, monitoring of
"total phenols" provides an indication of the concentration of
this group of priority pollutants as well as those phenols not
selected as priority pollutants. A further advantage is that the
method is widely used in water quality determinations.
In an EPA survey of 103 POTW the concentration of "total phenols"
ranged from 0.0001 mg/1 to 0.176 mg/1 in the influent, with a
median concentration of 0.016 mg/1. Analysis of effluents from
22 of these same POTW which had biological treatment meeting
secondary treatment performance levels showed "total phenols"
concentrations ranging from 0 mg/1 to 0.203 mg/1 with a'median of
0.007. Removals were 64 to 100 percent with a median of 78
percent.
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It must be recognized, however, that six of the eleven priority
pollutant phenols could be present in high concentrations and not
be detected. Conversely, it is possible, but not probable, to
have a high "total phenol" concentration without any phenol
itself or any of the ten other priority pollutant phenols
present. A characterization of the phenol mixture to be
monitored to establish constancy of composition will allow "total
phenols" to be used with confidence.
Strontium. Strontium, a nonconventional pollutant, is a hard
silver-white alkaline earth metal. The metal reacts readily with
water and moisture in the air. It does not occur as the free
metal in nature. Principal ores are strontianite (SrC03) and
celestite (SrS04). The metal is produced from the oxide .by
heating with aluminum, but no commerical uses for the pure metal
are known.
Small percentages of strontium are alloyed with the lead used to
cast grids for some maintenance free lead acid batteries.
Strontium compounds are used in limited quantites in special
applications. Strontium hydroxide [Sr(OH)2] import thermal and
mechanical stability and moisture resistance. The hydroxide is
also used in preparation of stabilizers for vinyl plastics.
Several strontium compounds are used in pyrotechnics.
Very few data are available regarding toxic effects of strontium
in humans. Some studies indicate that strontium may be essential
to growth in mammals. Large amounts of strontium compounds
orally administered, have retarded growth and caused rickets in
laboratory animals. Strontium is considered to be nontoxic or of
very low toxicity in humans. Specific involvement of strontium
toxicity in enzyme or biochemical systems is not known.
No reports were found regarding behavior of strontium in POTW.
At the low concentrations of strontium to be expected under
normal conditions, the strontium is expected to pass through into
the POTW effluent in the dissolved state.
Oil and Grease. Oil and grease are taken together as one
pollutant parameter. This is a conventional polluant and some of
its components are:
1. Light Hydrocarbons - These include light fuels such as
gasoline, kerosene, and jet fuel, and miscellaneous solvents
used for industrial processing, degreasing, or cleaning
purposes. The presence of these light hydrocarbons may make
the removal of other heavier oil wastes more difficult.
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2. Heavy Hydrocarbons, Fuels, and Tars - These include the
crude oils, diesel oils, 16 fuel oil, residual oils, slop
oils, and in some cases, asphalt and road tar.
3. Lubricants and Cutting Fluids - These generally fall into
two classes: non-emulsifiable oils such as lubricating oils
and greases and emulsifiable oils such as water soluble
oils, rolling oils, cutting oils, and drawing compounds.
Emulsifiable oils may contain fat soap or various other
additives.
4. Vegetable and Animal Fats and Oils - These originate
primarily from processing of foods and natural products.
These compounds can settle or float and may exist as solids or
liquids depending upon factors such as method of use, production
process, and temperature of wastewater.
Oil and grease 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 adhere to the gills of fish causing suffocation,
and the flesh of fish is tainted when microorganisms that were
exposed to waste oil are eaten. Deposition of oil in the bottom
sediments of water can serve to inhibit normal benthic growth.
Oil and grease exhibit an oxygen demand.
Many of the organic priority pollutants will be found distributed
between the oily phase and the aqueous phase in industrial
wastewaters. The presence of phenols, PCBs, PAHs, and almost any
other organic pollutant in the oil and grease make
characterization of this parameter almost impossible. However,
all of these other organics add to the objectionable nature of
the oil and grease.
Levels of oil and grease which are toxic to aquatic organisms
vary greatly, depending on the type and the species
susceptibility. However, it has been reported that crude oil in
concentrations as low as 0.3 mg/1 is extremely toxic to fresh-
water fish. It has been recommended that public water supply
sources be essentially free from oil and grease.
Oil and grease in quantities of 100 1/sq km show up as a sheen on
the surface of a body of water. The presence of oil slicks
decreases the aesthetic value of a waterway.
Oil and grease is compatible with a POTW activated sludge process
in limited quantity. However, slug loadings or high
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concentrations of oil and grease interfere with biological
treatment processes. The oils coat surfaces and solid particles,
preventing access of oxygen, and sealing in some microorganisms.
Land spreading of POTW sludge containing oil and grease
uncontaminated by toxic pollutants is not expected to affect
crops grown on the treated land, or animals eating those crops.
Total Suspended Solids(TSS). Suspended solids include both
organic and inorganic materials. The inorganic compounds include
sand, silt, and clay. The organic fraction includes such
materials as grease, oil, tar, and animal and vegetable waste
products. These solids may settle out rapidly, and bottom
deposits are often a mixture of both organic and inorganic
solids. Solids may be suspended in water for a time and then
settle to the bed of the stream or lake. These solids discharged
with man's wastes may be inert, slowly biodegradable materials,
or rapidly decomposable substances. While in suspension,
suspended solids increase the turbidity of the water, reduce
light penetration, and impair the photosynthetic activity of
aquatic plants.
Supended solids in water interfere with many industrial processes
and cause foaming in boilers and incrustastions on equipment
exposed to such water, especially as the temperature rises. They
are undesirable in process water used in the manufacture of
steel, in the textile industry, in laundries, in dyeing, and in
cooling systems.
Solids in suspension are aesthetically displeasing. When they
settle to form sludge deposits on the stream or lake bed, they
are often damaging to the life in the water. Solids, when
transformed to sludge deposit, may do a variety of damaging
things, including blanketing the stream or lake bed and thereby
destroying the living spaces for those benthic organisms that
would otherwise occupy the habitat. When of an organic nature,
solids use a portion or all of the dissolved oxygen available in
the area. Organic materials also serve as a food source for
sludgeworms and associated organisms.
Disregarding any toxic effect attributable to substances leached
out by water, suspended solids may kill fish and shellfish by
causing abrasive injuries and by clogging the gills and
respiratory passages of various aquatic fauna. Indirectly,
suspended solids are inimical to aquatic life because they screen
out light, and they promote and maintain the development of
noxious conditions through oxygen depletion. This results in the
killing of fish and fish food organisms. Suspended solids also
reduce the recreational value of the water.
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Total suspended solids is a traditional pollutant which is
compatible with a well-run POTW. This pollutant with the
exception of those components which are described elsewhere in
this section, e.g., heavy metal components, does not interfere
with the operation of a POTW. However, since a considerable
portion of the innocuous TSS may be inseparably bound to the
constituents which do interfere with POTW operation, or produce
unusable sludge, or subsequently dissolve to produce unacceptable
POTW effluent, TSS may be considered a toxic waste hazard.
pH. Although not a specific pollutant, pH is related to the
acidity or alkalinity of a wastewater stream. It is not,
however, a measure of either. The term pH is used to describe
the hydrogen ion concentration (or activity) present in a given
solution. Values for pH range from 0 to 14, and these numbers
are the negative logarithms of the hydrogen ion concentrations.
A pH of 7 indicates neutrality. Solutions with a pH above 7 are
alkaline, while those solutions with a pH below 7 are acidic.
The relationship of pH and acidity and alkalinity is not
necessarily linear or direct. Knowledge of the water pH is
useful in determining necessary measures for corroison control,
sanitation, and disinfection. Its value is also necessary in the
treatment of industrial wastewaters to determine amounts of
chemicals required to remove pollutants and to measure their
effectiveness. . Removal of pollutants, especially .dissolved
solids is affected by the pH of the wastewater.
4
Waters with a pH below 6.0 are corrosive to water works
structures, distribution lines, and household plumbing fixtures
and can thus add constituents to drinking water such as iron,
copper, zinc, cadmium, and lead. The hydrogen ion concentration
can affect the taste of the water and at a low pH, water tastes
sour. The bactericidal effect of chlorine is weakened as the pH
increases, and it is advantageous to keep the pH close to 7.0.
This is significant for providng safe drinking water.
Extremes of pH or rapid pH changes can exert stress conditions or
kill aquatic life outright. Even moderate changes from
acceptable criteria limits of pH are deleterious to some species.
The relative toxicity to aquatic life of many materials is
increased by changes in the water pH. For example,
metallocyanide complexes can increase a thousand-fold in toxicity
with a drop of 1.5 pH units.
Because of the universal nature of pH and its effect on water
quality and treatment, it is selected as a pollutant parameter
for many industry categories. A neutral pH range (approximately
6-9) is generally desired because either extreme beyond this
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range has a deleterious effect on receiving waters or the
pollutant nature of other wastewater constituents.
Pretreatment for regulation of pH is covered by the "General
Pretreatment Regulations for Exisiting and New Sources of
Pollution," 40 CFR 403.5. This section prohibits the discharge
to a POTW of "pollutants which will cause corrosive structural
damage to the POTW but in no case discharges with pH lower than
5.0 unless the works is specially designed to accommodate such
discharges."
SPECIFIC POLLUTANTS CONSIDERED FOR REGULATION
For the lead subcategory, discussion of individual pollutant
parameters selected for consideration for specific regulation are
based on an evaluation of pollutant concentrations in total raw
wastewater streams from eight plants (Table V-34, page 220), an
evaluation of pollutant concentrations in process elements
streams (Tables V-5 to V-31, pages 178 to 210), and an evaluation
of the raw materials and the manufacturing processes employed.
Parameters Selected for Consideration for Specific Regulation.
Based on the subcategory pollutant selection analysis, 15
pollutant parameters are considered for specific regulation. The
parameters selected are: antimony, cadmium, chromium, copper,
lead, mercury, nickel, silver, zinc, aluminum, iron, manganese,
oil and grease, total suspended solids and pH. These pollutants
were observed at significant levels in raw wastewater produced in
the subcategory and are amenable to control by identified
wastewater treatment and control practices.
Antimony concentrations appeared in 11 of 20 total raw wastewater
streams from the lead subcategory. Antimony is used as an
alloying element in the lead grids used to make battery plates,
therefore, its presence is expected in raw wastewaters. The
maximum concentration in the total raw wastewater was 0.536 mg/1
and in the pasting raw wastewater samples was as high as
3.67 mg/1. Since some measured raw wastewater concentrations are
above the level which can be achieved by specific treatment
methods, and since antimony is used as a raw material, it is
considered for specific regulation in this subcategory.
Cadmium concentration appeared in 17 of 20 total raw wastewater
streams from the lead subcategory. The maximum concentration was
0.03 mg/1 in the total raw wastewater streams and as high as
0.34 mg/1 in the battery repair raw wastewater samples. Since
some of the measured concentrations iq raw wastewaters are above
the concentration level which can be achieve by specific
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treatment methods, cadmium is considered for specific regulation
in this subcategory.
Chromium concentrations appeared in 19 of 19 total raw wastewater
streams in the lead subcategory. The maximum concentration was
3.27 mg/1 in the total raw wastewater streams and as high as
3.67 mg/1 in the battery wash (detergent) raw wastewater samples.
Specific treatment methods can reduce chromium below this level.
Therefore, chromium is considered for specific regulation.
Copper concentrations appeared in 19 of 19 total raw wastewater
streams, and individual process raw wastewater samples from the
lead subcategory. The maximum concentration in the total raw
wastewater streams was 2.50 mg/1, and as high as 9.83 mg/1 in the
battery repair raw wastewater samples. Copper is used for
electrical conductors in charging operations and may be present
in process equipment. It was not a primary raw material in the
sampled plants but may be introduced into wastewaters by
corrosion of equipment. Some of the measured copper
concentrations are greater than the levels which can be achieved
by specific treatment methods. Therefore, copper is considered
for specific regulation in this subcategory.
Lead concentrations appeared in all total raw wastewater streams
and individual process raw wastewater samples from the eight
plants in the lead subcategory. The maximum concentration was
135.4 mg/1 in the total raw wastewater streams and as high as
6000 mg/1 in the pasting raw wastewater samples. All total raw
wastewater streams and most individual process wastewater samples
contained concentrations which were above the level which can be
achieved by specific treatment methods. Therefore, lead is
considered for specific regulation in this subcategory.
Mercury concentrations appeared in 4 of 12 total raw wastewater
streams analyzed for this priority pollutant. Streams from two
plants contained this pollutant. The maximum concentration was
0.065 mg/1 which was from a battery wash (water only) raw
wastewater sample. Specific treatment methods remove mercury to
levels lower than some of those found in these samples.
Therefore, even though mercury is not a primary raw material or
added in the manufacturing process, specific regulation of
mercury is considered in this subcategory.
Nickel concentrations appeared in 17 of 19 total raw wastewater
streams in the lead subcategory. The maximum concentration was
2.8 mg/1 which appeared in the battery wash (detergent) raw
wastewater samples and a maximum of 2.49 mg/1 was in the total
raw wastewater streams. Some of the concentrations were greater
than the level which can be achieved with specific treatment
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methods. Therefore, although nickel is not a primary raw
material, and is not a recognizable addition of any process step,
this priority pollutant parameter is considered for specific
regulation in this subcategory.
Silver concentrations appeared in 8 of 13 total raw wastewater
streams analyzed for this priority pollutant in the lead
subcategory. The maximum concentration found was 0.03 mg/1 in
the total wastewater streams and as high as .71 mg/1 in the
pasting raw wastewater samples. Silver can be removed to
concentrations below those found in some samples. Silver is not
a primary raw material, but may be present in trace quantities in
the lead used for grids in this subcategory. Therefore, silver
is considered for specific regulation.
Zinc concentrations appeared in all total raw wastewater streams
from the eight plants in the lead subcategory. The maximum
concentration was 6.8 mg/1 in the total raw wastewater streams
and as high as 15.2 mg/1 in the floor wash raw wastewater
samples. Many concentrations are above the level achievable with
specific treatment methods. Thus, even though zinc is not a
primary raw material in this subcategory, it is considered for
specific regulation.
Aluminum concentrations appeared in all total raw wastewater
streams that were analyzed for aluminum. The maximum aluminum
concentration was 2.8 mg/1 in the total raw wastewater streams,
and concentrations were as high as 160 mg/1 in a truck wash raw
wastewater sample. These concentrations are greater than those
which can be achieved by specific treatment methods. Therefore,
aluminum is considered for specific regulation.
Iron concentrations appeared in all total raw wastewater streams
that were analyzed for iron in the lead subcategory. The maximum
iron concentration was 390 mg/1 in the total raw wastewater
streams and all concentrations were above 1 mg/1. Concentrations
were as high as 1050 mg/1 in the truck wash raw wastewater
samples. Iron in these raw wastewater streams is attributable to
corrosion of process equipment and charging racks by sulfuric
acid. The levels of iron in most of the sampled raw wastewater
streams may produce undesirable environmental effects. All total
raw wastewater samples contained concentrations which were
greater than those which can be achieved by specific treatment
methods. Therefore, iron is considered for specific regulation.
Manganese concentrations appeared in all total raw wastewater
streams that were analyzed for manganese. The maximum manganese
concentration was 0.42 mg/1 in the total raw wastewater streams,
and concentrations were as high as 7.2 mg/1 in a truck wash raw
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wastewater sample. These concentrations are above those which
can be achieved by specific treatment methods. Therefore,
manganese is considered for specific regulation.
Oil and grease concentrations appeared in all total raw
wastewater streams in the lead subcategory. Concentrations were
as high as 49.0 mg/1 in the total raw waste streams and as high
as 1620 mg/1 in the pasting process raw wastewater samples. This
pollutant can be removed by conventional treatment methods.
Therefore oil and grease is considered for specific regulation in
this subcategory.
Suspended solids appeared in all total raw wastewater streams at
concentrations as high as 1300 mg/1. TSS (Total Suspended
Solids) may be introduced into wastewater at numerous points in
the process, most notably in electrode grid pasting processes
where concentrations were as high as 42,300 mg/1, and are also
produced by the treatment of wastewater for precipitation of
metal pollutants. The TSS generated in this subcategory consists
of large proportions of priority pollutants and is treatable.
Therefore TSS is considered for specific regulation.
Raw waste streams in the lead subcategory are predominantly
acidic because of contamination by sulfuric acid which is used as
electrolyte and in process steps. The pH of these wastewater
samples range from 12 down to 1. Regulation of pH is considered
in this subcategory to maintain the pH within the 7.5 to 10.0
range.
Parameters Not Selected for Specific Regulation. A total of
fifteen pollutant parameters which were evaluated in verification
analysis were dropped from further consideration for specific
regulation in the lead subcategory. These parameters were found
to be present in raw wastewaters infrequently, or at
concentration below those usually achieved by specific treatment
methods. The fifteen are: 1,1,1-trichloroethane, chloroform,
methylene chloride, napththalene, phenol, bis(2-
ethylhexyDphthalate, butyl benzyl phthalate, di-n-butyl
phthalate, di-n-octyl phthalate, anthracene, phenanthrene,
pyrene, arsenic, strontium, and "total phenols."
1,ly1-Trichloroethane concentrations appeared in all of the 13
total raw wastewater ' streams analyzed for this priority
pollutant. This priority pollutant is an industrial solvent and
degreasing agent which might easily be present in any
manufacturing plant. The maximum concentration was 0.025 mg/1,
which is below the level considered achievable by available
specific treatment methods. Therefore 1,1,1-trichloroethane is
not considered for specific regulation in this subcategory.
292
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Chloroform concentrations appeared in 6 of the 13 total raw
wastewater streams analyzed for this pollutant. All
concentrations were below the quantification level for toxic
organic pollutants. Chloroform is not a specific raw material
nor is it part of a process in this subcategory. Specific
treatment methods do not bring chloroform concentrations down to
the levels found in the raw wastewater. Therefore, chloroform is
not considered for specific regulation in this subcategory.
Methylene chloride concentrations appeared in 8 of the 13 total
raw wastewater streams which were subjected to analysis for this
priority pollutant. All concentrations were below the
quantifiable limit for organic priority pollutants. Therefore
methylene chloride is not considered for specific regulation in
this subcategory.
Naphthalene concentrations appeared in 10 of the 13 total raw
wastewater streams analyzed for this pollutant. The maximum
concentration was 0.01 mg/1 in the total raw wastewater streams
and as high as 0.037 mg/1 in the battery wash raw wastewater
samples. This priority pollutant is not a raw material nor is it
part of a process. Concentrations were below the level
considered to be achievable with available specific treatment
methods. Therefore, naphthalene is not considered for specific
regulation in this subcategory.
Phenol concentrations appeared in only one of three total raw
wastewater streams from the lead subcategory which were subjected
to analysis for this priority pollutant. The concentration is
below the quantifiable limit. Therefore, phenol is not
considered for specific regulation.
Four priority pollutant phthalate ester concentrations appeared
in total raw wastewater streams from the lead subcategory. Bis
(2-ethylhexyl) phthalate concentrations appeared in all total raw
wastewater streams which were analyzed for this priority
pollutant at concentrations up to 0.135 mg/1. The other three
esters - butyl benzyl phthalate, di-n-butyl phthalate, and di-n-
octyl phthalate were present in fewer samples and, with the
exception of di-n-octyl phthalate which had a maximum of 0.14
mg/1, were found at lower concentrations. None of these esters
are raw materials, nor are they part of processes. All these
esters are used as plasticizers which would result in their
presence in the plant equipment and piping, and some have
additional uses such as denaturant for alcohol in personal care
items. Specific regulation of these four phthalate esters in the
lead subcategory is not considered because these unique
detections are not attributable to battery manufacturing waters.
293
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Three PAH - anthracene, phenanthrene, and pyrene concentrations
appeared in total raw wastewater streams analyzed for these
priority pollutant parameters. The maximum concentration was
0.032 mg/1 for anthracene and phenanthrene and all other values
were .below the quantifiable limit, where only detections are
recorded. None of these compounds are used in processes or as
raw materials in the lead subcategory, and only the greatest
concentration (for anthracene and phenathoene) measured is above
the level which is considered to be achievable by available
specific treatment methods. Therefore, none of these three PAH
are considered for specific regulation in this subcategory.
Arsenic concentrations appeared in 10 of the 19 total raw waste-
water streams analyzed for this priority pollutant. In the total
raw wastewater streams the maximum concentration was 0.12 mg/1
and as high as 0.19 mg/1 in a floor wash raw wastewater sample.
Arsenic is an additive of lead used in some battery plate grids.
However, concentration levels attainable by specific treatment
methods are higher than the maximum reported raw wastewater
concentration. Therefore, arsenic is not considered for specific
regulation in this subcategory.
Strontium concentrations appeared in 5 of 12 total raw wastewater
streams analyzed for this pollutant parameter. The maximum
concentration of 0.039 mg/1 which appeared in the battery wash
(water only) raw wastewater samples is lower than the level that
can be achieved by available specific treatment methods.
Therefore, strontium is not considered for specific regulation in
this subcategory.
"Total phenols" concentrations appeared in 8 of 13 total raw
wastewater streams analyzed for this pollutant parameter in the
lead subcategory. The maximum concentration appeared in the
battery repair raw wastewater samples and was 0.174 mg/1.
Concentrations ranged from 0.01 mg/1 to 0.05 mg/1 in the total
raw wastewater streams which are below those for which practical
specific treatment methods exist. Some phenols will be removed
with oil and grease removal treatments. Therefore, specific
regulation of "total phenols" is not considered in this
subcategory.
Summary
Table VI-1, (page 296) presents the selection of priority
pollutant parameters considered for regulation for the lead
subcategory. The selection is based on all sampling results.
The "Not Detected" notation includes pollutants which were not
detected and not selected during screening analysis of total
plant raw wastewater, and those that were selected at screening,
294
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but not detected during verification analysis of process raw
wastewater streams within the lead subcategory. "Not
Quantifiable" includes those pollutants which were at or below
the quantifiable limits in influent, raw or effluent waters and
not selected at screening, and those not quantifiable for all
verification raw wastewater stream analysis within the
subcategory. "Small Unique Sources" for both screening and
verification includes those pollutants which were present only in
small amounts and includes those samples which were detected at
higher concentrations in the influent or effluent than in the raw
process wastewater, were detected at only one plant, or were
detected and could not be attributed to this point source
category. "Not Treatable" means that concentrations were lower
than the level achievable with the specific treatment methods
considered in Section VII. The "Regulation" notation1 includes
those pollutants which are considered for regulation. Table VI-2
(page 301) summarizes the selection of nonconventional and
conventional pollutant parameters for consideration for specific
regulation in the lead subcategory.
295
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TABLE VI-1
PRIORITY POLLUTANT DISPOSITION
FOR THE LEAD SUBCATEGORY
Pollutant
001 Acenaphthene NQ
002 Acrolein ND
003 Acrylonitrile ND
004 Benzene NQ
005 Benzldine ND
006 Carbon tetrachloride
(tetrachloromethane) ND
007 Chlorobenzene ND
008 1,2,4-trichloro-
benzene ND-
009 Hexachlorobenzene ND
010 1,2-dichloroethane ND
011 1,1,1-trichloroethane NT
012 Hexachloroethane ND
013 1,1-dichloroethane ND
014 1,1,2-triehloroethane ND
015 1,1,2,2-tetra-
chloroethane ND
016 Chloroethane ND
017 Bis (chloromethyl)
ether ND
018 Bis (2-chloroethyl
ether ND
019 2-chloroethyl vinyl
ether (mixed) ND
020 2-ehloronaphthalene ND
021 2,4,6-trichlorophenol NQ
022 Parachlorometa cresol ND
023 Chloroform (trichloro-
methane) NT
024 2-chlorophenol NQ
025 1,2-dichlorobenzene ND
026 1,3-dichlorobenzene NQ
LEGEND:
ND - NOT DETECTED
NQ = NOT QUANTIFIABLE
SU = SMALL, UNIQUE SOURCES
NT = NOT TREATABLE
REG = REGULATION CONSIDERED
296
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TABLE VI-1 (Continued)
PRIORITY POLLUTANT DISPOSITION
FOR THE LEAD SUBCATEGORY
Pollutant
027 1,4-dichlorobenzene ND
028 3,3-dichlorobenzidine ND
029 1,1-dichloroethylene ND
030 1,2-trans-dichloro-
ethylene ND
031 2,4-dichlorophenol NQ
032 1,2-dichloropropane ND
033 1,2-dichloropropylene
(1,2-dichloropropene) ND
034 2,4-dimethylphenol ND
035 2,4-dinitrotoluene ND
036 2,6-dinitrotoluene ND
037 1,2-diphenylhydrazine ND
038 Ethylbenzene NQ
039 Fluoranthene NQ
040 4-ehlorophenyl phenyl
ether ND
041 4-bromophenyl phenyl
ether ND
042 Bis(2-ehloroisopropyl)
ether ND
043 Bis (2-chloroethoxyl)
methane ND
044 Methylene chloride
(dichloromethane) NQ
045 Methyl chloride
(chloromethane) ND
046 Methyl bromide
(bromomethane) ND
047 Bromoform (tribromo-
methane) ND
048 Dichlorobromomethane NQ
049 Trichlorofluoromethane ND
050 Dichlorodifluoromethane ND
051 Chlorodibromomethane NQ
052 Hexachlorobutadiene ND
053 Hexachlorocyclopenta-
diene ND
054 Isophorone ND
055 Naphthalene NT
056 Nitrobenzene ND
297
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TABLE VI-1 (Continued)
PRIORITY POLLUTANT DISPOSITION
FOR THE LEAD SUBCATEGORY
Pollutant
057 2-nitrophenol ND
058 4-nitrophenol ND
059 2,4-dinitrophenol ND
060 4,6-dinitro-o-cresol ND
061 N-nitrosodimethyl-
amine ND
062 N~nitrosodiphenyl-
amine ND
063 N-nitrosodi-n-propyl-
amine ND
064 Pentachlorophenol ND
065 Phenol NQ
066 Bis(2-ethylhexyl)
phthalate SU
067 Butyl benzyl-
phthalate SU
068 Di-n-butyl phthalate SU
069 Di-n-octyl phthalate SU
070 Diethyl phthalate ND
071 Dimethyl phthalate ND
072 1,2-benzanthracene
(benzo(a)anthracene) NQ
073 Benzo(a)pyrene (3,4-
benzopyrene) NQ
074 3,4-Benzofluoranthene
(benzo(b)fluoranthene) NQ
075 11,12-benzofluoranthene
(benzo(b)fluoranthene) NQ
076 Chrysene NQ
077 Acenaphthylene ND
078 Anthracene , SU
079 1,12-benzoperylene
(benzo(ghi)perylene) ND
080 Fluorene NQ
081 Phenanthrene SU
082 1,2,5,6-dibenzanthracene
dibenzo(h)anthracene ND
083 Indeno(1,2,3-cd) pyrene
(2,3-o-phenylene pyrene). ND
084 Pyrene NQ
085 Tetrachloroethylene ND
298
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TABLE VI-1 (Continued)
PRIORITY POLLUTANT DISPOSITION
FOR THE LEAD SUBCATEGORY
Pollutant
086 Toluene SU
087 ' Trichloroethylene NQ
088 Vinyl chloride
(chloroethylene) ND
089 Aldrin ND
090 Dieldrin ND
091 Chlorodane (technical
mixture and metabolites) ND
092 4, 4-DDT ND
093 4,4-DDE (p.p-DDX) ND
094 4,4-DDD (p.p-TDE) ND
095 Alpha-endosulfan ND
096 Beta-endosulfan ND
097 Endosulfan sulfate ND
098 Endrin ND
099 Endrin aldehyde ND
100 Heptachlor ND
101 Heptachlor epoxide (BHC
hexachlorohexane) NQ
102 Alpha-BHC NQ
103 Beta-BHC ND
104 Gamma-BHC (lindane) ND
105 Delta-BHC (PCB-polychlor-
inated biphenyls) ND
106 PCB-1232 (Arochlor 1242) ND
107 PCB-1254 (Arochlor 1254) ND
108 PCB-1221 (Arochlor 1221) ND
109 PCB-1232 (Arochlor 1232) ND
110 PCB-1248 (Arochlor 1248) ND
111 PCB-1260 (Arochlor 1260) ND
112 PCB-1016 (Arochlor 1016) ND
113 Toxaphene ND
114 Antimony REG
115 Arsenic NT
1 16 Asbestos ND
117 Beryllium NQ
118 Cadmium ' REG
119 Chromium REG
120 Copper . REG
121 Cyanide - NQ
122 Lead REG
299
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TABLE VI-1 (Continued)
PRIORITY POLLUTANT DISPOSITION
FOR THE LEAD SUBCATEGORY
Pollutant
123 Mercury REG
124 Nickel REG
125 Selenium ND
126 Silver REG
127 Thallium ND
128 Zinc REG
129 2,3,7,8-tetrachlorodi-
benzo-p-dioxin ND
300
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TABLE VI-2
OTHER POLLUTANTS CONSIDERED FOR REGULATION
IN THE LEAD SUBCATEGORY
Aluminum
Iron
Manganese
TSS
Oil and Grease
pH
301
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
This section describes the treatment techniques currently used or
available to remove or recover wastewater pollutants normally
generated by the lead subcategory of the battery manufacturing
industrial point source category. Included are discussions of
individual end-of-pipe treatment technologies and in-plant
technologies. These treatment technologies are widely used in
many industrial categories, and data and information to support
their effectiveness has been drawn from a similarly wide range of
sources and data bases.
END-OF-PIPE TREATMENT TECHNOLOGIES
Individual recovery and treatment technologies are described
which are used or are suitable for use in treating wastewater
discharges from lead subcategory plants. Each description
includes a functional description and discussion of application
and performance, advantages and limitations, operational factors
(reliability, maintainability, solid waste aspects), and
demonstration status. The treatment processes described include
both technologies presently demonstrated within the battery
manufacturing category, and technologies demonstrated in
treatment of similar wastes in other industries.
Battery manufacturing wastewaters characteristically may be acid
or alkaline; may contain substantial levels of dissolved or
particulate metals including cadmium, chromium, lead, mercury,
nickel, silver, zinc and manganese; contain only small or trace
amounts of toxic organics; and are generally free from strong
chelating agents. The toxic inorganic pollutants constitute the
most significant wastewater pollutants in this category.
In general, these pollutants are removed by chemical
precipitation and sedimentation or filtration. Most of them may
be effectively removed by precipitation of metal hydroxides or
carbonates utilizing the reaction with lime, sodium hydroxide, or
sodium carbonate. For some, improved removals are provided by
the use of sodium sulfide or ferrous sulfide to precipitate the
pollutants as sulfide compounds with very low solubilities.
Discussion of end-of-pipe treatment technologies is divided into
three parts: the major technologies; the effectiveness of major
technologies; and minor technologies.
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MAJOR TECHNOLOGIES
In Sections IX, X, XI, and XII the rationale for selecting
treatment systems is discussed. The individual technologies used
in the system are described here. The major end-of-pipe
technologies for treating lead subcategory wastewaters are: (1)
chemical reduction of chromium, (2) chemical precipitation, (3)
cyanide precipitation, (4) granular bed filtration, (5) pressure
filtration, (6) settling, and (7) skimming. In practice,
precipitation of metals and settling of the resulting
precipitates is often a unified two-step operation. Suspended
solids originally present in raw wastewaters are not appreciably
affected by the precipitation operation and are removed with the
precipitated metals in the settling operations. Settling
operations can be evaluated independently of hydroxide or other
chemical precipitation operations, but hydroxide and other
chemical precipitation operations can only be evaluated in
combination with a solids removal operation.
1 . Chemical Reduction of_ Chromium
Description of the Process. Reduction is a chemical reaction in
which electrons are transferred to the chemical being reduced
from the chemical initiating the transfer (the reducing agent).
Sulfur dioxide, sodium bisulfite, sodium metabisulfite, and
ferrous sulfate form strong reducing agents in aqueous solution
and are often used in industrial waste treatment facilities for
the reduction of hexavalent chromium to the trivalent form. The
reduction allows removal of chromium from solution in conjunction
with other metallic salts by alkaline precipitation. Hexavalent
chromium is not precipitated as the hydroxide.
Gaseous sulfur dioxide is a widely used reducing agent and
provides a good example of the chemical reduction process.
Reduction using other reagents is chemically similar. The
reactions involved may be illustrated as follows:
3 SO2 + 3 H20 > 3 H2SO3
3 H2SO3 + 2H2CrO4 > Cr2(SO4)3 + 5 H20
The above reaction is favored by low pH. A pH of from 2 to 3 is
normal for situations requiring complete reduction. At pH levels
above 5, the reduction rate is slow. Oxidizing agents such as
dissolved oxygen and ferric iron interfere with the reduction
process by consuming the reducing agent.
A typical treatment consists of 45 minutes retention in a
reaction tank. The reaction tank has an electronic recorder-
304
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controller device to control process conditions with respect to
pH and oxidation reduction potential (ORP). Gaseous sulfur
dioxide is metered to the reaction tank to maintain the ORP
within the range of 250 to 300 millivolts. Sulfuric acid is
added to maintain a pH level of from 1.8 to 2.0. The reaction
tank is equipped with a propeller agitator designed to provide
approximately one turnover per minute. Figure VI1-13 (Page 439)
shows a continuous chromium reduction system.
Application and Performance. Chromium reduction is used in
battery manufacturing for treating chromium containing cell wash
solutions and heat paper production wastewater. Chromium
reduction is most usually required to treat electroplating and
metal surfacing rinse waters/ but may also be required in battery
manufacturing plants. A study of an operational waste treatment
facility chemically reducing hexavalent chrbmium has shown that a
99.7 percent reduction efficiency is easily achieved. Final
concentrations of 0.05 mg/1 are readily attained, and
concentrations of 0.01 mg/1 are considered to be attainable by
properly maintained and operated equipment.
Advantages and Limitations. The major advantage of chemical
reduction to reduce hexavalent chromium is that it is a fully
proven technology based on many years of experience. Operation
at ambient conditions results in minimal energy consumption, and
the process, especially when using sulfur dioxide, is well suited
to automatic control. Furthermore, the equipment is readily
obtainable from many suppliers, and operation is straightforward.
One limitation of chemical reduction of hexavalent chromium is
that for high concentrations of chromium, the cost of treatment
chemicals may be prohibitive. When this situation occurs, other
treatment techniques are likely to be more economical. Chemical
interference by oxidizing agents is possible in the treatment of
mixed wastes, and the treatment itself may introduce pollutants
if not properly controlled. Storage and handling of sulfur
dioxide is.somewhat hazardous.
Operational Factors. Reliability: Maintenance consists of
periodic removal of sludge, the frequency of removal depends on
the input concentrations of detrimental constituents.
Solid Waste Aspects: Pretreatment to eliminate substances which
will interfere with the process may often be necessary. This
process produces trivalent chromium which can be controlled by
further treatment. However, small amounts of sludge may be
collected as the result of minor shifts in the solubility of the
contaminants. This sludge can be processed by the main sludge
treatment equipment.
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Demonstration Status. The reduction of chromium waste by sulfur
dioxide or sodium bisulfite is a classic process and is used by
numerous plants which have hexavalent chromium compounds in
wastewaters from operations such as electroplating conversion
coating and noncontact cooling.
2. Chemical Precipitation
Dissolved toxic metal ions and certain anions may be chemically
precipitated for removal by physical means such as sedimentation,
filtration, or centrifugation. Several reagents are commonly
used to effect this precipitation:
1) Alkaline compounds such as lime or sodium hydroxide may be
used to precipitate many toxic metal ions as metal
hydroxides. Lime also may precipitate phosphates as
insoluble calcium phosphate, fluorides as calcium fluoride
and arsenic as calcium arsinate.
2) Both "soluble" sulfides such as hydrogen sulfide or sodium
sulfide and "insoluble" sulfides such as ferrous sulfide may
be used to precipitate many heavy metal ions as metal
sulfides.
3) Ferrous sulfate, zinc sulfate or both (as is required) may
be used to precipitate cyanide as a ferro or zinc
ferricyanide complex.
4) Carbonate precipitates may be used to remove metals either
by direct precipitation using a carbonate reagent such as
calcium carbonate or by converting hydroxides into
carbonates using carbon dioxide.
These treatment chemicals may be added to a flash mixer or rapid
mix tank, to a presettling tank, or directly to a clarifier or
other settling device. Because metal hydroxides tend to be col-
loidal in nature, coagulating agents may also be added to faci-
litate' settling. After the solids have been removed, final pH
adjustment may be required to reduce the high pH created by the
alkaline treatment chemicals.
Chemical precipitation as a mechanism for removing metals from
wastewater is a complex process of at least two steps - pre-
cipitation of the unwanted metals and removal of the precipitate.
Some very small amount of metal will remain dissolved in the
wastewater after precipitation is complete. The amount of
resrdual dissolved metal depends on the treatment chemicals used
and related factors. The effectiveness of this method of
removing any specific metal depends on the fraction of the
306
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specific metal in the raw waste (and hence in the precipitate)
and the effectiveness of suspended solids removal. In specific
instances, a sacrifical ion such as iron or aluminum may be added
to aid in the removal of toxic metals by co-precipitation process
and reduce the fraction of a specific metal in the precipitate.
Application and Performance. Chemical precipitation is used in
battery manufacturing for precipitation of dissolved metals. It
can be used to remove metal ions such as antimony, arsenic,
beryllium, cadmium, chromium, copper, lead, mercury, zinc,
aluminum, cobalt, iron, manganese, molybdenum and tin. The
process is also applicable to any substance that can be
transformed into an insoluble form such as fluorides, phosphates,
soaps, sulfides and others. Because it is simple and effective,
chemical precipitation is extensively used for industrial waste
treatment.
The performance of chemical precipitation depends on several
variables. The more important factors affecting precipitation
effectiveness are:
1. Maintenance of an appropriate (usually alkaline) pH
throughout the precipitation reaction and subsequent
settling;
2. Addition of a sufficient excess of treatment ions to
drive the precipitation reaction to completion;
3. Addition of an adequate supply of sacrifical ions (such
as iron or aluminum) to ensure precipitation and
removal of specific target ions; and
4. Effective removal of precipitated solids (see
appropriate solids removal technologies).
Control of pH. Irrespective of the solids removal technology
employed, proper control of pH is absolutely essential for
favorable performance of precipitation-sedimentation
technologies. This is clearly illustrated by solubility curves
for selected metals hydroxides and sulfides shown in Figure VII-1
(page 427), and by plotting effluent zinc concentrations against
pH as shown in Figure VII-3 (page 429). Figure VII-3 was
obtained from Development Document for the Proposed Effluent
Limitations Guidelines and New Source Performance Standards for
the Zinc Segment of Nonferrous Metals Manufacturing Point Source
Category, U.S. E.P.A., EPA 440/1-74/033, November, 1974. Figure
VII-3 was plotted from the sampling data'from several facilities
with metal finishing operations. It is partially illustrated by
data obtained from 3 consecutive days of sampling at one metal
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processing plant (47432) as displayed in Table VII-1 (page 404).
Flow through this system is approximately 49,263 1/hr (13,000
gal/hr).
This treatment system uses lime precipitation (pH adjustment)
followed by coagulant addition and sedimentation. Samples were
taken before (in) and after (out) the treatment system. The best
treatment for removal of copper and zinc was achieved on day one,
when the pH was maintained at a satisfactory level. The poorest
treatment was found on the second day, when the pH slipped to an
unacceptably low level; intermediate values were achieved on the
third day, when pH values were less than desirable but in between
those for the first and second days.
Sodium hydroxide is used by one facility (plant 439) for pH
adjustment and chemical precipitation, followed by settling
(sedimentation and a polishing lagoon) of precipitated solids.
Samples were taken prior to caustic addition and following the
polishing lagoon. Flow through the system is approximately
22,700 1/hr (6,000 gal/hr). These data displayed in Table VI1-2
(page 404) indicate that the system was operated efficiently.
Effluent pH was controlled within the range of 8.6 to 9.3, and,
while raw waste loadings were not unusually high, most toxic
metals were removed to very low concentrations.
Lime and sodium hydroxide (combined) are sometimes used to
precipitate metals. Data developed from plant 40063, a facility
with a metal bearing wastewater, exemplify efficient operation of
a chemical precipitation and settling system. Table VII-3 (page
405) shows sampling data from this system, which uses lime and
sodium hydroxide for pH adjustment and chemical precipitation,
polyelectrolyte flocculant addition, and sedimentation. Samples
were taken of the raw waste influent to the system and of the
clarifier effluent. Flow through the system is approximately
19,000 1/hr (5,000 gal/hr).
At this plant, effluent TSS levels were below 15 mg/1 on each
day, despite average raw waste TSS concentrations of over 3500
mg/1. Effluent pH was maintained at approximately 8, lime
addition was sufficient to precipitate the dissolved metal ions,
and the flocculant addition and clarifier retention served to
remove effectively the precipitated solids.
Sulfide precipitation is sometimes used to precipitate metals
resulting in improved metals removals. Most metal sulfides are
less soluble than hydroxides, and the precipitates are frequently
more dependably removed from,water. Solubilities for selected
metal hydroxide, carbonate and sulfide precipitates are shown in
Table VII-4, (page 405). (Source: Lange's Handbook of
308
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Chemistry). Sulfide precipitation is particularly effective in
removing specific metals such as silver and mercury. Sampling
data from three industrial plants using sulfide precipitation
appear in Table VII-5 (page 406). In all cases except iron,
effluent concentrations are below 0.1 mg/1 and in many cases
below 0.01 mg/1 for the three plants studied.
Sampling data from several chlorine-caustic manufacturing plants
using sulfide precipitation demonstrate effluent mercury
concentrations varying between 0.009 and 0.03 mg/1. As shown in
Figure VII-1, the solubilities of PbS and Ag2S are lower at
alkaline pH levels than either the corresponding hydroxides or
other sulfide compounds. This implies that removal performance
for lead and silver sulfides should be comparable to or better
than that for the metal hydroxides. Bench scale tests on several
types of metal finishing and manufacturing wastewater indicate
that metals removal to levels of less than 0.05 mg/1 and in some
cases less than 0.01 mg/1 are common in systems using sulfide
precipitation followed by clarification. Some of the bench scale
data, particularly in the case of lead, do not support such low
effluent concentrations. However, lead is consistently removed
to very low levels (less than 0.02 mg/1) in systems using
hydroxide and carbonate precipitation and sedimentation.
Of particular interest is the ability of sulfide to precipitate
hexavalent chromium (Cr+6) without prior reduction to the tri-
valent state as is required in the hydroxide process. When
ferrous sulfide is used as the precipitant, iron and sulfide act
as reducing agents for the hexavalent chromium according to the
reaction:
Cr03+ FeS + 3H20 > Fe(OH)3 + Cr(OH)3 + S
The sludge produced in this reaction consists mainly of ferric
hydroxides, chromic hydroxides, and various metallic sulfides.
Some excess hydroxyl ions are generated in this process, possibly
requiring a downward re-adjustment of pH.
Based on the available data, Table VII-6 (page 407) shows the
minimum reliably attainable effluent concentrations for sulfide
precipitation-sedimentation systems. These values are used to
calculate performance predictions of sulfide precipitation-
sedimentation systems.
Carbonate precipitation is sometimes used to precipitate metals,
especially where precipitated metals values are to be recovered.
The solubility of most metal carbonates is intermediate between
hydroxide and sulfide solubilities; in addition, carbonates form
easily filtered precipitates.
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Carbonate ions appear to be particularly useful in precipitating
lead and antimony. Sodium carbonate has been observed being
added at treatment to improve lead precipitation and removal in
some industrial plants. The lead hydroxide and lead carbonate
solubility curves displayed in Figure VII-2 (page 428) (Source:
"Heavy Metals Removal," by Kenneth Lanovette, Chemical
Enq i neer i nq/Deskbook Issue, October 17, 1977) explain this
phenomenon.
Co-precipitation With Iron. The presence of substantial
quantites of iron in metal bearing wastewaters before treatment
has been shown to improve the removal of toxic metals. In some
cases this iron is an integral part of the industrial wastewater;
in other cases iron is deliberately added as a pre or first step
of treatment. The iron functions to improve toxic metal removal
by three mechanisms: the iron co-precipitates with toxic metals
forming a stable precipitate which desolubilizes the toxic metal;
the iron improves the settleability of the precipitate; and the
large amount of iron reduces the fraction of toxic metal in the
precipitate. Co-precipitation with iron has been practiced for
many years incidentally when iron was a substantial consitutent
of raw wastewater and intentionally when iron salts were added as
a coagulant aid. Aluminum or mixed iron-aluminum salt also have
been used. The addition of iron for co-precipitation to aid in
toxic metals removal is considered a routine part of state-of-
the-art lime and settle technology which should be implemented as
required to achieve optimal removal of toxic metals.
Co-precipitation using large amounts of ferrous iron salts is
known as ferrite co-precipitation because magnetic iron oxide or
ferrite is formed. The addition of ferrous salts (sulfate) is
followed by alkali precipitation and air oxidation. The
resultant precipitate is easily removed by filtration and may be
removed magnetically. Data illustrating the performance of
ferrite co-precipitation is shown in Table VII-7, (page 408).
Advantages and Limitations. Chemical precipitation has proved to
be an effective technique for removing many pollutants from
industrial wastewater. It-operates at ambient conditions and is
well suited to automatic control. The use of chemical
precipitation may be limited because of interference by chelating
agents, because of possible chemical interference with mixed
wastewaters and treatment chemicals, or because of the
potentially hazardous situation involved with the storage and
handling of those chemicals. Battery manufacturing wastewaters
do not normally contain chelating agents or complex pollutant
matrix formations which would interfere with or limit the use of
chemical precipitation. Lime is usually added as a slurry when
used in hydroxide precipitation. The slurry must be kept well
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mixed and the addition lines periodically checked to prevent
blocking of the lines, which may result from a buildup of solids.
Also, lime precipitation usually makes recovery of the
precipitated metals difficult, because of the heterogeneous
nature of most lime sludges.
The major advantage of the sulfide precipitation process is that
the extremely low solubility of most metal sulfides promotes very
high metal removal efficiencies; the sulfide process also has the
ability to remove chromates and dichromates without preliminary
reduction of the chromium to its trivalent state. In addition,
sulfide can precipitate metals complexed with most complexing
agents. The process demands care, however, in maintaining the pH
of the solution at approximately 10 in order to restrict the gen-
eration of toxic hydrogen sulfide gas. For this reason,
ventilation of the treatment tanks may be a necessary precaution
in most installations. The use of insoluble sulfides reduces the
problem of hydrogen sulfide evolution. As with hydroxide
precipitation, excess sulfide ion must be present to drive the
precipitation reaction to completion. Since the sulfide ion
itself is toxic, sulfide addition must be carefully controlled to
maximize heavy metals precipitation with a minimum of excess
sulfide to avoid the necessity of additional wastewater
treatment. At very high excess sulfide levels and high pH,
soluble mercury-sulfide compounds may also be formed. Where
excess sulfide is present, aeration of the effluent stream can
aid in oxidizing residual sulfide to the less harmful sodium
sulfate (Na2S04). The cost of sulfide precipitants is high in
comparison to hydroxide precipitants, and disposal of metallic
sulfide sludges may pose problems. An essential element in
effective sulfide precipitation is the removal of precipitated
solids from the wastewater and proper disposal in an appropriate
site. Sulfide precipitation will also generate a higher volume
of sludge than hydroxide precipitation, resulting in higher
disposal and dewatering costs. This is especially true when
ferrous sulfide is used as the precipitant.
Sulfide precipitation may be used as a polishing treatment after
hydroxide precipitation-sedimentation. This treatment
configuration may provide the better treatment effectiveness of
sulfide precipitation while minimizing the variability caused by
changes in raw waste and reducing the amount of sulfide
precipitant required.
Operational Factors. . Reliability: Alkaline chemical
precipitation is highly reliable, although proper monitoring and
control are required. Sulfide precipitation systems provide
similar reliability.
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Maintainability: The major maintenance needs involve periodic
upkeep of monitoring equipment, automatic feeding equipment,
mixing equipment, and other hardware. Removal of accumulated
sludge is necessary for efficient operation of precipitation-
sedimentation systems.
Solid Waste Aspects: Solids which precipitate out are removed in
a subsequent treatment step. Ultimately, these solids require
proper disposal.
Demonstration Status. Chemical precipitation of metal hydroxides
is a classic waste treatment technology used by most industrial
waste treatment systems. Chemical precipitation of metals in the
carbonate form alone has been found to be feasible and is
commercially used to permit metals recovery and water reuse.
Full scale commercial sulfide precipitation units are in
operation at numerous installations, including several plants in
the battery manufacturing category. As noted earlier,
sedimentation to remove precipitates is discussed separately.
Use iri Battery Manufacturing Plants. Chemical precipitation is
used at 81 battery manufacturing plants. The quality of
treatment provided, however, is variable. A review of collected
data and on-site observations reveals that control of system
parameters is often poor. Where precipitates are removed by
clarification, retention times are likely to be short and
cleaning and maintenance questionable. Similarly, pH control is
frequently inadequate. As a result of these factors, effluent
performance at battery plants nominally practicing the same
wastewater treatment is observed to vary widely.
3. Cyanide Precipitation
Cyanide precipitation, although a method for treating cyanide in
wastewaters, does not destroy cyanide. The cyanide is retained
in the sludge that is formed. Reports indicate that during
exposure to sunlight, the cyanide complexes can break down and
form free cyanide. For this reason, the sludge from this
treatment method must be disposed of carefully.
Cyanide may be precipitated and settled out of wastewaters by the
addition of zinc sulfate or ferrous sulfate. In the presence of
iron, cyanide will form extremely stable cyanide complexes. The
addition of zinc sulfate or ferrous sulfate forms zinc
ferrocyanide or ferro ferricyanide complexes.
Adequate removal of the precipitated cyanide requires that the pH
must be kept at 9.0 and an appropriate retention time be
maintained. A study has shown that the formation of the complex
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is very dependent on pH. At a pH of either 8 or 10, the residual
cyanide concentration measured is twice that of the same reaction
carried out at a pH of 9. Removal efficiencies also depend
heavily on the retention time allowed. The formation of the
complexes takes place rather slowly. Depending upon the excess
amount of zinc sulfate or ferrous sulfate added, at least a 30
minute retention time should be allowed for the formation of the
cyanide complex before continuing on to the clarification stage.
One experiment with an initial concentration of 10 mg/1 of
cyanide showed that 98 percent of the cyanide was complexed ten
minutes after the addition of ferrous sulfate at twice the
theoretical amount necessary. Interference from other metal
ions, such as cadmium, might result in the need for longer
retention times.
Table VII-8 (page 408) presents cyanide precipitation data from
three coil coating plants. A fourth plant was visited for the
purpose of observing plant testing of the cyanide precipitation
system. Specific data from this facility are not included
because: (1) the pH was usually well below the optimum level of
9.0; (2) the historical treatment data were not obtained using
the standard cyanide analysis procedure; and (3) matched input-
output data were not made available by the plant. Scanning the
available data indicates that the raw waste CN level was in the
range of 25.0; the pH 7.5; and treated CN level was from 0.1 to
0.2.
The concentrations are those of the stream entering and leaving
the treatment system. Plant 1057 allowed a 27-minute retention
time for the formation of the complex. The retention time for
the other plants is not known. The data suggest that over a wide
range of cyanide concentration in the raw waste, the
concentration of cyanide can be reduced in the effluent stream to
under 0.15 mg/1.
Application and Performance. Cyanide precipitation can be used
when cyanide destruction is not feasible because of the presence
of cyanide complexes which are difficult to destroy. Effluent
concentrations of cyanide well below 0.15 mg/1 are possible.
Advantages and Limitations. Cyanide precipitation is an
inexpensive method of treating cyanide. Problems may occur when
metal ions interfere with the formation of the complexes.
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4. Granular Bed Filtration
Filtration occurs in nature as the surface ground waters are
cleansed by sand. Silica sand, anthracite coal, and garnet are
common filter media used in water treatment plants. These are
usually supported by gravel. The media may be used singly or in
combination. The multi-media filters may be arranged to maintain
relatively distinct layers by virtue of balancing the forces of
gravity, flow, and buoyancy on the individual particles. This is
accomplished by selecting appropriate filter flow rates (gpm/sq-
ft), media grain size, and density.
Granular bed filters may be classified in terms of filtration
rate, filter media, flow pattern, or method of pressurization.
Traditional rate classifications are slow sand, rapid sand, and
high rate mixed media. In the slow sand filter, flux or
hydraulic loading is relatively low, and removal of collected
solids to clean the filter is therefore relatively infrequent.
The filter is often cleaned by scraping off the inlet face (top)
of the sand bed. In the higher rate filters, cleaning is
frequent and is accomplished by a periodic backwash, opposite to
the direction of normal flow.
A filter may use a single medium such as sand or diatomaceous
earth, but dual and mixed (multiple) media filters allow higher
flow rates and efficiencies. The dual media filter usually
consists of a fine bed of sand under a coarser bed of anthracite
coal. The coarse coal removes most of the influent solids, while
the fine sand performs a polishing function. At the end of the
backwash, the fine sand settles to the bottom because it is
denser than the coal, and the filter is ready for normal
operation. The mixed media filter operates on the same
principle, with the finer, denser media at the bottom and the
coarser, less dense media at the top. The usual arrangement is
garnet at the bottom (outlet end) of the bed, sand in the middle,
and anthracite coal at the top. Some mixing of these layers
occurs and is, in fact, desirable.
The flow pattern is usually top-to-bottom, but other patterns are
sometimes used. Upflow filters are sometimes used, and in a
horizontal filter the flow is horizontal. In a biflow filter,
the influent enters both the top and the bottom and exits
laterally. The advantage of an upflow filter is that with an
upflow backwash, the particles of a single filter medium are
distributed and maintained in the desired coarse-to-fine (bottom-
to-top) arrangement. The disadvantage is that the bed tends to
become fluidized, which ruins filtration efficiency. The biflow
design is an attempt to overcome this problem.
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The classic granular bed filter operates by gravity flow;
however, pressure filters are fairly widely used. They permit
higher solids loadings before cleaning and are advantageous when
the filter effluent must be pressurized for further downstream
treatment. In addition, pressure filter systems are often less
costly for low to moderate flow rates.
Figure VII-14 (page 439) depicts a high rate, dual media, gravity
downflow granular bed filter, with self-stored backwash. Both
filtrate and backwash are piped around the bed in an arrangement
that permits gravity upflow of the backwash, with the stored
filtrate serving as backwash. Addition of the indicated
coagulant and polyelectrolyte usually results in a substantial
improvement in filter performance.
Auxilliary filter cleaning is sometimes employed in the upper few
inches of filter beds. This is conventionally referred to as
surface wash and is accomplished by water jets just below the
surface of the expanded bed during the backwash cycle. These
jets enhance the scouring action in the bed by increasing the
agitation.
An important feature for successful filtration and backwashing is
the underdrain. This is the support structure for the bed. The
underdrain provides an area for collection of the filtered water
without clogging from either the filtered solids or the media
grains. In addition, the underdrain prevents loss of the media
with the water, and during the backwash cycle it provides even
flow distribution over the bed. Failure to dissipate the
velocity head during the filter or backwash cycle will result in
bed upset and the need for major repairs.
Several standard approaches are employed for filter underdrains.
The simplest one consists of a parallel porous pipe imbedded
under a layer of coarse gravel and manifolded to a header pipe
for effluent removal. Other approaches to the underdrain system
are known as the Leopold and Wheeler filter bottoms. Both of
these incorporate false concrete bottoms with specific porosity
configurations to provide drainage and velocity head dissipation.
Filter system operation may be manual or automatic. The filter
backwash cycle may be on a timed basis, a pressure drop basis
with a terminal value which triggers backwash, or a solids carry-
over basis from turbidity monitoring of the outlet stream. All
of these schemes have been used successfully.
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Application and Performance. Wastewater treatment plants often
use granular bed filters for polishing after clarification,
sedimentation-, or other similar operations. Granular bed
filtration thus has potential application to nearly all
industrial plants. Chemical additives which enhance the upstream
treatment equipment may or may not be compatible with or enhance
the filtration process. Normal operating flow rates for various
types of filters are:
Slow Sand 2.04 - 5.30 1/sq m-hr
Rapid Sand 40.74 - 51.48 1/sq m-hr
High Rate Mixed Media 81.48 - 122.22 1/sq m-hr
Suspended solids are commonly removed from wastewater streams by
filtering through a deep 0.3-0.9 m (1-3 feet) granular filter
bed. The porous bed formed by the granular media can be designed
to remove practically all suspended particles. Even colloidal
suspensions (roughly 1 to 100 microns) are adsorbed on the
surface of the media grains as they pass in close proximity in
the narrow bed passages.
Properly operated filters following some pretreatment to reduce
suspended solids below 200 mg/1 should produce water with less
than 10 mg/1 TSS. For example, multimedia filters produced the
effluent qualities shown in Table VII-9 (page 409).
Advantages and Limitations. The principal advantages of granular
bed filtration are its comparatively (to other filters) low
initial and operating costs, reduced land requirements over other
methods to achieve the same level of solids removal, and
elimination of chemical additions to the discharge stream.
However, the filter may require pretreatment if the solids level
is high (over 100 mg/1). Operator training must be somewhat
extensive due to the controls and periodic backwashing involved,
and backwash must be stored and dewatered for economical
disposal.
Operational Factors. Reliability: The recent improvements in
filter technology have significantly improved filtration
reliability. Control systems, improved designs, and good
operating procedures have made filtration a highly reliable
method of water treatment.
Maintainability: Deep bed filters may be operated with either
manual or automatic backwash. In either case, they must be
periodically inspected for media attrition, partial plugging, and
leakage. Where backwashing is not used, collected solids must be
removed by shoveling, and filter media must be at least partially
replaced.
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Solid Waste Aspects: Filter backwash is generally recycled
within the wastewater treatment system, so that the solids
ultimately appear in the clarifier sludge stream for subsequent
dewatering. Alternatively, the backwash stream may be dewatered
directly or, if there is no backwash, the collected solids may be
disposed of in a suitable landfill. In either of these
situations there is a solids disposal problem similar to that of
clarifiers.
Demonstration Status. Deep bed filters are in common use in
municipal treatment plants. Their use in polishing industrial
clarifier effluent is increasing, and the technology is proven
and conventional. Granular bed filtration is used in several
battery manufacturing plants. As noted previously, however,
little data is available characterizing the effectiveness of
filters presently in use within the industry.
5. Pressure Filtration
Pressure filtration works by pumping the liquid through a filter
material which is impenetrable to the solid phase. The positive
pressure exerted by the feed pumps or other mechanical means
provides the pressure differential which is the principal driving
force. Figure VII-15 (page 441) represents the operation of one
type of pressure filter.
A typical pressure filtration unit consists of a number of plates
or trays which are held rigidly in a frame to ensure alignment
and which are pressed together between a fixed end and a
traveling end. On the surface of each plate, a filter made of
cloth or synthetic fiber is mounted. The feed stream is pumped
into the unit and passes through holes in the trays along the
length of the press until the cavities or chambers between the
trays are completely filled. The solids are then entrapped, and
a cake begins to form on the surface of the filter material. The
water passes through the fibers, and the solids are retained.
At the bottom of the trays are drainage ports. The filtrate is
collected and discharged to a common drain. As the filter medium
becomes coated with sludge, the flow of filtrate through the
filter drops sharply, indicating that the capacity of the filter
has been exhausted. The unit must then be cleaned of the sludge.
After the cleaning or replacement of the filter media, the unit
is again ready for operation.
Application and Performance. Pressure filtration is used in
battery manufacturing for sludge dewatering and also for direct
removal of precipitated and other suspended solids from
wastewater. Because dewatering is such a common operation in
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treatment systems, pressure filtration is a technique which can
be found in many industries concerned with removing solids from
their waste stream.
In a typical pressure filter, chemically preconditioned sludge
detained in the unit for one to three hours under pressures
varying from 5 to 13 atmospheres exhibited final solids content
between 25 and 50 percent.
Advantages and Limitations. The pressures which may be applied
to a sludge for removal of water by filter presses that are
currently available range from 5 to 13 atmospheres. As a result,
pressure filtration may reduce the amount of chemical
pretreatment required for sludge dewatering. Sludge retained in
the form of the filter cake has a higher percentage of solids
than that from centrifuge or vacuum filter. Thus, it can be
easily accommodated by materials handling systems.
As a primary solids removal technique, pressure filtration
requires less space than clarification and is well suited to
streams with high solids loadings. The sludge produced may be
disposed without further dewatering, but the amount of sludge is
increased by the use of filter precoat materials (usually
diatomaceous earth). Also, cloth pressure filters often do not
achieve as high a degree of effluent clarification as clarifiers
or granular media filters.
Two disadvantages associated with pressure filtration in the past
have been the short life of the filter cloths and lack of
automation. New synthetic fibers have largely offset the first
of these problems. Also, units with automatic feeding and
pressing cycles are now available.
For larger operations, the relatively high space requirements, as
compared to those of a centrifuge, could be prohibitive in some
situations.
Operational Factors. Reliability: With proper pretreatment,
design, and control, pressure 'filtration is a highly dependable
system.
Maintainability: Maintenance consists of periodic cleaning or
replacement of the filter media, drainage grids, drainage piping,
filter pans, and other parts of the system. If the removal of
the sludge cake is not automated, additional time is required for
this operation.
Solid Waste Aspects: Because it is generally drier than other
types of sludges, the filter sludge cake can be handled with
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relative ease. The accumulated sludge may be disposed by any of
the accepted procedures depending on its chemical composition.
The levels of toxic metals present in sludge from treating
battery wastewater necessitate proper disposal.
Demonstration Status. Pressure filtration is a commonly used
technology in a great many commercial applications. Pressure
filtration is used in six battery manufacturing plants.
6. Settling
Settling is a process which removes solid particles from a liquid
matrix by gravitational force. This is done by reducing the
velocity of the feed stream in a large volume tank or lagoon so
that gravitational settling can occur. Figure VII-.16 (page 442)
shows two typical settling devices.
Settling is often preceded by chemical precipitation which
converts dissolved pollutants to solid form and by coagulation
which enhances settling by coagulating suspended precipitates
into larger, faster settling particles.
If no chemical pretreatment is used, the wastewater is fed into a
tank or lagoon where it loses velocity and the suspended solids
are allowed to settle out. Long retention times are generally
required. Accumulated sludge can be collected either
periodically or continuously and either manually or mechanically.
Simple settling, however, may require excessively large
catchments, and long retention times (days as compared with
hours) to achieve high removal efficiencies. Because of this,
addition of settling aids such as alum or polymeric flocculants
is often economically attractive.
In practice, chemical precipitation often precedes settling, and
inorganic coagulants or polyelectrolytic flocculants are usually
added as well. Common coagulants include sodium sulfate, sodium
aluminate, ferrous or ferric sulfate, and ferric chloride.
Organic polyelectrolytes vary in structure, but all usually form
larger floe particles than coagulants used alone.
Following this pretreatment, the wastewater can be fed into a
holding tank, or lagoon for settling, but is more often piped into
a clarifier for the same purpose. A clarifier reduces space
requirements, reduces retention time, and increases solids
removal efficiency. Conventional clarifiers generally consist of
a circular or rectangular tank with a mechanical sludge
collecting device or with a sloping funnel-shaped bottom designed
for sludge collection. In advanced settling devices, inclined
plates, slanted tubes, or a lamellar network may be included
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within the clarifier tank in order to increase the effective
settling area, increasing capacity. A fraction of the sludge
stream is often recirculated to the inlet, promoting formation of
a denser sludge.
Settling is based on the ability of gravity (Newton's Law) to
cause small particles to fall or settle (Stokes1 Law) through the
fluid they are suspended in. Presuming that the factors
affecting chemical precipitation are controlled to achieve a
readily settleable precipitate, the principal factors controlling
settling are the particle characteristics and the upflow rate of
the suspending fluid. When the effective settling area is great
enough to allow settling, any increase in the effective settling
area will produce no increase in solids removal.
Therefore, if a plant has installed equipment that provides the
appropriate overflow rate, the precipitated metals, including
lead, in the effluent can be effectively removed. The number of
settling devices operated in series or in parallel by a facility
is not important with regard to suspended solids removal, but
rather that the settling devices provide sufficient effective
settling area.
Another important facet of sedimentation theory is that
diminishing removal of suspended solids is achieved for a unit
increase in the effective settling area. Generally, it has been
found that suspended solids removal performance varies with the
effective up-flow rate. Qualitatively the performance increases
asymptotically to a maximum level beyond which a decrease in up-
flow rate provides incrementally insignificant increases in
removal. This maximum level is dictated by particle size
distribution, density characteristic of the particles and the
water matrix, chemicals used for precipitation and pH at which
precipitation occurs.
Application and Performance. Settling and clarification are used
in the battery manufacturing category to remove precipitated
metals. Settling can be used to remove most suspended solids in
a particular waste stream; thus it is used extensively by many
different industrial waste treatment facilities. Because most
metal ion pollutants are readily converted to solid metal
hydroxide precipitates, settling is of particular use in those
industries associated with metal production, metal finishing,
metal working, and any other industry with high concentrations of
metal ions in their wastewaters. In addition to toxic metals,
suitably precipitated materials effectively removed by settling
include aluminum, iron, manganese, cobalt, antimony, beryllium,
molybdenum, fluoride, phosphate, and many others.
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A properly operating settling system can efficiently remove
suspended solids, precipitated metal hydroxides, and other
impurities from wastewater. The performance of the process
depends on a variety of factors, including the density and
particle size of the solids, the effective charge on the
suspended particles, and the types of chemicals used in
pretreatment. The site of flocculant or coagulant addition also
may significantly influence the effectiveness of clarification.
If the flocculant is subjected to too much mixing before entering
the clarifier, the complexes may be sheared and the settling
effectiveness diminished. At the same time, the flocculant must
have sufficient mixing and reaction time in order for effective
set-up and settling to occur. Plant personnel have observed that
the line or trough leading into the clarifier is often the most
efficient site for flocculant addition. The performance of
simple settling is a function of the movement rate particle size
and density, and the surface area of the basin.
The data displayed in Table VI1-10 (page 409) indicate suspended
solids removal efficiencies in settling systems. The mean
effluent TSS concentration obtained by the plants shown in Table
VII-10 is 10.1 mg/1. Influent concentrations averaged 838 mg/1.
The maximum effluent TSS value reported is 23 mg/1. These plants
all use alkaline pH adjustment to precipitate metal hydroxides,
and most add a coagulant or flocculant prior to settling.
Advantages and Limitations. The major advantage of simple
settling is its simplicity as demonstrated by the gravitational
settling of solid particulate waste in a holding tank or lagoon.
The major problem with simple settling is the long retention time
necessary to achieve complete settling, especially if the
specific gravity of the suspended matter is close to that of
water. Some materials cannot be practically removed by simple
settling alone.
Settling performed in a clarifier is effective in removing slow-
settling suspended matter in a shorter time and in less space
than a simple settling system. Also, effluent quality is often
better from a clarifier. The cost of installing and maintaining
a clarifier, however, is substantially greater than the costs
associated with simple settling.
Inclined pfate, slant tube, and lamella settlers have even higher
removal efficiencies than conventional clarifiers, and greater
capacities per unit area are possible. Installed costs for these
advanced clarification systems are claimed to be one half the
cost of conventional systems of similar capacity.
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Operational Factors. Reliability: Settling can be a highly
reliable technology for removing suspended solids. Sufficient
retention time and regular sludge removal are important factors
affecting the reliability of all settling systems. Proper
control of pH adjustment, chemical precipitation, and coagulant
or flocculant addition are additional factors affecting settling
efficiencies in systems (frequently clarifiers) where these
methods are used.
Those advanced settlers using slanted tubes, inclined plates, or
a lamellar network may require pre-screening of the waste in
order to eliminate any fibrous materials which could potentially
clog the system. Some installations are especially vulnerable to
shock loadings, as from storm water runoff, but proper system
design will prevent this.
Maintainability: When clarifiers or other advanced settling
devices are used, the associated system utilized for chemical
pretreatment and sludge dragout must be maintained on a regular
basis. Routine maintenance of mechanical parts is also
necessary. Lagoons require little maintenance other than
periodic sludge removal.
Demonstration Status. Settling represents the typical method of
solids removal and is employed extensively in industrial waste
treatment. The advanced clarifiers are just beginning to appear
in significant numbers in commercial applications. Sedimentation
or clarification is used in many battery manufacturing plants as
shown below.
Settling Device No. Plants
Settling Tanks 55
Clarifier 13
Tube or Plate Settler 1
Lagoon 10
Settling is used both as part of end-of-pipe treatment and within
the plant to allow recovery of process solutions and raw
materials. As examples, settling tanks are commonly used on
pasting waste streams in lead acid battery manufacture to allow
recovery of process water and paste solids, and settling sump
tanks are used to recover nickel and cadmium in nickel cadmium
battery manufacture.
7. Skimming
Pollutants with a specific gravity less than water will often
float unassisted to the surface of the wastewater. Skimming
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removes these floating wastes. Skimming normally takes place in
a tank designed to allow the floating debris to rise and remain
on the surface, while the liquid flows to an outlet located below
the floating layer. Skimming devices are therefore suited to the
removal of non-emulsified oils from raw waste streams. Common
skimming mechanisms include the rotating drum type, which picks
up oil from the surface of the water as it rotates. A doctor
blade scrapes oil from the drum and collects it in a trough for
disposal or reuse. The water portion is allowed to flow under
the rotating drum. Occasionally, an underflow baffle is
installed after the drum; this has the advantage of retaining any
floating oil which escapes the drum skimmer. The belt type
skimmer is pulled vertically through the water, collecting oil
which is scraped off from the surface and collected in a drum.
Gravity separators, such as the API type, utilize overflow and
underflow baffles to skim a floating oil layer from the surface
of the wastewater. An overflow-underflow baffle allows a small
amount of wastewater (the oil portion) to flow over into a trough
for disposition or reuse while the majority of the water flows
underneath the baffle. This is followed by an overflow baffle,
which is set at a height relative to the first baffle such that
only the oil bearing portion will flow over the first baffle
during normal plant operation. A diffusion device, such as a
vertical slot baffle, aids in creating a uniform flow through the
system and in increasing oil removal efficiency.
Application and Performance. Oil skimming is used in battery
manufacture to remove free oil used as a preservative or forming
lubricant for various metal battery parts. Another source of oil
is lubricants for drive mechanisms and other machinery contacted
by process water. Skimming is applicable to any waste stream
containing pollutants which float to the surface. It is commonly
used to remove free oil, grease, and soaps. Skimming is often
used in conjunction with air flotation or clarification in order
to increase its effectiveness.
The removal efficiency of a skimmer is partly a function of the
retention time of the water in the tank. Larger, more buoyant
particles require less retention time than smaller particles.
Thus, the efficiency also depends on the composition of the waste
stream. The retention time required to allow phase separation
and subsequent skimming varies from 1 to 15 minutes, depending on
the wastewater characteristics.
API or other gravity-type separators tend to be more suitable for
use where the amount of surface oil flowing through the system is
consistently significant. Drum and belt type skimmers are
applicable to waste streams which evidence smaller amounts of
floating oil and where surges of floating oil are not a problem.
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Using an API separator system in conjunction with a drum type
skimmer would be a very effective method of removing floating
contaminants from nonemulsified oily waste streams. Sampling
data shown in Table VII-11 (page 410) illustrate the capabilities
of the technology with both extremely high and moderate oil
influent levels.
These data are intended to be illustrative of the very high level
of oil and grease removals attainable in a simple two-step oil
removal system. Based on the performance of installations in a
variety of manufacturing plants and permit requirements that are
consistently achieved, it is determined that effluent oil levels
may be reliably reduced below 10 mg/1 with moderate influent
concentrations. Very high concentrations of oil such as the 22
percent shown above may require two step treatment to achieve
this level.
Skimming which removes oil may also be used to remove base levels
of organics. Plant sampling data show that many organic
compounds tend to be removed in standard wastewater treatment
equipment. Oil separation not only removes oil but also organics
that are more soluble in oil than in water. Clarification
removes organic solids directly and probably removes dissolved
organics by adsorption on inorganic solids.
The source of these organic pollutants is not always known with
certainty, although in metal forming operations they seem to
derive mainly from various process lubricants. They are also
sometimes present in the plant water supply, as additives to
proprietary formulations of cleaners, or as the result of
leaching from plastic lines and other materials.
High molecular weight organics in particular are much more
soluble in organic solvents than in water. Thus they are much
more concentrated in the oil phase that is skimmed than in the
wastewater. The ratio of solubilities of a compound in oil and
water phases is called the partition coefficient. The logarithm
of the partition coefficients for selected polynuclear aromatic
hydrocarbon (PAH) and other toxic organic compounds in octanol
and water are shown in Table VII-12 (page 411).
A review of priority organic compounds commonly found in metal
forming operation waste streams indicated that incidental removal
of these compounds often occurs as a result of oil removal or
clarification processes. When all organics analyses from visited
plants are considered, removal of organic compounds by other
waste treatment technologies appears to be marginal in many
cases. However, when only raw waste concentrations of 0.05 mg/1
or greater are considered, incidental organics removal becomes
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much more apparent. Lower values, those less than 0.05 mg/1, are
much more subject to analytical variation, while higher values
indicate a significant presence of a given compound. When these
factors are taken into account, analysis data indicate that most
clarification and oil removal treatment systems remove
significant amounts of the toxic organic compounds present in the
raw waste. The API oil-water separation system performed notably
in this regard, as shown in Table VII-13 (page 412).
Data from five plant days demonstrate removal of organics by the
combined oil skimming and settling operations performed on coil
coating wastewaters. Days were chosen where treatment, system
influent and effluent analyses provided paired data points for
oil and grease and the organics present. All organics found at
quantifiable levels on those days were included. Further, only
those days were chosen where oil and grease raw wastewater
concentrations exceeded 10 mg/1 and where there was reduction in
oil and grease going through the treatment system. All plant
sampling days which met the above criteria are included below.
The conclusion is that when oil and grease are removed, organics
also are removed.
Percent Removal
Plant-Day Oil & Grease Organics
1054-3
13029-2
13029-3
38053-1
38053-2
Mean
The unit operation most applicable to removal of trace priority
organics is adsorption, and chemical oxidation is another
possibility. Biological degradation is not generally applicable
because the organics are not present in sufficient concentration
to sustain a biomass and because most of the organics are
resistant to biodegradation.
Advantages and Limitations. Skimming as a pretreatment is
effective in removing naturally floating waste material. It also
improves the performance of subsequent downstream treatments.
Many pollutants, particularly dispersed or emulsified oil, will
not float "naturally" but require additional treatments. There-
fore, skimming alone may not remove all the pollutants capable of
being removed by air flotation or other more sophisticated
technologies.
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Operational Factors. Reliability: Because of its simplicity,
skimming is a very reliable technique.
Maintainability: The skimming mechanism requires periodic
lubrication, adjustment, and replacement of worn parts.
Solid Waste Aspects,: The collected layer of debris must be
disposed of by contractor removal, landfill, or incineration.
Because relatively large quantities of water are present in the
collected wastes, incineration is not always a viable disposal
method.
Demonstration Status. Skimming is a common operation utilized
extensively by industrial waste treatment systems. Oil skimming
is used in seven battery manufacturing plants.
MAJOR TECHNOLOGY EFFECTIVENESS
The performance of individual treatment technologies was
presented above. Performance of operating systems is discussed
here. Two different systems are considered: L&S (hydroxide
precipitation and sedimentation or lime and settle) and LS&F
(hydroxide precipitation, sedimentation, and filtration or lime,
settle, and filter). Subsequently, an analysis of effectiveness
of such systems is made to develop one-day maximum, and ten-day
and thirty-day average concentration levels to be used in
regulating pollutants. Evaluation of the L&S and the LS&F
systems is carried out on the assumption that chemical reduction
of chromium, cyanide precipitation and oil removal are installed
and operating properly where appropriate.
L&S Performance — Combined Metals Data Base
A data base known as the "combined metals data base" (CMDB) was
used to determine treatment effectiveness of lime and settle
treatment for certain pollutants. The CMDB was developed over
several years and has been used in a number of regulations.
During the development of coil coating and other categorical
effluent limitations and standards, chemical analysis data were
collected of raw wastewater (treatment influent) and treated
wastewater (treatment effluent) from 55 plants (126 data days)
sampled by EPA (or its contractor) using EPA sampling and
chemical analysis protocols. These data are the initial data
base for determining the effectiveness of L&S technology in
treating nine pollutants. Each of the plants in the initial data
base belongs to at least one of the following industry
categories: aluminum forming, battery manufacturing, coil coating
(including canmaking), copper forming, electroplating and
porcelain enameling. All of the plants employ pH adjustment and
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hydroxide precipitation using lime or caustic, followed by
Stokes1 law settling (tank, lagoon or clarifier) for solids
removal. An analysis of this data was presented in the
development documents for the proposed regulations for coil
coating and porcelain enameling (January 1981). Prior to
analyzing the data, some values were deleted from the data base.
These deletions were made to ensure that the data reflect
properly operated treatment systems. The following criteria were
used in making these deletions:
Plants where malfunctioning processes or treatment
systems at the time of sampling were identified.
Data days where pH was less than 7.0 for extended
periods of time or TSS was greater than 50 mg/1 (these
are prima facie indications of poor operation).
In response to the coil coating and porcelain enameling
proposals, some commenters claimed that it was inappropriate to
use data from some categories for regulation of other categories.
In response to these comments, the Agency reanalyzed the data.
An analysis of variance was applied to the data for the 126 days
of sampling to test the hypothesis of homogeneous plant mean raw
and treated effluent levels across categories by pollutant. This
analysis is described in the report "A Statistical Analysis of
the Combined Metals Industries Effluent Data" which is in the
administrative record supporting this rulemaking. Homogeneity is
the absence of statistically discernable differences among the
categories, while heterogeneity is the opposite, i.e., the
presence of statistically discernable differences. The main
conclusion drawn from the analysis of variance is that, with the
exception of electroplating, the categories included in the data
base are generally homogeneous with regard to mean pollutant
concentrations in both raw and treated effluent. That is, when
data from electroplating facilities are included in the analysis,
the hypothesis of homogeneity across categories is rejected.
When the electroplating data are removed from the analysis the
conclusion changes substantially and the hypothesis of
homogeneity across categories is not rejected. On the basis of
this analysis, the electroplating data were removed from the data
base used to determine limitations for the final coil coating and
porcelain enameling regulations and proposed regulations for
copper forming, aluminum forming, battery manufacturing,
nonferrous metals (Phase I), and canmaking.
The statistical analysis provides support for the • technical
engineering judgment that electroplating wastewaters are
sufficiently different from the wastewaters of other industrial
categories in the data base to warrant removal of electroplating
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data from the data base used to determine treatment
effectiveness.
For the purpose of determining treatment effectiveness,
additional data were deleted from the data base. These deletions
were made, almost exclusively, in cases where effluent data
points were associated with low influent values. This was done
in two steps. First, effluent values measured on the same day as
influent values that were less than or equal to 0.1 mg/1 were
deleted. Second, the remaining data were screened for cases in
which all influent values at a plant were low although slightly
above the 0.1 mg/1 value. These data were .deleted not as
individual data points but as plant clusters of data that were
consistently low and thus not relevent to assessing treatment. A
few data points were also deleted where malfunctions not
previously identified were recognized. The data basic to the
CMDB are displayed graphically in Figures VII-4 to 12 (Pages 430-
438). The ranges of raw waste concentrations for battery
manufacturing are also shown in these figures. These levels of
metals concentrations in the raw waste are within the range of
raw waste concentrations commonly encountered in metals bearing
industrial wastewater.
After all deletions, 148 data points from 19 plants remained.
These data were used to determine the concentration basis of
limitations derived from the CMDB used for the proposed battery
manufacturing regulation.
The CMDB was reviewed following its use in a number of proposed
regulations (including battery manufacturing). Comments pointed
out a few errors in the data, and the Agency's review identified
a few transcription errors and some data points that were
appropriate for inclusion in the data that had not been used
previously because of errors in data record identification
numbers. Documents in the record of this rulemaking identify all
the changes, the reasons for the changes, and the effect of these
changes on the data base. Other comments on the CMDB asserted
that the data base was too small and that the statistical methods
used were overly complex. Responses to specific comments are
provided in a document included in the record of this rulemaking.
The Agency believes that the data base is adequate to determine
effluent concentrations achievable with lime and settle
treatment. The statistical methods employed in the analysis are
well known and appropriate statistical references are provided in
the documents in the record that describe the analysis.
The revised data base was reexamined for homogeneity. The
earlier conclusions were unchanged. The categories show good
overall homogeneity with respect to concentrations of the nine
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pollutants in both raw and treated wastewaters with the exception
of electroplating.
The same procedures used in developing proposed limitations from
the combined metals data base were then used on the revised data
base. That is, certain effluent data associated with low
influent values were deleted, and then the remaining data were
fit to a lognormal distribution to determine limitations values.
The deletion of data was done in two steps. First, effluent
values measured on the same day as influent values that were less
than or equal to 0.1 mg/1 were deleted. Second, the remaining
data were screened for cases in which all influent values at a
plant were low although slightly above the 0.1 mg/1 value. These
data were deleted not as individual data points but as plant
clusters of data that were consistently low and thus not relevant
to assessing treatment.
The revised combined - metals data base used for this final
regulation consists of 162 data points from 18 plants in the same
industrial categories used at proposal. .The changes that were
made since proposal resulted in slight upward revisions of the
concentration bases for the limitations and standards for zinc
and nickel. The limitations for iron decrease slightly. The
other limitations were unchanged. A comparison of Table VII-21
in the final development document with Table VII-21 in the
proposal development document will show the exact magnitude of
the changes.
One-day Effluent Values
The same procedures used to determine the concentration basis of
the limitations for lime and settle treatment from the CMDB at
proposal were used in the revised CMDB for the final limitations.
The basic assumption underlying the determination of treatment
effectiveness is that the data for a particular pollutant are
lognormally distributed by plant. The lognormal has been found
to provide a satisfactory fit to plant effluent data in a number
of effluent guidelines categories and there was no evidence that
the lognormal was not suitable in the case of the CMDB. Thus, we
assumed measurements of each pollutant from a particular plant,
denoted by X, were assumed followed a lognormal distribution with
log mean »/ and log variance a2. The mean, variance and 99th
percentile of X are then:
mean of X = E(X) = exp (» + a2 /2)
variance of X = V(X) - exp (2 M + a2) [exp( a2 )_i]
99th percentile = X.,, = exp ( ? +2.33 a)
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where exp is e, the base of the natural logarithm. The term
lognormal is used because the logarithm of X has a normal
distribution with mean v and variance az. Using the basic
assumption of lognormality the actual treatment effectiveness was
determined using a lognormal distribution that, in a sense,
approximates the distribution of an average of the plants in the
data base, i.e., an "average plant" distribution. The notion of
an "average plant" distribution is not a strict statistical
concept but is used here to determine limits that would represent
the performance capability of an avereige of the plants in the
data base.
This "average plant" distribution for a particular pollutant was
developed as follows: the log mean was determined by taking the
average of all the observations for the pollutant across plants.
The log variance was determined by the pooled within plant
variance. This is the weighted average of the plant variances.
Thus, the log mean represents the average of all the data for the
pollutant and the log variance represents the average of the
plant log variances or average plant variability for the
pollutant.
The one day effluent values were determined as follows:
Let Xij = the jth observation on a particular pollutant at
plant i where
i = 1, . . ., I
j = 1, ..., Ji
I = total number of plants
Ji = number of observations at plant i.
Then yij = In Xij
where In means the natural logarithm.
Then y = log mean over all plants
where
n = total number of observations
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and V(y) = pooled log variance
T
_ i\ t.2
where Si* « log variance at plant i
y~i * log mean at plant i.
Thus, y and V(y) are the log mean and log variance, respectively,
of the lognormal distribution used to determine the treatment
effectiveness. The estimated mean and 99th percentile of this
distribution form the basis for the long term average and daily
maximum effluent limitations, respectively. The estimates are
mean -1i:(X) = expfy) * n (0.5 V(y))
99th percentile = .,, = exp [y + 2.33>/ V(y) ]
where * (.) is a Bessel function and exp is e, the base of the
natural logarithms (See Aitchison, J. and J.A.C. Brown, The
Loqnormal Distribution, Cambridge University Press, 1963). In
cases where zeros were present in the data, a generalized form of
the lognormal, known as the delta distribution was used (See
Aitchison and Brown, op. cit., Chapter 9).
For certain pollutants, this approach was modified slightly to
ensure that well operated lime and settle plants in all CMDB
categories would achieve the pollutant concentration values
calculated from the CMDB. For instance, after excluding the
electroplating data and other data that did not reflect pollutant
removal or proper treatment, the effluent copper data from the
copper forming plants were statistically significantly greater
than the copper data from the other plants. This indicated that
copper forming plants might have difficulty achieving an effluent
concentration value calculated from copper data from all CMDB
categories. Thus, copper effluent values shown in Table VIl-14
(page 412) are based only on the copper effluent data from the
copper forming plants. That is, the log mean for copper is the
mean of the logs of all copper values from the copper forming
plants only and the log variance is the pooled log variance of
the copper forming plant data only. A similar situation occurred
in the case of lead. That is, after excluding the electroplating
data, the effluent lead data from battery manufacturing were
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significantly greater than the other categories. This indicated
that battery manufacturing plants might have difficulty achieving
a lead concentration calculated from all the CMDB categories.
The lead values proposed were therefore based on the battery
manufacturing lead data only. Comments on the proposed battery
manufacturing regulation objected to this procedure and asserted
that the lead concentration values were too low. Following
proposal, the Agency obtained additional lead effluent data from
a battery manufacturing facility with well operated lime and
settle treatment. These data were combined with the proposal
lead data and analyzed to determine the final treatment
effectiveness concentrations. The mean lead concentration is
unchanged at 0.12 mg/1 but the final one-day maximum and monthly
10-day average maximum increased to 0.42 and 0.20 mg/1,
respectively. A complete discussion of the lead data and
analysis is contained in a memorandum in the record of this
rulemaking.
In the case of cadmium, after excluding the electroplating data
and data that did not reflect removal or proper treatment, there
were insufficient data to estimate the log variance for cadmium.
The variance used to determine the values shown in Table VII-14
for cadmium was estimated by pooling the within plant variances
for all the other metals. Thus, the cadmium variability is the.
average of the plant variability averaged over all the other
metals. The log mean for cadmium is the mean of the logs of the
cadmium observations only. . A complete discussion of the data and
calculations for all the metals is contained in the
administrative record for this rulemaking.
Average Effluent Values
Average effluent values that form the basis for the monthly
limitations were developed in a manner consistent with the method
used to develop one-day treatment effectiveness in that the
lognormal distribution used for the one-day effluent values was
also used as the basis for the average values. That is, we
assume a number of consecutive measurements are drawn from the
distribution of daily measurements. The average of ten
measurements taken during a month was used as the basis for the
monthly average limitations. The approach used for the 10
measurements values was employed previously in regulations for
other categories and was proposed for the battery manufacturing
category. That is, the distribution of the average of 10 samples
from a lognormal was approximated by another lognormal
distribution. Although the approximation is not precise
theoretically, there is "empirical evidence based on effluent data
from a number of categories that the lognormal is an adequate
approximation for the distribution of small samples. In the
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course of previous work the approximation was verified in a
computer simulation study (see "Development Document for Existing
Sources Pretreatment Standards for the Electroplating Point
Source Category", EPA 440/1-79/003, U.S. Environmental Protection
Agency, Washington, B.C., August 1979). We also note that the
average values were developed assuming independence of the
observations although no particular sampling scheme was assumed.
Ten-Sample Average:
The formulas for the 10-sample limitations were derived on the
basis of simple relationships between the mean and variance o_f
the distributions of the daily pollutant measurements and the
average of 10 measurements. We assume the daily concentration
measurements for a particular pollutant, denoted by X, follow a
lognormal distribution with log mean and log variance denoted by
i» and lexp(.«r*10)-lJ
Now, if 10 and azlo can be derived in terms of » and ez as
* 10 " f + *a /2 - 0.5 In [l*(exp(
-------
Thirty-Sample Average
Monthly average values based on the average of 30 daily
measurements were also calculated. These are included because
monthly limitations based on 30 samples have been used in the
past and for comparison with the 10 sample values. The average
values based on 30 measurements are determined on the basis of a
statistical result known as the Central Limit Theorem. This
Theorem states that, under general and nonrestrictive
assumptions, the distribution of a sum of a number of random
variables, say n, is approximated by the normal distribution.
The approximation improves as the number of variables, n,
increases. The Theorem is quite general in that no particular
distributional form is assumed for the distribution of the
individual variables. In most applications (as in approximating
the distribution of 30-day averages) the Theorem is used to
approximate the distribution of the average of n observations of
a random variable. The result makes it possible to compute
approximate probability statements about the average in a wide
range of cases. For instance, it is possible to compute a value
below which a specified percentage (e.g., 99 percent) of the
averages of n observations are likely to fall. Most textbooks
state that 25 or 30 observations are sufficient for the
approximation to be valid. In applying the Theorem to the
distribution of the 30 day average effluent values, we
approximate the distribution of the average of 30 observations
drawn from the distribution of daily measurements and use the
estimated 99th percentile of this distribution.
Thirty-Sample Average Calculation
The formulas for the 30-sample average were based on an
application of the Central Limit Theorem. According to the
Theorem, the average of 30 observations drawn from the
distribution of daily measurements, denoted by X30, is
approximately normally distributed. The mean and variance of X30
are:
mean of ~X30 j. E(X30)_,- E(X)
variance of X30 = V(X30) = V(X) t 30.
The 30 sample average value was determined by the estimate of the
approximate 99th percentile of the distribution of the 30 sample
average given by
X?0(.99) = E?X)'+ 2.33VV?X) -r 30
where /\
E(X) = exp(y) «n(0.5V(y)).
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and vTx) = exp(2y) [ *,
The formulas for E?X) and V(X) are estimates of E(X) and V(X),
respectively, given in Aitchison, J. and J.A.C. Brown, The
Lognormal Distribution, Cambridge University Press, 1963, page
45.
Application
In response to the proposed coil coating and porcelain enameling
regulations, the Agency received comments pointing out that
permits usually required less than 30 samples to be taken during
a month while the monthly average used as the basis for permits
and pretreatment requirements usually is based on the average of
30 samples.
In applying the treatment effectiveness values to regulations we
have considered the comments, examined the sampling frequency
required by many permits and considered the change in values of
averages depending on the number of consecutive sampling days in
the averages. The most common frequency of sampling required in
permits is about ten samples per month or slightly greater than
twice weekly. The 99th percentiles of the distribution of
averages of ten consecutive sampling days are not substantially
different from the 99th percentile of the distribution's 30-day
average. (Compared to the one-day maximum, the ten-day average
is about 80 percent of the difference between one- and 30-day
values). Hence the ten-day average provides a reasonable basis
for a monthly average limitation and is typical of the sampling
frequency required by existing permits.
The monthly average limitation is to be achieved in all permits
and pretreatment standards regardless of the number of samples
required to be analyzed and averaged by the permit or the
pretreatment authority.
Additional Pollutants
Ten additional pollutant parameters were evaluated to determine
the performance of lime arid settle treatment systems in removing
them from industrial wastewater. Performance data for these
parameters is not a part of the CMDB so other data available to
the Agency from other categories has been used to determine the
long term average performance of lime and settle technology for
each pollutant. These data indicate that the concentrations
shown in Table VII-15 (page 413) are reliably attainable with
hydroxide precipitation and settling. Treatment effectiveness
values were calculated by multiplying the mean performance from
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Table VII-15 (page 413) by the appropriate variability factor.
(The variability factor is the ratio of the value of concern to
the mean). The pooled variability factors are: one-day maximum -
4.100; ten-day average - 1.821; and 30-day average - 1.618 these
one-, ten-, and thirty-day values are tabulated in Table VI1-21
(page 418).
In establishing which data were suitable for use in Table VII-15
two factors were heavily weighed; (1) the nature of the
wastewater; and (2) the range of pollutants or pollutant matrix
in the raw wastewater. These data have been selected from
processes that generate dissolved metals in the wastewater and
which are generally free from complexing agents. The pollutant
matrix was evaluated by comparing the concentrations of
pollutants found in the raw wastewaters with the range of
pollutants in the raw wastewaters of the combined metals data
set. These data are displayed in Tables VII-16 (page 413) and
VII-17 (page 414) and indicate that there is sufficient
similarity in the raw wastes to logically assume transferability
of the treated pollutant concentrations to the combined metals
data base. Battery manufacturing wastewaters also were compared
to the wastewaters from plants in categories from which treatment
effectiveness values were calculated. The available data on
these added pollutants do not allow homogeneity analysis as was
performed on the combined metals data base. The data source for
each added pollutant is discussed separately.
Antimony (Sb) - The achievable performance for antimony is based
on data from a battery and secondary lead plant. Both EPA
sampling data and recent permit data (1978-1982) confirm the
achievability of 0.7 mg/1 in the battery manufacturing wastewater
matrix included in the combined data set.
Arsenic (As) - The achievable performance of 0.5 mg/1 for arsenic
is based on permit data from two nonferrous metals manufacturing
plants. The untreated wastewater matrix shown in Table VII-17
(page.414) is comparable with the combined data set matrix.
Beryllium (Be) - The treatability of beryllium is transferred
from the nonferrous metals manufacturing industry. The 0.3 mg/1
performance is achieved at a beryllium plant with the comparable
untreated wastewater matrix shown in Table VII-17.
Mercury (Hg) - The 0.06 mg/1 treatability of mercury is based on
data from four battery plants. The untreated wastewater matrix
at these plants was considered in the combined metals data set.
Selenium (Se) - The 0.30 mg/1 treatability of selenium is based
on recent permit data from one of the nonferrous metals
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manufacturing plants also used for antimony performance. The
untreated wastewater matrix for this plant is shown in Table VII-
17.
Silver - The treatability of silver is based on a 0.1 mg/1
treatability estimate from the inorganic chemicals industry.
Additional data supporting a treatability as stringent or more
stringent than 0.1 mg/1 is also available from seven nonferrous
metals manufacturing plants. The untreated wastewater matrix for
these plants is comparable and summarized in Table VI1-17.
Thallium (Tl) - The 0.50 mg/1 treatability for thallium is
transferred from the inorganic chemicals industry. Although no
untreated wastewater data are available to verify comparability
with the combined metals data set plants, no other sources of
data for thallium treatability could be identified.
Aluminum (Al) - The 2.24 mg/1 treatability of aluminum is based
on the mean performance of three aluminum forming plants and one
coil coating plant. These plants are from categories included in
the combined metals data set, assuring untreated wastewater
matrix comparability.
Cobalt (Co) - The 0.05 mg/1 treatability is based on nearly
complete removal of cobalt at a porcelain enameling plant with a
mean untreated wastewater cobalt concentration of 4.31 mg/1. In
this case, the analytical detection using aspiration techniques
for this pollutant is used as the basis of the treatability.
Porcelain enameling was considered in the combined metals data
base, assuring untreated wastewater matrix comparability.
Fluoride (F) - The 14.5 mg/1 treatability of fluoride is based on
the mean "performance {216 samples) of an electronics
manufacturing plant. The untreated wastewater matrix for this
plant shown in Table VI1-17 is comparable to the combined metals
data set. The fluoride level in the electronics wastewater {760
mg/1) is significantly greater than the fluoride level in raw
battery manufacturing wastewater leading to the conclusion that
the battery manufacturing wastewater should be no more difficult
to treat for fluoride removal than the electronics wastewater.
The fluoride level in the CMDB - electroplating data ranges from
1.29 to 70.0 mg/1 while the fluoride level in the battery
manufacturing wastewater was lower ranging from 0.44 to 3.05 mg/1
and leading to the conclusion that the battery manufacturing
wastewater should be no more difficult to treat to remove
fluoride them electroplating wastewater.
Phosphorus (PJ_- The 4.08 mg/1 treatability of phosphorus is
based on the mean of 44 samples including 19 samples from the
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Combined Metals Data Base and 25 samples from the electroplating
data base. Inclusion of electroplating data with the combined
metals data was considered appropriate, since the removal
mechanism for phosphorus is a precipitation reaction with calcium
rather than hydroxide.
LS&F Performance
Tables VII-18 and VII-19 (pages 415 and 416) show long term data
from two plants which have well operated precipitation-settling
treatment followed by filtration. The wastewaters from both
plants contain pollutants from metals processing and finishing
operations (multi-category). Both plants reduce hexavalent
chromium before neutralizing and precipitating metals with lime.
A clarifier is used to remove much of the solids load and a
filter is used to "polish" or complete removal of suspended
solids. Plant A uses a pressure filter, while Plant B uses a
rapid sand filter.
Raw wastewater data was collected only occasionally at each
facility and the raw wastewater data is presented as an
indication of the nature of the wastewater treated. Data from
plant A was received as a statistical summary and is presented as
received. Raw laboratory data was collected at plant B and
reviewed for spurious points and discrepancies. The method of
treating the data base is discussed below under lime, settle, and
filter treatment effectiveness.
Table VII-20 (page 417) shows long-term data for zinc and cadmium
removal at Plant C, a primary zinc smelter, which operates a LS&F
system. This data represents about 4 months (103 data days)
taken immediately before the smelter was closed. It has been
arranged similarily to Plants A and B for comparison and use.
These data are presented to demonstrate the performance of
precipitation-settling-filtration (LS&F) technology under actual
operating conditions and over a long period of time. •
It should be noted that the iron content of the raw wastewater of
plants A and B is high while that for Plant C is low. This
results, for plants A and B, in co-precipitation of toxic metals
with iron. Precipitation using high-calcium lime for pH control
yields the results shown above. Plant operating personnel
indicate that this chemical treatment combination (sometimes with
polymer assisted coagulation) generally produces better and more
consistent metals removal than other combinations of sacrificial
metal ions and alkalis.
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The LS&F performance data presented here are based on systems
that provide polishing filtration after effective L&S treatment.
We have previously shown that L&S treatment is equally applicable
to wastewaters from the five categories because of the
homogeneity of its raw and treated wastewaters, and other
factors. Because of the similarity of the wastewaters after L&S
treatment, the Agency believes these wastewaters are equally
amenable to treatment using polishing filters added to the L&S
treatment system. The Agency concludes that LS&F data based on
porcelain enameling and nonferrous smelting and refining is
directly applicable to the aluminum forming, copper forming,
battery manufacturing, coil coating, and metal molding and
casting categories, and the canmaking subcategory as well as it
is to porcelain enameling and nonferrous melting and refining.
Analysis of_ Treatment System Effectiveness
Data are presented in Table VII-14 showing the mean, one-day, 10-
day, and 30-day values for nine pollutants examined in the L&S
combined metals data base. The pooled variability factor for
seven metal pollutants (excluding cadmium because of the small
number of data points) was determined and is used to estimate
one-day, 10-day and 30-day values. (The variability factor is
the ratio of the value of concern to the mean: the pooled
variability factors are: one-day maximum - 4.100; ten-day average
- 1.821; and 30-day average - 1.618.) For values not calculated
from the CMDB as previously discussed, the mean value for
pollutants shown in Table VI1-15 were multiplied by the
variability factors to derive the value to obtain the one-, ten-
and 30-day values. These are tabulated in Table VII-21.
The treatment effectiveness for sulfide precipitation and
filtration has been calculated similarly. Long term average
values shown in Table VI1-6 (page 407) have been multiplied by
the appropriate variability factor to estimate one-day maximum,
and ten-day and 30-day average values. Variability factors
developed in the combined metals data base were used because the
raw wastewaters are identical and the treatment methods are
similar as both use chemical precipitation and solids removal to
control metals.
LS&F technology data are presented in Tables VII-18 and VII-19.
These data represent two operating plants (A and B) in which the
technology has been installed and operated for some years. Plant
A data was received as a statistical summary and is presented
without change. Plant B data was received as raw •laboratory
analysis data. Discussions with plant personnel indicated that
operating experiments and changes in materials and reagents and
occasional operating errors had occurred during the data
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collection period. No specific information was available on
those variables. To sort out high values probably caused by
methodological factors from random statistical variability, or
data noise, the plant B data were analyzed. For each of four
pollutants (chromium, nickel, zinc, and iron), the mean and
standard deviation (sigma) were calculated for the entire data
set. A data day was removed from the complete data set when any
individual pollutant concentration for that day exceeded the sum
of the mean plus three sigma for that pollutaftit. Fifty-one data
days (from a total of about 1300) were eliminated by this method.
Another approach was also used as a check on the above method of
eliminating certain high values. The minimum values of raw
wastewater concentrations from Plant B for the same four
pollutants were compared to the total set of values for the
corresponding pollutants. Any day on which the treated
wastewater pollutant concentration exceeded the minimum value
selected from raw wastewater concentrations for that pollutant
was discarded. Forty-five days of data were eliminated by that
procedure. Forty-three days of data in common were eliminated by
either procedures. Since common engineering practice (mean plus
3 sigma) and logic (treated wastewater concentrations should be
less than raw wastewater concentrations) seem to coincide, the
data base with the 51 spurious data days eliminated is the basis
for all further analysis. Range, mean plus standard deviation
and mean plus two standard deviations are shown in Tables VII-18
and VII-19 for Cr, Cu, Ni, Zn and Fe.
The Plant B data was separated into 1979, 1978, and total data
base (six years) segments. With the statistical analysis from
Plant A for 1978 and 1979 this in effect created five data sets
in which there is some overlap between the individual years and
total data sets from Plant B. By comparing these five parts it
is apparent that they are quite similar and all appear to be from
the same family of numbers. The largest mean found among the
five data sets for each pollutant was selected as the long term
mean for LS&F technology and is used as the LS&F mean in Table
VII-21.
Plant C data was used as a basis for cadmium removal performance
and as a check on the zinc values derived from Plants A and B.
The cadmium data is displayed in Table VII-20 (page 417) and is
incorporated into Table VII-21 for LS&F. The zinc data was
analyzed for compliance with the 1-day and 30-day values in Table
VII-21; no zinc value of the 103 data points exceeded the 1-day
zinc value of 1.02 mg/1. The 103 data points were separated into
blocks of 30 points and averaged. Each of the 3 full 30-day
averages was less than the Table VII-21 value of 0.31 mg/1.
Additionally, the-Plant C raw wastewater pollutant concentrations
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(Table VI1-20) are well within the range of raw wastewater
concentrations of the combined metals data base (Table VII-16),
further supporting the conclusion that Plant C wastewater data is
compatible with similar data from Plants A and B.
Concentration values for regulatory use are displayed in Table
VII-21. Mean one-day, ten-day and 30-day values for L&S for nine
pollutants were taken from Table VII-14; the remaining L&S values
were developed using the mean values in Table VII-15 and the mean
variability factors discussed above.
LS&F mean values for Cd, Cr, Ni, Zn and Fe are derived,from
plants A, B, and C as discussed above. One-, ten- and thirty-day
values are derived by applying the variability factor developed
from the pooled data base for the specific pollutant to the mean
for that pollutant. Other LS&F values are calculated using the
long term average or mean and the appropriate variability
factors.
Copper levels achieved at Plants A and B may be lower than
generally achievable because of the high iron content and low
copper content of the raw wastewaters. Therefore, the mean
concentration value from plants A and B achieved is not used? the
LS&F mean for copper is derived from the L&S technology.
L&S cyanide mean levels shown in Table VI1-8 are ratioed to one-
day, ten-day and 30-day values using mean variability factors.
LS&F mean cyanide is calculated by applying the ratios of
removals L&S and LS&F as discussed previously for LS&F metals
limitations. The cyanide performance was arrived at by using the
average metal variability factors. The treatment method used
here is cyanide precipitation. Because cyanide precipitation is
limited by the same physical processes as the metal
precipitation, it is expected that the variabilities will be
similar. Therefore, the average of the metal variability factors
has been used as a basis for calculating the cyanide one-day,
ten-day and thirty-day average treatment effectiveness values.
The filter performance for removing TSS as shown in Table VH-9
(page 409) yields a mean effluent concentration of 2.61 mg/1 and
calculates to a 10-day average of 4.33, 30-day average of 3.36
mg/1; a one-day maximum of 8.88. These calculated values more
than amply support the classic thirty-day and one-day values of
10 mg/1 and 15 mg/1, respectively, which are used for LS&F.
Although iron concentrations were decreased in some LS&F
operations, some facilities using that treatment introduce iron
compounds to aid settling. Therefore, the one-day, ten-day and
30-day values for iron at LS&F were held at the L&S level so as
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to not unduly penalize the operations which use the relatively
less objectionable iron compounds to enhance removals of toxic
metals.
The removal of additional fluoride by adding polishing filtration
is suspect because lime and settle technology removes calcium
fluoride to a level near its solubility. The one available data
point appears to question the ability of filters to achieve high
removals of additional fluoride. The fluoride levels
demonstrated for L&S are used as the treatment effectiveness for
LS&F.
MINOR TECHNOLOGIES
Several other treatment technologies were considered for possible
application in this subcategory. These technologies are
presented here.
8. Carbon Adsorption
The use of activated carbon to remove dissolved organics from
water and wastewater is a long demonstrated technology. It is
one of the most efficient organic removal processes available.
This sorption process is reversible, allowing activated carbon to
be regenerated for reuse by the application of heat and steam or
solvent. Activated carbon has also proved to be an effective
adsorbent for many toxic metals, including mercury. Regeneration
of carbon which has adsorbed significant metals, however, may be
difficult.
The term activated carbon applies to any amorphous form of carbon
that has been specially treated to give high adsorption
capacities. Typical raw materials include coal, wood, coconut
shells, petroleum base residues, and char from sewage sludge
pyrolysis. A carefully controlled process of dehydration,
carbonization, and oxidation yields a product which is called
activated carbon. This material has a high capacity for
adsorption due primarily to the .large surface area available for
adsorption, 500 to 1500 mz/sq m resulting from a large number of
internal pores. Pore sizes generally range from 10 to 100
angstroms in radius.
Activated carbon removes contaminants from water by the process
of adsorption, or the attraction and accumulation of one
substance on the surface of another. Activated carbon
preferentially adsorbs organic compounds arid, because of this
selectivity, is particularly effective in removing organic
compounds from aqueous solution.
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Carbon adsorption requires pretreatment to remove excess
suspended solids, oils, and greases. Suspended solids in the
influent should be less than 50 mg/1 to minimize backwash
requirements; ,a downflow carbon bed can handle much higher levels
(up to 2000 mg/1) but requires frequent backwashing. Backwashing
more than two or three times a day is not desirable; at 50 mg/1
suspended solids, one backwash will suffice. Oil and grease
should be less than about 10 mg/1. A high level of dissolved
inorganic material in the influent may cause problems with
thermal carbon reactivation (i.e., scaling and loss of activity)
unless appropriate preventive steps are taken. Such steps might
include pH control, softening, or the use of an acid wash on the
carbon prior to reactivation.
Activated carbon is available in both powdered and granular form.
An adsorption column packed with granular activated carbon is
shown in Figure VII-17 (page 443). Powdered carbon is less
expensive per unit weight and may have slightly higher adsorption
capacity, but it is more difficult to handle and to regenerate.
Application and Performance. Carbon adsorption is used to remove
mercury from wastewaters. The removal rate is influenced by the
mercury level in the influent to the adsorption unit. In Table
VII-24, removal levels found at three manufacturing facilities
are listed.
In the aggregate these data indicate that very low effluent
levels could be attained from any raw waste by use of multiple
adsorption stages. This is characteristic of adsorption
processes.
Isotherm tests have indicated that activated carbon is very
effective in adsorbing 65 percent of the organic priority
pollutants and is reasonably effective for another 22 percent.
Specifically, for the organics of particular interest, activated
carbon was very effective in removing 2,4-dimethylphenol,
fluoranthene, isophorone, naphthalene, all phthalates, and
phenanthrene. It was reasonably effective on 1,1,1-
trichloroethane, 1,1-dichloroethane, phenol, and toluene. Table
VII-22 (page 419) summarizes the treatment effectiveness for most
of the organic priority pollutants by activated carbon as
compiled by EPA. Table VII-23 (page 420) summarizes classes of
organic compounds together with examples of organics that are
readily adsorbed on carbon.
Advantages and Limitations. The major benefits of carbon
treatment include applicability to a wide variety of organics and
high removal efficiency. Inorganics such as cyanide, chromium,
and mercury are also removed effectively. Variations in
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concentration and flow rate are well tolerated. The system is
compact, and recovery of adsorbed materials is sometimes
practical. However, destruction of adsorbed compounds often
occurs during thermal regeneration. If carbon cannot be
thermally desorbed, it must be disposed of along with any
adsorbed pollutants. The capital and operating costs of thermal
regeneration are relatively high. Cost surveys show that thermal
regeneration is generally economical when carbon use exceeds
about 1,000 Ib/day. Carbon cannot remove low molecular weight or
highly soluble organics. It also has a low tolerance for
suspended solids, which must be removed to at least 50 mg/1 in
the influent water.
Operational Factors. Reliability: This system should be very
reliable with upstream protection and proper operation and
maintenance procedures.
Maintainability: This system requires periodic regeneration or
replacement of spent carbon and is dependent upon raw waste load
and process efficiency.
Solid Waste Aspects: Solid waste from this process is
contaminated activated carbon that requires disposal. Carbon
undergoes regeneration, reduces the solid waste problem by
reducing the frequency of carbon replacement.
Demonstration Status. Carbon adsorption systems have been
demonstrated to be practical and economical in reducing COD, BOD,
and related parameters in secondary municipal and industrial
wastewaters; in removing toxic or refractory organics from
isolated industrial wastewaters; in removing and recovering
certain organics from wastewaters; and in removing and some times
recovering selected inorganic chemicals from aqueous wastes.
Carbon adsorption is a viable and economic process for organic
waste streams containing up to 1 to 5 percent of refractory or
toxic organics. Its applicability for removal of inorganics such
as metals has also been demonstrated.
9. Centrif'ugation
Centrifugation is the application of centrifugal force to
separate solids and liquids in a liquid-solid mixture or to
effect concentration of the solids. The application of
centrifugal force is effective because of the density
differential normally found between the insoluble solids and the
liquid in which they are contained. As a waste treatment
procedure, centrifugation is applied to dewatering of sludges.
One type of centrifuge is shown in Figure VII-18 (page 444).
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There are three common types of centrifuges; disc, basket, and
conveyor. All three operate by removing solids under the
influence of centrifugal force. The fundamental difference among
the three types is the method by which solids are collected in
and discharged from the bowl.
In the disc centrifuge, the sludge feed is distributed between
narrow channels that are present as spaces between stacked
conical discs. Suspended particles are collected and discharged
continuously through small orifices in the bowl wall. The
clarified effluent is discharged through an overflow weir.
A second type of centrifuge which is useful in dewatering sludges
is the basket centrifuge. In this type of centrifuge, sludge
feed is introduced at the bottom of the basket, and solids
collect at the bowl wall while clarified effluent overflows the
lip ring at the top. Since the basket centrifuge does not have
provision for continuous discharge of collected cake, operation
requires interruption of the feed for cake discharge for a minute
or two in a 10 to 30 minute overall cycle.
The third type of centrifuge commonly used in sludge dewatering
is the conveyor type. Sludge is fed through a stationary feed
pipe into a rotating bowl in which the solids are settled out
against the bowl wall by centrifugal force. From the bowl wall,
the solids are moved by a screw to the end of the machine, at
which point they are discharged. The liquid effluent is
discharged through ports after passing the length of the bowl
under centrifugal force.
Application And Performance.' Virtually all industrial waste
treatment systems producing sludge can use centrifugation to
dewater it. Centrifugation is currently being used by a wide
range of industrial concerns.
The performance of sludge dewatering by centrifugation depends on
the feed rate, the rotational velocity of the drum, and the
sludge composition and concentration. Assuming proper design and
operation, the solids content of the sludge can be increased to
20 to 35 percent.
Advantages And Limitations. Sludge dewatering centrifuges have
minimal space requirements and show a high degree of effluent
clarification. The operation is simple, clean, and relatively
inexpensive. The area required for a centrifuge system
installation is less than that required for a filter system or
sludge drying bed of equal capacity, and the initial cost is
lower.
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Centrifuges have a high power cost that partially offsets the low
initial cost. Special consideration must also be given to
providing sturdy foundations and soundproofing because of the
vibration and noise that result from centrifuge operation.
Adequate electrical power must also be provided since large
motors are required. The major difficulty encountered in the
operation of centrifuges has been the disposal of the concentrate
which is relatively high in suspended, non-settling solids.
Operational Factors. Reliability: Centrifugation is highly
reliable with proper control of factors such as sludge feed,
consistency, and temperature. Pretreatment such as grit removal
and coagulant addition may be necessary, depending on the
composition of the sludge and on the type of centrifuge employed.
Maintainability: Maintenance consists of periodic lubrication,
cleaning, and inspection. The frequency and degree of inspection
required varies depending on the type of sludge solids being
dewatered and the maintenance service conditions. If the sludge
is abrasive, it is recommended that the first inspection of the
rotating assembly be made after approximately 1,000 hours of
operation. If the sludge is not abrasive or corrosive, then the
initial inspection might be delayed. Centrifuges not equipped
with a continuous sludge discharge system require periodic
shutdowns for manual sludge cake removal.
Solid Waste Aspects: Sludge dewatered in the centrifugation
process may be disposed of by landfill. The clarified effluent
(centrate), if high in dissolved or suspended solids, may require
further treatment prior to discharge.
Demonstration Status. Centrifugation is currently used in a
great many commercial applications to dewater sludge. Work is
underway to improve the efficiency, increase the capacity, and
lower the costs associated with centrifugation.
10. Coalescing
The basic principle of coalescence • involves the preferential
wetting of a coalescing medium by oil droplets which accumulate
on the medium and then rise to the surface of the solution as
they combine to form larger particles. The most important
requirements for coalescing media are wettability for oil and
large surface area. Monofilament line is sometimes used as a
coalescing medium.
Coalescing stages may be integrated with a wide variety of
gravity oil separation devices, and some systems may incorporate
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several coalescing stages. In general, a preliminary oil
skimming step is desirable to avoid overloading the coalescer.
One commercially marketed system for oily waste treatment
combines coalescing with inclined plate separation and
filtration. In this system, the oily wastes flow into an
inclined plate settler. This unit consists of a stack of
inclined baffle plates in a cylindrical container with an oil
collection chamber at the top. The oil droplets rise and impinge
upon the undersides of the plates. They then migrate upward to a
guide rib which directs the oil to the oil collection chamber,
from which oil is discharged for reuse or disposal.
The oily water continues on through another cylinder containing
replaceable filter cartridges, which remove suspended particles
from the waste. From there the wastewater enters a final
cylinder in which the coalescing material is housed. As the oily
water passes through the many small, irregular, continuous
passages in the coalescing material, the oil droplets coalesce
and rise to an oil collection chamber.
Application and Performance. Coalescing is used to treat oily
wastes which do not separate readily in simple gravity systems.
The three-stage system described above has achieved effluent
concentrations of 10 to 15 mg/1 oil and grease from raw waste
concentrations of 1000 mg/1 or more.
Advantages and Limitations. Coalescing allows removal of oil
droplets too finely dispersed for conventional gravity
separation-skimming technology. It also can significantly reduce
the residence times (and therefore separator volumes) required to
achieve separation of oil from some wastes. Because of its
simplicity, coalescing provides generally high reliability and
low capital and operating costs. Coalescing is not generally
effective in removing soluble or chemically stabilized emulsified
oils. To avoid plugging, coalescers must be protected by
pretreatment from very high concentrations of free oil and grease
and suspended solids. Frequent replacement of prefliters may be
necessary when raw waste oil concentrations are high.
Operational Factors. Reliability: Coalescing is inherently
highly reliable since the're are no moving parts, and the
coalescing substrate (monofilament, etc.) is inert in the
process and therefore not subject to frequent regeneration or
replacement requirements. Large loads or inadequate
pretreatment, however, may result in plugging or bypass of
coalescing stages.
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Maintainability: Maintenance requirements are generally limited
to replacement of the coalescing medium on an infrequent basis.
Solid Waste Aspects: No appreciable solid waste is generated by
this process.
Demonstration Status. Coalescing has been fully demonstrated in
industries generating oily wastewater, although none are
currently in use at any battery manufacturing facilities.
11. Cyanide Oxidation by Chlorine
Cyanide oxidation using chlorine is widely used in industrial
waste treatment to oxidize cyanide. Chlorine can be utilized in
either the elemental or hypochlorite forms. This classic
procedure can be illustrated by the following two step chemical
reaction:
1. C12 + NaCN + 2NaOH > NaCNO + 2NaCl + H20
2. 3C12 + 6NaOH + 2NaCNO > 2NaHC03 + N2 + 6NaCl + 2H2O
The reaction presented as Equation 2 for the oxidation of cyanate
is the final step in the oxidation of cyanide. A complete system
for the alkaline chlorination of cyanide is shown in Figure VII-
19 (page 445).
The alkaline chlorination process oxidizes cyanides to carbon
dioxide and nitrogen. The equipment often consists of an
equalization tank followed by two reaction tanks, although the
reaction can be carried out in a single tank. Each tank has an
electronic recorder-controller to maintain required conditions
with respect to pH and oxidation reduction potential (ORP). In
the first reaction tank, conditions are adjusted to oxidize
cyanides to cyanates. To effect the reaction, chlorine is
metered to the reaction tank as required to maintain the ORP in
the range of 350 to 400 millivolts, and 50 percent aqueous
caustic soda is added to maintain a pH range of 9.5 to 10. In
the second reaction tank, conditions are maintained to oxidize
cyanate to carbon dioxide and nitrogen. The desirable ORP and pH
for this reaction are 600 millivolts and a pH of 8.0. Each of
the reaction tanks is equipped with a propeller agitator designed
to provide approximately one turnover per minute. Treatment by
the batch process is accomplished by using two tanks, one for
collection of water over a specified time period, and one for the
treatment of an accumulated batch. If dumps of concentrated
wastes are frequent, another tank may be required to equalize the
flow to the treatment tank. When the holding tank is full, the
liquid is transferred to the reaction tank for treatment. After
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treatment, the supernatant is discharged and the sludges are
collected for removal and ultimate disposal.
Application and Performance. The oxidation of cyanide waste by
chlorine is a classic process and is found in most industrial
plants using cyanide. This process is capable of achieving
effluent levels that are nondetectable. The process is
potentially applicable to battery facilities where cyanide is a
component in cell wash formulations.
Advantages and Limitations. Some advantages of chlorine
oxidation for handling process effluents are operation at ambient
temperature, suitability for automatic control, and low cost.
Disadvantages include the need for careful pH control, possible
chemical interference in the treatment of mixed wastes, and the
potential hazard of storing and handling chlorine gas.
Operational Factors. Reliability: Chlorine oxidation is highly
reliable with proper monitoring and control and proper
pretreatment to control interfering substances.
Maintainability: Maintenance consists of periodic removal of
sludge and recalibration of instruments.
Solid Waste Aspects: There is no solid waste problem associated
with chlorine oxidation.
Demonstration Status. The oxidation of cyanide wastes by
chlorine is a widely used process in plants using cyanide in
cleaning and metal processing baths. Alkaline chlorination is
also used for cyanide treatment in a number of inorganic chemical
facilities producing hydroganic acid and various metal cyanides.
12. Cyanide Oxidation By Ozone
Ozone is a highly reactive oxidizing agent which is approximately
ten times more soluble than oxygen on a weight basis in water.
Ozone may be produced by several methods, but the silent
electrical discharge method is predominant in the field. The
silent electrical discharge process produces ozone by passing
oxygen or air between electrodes separated by an insulating
material. A complete ozonation system is represented in Figure
VII-20 (page 446).
Application and Performance. Ozonation has been applied
commercialfy to oxidize cyanides, phenolic chemicals, and organo-
metal complexes. Its applicability to photographic wastewaters
has been studied in the laboratory with good results. Ozone is
used in industrial waste treatment primarily to oxidize cyanide
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to cyanate and to oxidize phenols and dyes to a variety of
colorless nontoxic products.
Oxidation of cyanide to cyanate is illustrated below:
CN- + O3 > CNO- + O2
Continued exposure to ozone will convert the cyanate formed to
carbon dioxide and ammonia; however, this is not economically
practical.
Ozone oxidation of cyanide to cyanate requires 1.8 to 2.0 pounds
ozone per pound of CN-; complete oxidation requires 4.6 to 5.0
pounds ozone per pound of CN-. Zinc, copper, and nickel cyanides
are easily destroyed to a nondetectable level, but cobalt and
iron cyanides are more resistant to ozone treatment.
Advantages and Limitations. Some advantages of ozone oxidation
for handling process effluents are its suitability to automatic
control and on-site generation and the fact that reaction
products are not chlorinated organics and no dissolved solids are
added in the treatment step. Ozone in the presence of activated
carbon, ultraviolet, arid other promoters shows promise of
reducing reaction time and improving ozone utilization, but the
process at present is limited by high capital expense, possible
chemical interference in the treatment of mixed wastes, and an
energy requirement of 25 kwh/kg of ozone generated. Cyanide is
not economically oxidized beyond the cyanate form.
Operational Factors. Reliability: Ozone oxidation is highly
reliable with proper monitoring and control, and proper
pretreatment to control interfering substances.
Maintainability: Maintenance consists of periodic removal of
sludge, and periodic renewal of filters and desiccators required
for the input of clean dry air; filter life is a function of
input concentrations of detrimental constituents.
Solid Waste Aspects: Pretreatment to eliminate substances which
will interfere with the process may be necessary. Dewatering of
sludge generated in the ozone oxidation process or in an "in
line" process may be desirable prior to disposal.
13. Cyanide Oxidation By Ozone With UV Radiation
One of the modifications of the ozonation process is the
simultaneous application of ultraviolet light and ozone for the
treatment of wastewater, including treatment of halogenated
organics. The combined action of these two forms produces
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reactions by photolysis, photosensitization, hydroxylation,
oxygenation, and oxidation. The process is unique because
several reactions and reaction species are active simultaneously.
Ozonation is facilitated by ultraviolet absorption because both
the ozone and the reactant molecules are raised to a higher
energy state so that they react more rapidly. In addition, free
radicals for use in the reaction are readily hydrolyzed by the
water present. The energy and reaction intermediates created by
the introduction of both ultraviolet and ozone greatly reduce the
amount of ozone required compared with a system using ozone
alone. Figure VI1-21 (page 447) shows a three-stage UV-ozone
system. A system to treat mixed cyanides requires pretreatment
that involves chemical coagulation, sedimentation, clarification,
equalization, and pH adjustment.
Application and Performance. The ozone-UV radiation process was
developed primarily for cyanide treatment in the electroplating
and color photo-processing areas. It has been successfully
applied to mixed cyanides and organics from organic chemicals
manufacturing processes. The process is particularly useful for
treatment of complexed cyanides such as ferricyanide, copper
cyanide, and nickel cyanide, which are resistant to ozone alone.
Ozone combined with UV radiation is a relatively new technology.
Four units are currently in operation, and all four treat cyanide
bearing waste.
Ozone-UV treatment could be used in battery plants to destroy
cyanide present in waste streams from some cell wash operations.
14. Cyanide Oxidation By Hydrogen Peroxide
Hydrogen peroxide oxidation removes both cyanide and metals in
cyanide containing wastewaters. In this process, cyanide bearing
waters are heated to 49 to 54°C (120 to 130°F) and the pH is
adjusted to 10.5 to 11.8. Formalin (37 percent formaldehyde) is
added while the tank is vigorously agitated. After 2 to 5
minutes, a proprietary peroxygen compound (41 percent hydrogen
peroxide with a catalyst and additives) is added. After an hour
of mixing, the reaction is complete. The cyanide is converted to
cyanate, and the metals are precipitated as oxides or hydroxides.
The metals are then removed from solution by either settling or
filtration.
The main equipment required for this process is two holding tanks
equipped with heaters and air spargers or mechanical stirrers.
These tanks may be used in a batch or continuous fashion, with
one tank being used for treatment while the other is being
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filled. A settling tank or a filter is needed to concentrate the
precipitate.
Application and Performance. The hydrogen peroxide oxidation
process is applicable to cyanide-bearing wastewaters, especially
those containing metal-cyanide complexes. In terms of waste
reduction performance, this process can reduce total cyanide to
less than 0.1 mg/1 and the zinc or cadmium to less than 1.0 mg/1.
Advantages and Limitations. Chemical costs are similar to those
for alkaline chlorination using chlorine and lower than those for
treatment with hypochlorite. All free cyanide reacts and is
completely oxidized to the less toxic cyanate state. In
addition, the metals precipitate and settle quickly, and they may
be recoverable in many instances. However, the process requires
energy expenditures to heat the wastewater prior to treatment.
Demonstration Status. This treatment process was introduced in
1971 and is used in several facilities. No battery manufacturing
plants use oxidation by hydrogen peroxide.
15. Evaporation
Evaporation is a concentration process. Water is evaporated from
a solution, increasing the concentration of solute in the
remaining solution. If the resulting water vapor is condensed
back to liquid water, the evaporation-condensation process is
called distillation. However, to be consistent with industry
terminology, evaporation is used in this report to describe both
processes. Both atmospheric and vacuum evaporation are commonly
used in industry today. Specific evaporation techniques are
shown in Figure VII-22 (page 448) and discussed below.
Atmospheric evaporation could be accomplished simply by boiling
the liquid. However, to aid evaporation, heated liquid is
sprayed on an evaporation surface, and air is blown over the
surface and subsequently released to the atmosphere. Thus,
evaporation occurs by humidification of the air stream, similar
to a drying process. Equipment for carrying out atmospheric
evaporation is quite similar for most applications. The major
element is generally a packed column with an accumulator bottom.
Accumulated wastewater is pumped from the base of the column,
through a heat exchanger, and back into the top of the column,
where it is sprayed into the packing. At the same time, air
drawn upward through the packing by a fan is heated as it
contacts the hot liquid. The liquid partially vaporizes and
humidifies the air stream. The fan then blows the hot, humid air
to the outside atmosphere. A scrubber is often unnecessary
because the packed column itself acts as a scrubber.
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Another form of atmospheric evaporator also works on the air
humidification principle, but the evaporated water is recovered
for reuse by condensation. These air humidification techniques
operate well below the boiling point of water and can utilize
waste' process heat to supply the energy required.
In • y.§.c.MPl evaporation, the evaporation pressure is lowered to
cause the liquid to boil at reduced temperature. All of the
water vapor is condensed, and to maintain the vacuum condition,
noncondensible gases (air in particular) are removed by a vacuum
pump. Vacuum evaporation may be either single or double effect.
In double effect evaporation, two evaporators are used, and the
water vapor from the first evaporator (which may be heated by
steam) is used to supply heat to the second evaporator. As it
supplies heat, the water vapor from the first evaporator
condenses. Approximately equal quantities of wastewater are
evaporated in each unit; thus, the double effect system
evaporates twice the amount of water that a single effect system
does, at nearly the same cost in energy but with added capital
cost and complexity. The double effect technique is
thermodynamically possible because the second evaporator is
maintained at lower pressure (higher vacuum) and, therefore,
lower evaporation temperature. Vacuum evaporation equipment may
be classified as submerged tube or climbing film evaporation
units.
Another means of increasing energy efficiency is vapor
recompression evaporation, which enables heat to be transferred
from the condensing water vapor to the evaporating wastewater.
Water vapor generated from incoming wastewaters flows to a vapor
compressor. The compressed steam than travels through the
wastewater via an enclosed tube or coil in which it condenses as
heat is transferred to the surrounding solution. In this way,
the compressed vapor serves as a heating medium. After
condensation, this distillate is drawn off continuously as the
clean water stream. The heat contained in the compressed vapor
is used to heat the wastewater, and energy costs for system
operation are reduced.
In the most commonly used submerged tube evaporator, the heating
and condensing coil are contained in a single vessel to reduce
capital cost. The vacuum in the vessel is maintained by an
eductor-type pump, which creates the required vacuum by the flow
of the condenser cooling water through a venturi. Wastewater
accumulates in the bottom of the vessel, and it is evaporated by
means of submerged steam coils. The resulting water vapor
condenses as it contacts the condensing coils in the top of the
vessel. The condensate then drips off the condensing coils into
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a collection trough that carries it out of the vessel.
Concentrate is removed from the bottom of the vessel.
The major elements of the climbing film evaporator are the
evaporator, separator, condenser, and vacuum pump. Wastewater is
"drawn" into the system by the vacuum so that a constant liquid
level is maintained in the separator. Liquid enters the steam-
jacketed evaporator tubes, and part of it evaporates so that a
mixture of vapor and liquid enters the separator. The design of
the separator is such that the liquid is continuously circulated
from the separator to the evaporator. The vapor entering the
separator flows out through a mesh entrainment separator to the
condenser, where it is condensed as it flows down through the
condenser tubes. The condensate, along with any entrained air,
is pumped out of the bottom of the condenser by a liquid ring
vacuum pump. The liquid seal provided by the condensate keeps
the vacuum in the system from being broken.
Application and Performance. Both atmospheric and vacuum
evaporation are used in many industrial plants, mainly for the
concentration and recovery of process solutions. Many of these
evaporators also recover water for rinsing. Evaporation has also
been applied to recovery of phosphate metal cleaning solutions.
In theory, evaporation should yield a concentrate and a deionized
condensate. Actually, carry-over has resulted in condensate
metal concentrations as high as 10 mg/1, although the usual level
is less than 3 mg/1, pure enough for most final rinses. The
condensate may also contain organic brighteners and antifoaming
agents. These can be removed with an activated carbon bed, if
necessary. Samples from one plant showed 1,900 mg/1 zinc in the
feed, 4,570 mg/1 in the concentrate, and 0.4 mg/1 in the
condensate. Another plant had 416 mg/1 copper in the feed and
21,800 mg/1 in the concentrate. Chromium analysis for that plant
indicated 5,060 mg/1 in the feed and 27,500 mg/1 in the
concentrate. Evaporators are available in a range of capacities,
typically from 15 to 75 gph, and may be used in parallel
arrangements for processing of higher flow rates.
Advantages and Limitations. Advantages of the evaporation
process are that it permits recovery of a wide variety of process
chemicals, and it is often applicable to concentration or removal
of compounds which cannot be accomplished by any other means.
The major disadvantage is that the evaporation process consumes
relatively large amounts of energy for the evaporation of water.
However, the recovery of waste heat from many industrial
processes (e.g., diesel generators, incinerators, boilers, and
furnaces) should be considered as a source of this heat for a
totally integrated evaporation system. Also, in some cases solar
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heating could be inexpensively and effectively app.lied to
evaporation units. Capital costs for vapor compression
evaporators are substantially higher than for other types of
evaporation equipment. However, the energy costs associated with
the operation of a vapor compression evaporator are significantly
lower than costs of other evaporator types. For some
applications, pretreatment may be required to remove solids or
bacteria which tend to cause fouling in the condenser or
evaporator. The buildup of scale on the evaporator surfaces
reduces the heat transfer efficiency and may present a
maintenance problem or increase operating cost. However, it has
been demonstrated that fouling of the heat transfer surfaces can
be avoided or minimized for certain dissolved solids by
maintaining a seed slurry which provides preferential sites for
precipitate deposition. In addition, low temperature differences
in the evaporator will eliminate nucleate boiling and
supersaturation effects. Steam distiliable impurities in the
process stream are carried over with the product water and must
be handled by pre-or post treatment.
Operational Factors. Reliability: Proper maintenance will
ensure a high degree of reliability for the system. Without such
attention, rapid fouling or deterioration of vacuum seals may
occur, especially when corrosive liquids are handled.
Maintainability: Operating parameters can be automatically
controlled. Pretreatment m.ay be required, as well as periodic
cleaning of the system. Regular replacement of seals, especially
in a corrosive environment, may be necessary.
Solid Waste Aspects: With only a few exceptions, -the process
does not generate appreciable quantities of solid waste.
Demonstration Status. Evaporation is a fully developed,
commercially available wastewater treatment system. It is used
extensively to recover plating chemicals in the electroplating
industry, and a pilot scale unit has been used in connection with
phosphating of aluminum. Proven performance in silver recovery
indicates that evaporation could be a useful treatment operation
for the photographic industry, as well as for metal finishing.
Vapor compression evaporation has been practically demonstrated
in a number of industries, including chemical manufacturing, food
processing, pulp and papery and metal working. One battery plant
has recently reported showing the use of evaporation.
16. Flotation
Flotation is the process of causing particles such as metal
hydroxides or oil to float to the surface of a tank where they
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can be concentrated and removed. This is accomplished by
releasing gas bubbles which attach to the solid particles,
increasing their buoyancy and causing them to float. In
principle, this process is the opposite of sedimentation. Figure
VII-23 (page 449) shows one type of flotation system.
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 1.0, which would require abnormally long sedimentation
times, may be removed in much less time by flotation. Dissolved
air flotation is of greatest interest in removing oil from water
and is less effective in removing heavier precipitates.
This process may be performed in several ways: foam, dispersed
air, dissolved air, gravity, and vacuum flotation are the most
commonly used techniques. Chemical additives are often used to
enhance the performance of the flotation process.
The principal difference among types of flotation is the method
of generating the minute gas bubbles (usually air) in a
suspension of water and small particles. Chemicals may be used
to improve the efficiency with any of the basic methods. The
following paragraphs describe the different flotation techniques
and the method of bubble generation for each process.
Froth Flotation - Froth flotation is based on differences in the
physiochemical properties in various particles. Wettability and
surface properties affect the particles' ability to attach
themselves to gas bubbles in an aqueous medium. In froth
flotation, air is blown through the solution containing flotation
reagents. The particles with water repellant surfaces stick to
air bubbles as they rise and are brought to the surface. A
mineralized froth layer, with mineral particles attached to air
bubbles, is formed. Particles of other minerals which are
readily wetted by water do not stick to air bubbles and remain in
suspension.
Dispersed Air Flotation - In dispersed air flotation, gas bubbles
are generated by introducing the air by means of mechanical
agitation with impellers or by forcing air through porous media.
Dispersed air flotation is used mainly in the metallurgical
industry.
Dissolved Air Flotation - In dissolved air flotation, bubbles are
produced by releasing air from a supersaturated solution under
relatively high pressure. There are two types of contact between
the gas bubbles and particles. The first type is predominant in
the flotation of flocculated materials and involves the
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entrapment of rising gas bubbles in the flocculated particles as
they increase in size. The bond between the bubble and particle
is one of physical capture only. The second type of contact is
one of adhesion. Adhesion results from the intermolecular
attraction exerted at the interface between the solid particle
and gaseous bubble.
Vacuum Flotation - This process consists of saturating the
wastewater with air either directly in an aeration tank, or by
permitting air to enter on the suction of a wastewater pump. A
partial vacuum is applied, which causes the dissolved air to come
out of solution as minute bubbles. The bubbles attach to solid
particles and rise to the surface to form a scum blanket, which
is normally removed by a skimming mechanism. Grit and other
heavy solids that settle to the bottom are generally raked to a
central sludge pump for removal. A typical vacuum flotation unit
consists of a covered cylindrical tank in which a partial vacuum
is maintained. The tank is equipped with scum and sludge removal
mechanisms. The floating material is continuously swept to the
tank periphery, automatically discharged into a scum trough, and
removed from the unit by a pump also under partial vacuum.
Auxiliary equipment includes an aeration tank for saturating the
wastewater with air, a tank with a short retention time for
removal of large bubbles, vacuum pumps, and sludge pumps.
Application and Performance. The primary variables for flotation
design are pressure, feed solids concentration, and retention
period. The suspended solids in the effluent decrease, and the
concentration of solids in the float increases with increasing
retention period. When the flotation process is used primarily
for clarification, a retention period of 20 to 30 minutes usually
is adequate for separation and concentration.
Advantages and Limitations. Some advantages of the flotation
process are the high levels of solids separation achieved in many
applications, .the relatively low energy requirements, and the
adaptability to meet the treatment requirements of different
waste types. Limitations of flotation are that it often requires
addition of chemicals to enhance process performance and that it
generates large quantities of solid waste.
Operational Factors. Reliability: Flotation systems normally
are very reliable with proper maintenance of the sludge collector
mechanism and the motors and pumps used for aeration.
Maintainability: Routine maintenance is required on the pumps
and motors. The sludge collector mechanism is subject to
possible corrosion or breakage and may require periodic
replacement.
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Solid Waste Aspects: Chemicals are commonly used to aid the
flotation process by creating a surface or a structure that can
easily adsorb or entrap air bubbles. Inorganic chemicals, such
as the aluminum and ferric salts, and activated silica, can bind
the particulate matter together and create a structure that can
entrap air bubbles. Various organic chemicals can change the
nature of either the air-liquid interface or the solid-liquid
interface, or both. These compounds usually collect on the
interface to bring about the desired changes. The added
chemicals plus the particles in solution combine to form a large
volume of sludge which must be further treated or properly
disposed.
Demonstration Status. Flotation is a fully developed process and
is readily available for the treatment of a wide variety of
industrial waste streams. Flotation separation has been used in
two battery manufacturing plants as a part of precipitation
systems for metals removal.
17. Gravity Sludge Thickening
In the gravity thickening process, dilute sludge is fed from a
primary settling tank or clarifier to a thickening tank where
rakes stir the sludge gently to density it and to push it to a
central collection well. The supernatant is returned to the
primary settling tank. The thickened sludge that collects on the
bottom of the tank is pumped to dewatering equipment or hauled
away. Figure VII-24 (page 450) shows the construction of a
gravity thickener.
Application and Performance. Thickeners are generally used in
facilities where the sludge is to be further dewatered by a
compact mechanical device such as a vacuum filter, or centrifuge.
Doubling the solids content in the thickener substantially
reduces capital and operating cost of the subsequent dewatering
device and also reduces cost for hauling. The process is
potentially applicable to almost any industrial plant.
Organic sludges from sedimentation units of one to two percent
solids concentration can usually be gravity thickened to six to
ten percent; chemical sludges can be thickened to four to six
percent.
Advantages and Limitations. The principal advantage of a grav-ity
sludge thickening process is that it facilitates further sludge
dewatering. .Other advantages are high reliability and minimum
maintenance requirements.
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Limitations of the sludge thickening process are its sensitivity
to the flow rate through the thickener and the sludge removal
rate. These rates must be low enough not to disturb the
thickened sludge.
Operational Factors. Reliability: Reliability is high with
proper design and operation. A gravity thickener is designed on
the basis of square feet per pound of solids per day, in which
the required surface area is related to the solids entering and
leaving the unit. Thickener area requirements are also expressed
in terms of mass loading, grams of solids per square meter per
day (Ibs/sq ft/day).
Maintainability: Twice a year, a thickener must be shut down for
lubrication of the drive mechanisms. Occasionally, water must be
pumped back through the system in order to clear sludge pipes.
Solid Waste Aspects: Thickened sludge from a gravity thickening
process will usually require further dewatering prior to
disposal, incineration, or drying. The clear effluent may be
recirculated in part, or it may be subjected to further treatment
prior to discharge.
Demonstration Status. Gravity sludge thickeners are used
throughout industry to reduce water content to a level where the
sludge may be efficiently handled. Further dewatering is usually
practiced to minimize costs of hauling the sludge to approved
landfill areas. Sludge thickening is used in seven battery
manufacturing plants.
18. Insoluble Starch Xanthate
Insoluble starch xanthate is essentially an ion exchange medium
used to remove dissolved heavy metals from wastewater. The water
may then either be reused (recovery application) or discharged
(end-of-pipe application). In a commercial electroplating oper-
ation, starch xanthate is coated on a filter medium. Rinse water
containing dragged out heavy metals is circulated through the
filters and then reused for rinsing. The starch-heavy metal
complex is disposed of and replaced periodically. Laboratory
tests indicate that recovery of metals from the complex is
feasible, with regeneration of the starch xanthate. Besides
electroplating, starch xanthate is potentially applicable to any
other industrial plants where dilute metal wastewater streams are
generated. Its present use is limited to one electroplating
plant.
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19. Ion Exchange
Ion exchange is a process in which ions, held by electrostatic
forces to charged functional groups on the surface of the ion
exchange resin, are exchanged for ions of similar charge from the
solution in which the resin is immersed. This is classified as a
sorption process because the exchange occurs on the surface of
the resin, and the exchanging ion must undergo a phase transfer
from solution phase to solid phase. Thus, ionic contaminants in
a waste stream can be exchanged for the harmless ions of the
resin.
Although the precise technique may vary slightly according to the
application involved, a generalized process description follows.
The wastewater stream being treated passes through a filter to
remove any solids, then flows through a cation exchanger which
contains the ion exchange resin. Here, metallic impurities such
as copper, iron, and trivalent chromium are retained. The stream
then passes through the anion exchanger and its associated resin.
Hexavalent chromium, for example, is retained in this.stage. If
one pass does not reduce the contaminant levels sufficiently, the
stream may then enter another series of exchangers. Many ion
exchange systems are equipped with more than one set of
exchangers for this reason.
The other major portion of the ion exchange process concerns the
regeneration of the resin, which now holds those impurities
retained from the waste stream. An ion exchange unit with in-
place regeneration is shown in Figure VII-25 (page 451). Metal
ions such as nickel are removed by an acid, cation exchange
resin, which is regenerated with hydrochloric or sulfuric acid,
replacing the metal ion with one or more hydrogen ions. Anions
such as dichromate are removed by a basic, anion exchange resin,
which is regenerated with sodium hydroxide, replacing the anion
with one or more hydroxyl ions. The three principal methods
employed by industry for regenerating the spent resin are:
A) Replacement Service: A regeneration service replaces the
spent resin with regenerated resin, and regenerates the
spent resin at its own facility. The service then has the
problem of treating and disposing of the spent regenerant.
B) In-Place Regeneration: Some establishments may find it less
expensive to do their own regeneration. The spent resin
column is shut down for perhaps an hour, and the spent resin
is regenerated. This results in one or more waste streams
which must be treated in an appropriate manner.
Regeneration is performed as the resins require it, usually
every few months.
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C) Cyclic Regeneration: In this process, the regeneration of
the spent resins takes place within the ion exchange unit
itself in alternating cycles with the ion removal process.
A regeneration frequency of twice an hour is typical. This
very short cycle time permits operation with a very small
quantity of resin and with fairly concentrated solutions,
resulting in a very compact system. Again, this process
varies according to application, but the regeneration cycle
generally begins with caustic being pumped through the anion
exchanger, carrying out hexavalent chromium, for example, as
sodium dichromate. The sodium dichromate stream then passes
through a cation exchanger, converting the sodium dichromate
to chromic acid. After concentration by evaporation or
other means, the chromic acid can be returned to the process
line. Meanwhile, the cation exchanger is regenerated with
sulfuric acid, resulting in a waste acid stream containing
the metallic impurities removed earlier. Flushing the
exchangers with water completes the cycle. Thus, the
wastewater is purified and, in this example, chromic acid is
recovered. The ion exchangers, with newly regenerated
resin, then enter the ion removal cycle again.
Application and Performance. The list of pollutants for which
the ion exchange system has proved effective includes aluminum,
arsenic, cadmium, chromium (hexavalent and trivalent), copper,
cyanide, gold, iron, lead, manganese, nickel, selenium, silver,
tin, zinc, and more. Thus,'it can be applied to a wide variety
of industrial concerns. Because of the heavy concentrations of
metals in their wastewater, the metal finishing industries uti-
lize ion exchange in several ways. As an end-of-pipe treatment,
ion exchange is certainly feasible, but its greatest value is in
recovery applications. It is commonly used as an integrated
treatment to recover rinse water and process chemicals. Some
electroplating facilities use ion exchange to concentrate and
purify plating baths. Also, many industrial concerns, including
a number of battery manufacturing plants, use ion exchange to
reduce salt concentrations in incoming water sources.
Ion exchange is highly efficient at recovering metal bearing
solutions. Recovery of chromium, nickel, phosphate solution, and
sulfuric acid from anodizing is commercial. A chromic acid
recovery efficiency of 99.5 percent has been demonstrated.
Typical data for purification of rinse water have been reported
and are displayed in Table VII-25 (page 421). Sampling at one
battery manufacturing plant characterized influent and effluent
streams for an ion exchange unit on a silver bearing waste. This
system was in start-up at the time of sampling, however, and was
not found to be operating effectively.
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Advantages and Limitations. Ion exchange is a versatile
technology applicable to a great many situations. This
flexibility, along with its compact nature and performance, makes
ion exchange a very effective method of wastewater treatment.
However, the resins in these systems can prove to be a limiting
factor. The thermal limits of the anion resins, generally in the
vicinity of 60°C, " could prevent its use in certain situations.
Similarly, nitric acid, chromic acid, and hydrogen peroxide can
all damage the resins, as will iron, manganese, and copper when
present with sufficient concentrations of dissolved oxygen.
Removal of a particular trace contaminant may be uneconomical
because of the presence of other ionic species that are preferen-
tially removed. The regeneration of the resins presents its own
problems. The cost of the regenerative chemicals can be high.
In addition, the waste streams originating from the regeneration
process are extremely high in pollutant concentrations, although
low in volume. These must be further processed for proper
disposal.
Operational Factors. Reliability: With the exception of
occasional clogging or fouling of the resins, ion exchange has
proved to be a highly dependable technology.
Maintainability: Only the normal maintenance of pumps, valves,
piping and other hardware used in the regeneration process' is
required.
Solid Waste Aspects: Few, if any, solids accumulate within the
ion exchangers, and those which do appear are removed by the re-
generation process. Proper prior treatment and planning can eli-
minate solid buildup problems altogether. The brine resulting
from regeneration of the ion exchange resin must usually be
treated to remove metals before discharge. This can generate
solid waste.
Demonstration Status. All of the applications mentioned in this
document are available for commercial use, and industry sources
estimate the number of units currently in the field at well over
120. The research and development in ion exchange is focusing on
improving the quality and efficiency of the resins, rather than
new applications. Work is also being done on a continuous
regeneration process whereby the resins are contained on a fluid-
transfusible belt. The belt passes through a compartmentalized
tank with ion exchange, washing, and regeneration sections. The
resins are therefore continually used and regenerated. No such
system, however, has been reported beyond the pilot stage.
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Ion exchange is used for nickel recovery at one battery plant,
for silver and water recovery at another, and for trace nickel
and cadmium removal at a third.
20. Membrane Filtration
Membrane filtration is a treatment system for removing
precipitated metals from a wastewater stream. It must therefore
be preceded by those treatment techniques which will properly
prepare the wastewater for solids removal. Typically, a membrane
filtration unit is preceded by pH adjustment or sulfide addition
for precipitation of the metals. These steps are followed by the
addition of a proprietary chemical reagent which causes the
precipitate to be nongelatinous, easily dewatered, and highly
stable. The resulting mixture of pretreated wastewater and
reagent is continuously recirculated through a filter module and
back into a recirculation tank. The filter module contains
tubular membranes. While the reagent-metal hydroxide precipitate
mixture flows through the inside of the tubes, the water and any
dissolved salts permeate the membrane. When the recirculating
slurry reaches a concentration of 10 to 15 percent solids, it is
pumped out of the system as sludge.
Application and Performance. Membrane filtration appears to be
applicable to any wastewater or process water containing metal
ions which can be precipitated using hydroxide, sulfide or
carbonate precipitation. It could function as the primary
treatment system, but also might find application as a polishing
treatment (after precipitation and settling) to ensure continued
compliance with metals limitations. Membrane filtration systems
are being used in a number of industrial applications,
particularly in the metal finishing area. They have also been
used for toxic metals removal in the metal fabrication industry
and the paper industry.
The permeate is claimed by one manufacturer to contain less than
the effluent concentrations shown in Table VII-26 (page 422)
regardless of the influent concentrations. These claims have
been largely substantiated by the analysis of water samples at
various plants in various industries.
In the performance predictions for this technology, pollutant
concentrations are reduced to the levels shown in Table VII-26
unless lower levels are present in the influent stream.
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Advantages and Limitations. A major advantage of the membrane
filtration system is that installations can use most of the
conventional end-of-pipe systems that may already be in place.
Removal efficiencies are claimed to be excellent, even with
sudden variation of pollutant input rates; however, the
effectiveness of the membrane filtration system can be limited by
clogging of the filters. Because pH changes in the waste stream
greatly intensify clogging problems, the pH must be carefully
monitored and controlled. Clogging can force the shutdown of the
system and may interfere with production. In addition, the
relatively high capital cost of this system may limit its use.
Operational Factors. Reliability: Membrane filtration has been
shown to be a very reliable system, provided that the pH is
strictly controlled. Improper pH can result in the clogging of
the membrane. Also, surges in the flow rate of the waste stream
must be controlled in order to prevent solids from passing
through the filter and into the effluent.
Maintainability: The membrane filters must be regularly
monitored, and cleaned or replaced as necessary. Depending on
the composition of the waste stream and its flow rate, frequent
cleaning of the filters may be required. Flushing with
hydrochloric acid for 6 to 24 hours will usually suffice. In
addition, the routine maintenance of pumps, valves, and other
plumbing is required.
Solid Waste Aspects: When the recirculating reagent-precipitate
slurry reaches 10 to 15 percent solids, it is pumped out of the
system. It can then be disposed of directly or it can undergo a
dewatering process. Because this sludge contains toxic metals,
it requires proper disposal.
Demonstration Status. There are more than 25 membrane filtration
systems presently in use on metal finishing and similar
wastewaters. Bench scale and pilot studies are being run in an
attempt to expand the list of pollutants for which this system is
known to be effective. Although there are no data on the use of
membrane filtration in battery manufacturing plants, the concept
has been successfully demonstrated using battery plant
wastewater. A unit has been installed at one battery
manufacturing plant based on these tests.
21. Peat Adsorption
Peat moss is a complex natural organic material containing lignin
and cellulose as major constituents. These constituents,
particularly lignin, bear polar functional groups, such as
alcohols, aldehydes, ketones, acids, phenolic hydroxides, and
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ethers, that can be involved in chemical bonding. Because of the
polar nature of the material, its adsorption of dissolved solids
such as transition metals and polar organic molecules is quite
high. These properties have led to the use of peat as an agent
for the purification of industrial wastewater.
Peat adsorption is a "polishing" process 'which can achieve very
low effluent concentrations for several pollutants. If the
concentrations of pollutants are above 10 mg/1, then peat
adsorption must be preceded by pH adjustment for metals
precipitation and subsequent clarification. Pretreatment is also
required for chromium wastes using ferric chloride and sodium
sulfide. The wastewater is then pumped into a large metal
chamber called a kier which contains a layer of peat through
which . the waste stream passes. The water flows to a second kier
for further adsorption. The wastewater is then ready for
discharge. This system may be automated or manually operated.
Application and Performance. Peat adsorption can be used in
battery manufacturing for removal of residual dissolved metals
from clarifier effluent. Peat moss may be used to treat
wastewaters containing heavy metals such as mercury, cadmium,
zinc, copper, iron, nickel, chromium, and lead, as well as
organic matter such as oil, detergents, and dyes. Peat
adsorption is currently used commercially at a textile plant, a
newsprint facility, and a metal reclamation operation.
Table VII-27 (page 422) contains performance figures obtained
from pilot plant studies. Peat adsorption was preceded by pH
adjustment for precipitation and by clarification.
In addition, pilot plant studies have shown that chelated metal
wastes, as well as the chelating agents themselves, are removed
by contact with peat moss.
Advantages and Limitations. The major advantages of the system
include its ability to yield low pollutant concentrations, its
broad scope in terms of the pollutants eliminated, and its
capacity to accept wide variations of waste water composition.
Limitations include the cost of purchasing,' storing, and
di'sposing of the peat moss; the necessity for regular replacement
of the peat may lead to high operation and maintenance costs.
Also, the pH adjustment must be altered according to the
composition of the waste stream.
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Operational Factors. Reliability: The question of long term
reliability is not yet fully answered. Although the manufacturer
reports it to be a highly reliable system, operating experience
is needed to verify the claim.
Maintainability: The peat moss used in this process soon
exhausts its capacity to adsorb pollutants. At that time, the
kiers must be opened, the peat removed, and fresh peat placed
inside. Although this procedure is easily and quickly
accomplished, it must be done at regular intervals, or the
system's efficiency drops drastically.
Solid Waste Aspects: After removal from the kier, the spent peat
must be eliminated. If incineration is used, precautions should
be taken to insure that those pollutants removed from the water
are not released again in the combustion process. Presence of
sulfides in the spent peat, for example, will give rise to sulfur
dioxide in the fumes from burning. The presence of significant
quantities of toxic heavy metals in battery manufacturing
wastewater will in general preclude incineration of peat used in
treating these wastes.
Demonstration Status. Only three facilities currently use
commercial adsorption systems in the United States - a textile
manufacturer, a newsprint facility, and a metal reclamation firm.
No data have been reported showing the use of peat adsorption in
battery manufacturing plants.
22. Reverse Osmosis
The process of osmosis involves the passage of a liquid through a
semipermeable membrane from a dilute to a more concentrated
solution. Reverse osmosis (RO) is an operation in which pressure
is applied to the more concentrated solution, forcing the per-
meate to diffuse through the membrane and into the more dilute
solution. This filtering action produces a concentrate and a
permeate on opposite sides of the membrane. The concentrate can
then be further treated or returned to the original operation for
continued use, while the permeate water can be recycled for use
as clean water. Figure VI1-26 (page 452) depicts a reverse
osmosis system.
As illustrated in Figure VII-27, (page 453), there are three
basic configurations used in commercially available RO modules:
tubular, spiral-wound, and hollow fiber. All of these operate on
the principle described above, the major difference being their
mechanical and structural design characteristics.
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The tubular membrane module uses a porous tube with a cellulose
acetate membrane lining. A common tubular module consists of a
length of 2.5 cm (1 inch) diameter tube wound on a supporting
spool and encased in a plastic shroud. Feed water is driven into
the tube under, pressures varying from 40 to 55 atm (600-800 psi).
The permeate passes through the walls of the tube and is
collected in a manifold while the concentrate is drained off at
the end of the tube. A less widely used tubular RO module uses a
straight tube contained in a housing, under the same operating
conditions.
Spiral-wound membranes consist of a porous backing sandwiched
between two cellulose acetate membrane sheets and bonded along
three edges. The fourth edge of the composite sheet is attached
to a large permeate collector tube. A spacer screen is then
placed on top of the membrane sandwich, and the entire stack is
rolled around the centrally located tubular permeate collector.
The rolled up package is inserted into a pipe able to withstand
the high operating pressures employed in this process, up to 55
atm (800 psi) with the spiral-wound module. When the system is
operating, the pressurized product water permeates the membrane
and flows through the backing material to the central collector
tube. The concentrate is drained off at the end of the container
pipe and can be reprocessed or sent to further treatment facili-
ties.
The hollow fiber membrane configuration is made up of a bundle of
polyamide fibers of approximately 0.0075 cm (0.003 in.) OD and
0.0043 cm (0.0017 in.) ID. A commonly used hollow fiber module
contains several hundred thousand of the fibers placed in a long
tube, wrapped around a flow screen, and rolled into a spiral.
The fibers are bent in a U-shape and their ends are supported by
an epoxy bond. The hollow fiber unit is operated under 27 atm
(400 psi), the feed water being dispersed from the center of the
module through a porous distributor tube. Permeate flows through
the membrane to the hollow interiors of the fibers and is
collected at the ends of the fibers.
The hollow fiber and spiral-wound modules have a distinct advan-
tage over the tubular system in that they are able to load a very
large membrane surface area into a relatively small volume.
However, these two membrane types are much more susceptible to
fouling than the tubular system, which has a larger flow channel.
This characteristic also makes the tubular membrane much easier
to clean and regenerate than either the spiral-wound or hollow
fiber modules. One manufacturer claims that their helical
tubular module can be physically wiped clean by passing a soft
porous polyurethane plug under pressure through the module.
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Application and Performance. In a number of metal processing
plants, the overflow from the first rinse in a countercurrent
setup is directed to a reverse osmosis unit, where it is
separated into two streams. The concentrated stream contains
dragged out chemicals and is returned to the bath to replace the
loss of solution caused by evaporation and dragout. The dilute
stream (the permeate) is routed to the last rinse tank to provide
water for the rinsing operation. The rinse flows from the last
tank to the first tank, and the cycle is complete.
The closed-loop system described above may be supplemented by the
addition of a vacuum evaporator after the RO unit in order to
further reduce the volume of reverse osmosis concentrate. The
evaporated vapor can be condensed and returned to the last rinse
tank or sent on for further treatment.
The largest application has been for the recovery of nickel solu-
tions. It has been shown that RQ can generally be applied to
most acid metal baths with a high degree of performance,
providing that the membrane unit is not overtaxed. The
limitations most critical here are the allowable pH range ancl
maximum operating pressure for each particular configuration.
Adequate prefiltration is also essential. Only three membrane
types are readily available in commercial RO units, and their
overwhelming use has been for the recovery of various acid metal
baths. For the purpose of calculating performance predictions of
this technology, a rejection ratio of 98 percent is assumed for
dissolved salts, with 95 percent permeate recovery.
Advantages and Limitations. The major advantage of reverse
osmosis for handling process effluents is its ability to
concentrate dilute solutions for recovery of salts and chemicals
with low power requirements. No latent heat of vaporization or
fusion is required for effecting separations; the main energy
requirement is for a high pressure pump. It requires relatively
little floor space for compact, high capacity units, and ' it
exhibits good recovery and rejection rates for a number of
typical^process solutions. A limitation of the reverse osmosis
process for treatment of process effluents is its limited
temperature range for satisfactory operation. For cellulose
acetate systems, the preferred limits are 18° to 30°C (65° to
85°F); higher temperatures will increase the rate of membrane
hydrolysis and reduce system life, while lower temperatures will
result in decreased fluxes with no damage to the membrane.
Another limitation is inability to handle certain solutions.
Strong oxidizing agents, strongly acidic or basic solutions,
solvents, and other organic compounds can cause dissolution of
the membrane. Poor rejection of some compounds such as borates
and low molecular weight organics is another problem. Fouling of
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membranes by slightly soluble components in solution or colloids
has caused failures, and fouling of membranes by feed waters with
high levels of suspended solids can be a problem. A final limi-
tation is inability to treat or achieve high concentration with
some solutions. Some concentrated solutions may have initial os-
motic pressures which are so high that they either exceed avail-
able operating pressures or are uneconomical to treat.
Operational Factors. Reliability: Very good reliability is
achieved so long as the proper precautions are taken to minimize
the chances of fouling or degrading the membrane. Sufficient
testing of the waste stream prior to application of an RO system
will provide the information needed to insure a successful
application.
Maintainability: Membrane life is estimated to range from six
months to three years, depending on the use of the system.
Downtime for flushing or cleaning is on the order of two hours as
often as once each week; a substantial portion of maintenance
time must be spent on cleaning any prefilters installed ahead of
the reverse osmosis unit.
Solid Waste Aspects: In a closed loop system utilizing RO there
is a constant recycle of concentrate .and a minimal amount of
solid waste. Prefiltration eliminates many solids before they
reach the module and helps keep the buildup to a minimum. These
solids require proper disposal.
Demonstration Status. There are presently at least one/ hundred
reverse osmosis wastewater applications in a variety of
industries. In addition to these, there are 30 to 40 units being
used to provide pure process water for several industries.
Despite the many types and configurations of membranes, only the
spiral-wound cellulose acetate membrane has had widespread suc-
cess in commercial applications. Reverse osmosis is used at one
battery plant to treat process wastewater for reuse as boiler
feedwater.
23. Sludge Bed Drying
As a waste treatment procedure, sludge bed drying is employed to
reduce the water content of a variety of sludges to the point
where they are amenable to mechanical collection and removal to
landfill. These beds usually consist of 15 to 45 cm (6 to 18
in.) of sand over a 30 cm (12 in.) deep gravel drain system made
up of 3 to 6 mm (1/8 to 1/4 in.) graded gravel overlying drain
tiles. Figure VII-28 (page 454) shows the construction of a
drying bed.
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Drying beds are usually divided into sectional areas
approximately 7.5 meters (25 ft) wide x 30 to 60 meters (TOO to
200 ft) long. The partitions may be earth embankments, but more
often are made of planks and supporting grooved posts.
To apply liquid sludge to the sand bed, a closed conduit or a
pressure pipeline with valved outlets at each sand bed section is
often employed. Another method of application is by means of an
open channel with appropriately placed side openings which are
controlled by slide gates. With either type of delivery system,
a concrete splash slab should be provided to receive the falling
sludge and prevent erosion of the sand surface.
Where it is necessary to dewater sludge continuously throughout
the year regardless of the weather, sludge beds may be covered
with a fiberglass reinforced plastic or other roof. Covered
drying beds permit a greater volume of sludge drying per year in
most climates because of the protection afforded from rain or
snow and because of more efficient control of temperature.
Depending on the climate, a combination of open and enclosed beds
will provide maximum utilization of the sludge bed drying
facilities.
Application and Performance. Sludge drying beds are a means of
dewatering sludge from clarifiers and thickeners. They are
widely used both in municipal and industrial treatment
facilities.
Dewatering of sludge on sand beds occurs by two mechanisms:
filtration of water through the bed and evaporation of water as a
result of radiation and convection. Filtration is generally
complete in one to two days and may result in solids
concentrations as high as 15 to 20 percent. The rate of
filtration depends on the drainability of the sludge.
The rate of air drying of sludge is related to temperature,
relative humidity, and air velocity. Evaporation will proceed at
a constant rate to a critical moisture content, then at a falling
rate to an equilibrium moisture'content. The average evaporation
rate for a sludge is about 75 percent of that from a free water
surface.
Advantages and Limitations. The main advantage of sludge drying
beds over other types of sludge dewatering is the relatively low
cost of construction, operation, and maintenance.
Its disadvantages are the large area of land required and long
drying times that depend, to a great extent, on climate and
weather.
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Operational Factors. Reliability: Reliability is high with
favorable climactic conditions, proper bed design and care to
avoid excessive or unequal sludge application. If climatic
conditions in a given area are not favorable for adequate drying,
a cover may be necessary.
Maintainability: Maintenance consists basically of periodic
removal of the dried sludge. Sand removed from the drying bed
with the sludge must be replaced and the sand layer resurfaced.
The resurfacing of sludge beds is the major expense item in
sludge bed maintenance, but there are other areas which may
require attention. Underdrains occasionally become clogged and
have to be cleaned. Valves or sludge gates that control the flow
of sludge to the beds must be kept watertight. Provision for
drainage of lines in winter should be provided to prevent damage
from freezing. The partitions between beds should be tight so
that sludge will not flow from one compartment to another. The
outer walls or banks around the beds should also be watertight.
Solid Waste Aspects: The full sludge drying bed must either be
abandoned or the collected solids must be removed to a landfill.
These solids contain whatever metals or other materials were
settled in the clarifier. Metals will be present as hydroxides,
oxides, sulfides, or other salts. They have the potential for
leaching and contaminating ground water, whatever the location of
the semidried solids. Thus the abandoned bed or landfill should
include provision for runoff control and leachate monitoring.
Demonstration Status. Sludge beds have been in common use in
both municipal and industrial facilities for many years.
However, protection of ground water from contamination is not
always adequate.
24. Ultrafiltration
Ultrafiltration (UF) is a process which uses semipermeable
polymeric membranes to separate emulsified or colloidal materials
suspended in a liquid phase by pressurizing the liquid so that it
permeates the membrane. The membrane of an ultrafilter forms a
molecular screen which retains molecular particles based on their
differences in size, shape, and chemical structure. The membrane
permits passage of solvents and lower molecular weight molecules.
At present, an ultrafilter is capable of removing materials with
molecular weights in the range of 1,000 to 100,000 and particles
of comparable or larger sizes.
In an ultrafiltration process, the feed solution is pumped
through a tubular membrane unit. Water and some low molecular
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weight materials pass through the membrane under the applied
pressure of 2 to 8 atm (10 to 100 psig). Emulsified oil droplets
and suspended particles are retained, concentrated, and removed
continuously. In contrast to ordinary filtration, retained
materials are washed off the membrane filter rather than held by
it. Figure VII-29 (page 455) represents the ultrafiltration
process.
Application and Performance. Ultrafiltration has potential
application to battery manufacturing for separation of oils and
residual solids from a variety of waste streams. In treating
battery manufacturing wastewater, its greatest applicability
would be as a polishing treatment to remove residual precipitated
metals after chemical precipitation and clarification.
Successful commercial use, however, has been primarily for
separation of emulsified oils from wastewater. Over one hundred
such units now operate in the United States, treating emulsified
oils from a variety of industrial processes. Capacities of
currently operating units range from a few hundred gallons a week
to 50,000 gallons per day. Concentration of oily emulsions to 60
percent oil or more is possible. Oil concentrates of 40 percent
or more are generally suitable for incineration, and the permeate
can be treated further and in some cases recycled back to the
process. In this way, it is possible to eliminate contractor
removal costs for oil from some oily waste streams.
The test data in Table VII-28 (page 423) indicate ultrafiltration
performance (note that UF is not intended to remove dissolved
solids).
The removal percentages shown are typical, but they can be
influenced by pH and other conditions.
The permeate or effluent from the ultrafiltration unit is
normally of a quality that can be reused in industrial
applications or discharged directly. The concentrate from the
ultrafiltration unit can be disposed of as any oily or solid
waste.
Advantages and Limitations. Ultrafiltration is sometimes an
attractive alternative to chemical treatment because of lower
capital equipment, installation, and operating costs, very high
oil and suspended solids removal, and little required
pretreatment. It places a positive barrier between pollutants
and effluent which reduces the possibility of extensive pollutant
discharge due to operator error or upset in settling and skimming
systems. Alkaline values in alkaline cleaning solutions can be
recovered and reused in process.
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A limitation of ultrafiltration for treatment of process
effluents is its narrow temperature range {18° to 30°C) for
satisfactory operation. Membrane life decreases with higher
temperatures, but flux increases at elevated temperatures.
Therefore, surface area requirements are a function of
temperature and become a tradeoff between initial costs and
replacement costs for the membrane. In addition, ultrafiltration
cannot handle certain solutions. Strong oxidizing agents,
solvents, and other organic compounds can dissolve the membrane.
Fouling is sometimes a problem, although the high velocity of the
wastewater normally creates enough turbulence to keep fouling at
a minimum. Large solids particles can sometimes puncture the
membrane and must be removed by gravity settling or filtration
prior to the ultrafiltration unit.
Operational Factors. Reliability: The reliability of an
ultrafiltration system is dependent on the proper filtration,
settling or other treatment of incoming waste streams to prevent
damage to the membrane. Careful pilot studies should be done in
each instance to determine necessary pretreatment steps and the
exact membrane type to be used.
Maintainability: A limited amount of regular maintenance is
quired for the pumping system. In addition, membranes must be
periodically changed. Maintenance associated with membrane plug-
ging can be reduced by selection of a membrane with optimum phy-
sical characteristics and, sufficient velocity of the waste
stream. It is occasionally necessary to pass a detergent
solution through the system to remove an oil and grease film
which accumulates on the membrane. With proper maintenance,
membrane life can be greater than twelve months.
Solid Waste Aspects: Ultrafiltration is used primarily to
recover solids and liquids. It therefore eliminates solid waste
problems when the solids (e.g., paint solids) can be recycled to
the process. Otherwise, the stream containing solids must be
treated by end-of-pipe equipment. In the most probable
applications within the battery manufacturing category, the
ultrafilter would remove hydroxides or .sulfides of metals which
have recovery value.
Demonstration Status. The ultrafiltration process is well
developed and commercially available for treatment of wastewater
or recovery of certain high molecular weight liquid and solid
contaminants.
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25. Vacuum Filtration
In wastewater treatment plants, sludge dewatering by vacuum
filtration generally uses cylindrical drum filters. These drums
have a filter medium which may be cloth made of natural or
synthetic fibers or a wire-mesh fabric. The drum is suspended
above and dips into, a vat of sludge. As the drum rotates slowly,
part of its circumference is subject to an internal vacuum that
draws sludge to the filter medium. Water is drawn through the
porous filter cake to a discharge port, and the dewatered sludge,
loosened by compressed air, is scraped from the filter mesh.
Because the dewatering of sludge on vacuum filters is relativley
expensive per kilogram of water removed, the liquid sludge is
frequently thickened prior to processing. A vacuum filter is
shown in Figure VII-30 (page 456).
Application and Performance. Vacuum filters are frequently used
both in municipal treatment plants and in a wide variety of
industries. They are most commonly used in larger facilities,
which may have a thickener to double the solids content of
clarifier sludge before vacuum filtering.
The function of vacuum filtration .is to reduce the water content
of sludge, so that the solids content increases from about 5
percent to about 30 percent.
Advantages and Limitations. Although the initial cost and area
requirement of the vacuum filtration system are higher than those
of a centrifuge, the operating cost is lower, and no special
provisions for sound and vibration protection need be made. The
dewatered sludge from this process is in the form of a moist cake
and can be conveniently handled.
Operational Factors. Reliability: Vacuum filter systems have
proven reliable at many industrial and municipal treatment
facilities. At present, the largest municipal installation is at
the West Southwest wastewater treatment plant of Chicago,
Illinois, where 96 large filters were installed in 1925,
functioned approximately 25 years, and then were replaced with
larger units. Original vacuum filters at Minneapolis-St. Paul,
Minnesota, now have over 28 years of continuous service, and
Chicago has some units with similar or greater service life.
Maintainability: Maintenance consists of the cleaning or
replacement of the filter media, drainage grids, drainage piping,
filter pans, and other parts of the equipment. Experience in a
number of vacuum filter plants indicates that maintenance
consumes approximately 5 to 15 percent of the total time. If
carbonate buildup or other problems are unusually severe,
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maintenance time may be as high as 20 percent. For this reason,
it is desirable to maintain one or more spare units.
If intermittent operation is used, the filter equipment should be
drained and washed each time it is taken out of service. An
allowance for this wash time must be made in filtering schedules.
Solid Waste Aspects: Vacuum filters generate a solid cake which
is usually trucked directly to landfill. All of the metals
extracted from the plant wastewater are concentrated in the
filter cake as hydroxides, oxides, sulfides, or other salts.
Demonstration Status. Vacuum filtration has been widely used for
many years. It is a fully proven, conventional technology for
sludge dewatering. Vacuum filtration is used in at least two
battery manufacturing plants for sludge dewatering.
26. Permanganate Oxidation
Permanganate oxidation is a chemical reaction by which wastewater
pollutants can be oxidized. When the reaction is carried to
completion, the byproducts of the oxidation are not
environmentally harmful. A large number of pollutants can be
practically oxidized by. permanganate, including cyanides,
hydrogen sulfide, and phenol. In addition, the chemical oxygen
demand (COD) and many odors in wastewaters and sludges can be
significantly reduced by permanganate oxidation carried to its
end point. Potassium permanganate can be added to wastewater in
either dry or slurry form. The oxidation occurs optimally in the
8 to 9 pH range. As an example of the permanganate oxidation
process, the following chemical equation shows the oxidation of
phenol by potassium permanganate;
3 C«H5(OH).+ 28KMnO4 + 5H2 -> 18 C02 + 28KOH + 28 Mn02.
One of the byproducts of this oxidation is manganese dioxide
(MnO2), which occurs as a relatively stable hydrous colloid
usually having a negative charge. These properties, in addition
to its large surface area, enable manganese dioxide to act as a
sorbent for metal cation, thus enhancing their removal from the
wastewater.
Application and Performance. Commercial use of permanganate
oxidation has been primarily for the control of phenol and waste
odors. Several municipal waste treatment facilities report that
initial hydrogen sulfide ' concentrations (causing serious odor
problems) as high as 100 mg/1 have been reduced to zero through
the application of potassium permanganate. A variety of
industries (including metal finishers and agricultural chemical
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manufacturers) have used permanganate oxidation to totally
destroy phenol in their wastewaters.
Advantages and Limitations. Permanganate oxidation has several
advantages as a wastewater treatment technique. Handling and
storage are facilitated by its non-toxic and non-corrosive
nature. Performance has been proved in a number of municipal and
industrial applications. The tendency of the manganese dioxide
by-product to act as a coagulant aid is a distinct advantage over
other types of chemical treatment.
The cost of permanganate oxidation treatment can be limiting
where very large dosages are required to oxidize wastewater
pollutants. In addition, care must be taken in storage to
prevent exposure to intense heat, acids, or reducing agents;
exposure could create a fire hazard or cause explosions. Of
greatest concern is the environmental hazard which the use of
manganese chemicals in treatment could cause. Care must be taken
to remove the manganese from treated water before discharge.
Operational Factors. Reliability: Maintenance consists of
periodic sludge removal and cleaning of pump feed lines.
Frequency of maintenance is dependent on wastewater
characteristics.
Solid Waste Aspects: Sludge is generated by the process where
the manganese dioxide byproduct tends to act as a coagulant aid.
The sludge from permanganate oxidation can be collected and
handled by standard sludge treatment and processing equipment.
No battery manufacturing facilities are known to use permanganate
oxidation for wastewater treatment at this time.
Demonstration Status. The oxidation of wastewater pollutants by
potassium permanganate is a proven treatment process in several
types of industries. It has been shown effective in treating a
wide variety of pollutants in both municipal and industrial
wastes.
IN-PROCESS POLLUTION CONTROL TECHNIQUES
In general, the most cost-effective pollution reduction tech-
niques available to any industry are those which prevent
completely the entry of pollutants into process wastewater or
reduce the volume of wastewater requiring treatment. These "in-
process" controls can increase treatment effectiveness by
reducing the volume of wastewater to treatment as more
concentrated waste streams from which the pollutants can be more
completely removed, or by eliminating pollutants which are not
readily removed or which interfere with the treatment of other
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pollutants. They also frequently yield economic benefits in
reduced water consumption, in decreased waste treatment costs and
in decreased consumption or recovery of process materials.
Process water use in battery manufacturing provides many
opportunities for in-process control and, as Table VI1-29 (Page
424) shows, some in-process control measures have been
implemented by many battery manufacturing facilities. The wide
range of in-process water use and wastewater discharge exhibited
by battery manufacturing plants {as shown in the data presented
in Section V) reflects the present variability of in-process
wastewater control at these facilities.
Many in-process pollution control techniques are of a general
character, although specific applications of these techniques
vary among different battery manufacturing subcategories. Some
of the available in-process control techniques apply only to
specific processing steps.
Generally Applicable In-Process Control Techniques
Techniques which may be applied to reduce pollutant discharges
from most battery manufacturing subcategories include wastewater
segregation, water recycle and reuse, water use reduction, pro-
cess modification, and plant maintenance and good housekeeping.
Effective in-process control at most plants will entail a
combination of several techniques. Frequently, the practice of
one in-process control technique is required for the successful
implementation of another. For example, wastewater segregation
is frequently a prerequisite for the extensive practice of
wastewater recycle or reuse.
Wastewater Segreqati on - The segregation of wastewater streams is
a key element in implementing effective pollution control for
plants in the lead subcategory. Segregation is implemented to
separate streams of widely varying physical and chemical
characteristics for subsequent reuse, discharge, or treatment.
This is done to prevent dilution of the process wastewaters and
also to maintain the character of the nonprocess stream for reuse
or discharge. The cumulative effect of segregation is to reduce
treatment costs and increase pollutant removal.
The specific effects of commingling process wastewater with
nonprocess wastewater is to increase the total volume of process
wastewater to be treated. This has an adverse effect on both
treatment performance and cost. The increased volume of
wastewater increases the size and, therefore, cost of wastewater
treatment facilities. Since a given treatment technology has a
specific treatment effectiveness and can only achieve certain
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discharge concentrations of pollutants, the total mass of
pollutants which is discharged increases with dilution. Thus, a
plant which segregates noncontact cooling water and other
nonprocess waters from process wastewater will almost always
achieve a lower mass discharge of pollutants while substantially
reducing treatment costs.
Lead battery manufacturing plants commonly produce multiple
process and nonprocess wastewater streams. The identified
nonprocess streams include wastewater streams that are reuseable
after minimal treatment and other streams that are not reusable.
Reuseable waters are most often noncontact cooling waters. This
water is uncontaminated and can be recycled in a closed indirect
cooling configuration as well as used as makeup for process water
using operations. Noncontact cooling water is commonly recycled
for reuse in lead battery plants.
The segregation of dilute process waste streams from those
bearing high lead loadings may allow further use of the dilute
streams. Sometimes the lightly polluted stream may be recycled
to the process from which they were discharged, such as in lead
strip casting. Other waste streams may be suitable for use in
another process with only minimal treatment, such as the use of
humidity curing water in paste machine washdown. Selected dilute
process waste streams are suitable for incorporation into the
product, such as the use of battery rinse water in acid cutting.
Segregation of wastewater streams may allow lower cost, and
separate treatment of the streams. For example, wastewater
streams containing high levels of suspended solids may be treated
in separate inexpensive settling systems rather than more
expensive lime and settle treatment. Often the clarified
wastewater is suitable for further process use and both pollutant
loads and the wastewater volume requiring further treatment are
reduced.
Segregation and separate treatment of selected wastewater streams
may yield an additional economic benefit to the plant by
promoting recovery of process materials. The solids borne by
wastewater from a specific process operation are primarily
composed of materials used in that operation. These sludges
resulting from separate settling of these streams may be
reclaimed for use in the process with little or no processing or
recovered for reprocessing. For example, this technique
presently is used to recover lead used in processing pasted
plates at lead battery manufacturing plants.
Certain nonprocess wastewater streams are not usually reused due
to the nature of the stream or operation. At lead subcategory
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plants, these streams include discharges from water softener and
deionizer backflushes, cooling tower and boiler water blowdowns,
and regular production employee showers and other sanitary
waters. Segregation and separate discharge of these streams is
commonly observed in lead subcategory plants.
Wastewater Recycle and Reuse - The recycle or reuse of process
wastewater is a particularly effective technique for the re-
duction of both pollutant discharges and treatment costs. The
term "recycle" is used to designate the return of process
wastewater usually after some treatment to the process or
processes from which it originated, while "reuse" refers to the
use of wastewater from one process in another. Both recycle and
reuse of process wastewater are presently practiced at battery
manufacturing plants although recycle is more extensively used.
The most frequently recycled waste streams include air pollution
control scrubber discharges, product rinsing and wastewater from
equipment and area cleaning. Numerous other process wastewater
streams from lead battery manufacturing activities may also be
recycled or reused. Common points of wastewater recycle in
present practice include air pollution .control scrubbers,
equipment and area washdown, some product rinsing operations and
contact cooling.
Both recycle and reuse are frequently possible without extensive
treatment of the wastewater; process pollutants present in the
waste stream are ofteq tolerable (or occasionally even
beneficial) for process use. Recycle or reuse in these instances
yields cost savings by reducing the volume of wastewater
requiring treatment. Where treatment is required for recycle or
reuse, it is frequently considerably simpler than the treatment
necessary to achieve effluent quality suitable for release to the
environment. Treatment prior to recycle or reuse observed in
present practice is generally restricted to simple settling or
neutralization. Since these treatment practices are less costly
than those used prior to discharge, economic as well as
environmental benefits are usually realized. In addition to
these in-process recycle and reuse practices, some plants are
observed to return part or all of the treated effluent from an
end-of-pipe treatment system for further process use.
Recycle can usually be implemented with minimal expense and comp-
lications because the required treatment is often minimal and the
water for recycle is immediately available. As an example,
pasting area washdown water can be collected in the immediate
area of pasting, settled and the supernatant reused for washdown
of the pasting area.
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The rate of water used in wet air scrubbers is determined by the
requirement for adequate contact with the air being scrubbed and
not by the mass of pollutants to be removed. As a result,
wastewater streams from once-through scrubbers are character-
istically very dilute and high in volume. These streams can
usually be recycled extensively without treatment with no
deleterious effect on scrubber performance. Limited treatment
such as neutralization where acid fumes are scrubbed can signifi-
cantly increase the practical recycle rate.
Water used in washing process equipment and production floor
areas frequently serves primarily to remove solid materials and
is often treated by settling and recycled. This practice is
especially prevalent at lead subcategory plants but is observed
in other subcategories as well. In some instances the settled
solids as well as the clarified wastewater are returned for use
in the process. The extent of recycle of these waste streams may
be very high, and in many cases no wastewater is discharged from
the recycle loop.
Water used in product rinsing is also recirculated in some cases,
especially from battery rinse operations. This practice is ulti-
mately limited by the concentrations of materials rinsed off the
product in the rinsewater. Wastewater from contact cooling oper-
ations also may contain low concentrations of pollutants which do
not interfere with the recycle of these streams. In some cases,
recycle of contact cooling -water with no treatment is observed
while in others, provisions for heat removal in cooling towers or
closed heat exchangers is required. Where contact cooling water
becomes heavily contaminated with acid, neutralization may be
required to minimize corrosion.
Water used in vacuum pump seals and ejectors commonly becomes
contaminated with process pollutants. The levels of contaminants
in these high volume waste streams are usually low enough to
allow recycle to the process with minimal treatment. A high
degree of recycle of wastewater from contact cooling streams may
require provisions for neutralization or removal of heat.
The extent of recycle possible in most process water uses is
ultimately limited by increasing concentrations of dissolved
solids in the water. The buildup of dissolved salts generally
necessitates some small discharge or "blowdown" from the process
to treatment. In those cases, where the rate of addition of
dissolved salts is balanced by removal of dissolved solids in
water entrained in settled solids, complete recycle with no
discharge can be achieved. In other instances, the contaminants
which build up in the recycle loop may be compatible with another
process operation, and the "blowdown" may be used in another
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process. Examples of this condition are observed in lead
subcategory scrubbers, battery rinse, and contact cooling wastes
which become increasingly laden with sulfuric acid and lead
during recycle. Small volumes bled from these recycle loops may
be used in diluting concentrated acid to prepare battery
electrolyte as observed at some existing facilities.
Water Use Reduction - The volume of wastewater discharge from a
plant or specific process operation may be reduced by simply
eliminating excess flow and unnecessary water use. Often this
may be accomplished with no change in the manufacturing process
or equipment and without any capital expenditure. A comparison
of the volumes of process water used in and discharged from
equivalent process operations at different battery manufacturing
plants or on different days at the same plant indicates
substantial opportunities for water use reductions. Additional
reductions in process water use and discharge may be achieved by
modifications to process techniques and equipment.
Many production units in battery manufacturing plants were
observed to operate intermittently or at highly variable pro-
duction rates. The practice of shutting off process water flow
during periods when the unit is not operating and of adjusting
flow rates during periods of low production can prevent much
unnecessary water use. Water may be shut off and controlled
manually or through automatically controlled valves. Manual
adjustment involving the human factor have been found to be
somewhat unreliable in practice; production personnel often fail
to turn off manual valves when production units are shut.down and
tend to ' increase water flow rates to maximum levels "to insure
good operation" regardless of production activity. Automatic
shut off valves may be used to turn off water flows when
production units are inactive. Automatic adjustment of flow
rates according to production levels requires more sophisticated
control systems incorporating production rate sensors.
Observations and flow measurements at visited battery manufactur-
ing plants indicate that automatic flow controls are rarely
employed. Manual control of process water use is generally
observed in process rinse operations, and little or no adjustment
of these flows to production level was practiced. The present
situation is exemplified by a rinse operation at one plant where
the daily average production normalized discharge flow rate was
observed to vary from 90 to 1200 I/kg over a three-day span.
Thus, significant reductions in pollutant discharges can be
achieved by the application of flow control in this category at
essentially no cost; (A net saying may be realized from the
reduced cost of water and sewage charges). Additional flow
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reductions may be achieved by the implementation of more
effective water use in some process operations.
Rinsing is a common operation in the manufacture of batteries and
a major source of wastewater discharge at most plants. Efficient
rinsing requires the removal of the greatest possible mass of
material in the smallest possible volume of water. It is
achieved by ensuring that the material removed is distributed
uniformly through the rinse water. (The high porosity of many of
the electrode structures makes the achievement of uniform mixing
difficult, necessitating longer product residence times and high
mixing rates in rinses.) Rinsing efficiency is also increased by
the use of multi-stage and countercurrent cascade rinses. Multi-
stage rinses reduce the total rinse water requirements by
allowing the removal of much of the contaminant in a more
concentrated rinse with only the final stage rinse diluted to the
levels required for final product cleanliness. In a
countercurrent cascade rinse, dilute wastewater from each rinse
stage is reused in the preceding rinse stage and all of the
contaminants are discharged in a single concentrated waste
stream. The technical aspects of countercurrent cascade rinsing
are detailed in the following subsection.
Equipment and area cleanup practices observed at battery manu-
facturing plants vary widely. While some plants employ
completely dry cleanup techniques, many others use water with
varying degrees of efficiency. The practice of "hosing down"
equipment and production areas generally represents a very in-
efficient use of water, especially when hoses are left running
during periods when they are not used. Alternative techniques
which use water more efficiently include vacuum pick up floor
wash machines and bucket and sponge or bucket and mop techniques
as observed at some plants.
A major factor contributing in many cases to the need for battery
washing is electrolyte spillage on the battery case during
filling. This spillage and subsequent battery washing
requirement is maximized when batteries are filled by immersion
or by "overfill and withdraw" techniques. Water use in battery
washing may be significantly reduced by the use of filling
techniques and equipment which add the correct amount of
electrolyte to the battery without overfilling and which minimize
drips and spills on the battery case. These electrolyte addition
techniques and the production of finished batteries with little
or no battery washing are observed at numerous plants in the
category.
Additional reduction in process water use and wastewater dis-
charge may be achieved by the substitution of dry air pollution
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control devices such as baghouses for wet scrubbers where the
emissions requiring control are amenable to these techniques.
Counter current Cascade Rinsing and Mul.ti-Stage Rinsing
Of the many schemes discussed above for reduction of water use in
a battery production plant, countercurrent cascade rinsing is
most likely to result in the greatest reduction of water
consumption and use.
Countercurrent cascade rinses are employed at many plants in the
battery manufacturing category. In most cases, however, these
techniques are not combined with effective flow control, and the
wastewater discharge volumes from the countercurrent cascade
rinses are as large as or larger than corresponding single stage
rinse flows at other plants. Three instances of countercurrent
cascade rinsing with reasonable levels of flow control are noted
to illustrate the benefits achievable by this technique within
the battery manufacturing category.
Two lead subcategory plants use two-stage countercurrent cascade
rinses to rinse electrodes after open-case formation. These
rinses discharge 3.3 and 3.6 I/kg. At 28 other plants, single
stage rinses are used after open-case formation with an average
discharge of 20.9 I/kg. Thus, the use of two-stage
countercurrent cascade rinsing in this application is seen to
reduce rinse wastewater flow by a factor of 6
reduction). Still further reductions would result
operation of these rinse installations or from
additional countercurrent cascade rinse stages.
05" (83% flow
from better
the use of
Rinse water requirements and the benefits of countercurrent
cascade rinsing may be influenced by the volume of drag-out
solution carried into each rinse stage by the electrode or
material being rinsed, by the number of rinse stages used, by the
initial concentrations of impurities being removed, and by the
final product, cleanliness required. The influence of these
factors is expressed in the rinsing equation which may be stated
simply as:
Vr
Co
Cf
d/n)
X VD
Vr is the flow through each rinse stage.
Co is the concentration of the contaminant(s) in
the initial process bath
Cf is the concentration of the contaminant(s) in
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the final rinse to give acceptable product
cleanliness
n is the number of rinse stages employed,
and
VD is the flow of drag-out carried into each
rinse stage
Drag-out is solution which remains in the pores and on the
surface of electrodes or materials being rinsed when they are
removed from process baths or rinses. In battery manufacturing,
drag-out volumes may be quite high because the high porosity and
surface areas of electrodes. Based on porosity and surface
characteristics, it is estimated that the drag-out volume will be
approximately 20 percent of the apparent electrode volume
(including pores). Because of the highly porous nature of many
electrodes, perfect mixing in each rinse generally is not
achieved, and deviation from ideal rinsing is anticipated.
The application of the rinsing equation with these considerations
to the lead subcategory example cited above provides a basis for
the transfer of countercurrent rinse performance to other
subcategories and process elements. Based on the specific
gravities of component materials and approximately 20 percent
porosity, the apparent specific gravity of lead electrodes may be
estimated as 7.0; the volume of drag-out per unit weight of lead
is therefore:
VD = 0.2 = 0.029 I/kg.
7.0
Based on the average single stage rinse flow, the rinse
ratio (equal to Co/Cf) is:
Co (V. ) = Vr * 20.9 = 720
Cf VD 0.029
The calculated flow for a two stage countercurrent rinse
providing equivalent product cleaning is then given by
Vr » Co (Vn) x Vd = 720 o.s x 0.029 = 0.78 I/kg.
Cf
This calculated flow yields a rinse ratio of 26.8 and is 4.4
times (26.8 t- 6.05) lower than the observed countercurrent rinse
flow reflecting the extent to which ideal mixing is not achieved
in the rinses. One of these two plants was visited for sampling
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and was observed to employ no mixing or agitation in the rinse
tanks. Therefore, performance significantly closer to the ideal
should be attainable simply by adding agitation to the rinse
tanks.
To transfer countercurrent rinse results to other process ele-
ments, allowance must be made for the fact that required rinse
ratios may be substantially different in order to provide
adequate contaminant removal from some electrodes. To encompass
all process element requirements, an extreme case is considered
in which contaminants initially prasent at 10 percent (100,000
mg/1) in a process bath must be reduced to a nearly immeasurable
1.0 mg/kg (one part per million) in the final rinsed electrode.
The 20 percent drag-out found, appropriate for lead electrodes is
also applicable to other electrode types and materials rinsed,
since all have high porosity and surface area requirements in
order to sustain high current densities. The specific gravities
of most electrode materials are lower than those of lead and its
salts. Consequently, lower electrode densities are expected. An
estimated specific gravity of 4.5 is used tor purposes of this
calculation. Also, the active materials used as the basis of
most production normalizing parameters except lead make up only
approximately 45 percent of the total electroda saicht.
On the basis of these figures, it may be calculated that the
volume of drag-out amounts to:.
VD = 0.2 = 0.044 I/kg of electrode
. 4.5
or
VD = 0.2 x 1 = 0.1 I/kg of pnp
4.5 0.45
The concentration of pollutant in the .final rinse may be
calculated as 10 mg/1 based on the factors postulated and
calculated above. The rinse ratio (Co/Cf) is 10,000.
Multi-stage rinsing uses two or more stages of rinsinc each of
shich is supplied with fresh water and discharges to sewer or
treatment. For a multi-stage rinse, the total volume of rinse
wastewater is equal to n times Vr while for a countercurrent
rinse, vr is the total volume of wastewater discharge.
Using these rinsing parameters, theoretical rinse flow require-
ments may be calculated for single stage rinses and for a variety
of multi-stage and countercurrent rinses. Both ideal flows and
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flows increased by the 4.4 factor found in the lead subcategory
are shown for countercurrent rinses.
Number of Required Rinse Water per Mass of Product (pnp)
Rinse (I/kg)
Stages Multi-stage Countercurrent
Ideal Ideal Adjusted Rinse
Ratio
1 1000 1000
2 20 10 44.0 22.7
3 6.6 2.2 9.68 103.3
4 4.0 1.0 4.4 227.3
5 3.2 0.63 2.77 361.
7 2.6 0.37 1.63 613.
10 2.5 0.25 1.1 909.
Single stage rinse flow requirements calculated for these
conditions are somewhat higher than those presently observed in
the battery manufacturing category. The highest reported rinse
flow is approximately 2000 I/kg, and most are substantially less
than 1000 I/kg. This indicates that the cleanliness level has
been conservatively estimated.
In general, these calculations confirm that extreme conditions
have been chosen for the calculations and that the lead
subcategory data have been transferred to rinsing requirements
more severe in terms of drag-out and cleanliness than any
presently encountered in practice. Therefore, countercurrent
rinse discharge flows lower than those calculated should be
attainable in all process elements in the category.
In later sections of this document it is necessary to calculate
the wastewater generation when countercurrent cascade rinsing is
substituted for single stage rinsing. A rinse ratio of 6.6 is
used later for this calculation. It is based on the 6.05 rinse
ratio found in existing lead subcategory plants with an allowance
of 10 percent added for increased efficiency obtained by improved
agitation. As shown above, a rinse ratio of 22 would be expected
from a two stage system and much higher ratios are obtained by
using additional stages.
Lead Subcategory Process Element In-Process Control Techniques
In this subcategory, some in-process control technologies which
significantly reduce pollutant discharge are commonly practiced
and are consequently included in BPT technology. Other
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techniques are included in the BAT technology. Some of these
control technologies are discussed below.
Process water uses in lead subcategory plants include leady oxide
production, paste preparation and applications, grid manufacture
(including mold release preparation and direct chill casting),
plate (electrode) curing, plate or battery formation, plate soak,
battery wash, floor wash, wet air pollution control, battery
repair, laboratory, truck wash, handwash, respirator wash, and
laundry. The following discussions address waste segregation,
recycle and reuse, and other process modifications in the lead
subcategory process elements which will reduce the generation of
process wastewater.
Leady Oxide Production - Leady oxide is produced either in a ball
mill or by the Barton process. The Barton process does not
generate process wastewater, but uses noncontact cooling water
for certain mechanical portions of the process. Surface cooling
of ball mills does, however, generate wastewater because the
water is contaminated by lead particles scrubbed from the ambient
air. Process change can eliminate this process wastewater by
several alternative procedures. The first alternative is to shut
off the cooling water entirely, as the ball mills are observed to
be operated without cooling water. A second alternative is to
use internal cooling. This is accomplished by the closely
controlled injection (spray) of water into the open end of the
ball mill. The cooling water is evaporated in the ball mill and
passes out as water vapor through the baghouse which collects
lead dust. Another alternative is to install water recirculation
equipment for shell cooling if this method of cooling is
considered to be necessary. This would require the installation
of a water collection device, piping for return water to the ball
mill, and a pump. Still an additional alternative is to cool
only the trunion bearings of the ball mill, allowing the ball
mill to be operated at a higher temperature and production rate.
This alternative requires a small amount of noncontact process
wastewater which can be recirculated or routed directly to
discharge.
Maintenance practices are observed to be important in eliminating
unnecessary leaks in ball mill cooling which would generate
contamination of noncontact cooling water. One lead subcategory
plant was observed to have a leaking ball mill cooling jacket
resulting in increased volume of water to be treated and loss of
leady oxide material.
Good housekeeping practices are also important in leady oxide
production. Reduction in spillage in bulk handling can be
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achieved using dust control and rapid dry cleanup of spilled
materials.
Grid Manufacture - Grid Manufacture includes grid casting (making
battery plate grids in a die casting type machine), connectors
and tabs (parts) casting, continuous strip (direct chill or DC)
casting of lead, lead rolling and mold release formulation.
Melting furnaces are used to melt the lead, scrubbers or
baghouses are sometimes used to control lead fumes, and mold
releases are often compounded on site at battery manufacturing
plants. Lead casting was performed at 32 of the 34 sites visited
before and after proposal.
Both grid casting and small parts casting are performed by
cooling molten lead in dies, or molds. Cooling water is used to
cool the lead indirectly by passing the water through the mold
without contacting the lead itself. Many plants recirculate. this
cooling water in a closed loop system. Some plants use a glycol
indirect heat exchanger as part of their closed cooling system
which generates neither process nor nonprocess wastewaters.
Grid casting requires the use of mold release compounds which
prevent the molten lead from adhering to the mold surface. Mold
release compound can either be purchased or formulated on-site;
most plants formulate the compound on-site. Commercial mold
releases (both cork-kerosene and silica-silicon oil based
formulations) are available. Process wastewater is generated
from mold release formulation by cleaning equipment after mixing
batches of the release material. No specific technology for
reducing the wastewater generated in mold release formulation has
been identified.
Direct chill lead casting uses a process which continuously melts
lead ingots, draws the solidifying molten lead through a die and
sprays the die and lead strip directly with cooling water to cool
and solidify the continuous strip. This strip is fed to a
rolling mill for forming. The contact cooling water is
continuously recirculated with only an occassional (semi-annual)
blowdown to wastewater treatment. No further flow reduction
techniques . have been identified. An oil emulsion is used for
lubrication during lead rolling. This emulsion is contract
hauled to offsite land disposal by all plants which perform lead
rolling in conjunction with battery manufacturing.
Melting pots are used by all plants which perform grid
manufacture. This operation only generates a wastewater from wet
air scrubbers. Flow reduction for air scrubbers are discussed
below.
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Pasting - Recycle from paste preparation and application areas is
widespread. These recycle systems commonly include settling for
suspended solids removal and operate as completely closed loop
systems resulting in the complete elimination of process
wastewater discharge from this source. Water is removed from the
recirculation system with the settled solids and by evaporation
resulting in a negative water balance and requiring the
introduction of fresh make-up water. Water from the recirculated
wash-down stream is sometimes used in the paste mixing operation
and ultimately is evaporated from the plates in drying and
curing. Fifty-seven plants in the subcategory reported zero
discharge of pasting area wastewater. In addition, solids
recovery is practiced at many plants by reusing the settled
solids in the paste mix or shipping the solids to a smelter.
Curing - Curing may be performed by stacking plates with ambient
curing, the use of controlled temperature and humidity rooms, or
by the use of steam chests. Discharges have been observed from
both humidity-controlled and steam curing operations. Discharge
flow control methods have also been observed. Flow reduction or
elimination techniques are discussed below for each curing
method.
Humidity curing ovens sometimes generate a process wastewater
discharge. This discharge may be eliminated by the use of a
variety of design alternatives. A vendor of humidity-controlled
ovens maintains that these ovens may be operated in either a dry
or wet mode and still produce high quality cured plates. The dry
mode eliminates any need for water and allows the use of existing
equipment for curing.
Internal recirculation of spray water can be used to eliminate
the discharge of wastewater from the wet mode of operation.
Elevated temperatures (100-210°F) result in the loss of water
vapor requiring makeup to the internal collection area. To
eliminate problems with spray nozzle plugging, various in-line
filtration devices and nozzles can be used to screen out or pass
particles. Extended operation of this recirculation system may
result in the accumulation of leady oxide particles in the
collection area. This material may be periodically collected for
reclaim at a smelter. Membrane evaporation (simultaneously
passing air through and water across a coarse membrane or cloth)
is also used for water distribution. This method precludes the
need for filtration since spray nozzles are not used.
Drainage water from the humidity oven may be directed to the
pasting area as makeup water for equipment and floor washdown.
Some plants keep their pasting area floors continuously wet to
suppress lead dust. This practice evaporates large amounts of
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water and can readily accomodate the typical 14 gph flow from a
curing oven.
All of the water reuse and discharge reduction techniques
outlined above have been observed at visited battery plants.
Other techniques used to humidify air or combinations of these
can be adapted to eliminate discharge from humidity curing ovens.
Another approach is to use an external water recycle design
configuration. Drainage water from the curing oven is collected
in a trench at the base of the oven, pumped to a holding tank
with a level control, and is subsequently returned to the spray
nozzles. Settling in the holding tank plus in-line filtration is
used to prevent nozzle plugging.
Steam curing is done by some plants which achieve faster plate
curing by the direct impingment of steam on the plates. In this
process, steam condenses on the electrodes producing a
contaminated process wastewater. This source of wastewater may
be eliminated by the use of the more conventional "dry" curing
technique. Alternatively, the process wastewater from curing may
be reused elsewhere in the process.
There are also a number of alternative ways to maintain the use
of steam curing and still achieve zero discharge from this
operation. Existing steam curing designs generally employ a
water sealed chest. The steam injected into the chest is
subsequently vented to the plant atmosphere. In this manner, the
temperature (and humidity) is controlled in the chest by virtue
of the steam addition rate and steam properties (temperature and
pressure).
This discharge flow may be avoided altogether by the use of
electric heaters submerged in water-filled troughs inside the
steam chest. Condensed steam is then internally recirculated
back to the trough for re-evaporization. Variation of
temperature and relative humidity can be achieved by varying the
wattage employed in the heating elements. As a similar
alternative, steam can be used as. the heating medium for the
curing oven humidification water. Once again, with internal
recirculation of condensed steam, no discharge need be incurred.
Closed Formation (In-Case) - Closed formation comprises three
process elements: single fill, double fill, and fill and dump.
The wastewaters from each of these elements are similar. The
principal wastewater sources are (1) electrolyte spills, (2)
battery case product rinse water, (3) floor area and equipment
washdown, and (4) contact cooling of battery cases during rapid
formation. The type of formation process primarily impacts the
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need for battery rinsing and area equipment washdown. Spills are
controllable by proper filling procedures and good housekeeping;
area washdown water can be treated and recycled; battery rinsing
can be minimized and reused; contact cooling water can be
recycled or obviated by process modification. Each of these
control techniques as well as other in-process techniques which
impact closed formation are discussed below.
Spills - Electrolyte spills can be greatly reduced or eliminated
by the use of proper filling techniques, such as automatic or
vacuum controlled filling rather than overfill and withdraw.
Also, unavoidable spills can be collected, segregated, and reused
in acid cutting. This practice is performed in a number of lead
subcategory plants.
Product Rinsing - Product rinsing is observed predominately at
plants where immersion filling techniques are used. Flow
elimination is achieved by minimization of water use in the
rinsing station followed by reuse of the rinse in acid cutting.
These operations are discussed in more detail in the discussions
of battery washing.
Equipment and Other Area Washdown - Floor area washdown water can
be minimized by the efficient use of power (vacuum pick up) floor
scrubbing techniques. Water volume reduction may be achieved by
proper maintenance of floors to minimize cracks and pores in
which spilled materials may lodge. Treated wastewater can be
used in floor wash hoses in the formation and other plant areas.
This technique was observed during site visits.
Contact Cooling Water - The formation process generates heat
which must be removed from the batteries being formed if
acceptable product quality is to be achieved. The rate at which
this heat is generated depends upon the charge rate (amperage)
and the size of the battery; the rate of heat accumulation is a
function of generation rate, area available for dissipation and
the medium used for heat transfer from the electrolyte. When
batteries are formed rapidly as is practiced in some plants, heat
generation is so rapid that the batteries must be cooled using
water on the battery cases. This has been observed for both
small (SLI) and large (industrial) batteries. This contact
cooling water constitutes a significant source of wastewater
discharge at these plants.
Flow reduction or elimination of contact cooling water during
formation can be achieved in a number of ways. The water can be
extensively recycled with a small bleed stream removed to
maintain a tolerable contaminant level. The charging rate can be
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altered to eliminate the need for cooling water by slow charging,
or the use of controlled charging techniques.
Extensive recycling of cooling water is practiced at one plant
visited. To dissipate heat, a "cooling tank" is used in the area
where the cooling takes place. Other techniques are used as
well, such as the addition of caustic to maintain a safe operable
pH range. To control metal (e.g., iron) contamination, a water
softener is used to treat a small portion of the recycled water.
The buildup of iron, which presumably stains battery cases, can
also be avoided by the use of epoxy; coatings on racks or
conveyors to eliminate corrosion, and control of contact cooling
water flow patterns. Ultimately the recycle water bleed stream
can be used in acid cutting, pasting area washdown, or as makeup
to the battery wash system.
Slow or Controlled Formation - A number of closed formation
techniques are used in lead battery plants which eliminate the
need for cooling water during formation. Some of these
techniques allow for forming to take place at an overall rate
equal to or less than that rate which utilizes cooling water.
These practices include (1) slow rate formation, (2) controlled
charge rate formation, (3) air cooling, and (4) use of chilled
acid. At some plants, a combination of these practices is
applied, such as controlled charging in tunnels with air cooling.
The convective passage of air over batteries during formation has
been observed to serve as a mechanism to convey acid fumes to an
air scrubber as well as for heat dissipation.
The primary reduction in heat accumulation and maintenance of a
lower product temperature is due to charging rate control. When
batteries are charged more slowly, the heat is dissipated to the
atmosphere without the need for contact cooling water. Formation
at a lower rate reduces gassing during formation and consequently
reduces acid load on wet air pollution control scrubbers as well
as the extent of acid contamination of battery cases and
formation areas and equipment. The additional heat generated
during rapid, uncontrolled formation is a direct result of the
inefficient conversion of electrical energy to heat as opposed to
chemical reaction. Slow, controlled formation will require less
overall energy input to form a battery.
The term slow formation denotes a charging rate such that the
heat generated is adequately dissipated without cooling water and
the battery temperature is maintained so that battery quality is
not adversely affected. It does not require a specific forming
time. Observations made during site visits demonstrate that
batteries can be formed in much less than 24 hours using a
combination of these techniques.
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Controlled charging denotes the use of current variation during
the course of formation to maintain acceptable electrolyte
temperature. Current variation is achieved manually, by use of
automatic timing or small computer devices. Controlled charging
was observed at five sites. Overall
(formation) times varied at the plants
product type) from 9 hours to a total of 72
time has an associated maximum charge
hours.
controlled charging
visited (for a given
hours. The latter
rate of 4 amps for 30
It was observed during site visits that batteries formed at lower
rates were predominantly stacked on stationary racks as opposed
to conveyors. It was stated at proposal that more floor area
would be required for slow formation which could last up to seven
days. Based on information gathered, it is feasible for slow or
controlled-charge formation to be achieved in much less time and
without the need for additional building space. Concerning
additional building space requirements, several factors may be
considered as follow:
(1) At sites where conveyors are used, they were observed
to have sufficient additional floor space to add
stationary racks to handle any additional in-process
inventory where slow forming is instituted.
(2) If a site already uses racks and maintains that there
is no additional floor space available for more racks,
then racks with additional levels can be used. It was
observed that charging racks (for trickle charging)
have been used with as many as 15 batteries stacked
vertically. More usually, batteries are stacked in
racks four to six batteries high.
(3) Based on observed practices, it is unlikely that
formation duration would need to be increased by more
than about 50 percent if the current operation at a
site uses as long as 24 hours. It is possible that no
increase be incurred at all if the appropriate
technology is used. However, any anticipated increase
in in-process inventory can easily be handled by
existing building space.
Contact with vendors of rectification
feasibility of using existing rectifiers
reconfiguring the charging circuits.
equipment
for slow
confirms the
charging by
Plant Water Balance - Several closed formatipn procedures are
employed in the production of wet and damp charged batteries
(single fill, double fill, and fill and dump) resulting in
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significant variations in wastewater discharge flow rate. In
addition to the difference between wet and damp charged battery
formation, formation processes differ in the concentration of the
formation electrolyte and in the rate of charging. All of these
variations are observed to have an influence on wastewater
discharge from the formation process and from the plant as a
whole.
The formation of damp charged batteries concludes with dumping
the formation acid from the battery which is shipped empty.
Although no process wastewater is directly discharged from the
electrolyte dumping operations, the production of damp batteries
influences wastewater discharge in two ways. First, the practice
of dumping acid from the batteries increases the amount of acid
contamination of the outside of the battery case. This effect,
however, is also observed in double fill closed formation.
Second, since the batteries are shipped dry, electrolyte usage
on-site is significantly reduced. This reduces the amount of
water needed in acid cutting and therefore the potential amount
of process wastewater which may be used in battery acid cutting.
Closed formation may be accomplished using dilute electrolyte
which is subsequently dumped and replaced with more concentrated
acid for shipment with the battery. This double-fill process
allows maximum formation rates, but increases the extent of acid
contamination of battery cases. Battery wash requirements are
consequently increased as well. As an alternative, batteries may
be formed using acid which is sufficiently concentrated to be
shipped with the battery after formation has been completed.
This single fill battery formation process is widely used in
present practice, and is most amenable to wastewater discharge
reduction. No significant differences in product characteristics
between batteries formed by single fill and double fill
techniques are reported.
Open Formation - Open formation is performed by charging plates
in open tanks of electrolyte. These plates may then also be
assembled and placed into cases followed by filling the case with
electrolyte for shipping; this is open wet formation. Open
dehydrated formation requires rinsing and drying the charged
plates prior to assembly and shipping.
Both open wet and open dehydrated formations incur the same
potential sources of wastewater during formation: electrolyte
spills, area and equipment washdown, and electrolyte dumping.
Electrolyte spills can be reduced or avoided by careful filling;
this will also result in a reduced need for area washdown water.
As in closed formation, spill collection mechanisms can be
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instituted such as catch trays beneath the forming table which
direct the spills to a common collection tank.
As in closed formation, area washdown which is usually performed
with hoses can utilize treated wastewater. Equipment washdown
can also be performed with treated wastewater; one plant visited
performed both functions with treated wastewater.
Open formation electrolyte is dumped periodically after a
specified number of formation cycles are performed. Some plants
were observed to reuse this acid in wet battery filling and boost
charging which would eliminate the discharge.
In addition to the above sources of wastewater, dehydrated plate
formation generates"wastewater from plate rinsing and from plate
dehydrating. Some plants also rinse plates after open wet
formation, however, the flows from these rinsing operations are
substantially lower than flows from open dehydrated formation
plate rinsing. Thorough rinsing is required in open dehydrated
formation to remove residual sulfuric acid from the formed plates
and this operation characteristically produces a large volume of
wastewater. Water is used in dehydration of the plates either in
ejectors used to maintain a vacuum and enhance drying or in the
water seals of vacuum pumps used for the same purpose.
Plate rinse water is generally the major source of wastewater
from a lead battery plant making dehydrated batteries. This flow
can be reduced by the use of countercurrent cascade rinsing
techniques discussed earlier in this section. Currently, plants
vary widely in rinsing techniques, from single step continuous
flowing rinses to multiple stage countercurrent rinsing. Plate
rinse water use can be substantially reduced or even eliminated
by using treated wastewater as was done at one plant visited.
Wastewater from vacuum pump seals and ejectors used in
dehydrating formed plates for use in dry charged batteries also
may be extensively recycled. Since the level of contamination in
waste streams from this use is low, recycle may drastically
reduce the high volume discharges presently produced at some
facilities.
While rinsing and drying the plates is an indispensable part of
the formation process, plate dehydration can be accomplished
without the use. of ejector or vacuum pump seal water. Oven
drying without process water use for the dehydration of dry-
charged plates was observed, and approximately 85 percent of all
plants producing dehydrated plate batteries showed no wastewater
discharge from dehydration of the plates. Oxidation of negative
plates during the heat drying process may be controlled by the
395
-------
introduction of inert or reducing atmospheres into the drying
ovens, as observed at one site visited.
Plate Soaking - Plate soaking is an operation which is performed
after curing and prior to formation in order to enhance lead
oxide sulfation and to allow the heat of sulfation to be
dissipated before charging or formation is begun. This is
generally performed on thick battery plates approximately 0.25 cm
(0.10 inch) as opposed to thinner battery plates. Plates are
soaked in an open tank of acid which must be replaced
periodically. Discharges from this operation may include spills,
area hosedown, tank cleaning, and acid dumping.
As in open formation, careful loading and draining of the soaked
plates will minimize spills as well as the need for hosedown
water. Hosedown water and tank cleaning can be treated
wastewater, thus eliminating' any additional discharge. Acid
dumping to treatment should only occur when the product mix at
the plant will not allow its use in other products and after
extensive reuse.
Battery Washing and Rinsing - Battery washing is the water using
activity associated with preparation of the battery for shipping.
Battery washing may be performed using a detergent or using water
only. Battery washing using water only is performed primarily to
remove sulfuric acid spilled on the outside of the battery case
while washing (using a detergent) is used to remove acid, oil and
grease and other soil. Battery rinsing with water also has been
observed to be used as part of the forming operations (sometimes
referred to as product rinse) to remove the acid from immersing
or overfilling the battery or dumping electrolyte from the
battery. The wastewater from rinsing the batteries contains
acid, lead, and other contaminants from process conveyors, racks,
or floors over which the acidic water has contacted.
Reduction or elimination of the wastewater generated by battery
washing or rinsing may be accomplished by using manufacturing
processes which require less cleaning of the battery case, by
reducing the water used for washing or rinsing, and by reusing
some or all of the water used for washing or rinsing. Batteries
can be filled manually, automatically or semi-automatically with
vacuum type injection filling devices which fill the battery to
the correct level. Well operated injection filling methods do
not require immediate rinsing.
Immersion filling (immersing the batteries in a vat of
electrolyte) results in the battery case being heavily
contaminated with acid and requires rinsing. Immersion filling
is used by about one third of the visited plants and for all
396
-------
types of closed formation. Where double fill formation is used,
some plants use injection filling initially and immersion for the
second fill with a rinse associated only with the immersion fill.
Where immersion filling is performed twice, the batteries are
rinsed twice.
From site visits, about twice as many operations use an injection
filling method as opposed to immersion. All plants which have a
rinse associated with filling and formation use only water so as
not to contaminate the electrolyte with detergent when immersed.
The water from rinsing after filling, or topping off (an
additional filling step sometimes used to ensure the proper
electrolyte level), can be controlled and reused in other
manufacturing processes. Some plants with immersion filling do
not recycle the water at the rinsing station. This could be
achieved by installation of a small tank and some return piping
to the spray nozzles. Overflow is then collected in a holdup
tank until acid cutting operations are performed - usually about
once a week. This requires a tank and overhead piping to the
acid cutting area.
Samples taken at one site, demonstrated that most metal
concentrations were well below engineering specifications for
acid cutting water. Metals present at concentrations above
engineering specifications can be chemically removed or diluted
to suitable concentrations with fresh water. If the mechanisms
discussed below for minimizing water use in rinsing are
implemented, all of the diluted rinse water can be reused in acid
cutting. In the case of rinsing after filling, continuous makeup
of water to the rinse cycle serves to only dilute the electrolyte
being rinsed off. Therefore, for rinsing operations in the
formation area the overflow should be suitable for acid cutting.
The required holdup period of about a week would also provide
plant personnel time to assay the chemical species of concern in
two collected rinse waters prior to using each batch of water for
acid cutting.
The primary mechanisms for minimizing water use in rinsing are:
(1) Use of a switching device (mechanical or electronic) to
stop the flow of water to the spray nozzles when
batteries are not actually being rinsed. This practice
was observed at several plants visited.
(2) Use of the appropriate types of spray nozzles to
properly disperse the rinse water.
(3) Use of recycle at the rinse stations and overflow to a
collection tank for water reuse.
397
-------
Some plants were found to run water continuously through spray
nozzles and some do not use spray nozzles. One plant discharges
rinse water to the on-site wastewater treatment system after the
volume necessary for acid cutting is fulfilled. This plant did
not employ a recycle mechanism and used an excessive amount of
water for rinsing.
The mechanisms for r'ecycle, segregation, and reuse of battery
rinse water as a finishing step are .the same as those described
above for battery rinsing after filling operations. Usually
smaller battery products, such as SLI batteries are washed
automatically in a conveyor spray mechanism. Industrial and
specialty batteries are generally hosed down by hand prior to
finishing since they are produced in smaller numbers than the SLI
batteries. Water recirculation and reuse can be instituted in
hand washing or using stations similarly to those described for
automatic or machine washing.
Five visited plants use detergent wash systems with automatic
spray washers. Some washing lines comprise an initial water
rinse to remove acid, then a detergent wash, and a final water
rinse; others do not include the initial water rinse.
Segregation and reuse of initial battery rinse water is feasible
for the automatic detergent washer system. This can be done
using recycle and collection systems for routing the water to
acid cutting. Water contaminated with detergent has been
reported by lead battery manufacturers to be unsuitable for
process-related reuse. Water use can be minimized, however, by
using the final rinse as makeup to the detergent portion of the
system.
Some lead battery manufacturing operations do not use battery
washing or rinsing procedures. This largely stems from two
conditions! (1) the plant utilizes extensive contact cooling
during closed forming operations which acts as a rinsing
operation, or (2) dehydrated batteries are produced. Some plants
use dry battery production techniques and still maintain a
washing operation.
Floorwash - Floor washing procedures include the use of hoses for
general area washdown, buckets and mops for miscellaneous
cleanup, and power (vacuum) scrubbers for general plant floor
area cleanup.
To achieve minimization of floor wash pollutant discharge the
following measures can be taken:
398
-------
(1) settle power scrubber solids prior to treatment; this
water has been assayed to contain high concentrations
of suspended lead
(2) dry vacuum major dry spills such as in the leady oxide
production area, or pasting area. This has been
observed during one site visit
(3) use treated wastewater in hoses for general washdown
Wet Air Pollution Control - Wet air pollution control (WAPC)
devices are reported to be used in lead battery plants to varying
degrees in the following process activities: leady oxide
production, grid manufacture, pasting, formation, battery
assembly, battery washing, boost charging, acid mixing, painting
(of cases) and laboratories.
The scrubbers reported for battery washing and acid mixing are at
sites associated with one Corporation and are now used as static
demisters without use of or generation of water. The site using
a boost charging scrubber utilizes recycle of coalescer-demister
washdown water with caustic addition, incurring infrequent low
volume blowdown to treatment. No information is available
concerning the paint fume scrubber.
Two types of scrubbers were identified being used in lead battery
manufacturing plants. These are; (1) a static vessel of scrubber
water, or internally recirculated water, through which fumes are
sparged and (2) an acid mist or fume coalescer with intermittent
washdown. The static vessel design typifies leady oxide
production, grid manufacture, battery assembly, and pasting
applications; the latter design typifies formation area air
scrubbing.
The static and internally recirculated designs are from two
different manufacturers but both result in the same effective
wastewater generation rates and blowdown requirements. The
static design uses an induced draft system to pull the fumes to
be controlled into a vessel of water. Submerged baffles direct
the air stream through the water layer and subsequently to the
atmosphere via a demister. No overflow is usually required and
makeup is needed for water lost by evaporation and entrainment in
the air stream. Some plants, however, steadily drain the tank
while adding fresh makeup water. ,
The internal recirculation design reported recirculation. of the
scrubbing water through a set of baffles above the water layer to
impinge particulates and absorb acid fumes. As with the static
design, a demister removes most or all of the entrained water,
399
-------
requiring little makeup. Also, in current practice, these tanks
are sometimes steadily drained and fresh water is added.
The primary function of these static and internal recirculation
scrubber designs is to remove acid mists and to collect
particulates. They are used on ball mills, lead melting pots,
and paste mixers and collect lead particles which can be
reclaimed. The predominate use of WAPC for paste mixing in the
lead subcategory is as a precaution to avoid corrosion due to the
possibility of acid in the paste mixing fumes.
Baghouses have been observed in use on ball mills, Barton
process, paste mixers, and lead melt pots. When they can be
used, they preclude the generation of wastewater. Baghouses are
observed on paste mixing in order to recover and reuse lead dust.
Acid in fumes from paste mixing and application does not appear,
probably because of the neutralizing effect of lead oxides.
In summary, there are several ways to minimize water flow from
static, batch WAPC scrubbers:
(1) Use of baghouses which is demonstrated in leady oxide
production, pasting, and casting.
(2) Use an alkali to periodically adjust the pH in the tank
to avoid equipment corrosion. This eliminates the need
for continuous blowdown and allows batch dumping semi-
annually.
(3) Use an external recycle system with a settling tank to
collect bulk residuals which accumulate. This would
still allow batch dumping of the stream water semi-
annually.
One particular scrubber design is typically used in the formation
area by lead subcategory plants. All major corporation plants
which reported the use of a wet scrubber reported this type and
no other type was reported at all.
In this type of scrubber, sulfuric acid fumes are scrubbed by two
mechanisms. In the first mechanism, the centrifugal action of a
fan removes about 60 percent of the sulfuric acid in the incoming
air stream. In the second mechanism, the air passes through a
mesh arrangement where the remaining acid fumes coalesce. The
overall sulfuric acid removal efficiency is above 98 percent.
The vendor of this system indicated that the scrubber should be
operated dry with intermittent washdown of the mesh when
scrubbing sulfuric acid fumes. The vendor also indicated that at
some battery sites, a fine water spray is used in the fan section
400
-------
of the scrubber. The vendor indicated that this water spray is
unnecessary when scrubbing sulfuric acid fumes. Sulfuric acid
has a high molecular weight, consequently, the centrifugal action
of the fan is sufficient to separate the sulfuric acid from the
low molecular weight air stream. The water spray stream is
unnecessary.
The sites reporting data vary in how mesh washdown water is
handled, plus some sites report no washdown at all. This
difference is believed to result entirely from the manner in
which the mesh washdown is handled. Current washdown practice is
largely represented by the use of once-through discharge designs.
According to vendor-specified washdown techniques, a plant can
recycle this water, with or without the use of an alkali, and
maintain a minimum blowdown rate without resulting in equipment
corrosion. The use of an alkali addition was reported to reduce
the necessary blowdown rate by a factor of 100.
Based on observed and reported design and operating practices,
the following alternative flow minimization techniques can be
used with this type of scrubbing system:
(1) Do not use a water spray, as this practice is not
necessary when scrubbing sulfuric acid fumes.
(2) Do not use a washdown, as some plants report only the
use of the mesh to impinge and coalesce acid droplets
resulting in negligible flow.
(3) Use external recirculation with no caustic addition,
and use the blow down in acid cutting, plate rinsing or
other processes.
(4) Use external recirculation with alkali addition to
control pH and use the minimum required blowdown rate.
Virtually all plants use laboratories for quality control checks.
Part of the laboratory equipment is a hood for ventilation during
certain tests which generate .lead dust or fumes. At two sites
WAPC scrubbers were observed being used to control emissions from
these hoods. These scrubbers are operated intermittently in
conjunction with the hood operation. One plant operates a
recirculating scrubber which incurs an intermittent overflow from
the recirculation tank to treatment as a result of fresh water
addition. The other plant operates the scrubber in a once-
through mode. Flow minimization for laboratory scrubbers
comprises operation of the scrubber (i.e., water flow) only when
the hood is operated.
401
-------
Truck Wash - Trailers are used for hauling finished batteries to
distribution, batteries to repair facilities and for other non-
secondary lead related activities. These trailers are sometimes
washed down on-site. A mechanism for reducing overall water use
is to conduct the washdown procedure in two phases: the first
phase would use treated wastewater to remove contamination, and
the second phase would use fresh water to avoid any dissolved
salt buildup.
Lead Subcateqory Other Iji-Process Control Techniques
Material Recovery - The recovery of particulate lead oxide from
paste preparation and application wastes is a common practice at
lead subcategory plants which reduces both wastewater pollutant
loads and the mass of solid waste requiring disposal. This
material is generally recovered by settling from the equipment
and area wash water as a part of treatment of this stream for
recycle. Approximately 30 percent of lead subcategory plants
reuse the settled solids directly in paste formulation.
Plant Maintenance and Good Housekeeping - At lead subcategory
plants, maintenance and housekeeping practices are of great
importance for the implementation of the other in-process control
measures which have been previously discussed. Recycle and reuse
are especially dependent on the exclusion of contaminants from
the process water streams. In addition, effective plant
maintenance and housekeeping practices may reduce or eliminate
some process wastewater sources. Plant maintenance practices,
such as (1) epoxy coating of racks and equipment which contact
process wastewater and (2) containment of the wastewater to
minimize such contact, reduce the extent of contamination with
materials inimical to further use of the water. In addition,
these measures minimize corrosion by the acidic wastewater and
extend the useful life of production equipment.
Both lead and sulfuric acid are hazardous materials which must be
controlled in the work place, At\some plants, large quantities
of water are used and wastewater 'discharged in washing down
production areas to control workers exposure to these materials.
This water use may be substantially reduced or eliminated by the
application of plant maintenance and housekeeping practices to
reduce spillage and loss of these materials and by the use of dry
or water efficient cleanup techniques.
Control of lead dust within the plant also represents a
significant water use at some plants where production floor areas
are washed down with hoses or other similarly inefficient
techniques. The use of proper material handling techniques to
minimize the dust problem and dry clean-up or water efficient
402
-------
cleanup techniques can reduce or eliminate the volume of
discharge from this source. Examples of water efficient cleanup
techniques include floor wash machines and bucket and mop floor
washing.
Equipment maintenance may also contribute significantly to
wastewater discharge reduction. At one plant, a leaking cooling
jacket on a ball mill resulted in contamination of non-contact
cooling water with lead creating an additional process wastewater
discharge. In addition, leaks in pumps and piping used to handle
electrolyte are likely because of the corrosive nature of
sulfuric acid and may constitute a source of pollutant discharge
and necessitate the use of water for washing down affected areas.
Proper maintenance of this equipment can minimize discharge from
this source.
403
-------
TABLE VII-1
pH CONTROL EFFECT ON METALS REMOVAL
pH Range
(mg/1)
TSS
Copper
Zinc
Day 1
In
2.4-3.4
39
312
250
Out
8.5-8.7
8
0.22
0.31
Day
In
1 .0-3.0
16
120
. 32.5
2
Out
5.0-6.0
19
5.12
25.0
Day
In
2.0-5.0
16
107
43.8
3
Out
6.5-8.1
7
0.66
0.66
TABLE VI 1-2
EFFECTIVENESS
pH Range
(mg/1)
Cr
Cu
Fe
Pb
Mn
Ni
Zn
TSS
Day 1
In
2.1-2.9
0.097
0.063
9.24
1 .0
0.11
0.077
.054
1
OF SODIUM
Out
9.0-9.3
0.0
0.018
0.76
0.11
0.06
0.011
0.0
3
HYDROXIDE
Day
In
2.0-2.4
0.057 ,
0.078
15.5
1 .36
0.12
0.036
0.12
FOR METALS
2
Out
8.7-9. 1
0.005
0.014
0.92
0.13
0.044
0.009
0.0
11
REMOVAL
Day
In
2.0-2.4
0.068
0.053
9.41
1 .45
0.11
0.069
0. 19
3
Out
8.6-9.1
0.005
0.019
0.95
0.11
0.044
0.011
0.037
1 1
404
-------
TABLE VI1-3 , '
EFFECTIVENESS OF LIME AND SODIUM HYDROXIDE FOR METALS REMOVAL
Day
In
pH Range 9.2-9,6
(mg/1)
Al 37.3
Co 3.92
Cu 0.65
Fe 137
Mn 175
Ni 6.86
Se 28.6
Ti 143
Zn 18.5
TSS 4390
THEORETICAL
OF
Metal
Cadmium (Cd++)
Chromium (Cr-*-**)
Cobalt (Co++)
Copper (Cu**)
Iron (Fe++)
Lead (Pb++)
Manganese (Mn++)
Mercury (Hg++)
Nickel (Ni++)
Silver (Ag+)
Tin
-------
TABLE VII-5
SAMPLING DATA FROM SULFIDE
PRECIPITATION-SEDIMENTATION SYSTEMS
Treatment
Lime, FeS, Poly-
electrolyte,
Settle, Filter
Lime, FeS, Poly-
electrolyte,
Settle, Filter
NaOH, Ferric
Chloride, Na2S
Clarify (1 stage)
pH
(mg/1
Cr+6
Cr
Cu
Fe
Ni
Zn
These
In Out
5.0-6.8 8-9
)
25.6 <0.014
32.3 <0.04
0.52 0.10
39.5 <0.07
data were obtained from
Summary Report, Control
Metal Finishing Industry:
In Out
7.7 7.38
0.022 <0.020
2.4 <0.1
108 0.6
0.68 <0.1
33.9 '0.01
three sources:
In Out
11.45 <.005
18.35 <.005
0.029 0.003
0.060 0.009
and Treatment Technology for the
Sulfide Precipitation,
USEPA, EPA
No. 625/8/80-003, 1979.
Industrial Finishing, Vol. 35, No. 11, November, 1979.
Electroplating sampling data from plant 27045.
406
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TABLE VII-6
SULFIDE PRECIPITATION-SEDIMENTATION PERFORMANCE
Parameter Treated Effluent
Cmg/1)
Cd 0.01
Cr (T) 0.05
Cu 0.05
Pb 0.01
Hg 0.03
Ni 0.05
Ag 0.05
Zn 0.01
Table VI1-6 is based on two reports:
Summary Report, Control and Treatment Technology for the
Metal Finishing Industry; Sulfi.de Precipitation, USEPA, EPA
No. 625/8/80-003, 1979.
Addendum to Development Document for Effluent Limitations
Guidelines and New Source Performance Standards, Major
Inorganic Products Segment of Inorganics Point Source
Category, USEPA., EPA Contract No. EPA-68-01-3281 (Task 7),
June, 1978.
407
-------
Table VI1-7
FERRITE CO-PRECIPITATION PERFORMANCE
Metal Influent(mg/l) Effluent(mg/1)
Mercury 7.4 0,001
Cadmium 240 0,008
Copper 10 0.010
Zinc 18 0.016
Chromium 10 <0.010
Manganese 12 0.007
Nickel 1,000 0.200
Iron 600 0.06
Bismuth 240 0.100
Lead 475 0.010
NOTE; These data are froms
Sources and Treatment of Wastewater in the Nonferrous
Metals Industry, USEPA, EPA No. 600/2-80-074, 1980.
TABLE VI1-8
CONCENTRATION OF TOTAL CYANIDE
Plant
1057
33056
12052
Mean
Method
FeS04
FeS04
ZnSO4
(mg/1)
In
2.57
2.42
3.28
0, 14
0.16
0.46
0. 12
Out
0.024
0.015
0.032
0.09
0.09
0.14
0.06
0.07
408
-------
Plant ID »
06097
13924
18538
30172
36048
mean
Table VI1-9
MULTIMEDIA FILTER PERFORMANCE
TSS EffluentConcentration, mg/1
0.
1 .
3.
1 .
1 .
2.
2.
0,
8,
o,
0
4,
1,
61
0.
2.
2.
7.
2.
o,
2,
o,
o,
6,
0.
5.
5.
1 .
1 .
5
6, 4.0, 4.0, 3.0, 2.
6, 3.6, 2.4, 3.4
0
5
2, 2.8
TABLE VII-10
PERFOEMANCE OF SELECTED SETTLING SYSTEMS
PLANT ID
01057
09025
11058
12075
19019
33617
40063
44062
46050
SETTLING
DEVICE
Lagoon
Clarifier &
Settling
Ponds
Clarifier
Settling
Pond
Settling
Tank
Clarifier &
Lagoon
Clarifier
Clarifier
Settling
Tank
SUSPENDED SOLIDS CONCENTRATION (mg/1)
Day 1
In
54
1100
451
284
170
-
4390
182
295
Out
6
9
17
6
1
—
9
13
10
Day
In
56
1900
—
242
50
1662
3595
118
42
2
Out
6
12
—
10
1
16
12
14
10
Day 3
In
50
1620
—
502
-
1298
2805
174
153
Out
5
5
—
14
-
4
13
23
8
409
-------
Table VII-11
SKIMMING PERFORMANCE
Oil & Grease
mg/1
Plant Skimmer-Type In Out
06058 API 224,669 17.9
06058 Belt 19.4 8.3
410
-------
TABLE VII-12
SELECTED PARITION COEFFICIENTS
Log Octanol/Water
Priority Pollutant Partition Coefficient
1 Acenaphthene 4.33
11 1,1,1-Trichloroethane 2.17
13 1,1-Dichloroethane 1.79
15 1,1,2,2-Tetrachloroethane 2.56
18 Bis(2-chloroethyl)ether 1.58
23 Chloroform 1.97
29 1,1-Dichloroethylene 1.48
39 Fluoranthene 5.33
44 Methylene chloride 1.25
64 Pentachlorophenol 5.01
66 Bis(2-ethylhexyl)
phthalate 8.73
67 Butyl benzyl phthalate 5.80
68 Di-n-butyl phthalate 5.20
72 Benzo( a) anthracene 5.61.
73 Benzo(a)pyrene 6.04
74 3,4-benzofluoranthene 6.57
75 Benzo(k)fluoranthene 6.84
76 Chrysene 5.61
77 Acenaphthylene 4.07
78 Anthracene 4.45
79 BenzoCghi)perylene 7.23
80 Fluorene 4.18
81 Phenanthrene 4.46
82 Dibenzo(a,h)anthracene 5.97
83 Indeno(1,2,3,cd)pyrene 7.66
84 Pyrene 5.32
85 Tetrachloroethylene 2.88
86 Toluene 2.69
411
-------
TABLE VI1-13
TRACE ORGANIC REMOVAL BY SKIMMING'
API PLUS BELT SKIMMERS
(From Plant 06058)
Inf.
mg/1
Oil & Grease 225,000 14.6
Chloroform 0.023 0.007
Methylene Chloride 0.013 0.012
Naphthalene 2.31 0.004
N-nitrosodiphenylamine 59.0 0.182
Bis-2-ethylhexyl phthalate 11.0 0.027
Diethyl phthalate
Butylbenzyl phthalate 0%005 0.002
Di-n-octyl phthalate 0.'019 0.002
Anthracene - phenanthrene 16.4 0.014
Toluene 0.02 0.012
Table VII-14
COMBINED METALS DATA EFFLUENT VALUES (mg/1)
One Day 10 Day Avg. 30 Day Avg,
Mean Max. Max. Max.
Cd 0.079 0.34 0.15 0.13
Cr 0.084 0.44 0.18 0.12
Cu 0.58 1.90 1.00- 0.73
Pb 0.12 0.42 0.20 0.16
Ni 0.74 1.92 1.27 1.00
Zn 0.33 1.46 0.61 0.45
Fe 0.41 1.20 0.61 0.50
Mn 0.16 0.68 0.29 0.21
TSS 12.0 41.0 19.5 15.5
412
-------
TABLE VII-15
L&S PERFORMANCE
ADDITIONAL POLLUTANTS
Pollutant Average Performance (mg/1)
Sb 0.7
As 0.51
Be 0.30
Eg 0.06
Se 0.30
Ag 0.10
Tl 0.50
Al 2.24
Co 0.05
F 14.5
TABLE VII-16
'COMBINED METALS DATA SET - UNTREATED WASTEWATER
Pollutant Min. Cone (rnq/1) Max. Cone. (mg/1)
Cd <0.1 3.83
Cr <0.1 116
Cu <0.1 108
Pb <0.1 29.2
Ni <0.1 27.5
Zn <0.1 337.
Fe <0.1 263
Mn <0.1 5.98
TSS 4.6 4390
413
-------
TABLE VII-17
MAXIMUM POLLUTANT LEVEL IN UNTREATED WASTEWATER
ADDITIONAL POLLUTANTS
(mg/1)
Pollutant As & Se Be Ag F Sb
Sb
As
Be
Cd
Cr
Cu
Pb
Ni
Ag
Zn
F
Fe
O&G
TSS
4
<0
0
33
6
3
16
352
.2
.1
.18
.2
.5
_
-
,62
_
—
.9
10.24
—
8.60
1 .24
0.35
_
-
0.12
_
646
_
796
-
<0.1
0.23
110.5
11 .4
100
4.7
1512
_
—
'16
587.8
_
<0.1
22.8
2.2
5.35
0.69
_
<0.1
760
—
2.8
5.6
8.5
0.024
0.83
_
0.41
76.0
_
_
0.53
_
—
_
134
414
-------
TABLE VII-18
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant A
Parameters
No Pts.
Range mg/1
For 1979-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
47
12
47
47
0.015
0.01
0.08
0.08
0.13
0.03
0.64
0.53
For 1978-Tireated Wastewater
Cr
Cu
Ni
Zn
Fe ..
Raw Waste
Cr
Cu
Ni
Zn
Fe
47
28
47
47
21
5
5
5
5
5
0.01
0.005
0.10
0.08
0.26
32.0
0.08
1 .£5
33.2
10.0
- 0.07
- 0.055
- 0.92
- 2.35
-1.1
- 72.0
- 0.45
- 20.0
- 32.0
-95.0
Mean +_
std. dev.
0.045 +0.029
0.019 +0.006
0.22 +0.13
0.17 +0.09
0.06 +_0.10
0.016 +0.010
0.20 +0.14
0.23 +_0.34
0.49 +0.18
Mean + 2
std. dev,
0.10
0.03
0.48
0.35
0.26
0.04
0.48
0.91
0.85
415
-------
TABLE VI1-19
>> • :
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant B
Parameters
For 1
For 1
Total
•
No Pts.
Range mq/1
Mean +_
std. dev.
Mean + 2
std. dev.
979-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
TSS
175
176
175
175
174
2
0.0
0.0
0.01
0.01
0.01.
1 .00
- 0.
- 0.
- 1 .
- 0.
- 2.
- 1 .
40
22
49
66
40
00
0.
0.
0.
0.
0.
068
024
219
054
303
+ 0.
+ 0.
+ 0.
+ 0.
+ 0.
075
021
234
064
398
0.
0.
0.
0.
1 .
22
07
69
18
10
978-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
1974-1
Cr
Cu
Ni
Zn
Fe
144
143
143
131
144 .
979-Treated
1288
1290
1287
1273
1287
0.0
0.0
0.0
0.0
0.0
- 0.
- 0.
- 1 .
- 0.
- 1 .
70
23
03
24
76
0.
0.
0.
0.
0.
059
017
147
037
200
+ 0.
+ 0.
+ 0.
+ 0.
+ 0.
088
020
142
034
223
0.
0.
0.
' 0.
0.
24
06
43
1 1
47
Wastewater
0.0
0.0
0.0 .
0.0
0.0
- 0.
- 0.
- 1 .
- 0.
- 3.
56
23
88
66
15
0.
0.
0.
0.
0.
038
on
184
035
402
+ 0.
+ 0.
+ 0.
+ 0.
+ 0.
055
016
211
045
509
0.
0.
0.
0.
1 .
15
04
60
13
42
Raw Waste
Cr
Cu
Ni
Zn
Fe
TSS
3
3
3
2
'3
2 1
2.80
0.09
1 .61
2.35
3.13
77
— 9
- o!
- 4.
- 3.
-35.
-466.
15
27
89
39
9
5.
0.
3.
22.
90
17
33
4
416
-------
TABLE VII-20
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant C
For Treated Wastewater
Parameters No Pts.
For Treated Wastewater
Cd
Zn
TSS
pH
103
103
103
103
For Untreated Wastewater
Cd
Zn
Fe
TSS
pH
103
103
3
103
103
Range mq/1
Mean +_
std. dev.
0.010 - 0.500 0.049 ±0.049
0.039 - 0.899 0.290- +0.131
0.100 - 5.00 1 .244 +.1 .043
7.1 - 7.9 9.2*
Mean + 2
std. dev.
0.147
0.552
3.33
0.039 - 2.319
0.949 -29.8
0.107 - 0.46
0.80 -19.6 .
6.8
- 8.2
0.542 +0.381
11.009 +6.933
0.255
5.616 +.2.896
7.6*
1 .304
24.956
11.408
* pH value is median of 103 values.
417
-------
TABLE VII-21
SUMMARY OF TREATMENT EFFECTIVENESS (mg/1)
Pollutant
Parameter
•114
115
117
1 18
119
120
£ 121
00 122
123
124
125
126
127,
128
Sb
As
Be
Cd
Cr
Cu
CN
Pb
Hg
Ni
Se
Ag
Tl
Zn
Al
Co
F
Fe
Mn
P
O&G
TSS
Mean
0.70
0.51
0.30
0.079
0.084
0.58
0.07
0.12
0.06
0.74
0.30
0.10
0.50
0.33
2.24
0.05
14.5
0.41
0.16
4.08
12.0
L & S
Technology
System
One
Day
Max.
2.87
2.09
1.23
0.34
0.44
1.90
0.29
0.42
0.25
1.92
1.23
0,41
2.05
,1.46
6.43
0.21
59.5
1.20
0.68
16.7
20.0
41.0
Ten
Day
Avg.
1.28
0.86
0.51
0.15
0.18
1.00
.0.12
0.20
0.10
1.27
0.55
0.17
0.84
0.61
3.20
0.09
26.4
0.61
0.29
6.83
12.0
19.5
Thirty
Day
Avg.
1.14
0.83
0.4.9
0.13
0.12
0.73
0.11
0.16
0.10
1.00
0.49
0.16
0.81
0.45
2.52
0.08
23.5
0.50
0.21
6.60
10.0
15.5
Mean
0.47
0.34
0.20
0.049
0.07
0.39
0.047
0.08
0.036
0.22
0.20
0.07
0.34
0.23
1.49
0.034
0.28
0.14
2.72
2.6
LS&F
Technology
System
One
Day
Max.
1.93
1.39
0,82
0.20
0.37
1.28
0.20
0.28
0.15
0.55
0.82
0.29
1.40
1.02
6.11
0. 14
59.5
1.20
0.30
11.2
10.0
15.0
Ten
Day
Avg.
0.86
0.57
0.34
0.08
0.15
0.61
0.08
0.13
0.06
0.37
0.37
0.12
0.57
0.42
2.71
0.07
26.4
0.61
0.23-
4.6
10.0
12.0
Thirty
Day
Avg.
0.76
0.55
0.32
0.08
0.10
0.49
0.08
0.11
0.06
0.29
0.33
0.10
0.55
0.31
2.41
0.06
23.5
0.50
0.19
4.4
10.0
10.0
Sulfide
Precipitation
Filtration
One
Day
Mean Max.
0.01 0.04
0.08 0.21
0.05 0.21
0.01 0.04
0.03 0.13
0.05 0.21
0.05 0.21
0.01 0.04
Ten
Day
Avg.
0.018
0.091
0.091
0.018
0.0555
0.091
0.091
0.018
Thirty
Day
Avg.
0.016
0.081
0.081
0.016
0.049
0.081
0.081
0.016
-------
TABLE VII-22
TREJkTABIIiITY SATING OP PRIORIW POLLUTANTS
UTILIZING CARBON ABSORPTION
Priority Pollutant
1.
2 .
3 •
4.
5 .
6.
7 .
8.
9.
10.
11.
12.
13.
14.
IS.
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 .
acenaphthane
° acrolain
aerylonitrile
ben.tnna .
benzidin*
carlson totrachlorido
{ tattrachloronethane)
chlorobenzone
1,2,3-trichlorotxmran*
ha>uichlorobenz«n«
l,2~dichloroethan«
1,1,1-trichloroathane
haxnchloroothana
1,1-dichloroethane
1,1,2-trichloroethana
1, 1,2, 2 -tetrachlor ethane
chloro«than«
bi*(chloroiuthyl) athar
bi«(2-chloroethyl) «th«r
2-chloroatJjylvinyl ethar
2-chloronaphthalane
2,4,6-trichlorophenol
parachloroa»ta ora*ol
chloroform (trichloronathane)
2-chlorophonol
1,2-dichlorobenzane
1,3-diehlorobanzafia
1 , 4-dichlorobenzma
3,3'-dichlorobenzidin«
l»l-dichloro»thyl«na
1 , 2 -trans-dichloroethy lona
2,4-dichlorophenol
1,2-dichloropropane
l,2-dichloropropylan«
(1, 3™dlclitoropi:op«n0 )
2,4-dimathylphenol
2,4-dinitrotoluen*
2 , 6- dinitr oto luono
1,2-diphenylhydraiine
etiiylbanzena
f luorenthona
4-chlorophanyl phony 1 achar
4-bromophenyl phanyl athar
bis (2-chloroisopropyl lather
bia(2-chloro«thojcy)«eth«ii«
aBth'/Lana chloridn
( dichloromathane )
machyl chlorida ( chlorcxnathane)
mathyl bromida ( bromome than* )
broaoform ( tr ibromooujthane )
dlchlorobroraotaathana
•Removal
sating
H
L
L
H
H
M
H
H
R
H
M
H
M
H
H
L
M
I,
R
H
a
L
H
R
R
R
H
L
L
H
R
H
R
R
M
H
H
H
II
M
L
L
' L
R
Priority Pollutant
49. triohlorofluoromathana
50. dichlorodifluoronethana
51* chlorodibromomathana
52. hexachlorobueadiena
53. hexachlorocyclopantadlana
54. iaophorona
55. naphthalan«
56. nitrobenzena
57. 2-nitrophanol
58. 4-nitroph*nol
59. 2,4-dlnitrophenol
SO. 4,6-dinitro-o-craaol
61. H-nitrosodimathylamina
62. N-nitroaodiphanylamina
63. H-nitro«odi-n-propylamina
64. pantachlorophanol
65. phenol
66. bis(2-«thylh«xyl)phthal«ta
67. butyl bsniyl phthalat*
68. di-n-butyl phthalata
69. di-n-octyl phthalata
70. dlathyl phthalat*
71. diawthyl phthalata
72. 1,2-banzjuithracena
(ban10(a)anthxacana)
73. b«nzo(a)pyr«n« [3,4-benro-
pyrana)
74. 3,4-banzofluoranthan*
(banzo < b)fluoranthana)
75. 11,12-benzofluoranthena
(b«nro(k)fluoranthan*)
76. chrysana
77. acanaphthylena
78. anthracana
79. l,12-benzop«rylena (b«nro
(ghl)—peryiane)
80. fluorena
81. phanar.threne
82. 1,2,3,5-dibanianthraceno
(dibenzo(a,h) anthracana)
83. indeno (1,2,3-cd) pyrena
(2,3-ej-phanylano pyrena)
84. pyrana
85. tetraehloroathylena
86. toluene
87. trichloroethylena
88. vinyl chlorida
(chloroethylane)
106, PCS-1242 (Aroclor 1242)
107. PCB-12S4 (Aroclor 1254)
108. PCB-1221 (Aroclor 1221)
109. PCB-1332 (Aroclor 1232)
110. PCB-1248 (Aroclor 1248)
111. PCB-1260 (Aroclor 1260)
112. PCB-L016 (Aroclor 1016)
•Noto Sxplanatlon of Removal Ratings
Category H (high' ranoval)
adsorbn at levels i 100 mg/q carbon at C» - 10 mg/1
adsorbs at levels > 100 mg/g carbon at C. < 1.0 ng/1
Category H (moderate removal)
adsorbs at levels i 100 mg/g carbon at C " 10 cng/1
adsorbs at levels £ 100 inj/ij carbon at c * 1.0 mg/1
Category L (low removal)
adsorbo it levels < 100 mg/f carbon at c. " 10 »
-------
TABLE VII - 23
CLASSES OF ORGANIC COMPOUNDS ADSORBED ON CARBON
Organic Chemical Class
Aromatic Hydrocarbons
Polynuclear Aromatics
Chlorinated Aromatics
Phenolics
Chorinated Phenolics
*High Molecular Weight Aliphatic and
Branch Chain hydrocarbons
Chlorinated Aliphatic hydrocarbons
*High Molecular Weight Aliphatic
Acids and Aram tic Acids
*High Molecular Weight Aliphatic
Amines and Aromatic Amines
*High Molecular Weight Ketones,
Esters, Ethers and Alcohols
Surfactants
Soluble Organic Dyes
Examples of Chemical Class
benzene, toluene, xylene
naphthalene, anthracene
biphenyls
chlorobenzene, polychlorinated
biphenyls, aldrin, endrin,
toxaphene, DDT
phenol, cresol, resorcenol
and polyphenyls
trichlorophenol, pentachloro-
phenol
gasoline, kerosine
carbon tetrachloride,
perchloroethylene
tar acids, benzoic acid
aniline, toluene diamine
hydroquinone, polyethylene
glycol
alkyl benzene sulfonates
nethylene blue, indigo carmine
* High Molecular Weight includes compounds in the broad range of from
4 to 20 carbon atoms
420
-------
Table VII-24
ACTIVATED CARBON PERFORMANCE (MERCURY)
Plant
A
B
C
Mercury levels - mg/1
in
28.0
0.36
0,008
Out
0.9
0.015
0.0005
Table VII-25
ION EXCHANGE PERFORMANCE
Parameter
Plant A
Prior To
Purifi-
All Values mg/1 cation
Al 5.6
Cd 5.7
Crt-3 3.1
Cr+6
Cu
CN
Au
Fe
Pb
Mn
Ni
Ag
S04
Sn
Zn
7
4
9
7
4
6
1
1
14
.1
.5
.8
_
.4
—
.4
.2
.5
_
.7
.8
After
Purifi-
cation
0.20
0.00
0.01
0
0
0
0
0
0
0
0
0
.01
.09
.04
_
.01
—
.00
.00
.00
_
.00
.40
Plant B
Prior To
Purifi-
cation
_
43.
3.
2.
-
1 .
_
1.
9.
210.
1.
-
0
40
30
70
60
10
00
10
After
Purifi-
cation
0
0
0
0
0
0
2
0
_
.10
.09
.10
-
.01
_
.01
.01
.00
.10
—
421
-------
Table VII-26
MEMBRANE FILTRATION SYSTEM EFFLUENT
Specific Manufacturers Plant 19066 Plant 31022 Predicted
Metal Guarantee I_n Out In Out Performance
Al
Cr, (+6)
Cr (T) 0.03 4.13 0.018 98.4 0.057 0.05
Cu 0.1 18.8 0.043 8.00 0.222 0.20
Manufacturers
Guarantee
0
0
0
0
0
0
0
0
0
-
.5
.02
.03
.1
.1
.05
.02
.1
.1
—
Plant
In
__
0.
4.
18.
288
0.
<0.
9.
2.
632
,_
46
13
8
652
005
56
09
19066
Out
m_ u
0.
0.
0.
0.
0.
<0.
0.
0.
0.
.
01
018
043
3
01
005
017
046
1
Plant
In
__
5.
98.
8.
21 .
0.
<0.
194
5.
13.
._
25
4
00
1
288
005
00
0
31022
Out
_
<0
0
0
0
0
<0
0
0
8
„
.005
.057
.222
.263
.01
.005
.352
.051
.0
Fe 0.1 288 0.3 21.1 0.263 0.30
Pb 0.05 0.652 0.01 0.288 0.01 0.05
CN 0.02 <0.005 <0.005 <0.005 <0.005 0.02
Ni 0.1 9.56 0.017 194 0.352 0.40
Zn 0.1 2.09 0.046 5.00 0.051 0.10
TSS 632 0.1 13.0 8.0 1.0
Table VII-27
PEAT ADSORPTION PERFORMANCE
Pollutant ^ri Out
(mg/1)
Cr+6 35,000 0.04
Cu 250 0.24
CN 36.0 0.7
Pb 20.0 0.025
Hg 1.0 0.02
Ni 2.5 0.07
Ag 1.0' 0.05
Sb 2.5 0.9
Zn 1.5 0.25
422
-------
Table VII-28
ULTRAFILTRATION PERFORMANCE
Parameter Feed (mq/1) Perme ate {mg/1)
Oil (freon extractable) 1230 4
COD 8920 148
TSS 1380 13
Total Solids 2900 296
423
-------
TABLE VII-29
PROCESS CONTROL TECHNOLOGIES IN USE AT BATTERY MANUFACTURE HANTS
WASTEWATER RECTCLE AND REUSE 1/
WATER USE REDUCTION
PROCESS MODIFICATION
COMBINED MULTI- FOIWATION
TREATED DRY AIR STAGE DRY ' BATTERY CONTACT IN CASE
EQUIPMENT WASTE POLLUTION COUNTER- PIAQUE WASH COOLING (EXCEPT DRY 4MAL-
EPA WASH & PASTE PROCESS SCRUBBER PIAQUE STREAMS CONTROL CURRENT SCRUB EUMI- ELIMI- LEAD SUB- GAMATION MATERIA
ID# FORMULATION SOLUTION RINSES WASTE SCRUBBING IN-PROCESS TECHNOLOGY RINSE TECHNIQUE NATION NATION CATEGORY PROCESS RECOVER
Lead Subcategory
-P-
Ni
-P-
X
*
*
*
X
*
X
X
X
*
X
*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
*
*
*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
. TABUS VII-29 (Continued)
PROCESS CONTROL TECHNOLOGIES IN USE AT BATTERY MANUFACTURE PLANTS
WASTEWATER RECTCLE AND REUSE I/
WATER USE REDUCTION
PROCESS MODIFICATION
EQUUMENT
EPA WASH & PASTE PROCESS
SCRUBBER PLAQUE
COMBINED
TREATED
WASTE
STREAMS
MULTI-
DRY AIR STAGE
POLLUTION COUNTER-
CONTROL CURRENT
ID* FORMULATION SOLUTION RINSES WASTE SCRUBBING IN-PROCESS TECHNOLOGY RINSE
FORMATION
DRY BATTERY CONTACT IN CASE
PIAQUE WASH COOLING (EXCEPT DRY AMAL-
SCRUB ELIMI- ELIMI- LEAD SUB- GAMATION MATERIAL
TECHNIQUE NATION NATION CATEGORY PROCESS RECOVERY
Lead Subcategory (Continued)
*
X
X
X
*
X
X
X
X
*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE VII-29 (Cbnttnued)
PROCESS CONTROL TECHNOLOGIES IN USE AT BATTERY MANUFACTURE PLANTS
WASTEWATER RECTCLE AND REUSE 1/
WATER USE REDUCTION
PROCESS MODIFICATION
EQUIPMENT
EPA WASH & PASTE
ID# PORMUIATION
PROCESS
SOLUTION RINSES
SCRUBBER
WASTE
PLAGUE
SCRUBBING
COMBINED
TREATED
WASTE
STREAMS
IN-PROCESS
DRY AIR
POLLUTION
CONTROL
TECHNOLOGY
MULTI-
STAGE
COUNTER-
CURRENT
RINSE
CRY
PLAQUE
SCRUB
TECHNIQUE
BATTERY CONTACT
WASH COOLING
ELMI- ELIMI-
NATION NATION
FOFMATION
IN CASE
(EXCEPT
LEAD SUB-
CATEGORY
CRY AMAL-
GAMATION
PROCESS
MATERIAL
RECOVERY
N>
Lead Subcategory (Concinued)
X X
X
X
X X
X
X
X
* X
* X
X
X X
*
X
X
X
X
X
*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
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427
-------
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428
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HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
CADMIUM
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HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
COPPER
(Number of observations = 18)
-------
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HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
LEAD
-------
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(Number of observations = 28)
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HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
IRON
-------
17 Values
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HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
MANGANESE
(Number of observations =*0)
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FIGURE VII-12
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
TSS
-------
SULFURIC SULFUR
ACID DIOXIDE
pH CONTROLLER
RAW WASTE "
(HEXAVALENT CHROMIUM)
00
r
ORP CONTROLLER
(TRIVALENT CHROMIUM)
LIME OR CAUSTIC
00
REACTION TANK
PRECIPITATION TANK
pH CONTROLLER
-TO CLARIFIER
(CHROMIUM
HYDROXIDE)
FIGURE VII-13. HEXAVALENT CHROMIUM REDUCTION WITH SULFUR DIOXIDE
-------
INFLUENT
EFFLUENT
STORED
BACKWASH
WATER
COLLECTION CHAMBER
DRAIN
FIGURE Vll-14. GRANULAR BED FILTRATION
440
-------
PERFORATED
BACKING PLATE
FABRIC
FILTER MEDIUM
\
SOLID
RECTANGULAR
END PLATE
INLET
SLUDGE
FABRIC
FILTER MEDIUM
ENTRAPPED SOLIDS
FILTERED LIQUID OUTLET
PLATES AND FRAMES ARE
PRESSED TOGETHER DURING
FJLTRATION CYCLE
RECTANGULAR
METAL PLATE
RECTANGULAR FRAME
FIGURE Vll-15. PRESSURE FILTRATION
441
-------
SEDIMENTATION BASIN
INLET, ZONE
INLET LIQUID
BAFFLES TO MAINTAIN
QUIESCENT CONDITIONS
SETTLING PARTICL|
* « TRAJECTORY « •
^» * * * """"*""^-jL.* TRAJECTORY « • §. S
OUTLET ZONE
OUTLET LIQUID
BELT-TYPE SOLIDS COLLECTION
MECHANISM
SETTLED PARTICLES COLLECTED
AND PERIODICALLY REMOVED
CIRCULAR CLAR1FIER
INLET LIQUID
CIRCULAR BAFFLE
SETTLING ZONE-
_j . ^ __ ..
INLET ZONE
* *
ANNULAR OVERFLOW WEIR
Tf^fHlL
REVOLVING COLLECTION
MECHANISM
\
OUTLET LIQUID
•SETTLING PARTICLES
SETTLED PARTICLES
COLLECTED AND PERIODICALLY
REMOVED
SLUDGE DRAWOFF
FIGURE VII-16. REPRESENTATIVE TYPES OF SEDIMENTATION
442
-------
FLANGE
WASTE WATER
WASH WATER
BACKWASH
SURFACE WASH
MANIFOLD
INFLUENT
DISTRIBUTOR
BACKWASH
REPLACEMENT CARBON
CARBON REMOVAL PORT
TREATED WATER
SUPPORT PLATE
FIGURE VIi -17. ACTIVATED CARBON ADSORPTION COLUMN
443
-------
CONVEYOR DRIVE ^ PRYING
ZONE
1—BOWL DRIVE
LIQUID
OUTLET
CONVEYOR BOWL REGULATING IMPELLER
CYCLOGEAR
FIGURE VII - 18, CENTRIFUGATION
444
-------
CAUSTIC
SODA
ui
CAUSTIC
SODA
PM
CONTROLLER
_J—I PM
——1 I CONTROLLER
TREATED
WASTE
REACTION TANK
REACTION TANK
FIGURE VII -19. TREATMENT OF CYANIDE WASTE BY ALKALINE CHLORINATfON
-------
CONTROLS
OZONE
GENERATOR
DRY AIR
D
OZONE
REACTION
TANK
RAW WASTE »v
-{x*
TREATED
WASTE
X
FIGURE VII - 20. TYPICAL OZONE PLANT FOR WASTE TREATMENT
446
-------
MIXER
FIF
ST
SE
ST
T!
WASTEWATER S1
FEED TANK
1 1
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— — TEMPERATURE
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-7— PH MONITORING
TEMPERATURE
CONTROL
— — PH MONITORING
— TEMPERATURE
— CONTROL
— — PH MONITORING
OZONE
OZONE
GENERATOR
FIGURE VII - 21, UV/OZONATION
447
-------
00
EXHAUST
WATER VAPOR
PACKED TOWER
EVAPORATOR
WASTEWATER
HEAT
EXCHANGER
•STEAM
STEAM
CONDENSATE
CONCENTRATE
ATMOSPHERIC EVAPORATOR
VACUUM LINE
«•"—
CONDENSATE
WASTEWATER
VACUUM
PUMP
STEAM
COOLING
WATER
STEAM
CONDENSER
EVAPORATOR
STEAM-
STEAM
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VAPOR-LIQUID |
~~~S. MIXTURE /SEPARATOR . ..1 ^
* t \ I WATER VAPOR 1
WASTEWATER
LIQUID
RETURN
WASTE
WATER-
FEED
CONCENTRATE
SUBMERGED TUBE EVAPORATOR
STEAM
CONDENSATE
COOLING
WATER
CONDENSATE
VACUUM PUMP
-CONCENTRATE
CLIMBING TILM EVAPORATOR
VAPOR
HOT VAPOR
STEAM
CONDENSATE
CONCENTRATE
COOLING
WATER
CONDEN-
SATE
CONDENSATE
1 VACUUM PUMP
^
•*- EXHAUST
ACCUMULATOR
CONDENSATE
FOR REUSE
CONCENTRATE FOR REUSE
DOUBLE-EFFECT EVAPORATOR
FIGURE VII-22. TYPES OF EVAPORATION EQUIPMENT
-------
OILY WATER
INFLUENT
WATER
DISCHARGE
OVERFLOW
SHUTOFF
VALVE
EXCESS
AIR OUT
LEVEL
CONTROLLER
TO SLUDGE
TANK •"
FIGURE VII-23. DISSOLVED AIR FLOTATION
449
-------
CONDUIT
TO MOTOR
INFLUENT
CONDUIT TO
OVERLOAD
ALARM
COUNTERFLOW
INFLUENT WELL
DRIVE UNIT
OVERLOAD ALARM
EFFLUENT WEIR
DIRECTION OF ROTATION
EFFLUENT PIPE
EFFLUENT CHANNEL
PLAN
TURNTABLE
BASE
HANDRAIL
INFLUENT
CENTER COLUMN
CENTER CAGE
WEIR
STILTS
CENTER SCRAPER
SQUEEGEE
SLUDGE PIPE
FIGURE VII-24. GRAVITY THICKENING
450
-------
WASTE WATER CONTAINING
DISSOLVED METALS OR
OTHER IONS
DIVERTER VALVE
RECENERANT
SOLUTION
DISTRIBUTOR
SUPPORT
REGENERANT TO REUSE,
TREATMENT, OR DISPOSAL
-DIVERTER VALVE
METAL-FREE WATER
FOR REUSE OR DISCHARGE
FIGURE VII - 25. ION EXCHANGE WITH REGENERATION
451
-------
MACROMOUECUt.es
AND SOLIDS
MOST
SALTS
MEMBRANE
450 PSil
WATER
PERMEATE fWATER)
MEMBRANE CROSS SECTrON,
IN TUBULAR, HOLLOW FIBER,
OR SPIRAL-WOUND CONFIGURATION
0 •.•<>• °
FEED
:•:•°.
_CONCENTRATE
IS ALTS)
O 0*0
o o
o,
O SALTS OR SOLIDS
* WATER MOLECULES
FIGURE VII-26. SIMPLIFIED REVERSE OSMOSIS SCHEMATIC
452
-------
PERMEATE
TUBE
PERMEATE
ADHESIVE BOUND
SPIRAL MODULE
CONCENTRATE
BACKING MATERIAL
•MESH SPACER
•MEMBRANE
SPIRAL MEMBRANE MODULE
POROUS SUPPORT TUBE
WITH MEMBRANE
• ".•* BRACKISH
° WATER
FEED FLOW
PRODUCT WATER
PERMEATE FLOW
BRINE
CONCENTRATE
FLOW
TUBULAR REVERSE OSMOSIS MODULE
"O" RING
SEAL
FEED ..
<==£>
OPEN ENDS
OF FIBERS
,— EPOXY
TUBE SHEET
POROUS
BACK-UP DISC
SNAP
RING
END PLATE
POROUS FEED
DISTRIBUTOR TUBE
PERMEATE
END PLATE
HOLLOW FIBER MODULE
FIGURE VII - 27. REVERSE OSMOSIS MEMBRANE CONFIGURATIONS
453
-------
t
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3-1N. COARSE SAND
3-IN. FINE GRAVEL
3-IN. MEDIUM GRAVEL
3 TO 6 IN. COARSE GRAVEL
2-1N. COARSE SAND
-Z-IN. PLANK
WALK
PIPE COLUMN FOR
CL, ASS-QVER
6-IN. UNDERDRAIN LAID
WITH OPEN JOINTS
SECTION A-A
FIGURE VII-28. SLUDGE DRYING BED
454
-------
ULTRAFIUTRATION
* •
• <
MACROMOLECULE3
F - 10-50 PS!
MEMBRANE
WATER SALTS
-MEMBRANE
PERMEATE
it
• # *
* *
o * ° * *
FEED *(-« * O • * • • « ,
* «
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o .. .
*. V* °*.o*.0
*•* * CONCENTR
O * •
_ v»«»»»_ O CONCENTRATE
- ° * «
O OIL PARTICLES
• DISSOLVED SALTS AND LOW-MOLECULAR-WEIGHT ORGANICS
FIGURE VII - 29. SIMPLIFIED ULTRAFILTRATION FLOW SCHEMATIC
455
-------
FABRIC OR WIRE
FILTER MEDIA
STRETCHED OVER
REVOLVING DRUM
DIRECTION OF ROTATION
ROLLER
SOLIDS SCRAPED
OFF FILTER MEDIA
STEEL
CYLINDRICAL
FRAME
VACUUM
SOURCE
LIQUID FORCE
THROUGH
MEDIA BY
MEANS OF
VACUUM
SOLIDS COLLECTION
HOPPER
INLET LIQUID
TO BE
FILTERED
-TROUGH
FILTERED LIQUID
FIGURE VU - 30. VACUUM FILTRATION
456
-------
SECTION VIII
COST OF WASTEWATER TREATMENT AND CONTROL
This section presents estimates of the costs of implementing the
major wastewater treatment and control technologies described in
Section VII. These cost estimates, together with the estimated
pollutant reduction performance for each treatment and control
option presented in Sections IX, X, XI, and XII, provide a basis
for evaluating the options presented and identification of the
best practicable technology currently available (BPT), best
available technology economically achievable (BAT), best
demonstrated technology (BDT), and the appropriate technology for
pretreatment. The cost estimates also provide the basis for
determining the probable economic impact on the battery
manufacturing lead subcategory of regulation at different
pollutant discharge levels. In addition, this section addresses
nonwater quality environmental impacts of wastewater treatment
and control alternatives, including air pollution, solid wastes,
and energy requirements.
GENERAL APPROACH *
Capital and annual costs associated with compliance with the lead
subcategory limitations and standards have been calculated on a
plant-by-plant basis for 85 discharging plants and extrapolated
for 26 discharging plants in the subcategory for which little or
no data were available.
These costs have been used as the basis for an economic impact
analysis of the lead subcategory (See "Economic Impact Analysis
of Effluent Limitations and Standards for the Battery
Manufacturing Industry," EPA 440/2-84-002). For that analysis
cost estimates were broken down for each facility producing lead
batteries and cost results were expressed in dollars per pound of
battery produced.
»
Prior to proposal, costs were generated using the cost estimation
methodology described in the development document of the proposed
regulation. Since proposal, a new computer model for estimating
end-of-pipe wastewater treatment system costs was developed for
this subcategory and several other point source categories with
similarly treatable wastewaters. In addition, in-plant costing
procedures were revised. -Capital and annual costs have been
recalculated for all plants in the lead subcategory using the new
computer model and the revised in-plant cost procedures. Table
VIII-1 (page 489) summarizes these costs for the lead
457
-------
subcategory. A comparison between the proposal costing
methodology and revised costing methodology is provided later in
this section.
COST ESTIMATION MODEL BASES
In this section, the end-of-pipe treatment system cost estimation
models are presented' for the lead subcategory. The assumptions
for the cost model and the in-plant cost procedure may be found
later in this section.
End-of-pipe compliance costs were estimated for each plant based
on the wastewater sources with discharge allowances. The
possible wastewater sources at each plant are double fill
formation, fill and dump formation, open dehydrated formation,
direct chill casting, mold release formulation equipment
washdown, battery wash with detergent, battery wash with water,
truck wash, laundry, battery repair, laboratory, floor wash,
handwash, respirator wash, and wet air pollution control
scrubbers. The last six streams were included in a miscellaneous
group, providing the entire flow of all six streams if any one
was present. Discharge allowances for plate soaking and open wet
formation were provided after costs for the lead subcategory were
determined. The flows from these areas are deminimus and do not
affect the cost estimates.
The treatment trains presented in Figure IX-1 and Figures X-l to
X-4 were used as the basis for cost estimation. Plant-by-plant
costs were determined for BPT and BAT (PSES) Options 1 and 2.
Costs for BAT Options 3 and 4 were determined for a normal plant
and a normal discharging plant. The normal and normal
discharging plant are discussed later in this section. As shown
in Figures X-l to X-4, a holding tank, used for recycling
wastewater back to the plant for use in hose washdown of
equipment and floor areas, is part of the BAT (PSES) treatment
train. Water is recycled after chemical precipitation and
settling. An additional option, option 5, was considered for new
sources only. The treatment train for this option is identical
to option 2.' For option 4 and option 5, the holding tank is also
used for recycling treated water for truck washing.
Compliance costs for chemical•precipitation were estimated using
costs for lime addition. Sludge produced through lime
precipitation is considered to be non-hazardous for the purposes
of estimating costs. However, sludge generated from sulfide
precipitation (normal plant only) is considered to be hazardous.
Miscellaneous wastewater has a smaller discharge allowance under
BAT than under BPT. The difference is taken into account by the
458
-------
holding tank, used to recycle water back to the plant for
miscellaneous use (hose washdown) under the BAT (PSES) Options.
Therefore, for the purposes of estimating compliance costs for
BAT, the chemical precipitation and settling units are sized on
the basis of the BPT flow with recycle occurring through the
holding tank after chemical precipitation and settling. The BAT
(PSES) flow is therefore equivalent to the final discharge flow
and, for BAT (PSES)-2, multimedia filtration is sized on the
basis of this flow. Since the flow into treatment for option 2
and the additional new source option (option 5) are nearly the
same and the treatment train is the same, costs for these two
options are equal. The only difference between options 2 and 5
is that the holding tank is also used to recycle water for truck
washing.
The following points should also be noted: (1) all of the costed
,plants were given an allowance for miscellaneous wastewater, and
(2) if the actual flow from a process at a plant was unknown,
costs were estimated on the basis of regulatory flow.
Required capital costs are determined by considering the
equipment and wastewater treatment system a plant currently has
in-place (see page 485). In the lead subcategory, four general
assumptions are made concerning treatment in-place: (1) if a
plant currently operates chemical precipitation but does not use
lime as the precipitating reagent, only the capital cost of the
lime feed system is included under required capital. (2) If the
plant reports sedimentation in lagoons, these are assumed to be
used as impoundments for sludge storage. Therefore, no solids
dewatering equipment is assumed to be required. To reflect the
annual cost of operating the lagoon ors pond and ultimate
disposition of the sludge, the annual costs of a vacuum filter
and contract hauling are included. In most cases, these costs
are overestimated for actual operation of the lagoon or pond.
(3) If a "sump" is reported to be in-place, it is assumed that it
will not provide adequate equalization or be an adequate tank to
operate chemical precipitation unless the sump volume is reported
and determined 'to have sufficient capacity. If a "pit" is
reported to be in-place, it is assumed that it will provide
adequate equalization but will not be an adequate tank to operate
chemical precipitation unless solids removal is reported. (4) If
a plant currently has treatment for the continuous operation of
chemical precipitation but compliance cost estimates are based on
a batch system (i.e., flow less than 10,600 l/hr)> required
capital costs are determined through evaluation of the specifics
of a plant's current treatment system including the type of
precipitating reagent(s) added.
459
-------
COST COMPARISON PROPOSAL VERSUS PROMULGATION
The costs estimated for the proposed regulation differ from those
estimated under this final rule. These differences stem from
different methodologies for estimation of costs for both in-plant
control technology and end-of-pipe treatment technology.
In-Plant Changes
As discussed earlier in this section, the Agency has revised its
lead subcategory in-plant cost procedures from proposal. In
addition, in-plant cost procedures for five technologies have
been added to the original in-plant procedures. The five new
technologies are:
o Steam curing
o Humidity curing water recycle
o Formation area wet air pollution control (WAPC) water
recycle
o Paste mixing WAPC water neutralization
o Power floor scrubber water settling.
Table VIII-2 (page 490) presents a summary of the in-plant cost
procedure changes.
The major revision to the in-plant cost procedures was in slow
formation. At proposal, slow formation costs included a building
and racks for stacking batteries. During post-proposal site
visits, sufficient vertical height was observed in existing
buildings to provide the necessary stacking for slow formation.
Erection of a new building is not required. Therefore, building
costs were removed from the in-plant costs for slow formation.
The Agency also revised its approach to plant-by-plant costing
for slow formation. At proposal, slow formation was costed for
all plants that reported a discharge from closed formation. For
promulgation, slow formation was only costed for those plants
that specified the use of contact cooling water in closed
formation. The costs for reducing other wastewater flows from
closed formation, such as battery rinse water, area washdown
water, and wet air pollution control water are estimated using
the appropriate in-plant cost procedures.
Another major revision to the in-plant cost procedures was to
countercurrent cascade rinsing labor costs. For proposal, a
$6.60 per mahhour labor rate was used to determine labor costs.
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The revised costs use a $21.00 per manhour labor rate. The
proposal costs were developed assuming approximately 0.001
manhours per kilogram of lead use were required for
countercurrent cascade rinsing labor. The revised costs assume
0.000169 manhours per kilogram of lead use are required for
labor. This value is based on observations made during sampling
visits. The revised costs are based on the incremental labor
required for countercurrent cascade rinsing. This incremental
labor is the labor needed to move plates from the first stage
rinse tank to the second stage rinse tank. The proposal labor
costs are based on a total labor requirement for running the
countercurrent cascade rinse. This represents an overestimate of
labor costs since plant personnel are already present to run the
rinse operation. Also, a difference between the proposal labor
costs and revised labor costs is an economy of scale factor. At
proposal, labor costs were assumed to be a linear function of
production. The revised labor costs account for the economy of
scale associated with increasing production by relating labor
costs to the six-tenths power of production.
Segregation costs have also been revised. Piping costs for
segregation are included in the individual in-plant technology
costs. A model-based segregation cost procedure was developed,
however, for segregating nonprocess waste streams from process
waste streams. For proposal, a segregation cost was estimated
for routing wastewater to end-of-pipe treatment. This cost was
based on a trench excavation cost and piping cost. The revised
costs more accurately reflect the cost of segregating water
flows. !
End-of-Pipe Comparison
Because a different contractor developed compliance cosjt
estimates for the final regulation, a different computer model
was used for cost estimation than was used for the proposed
regulation. As such, the cost estimates reflected the
assumptions and design and cost data upon which each model was
based. As can be seen from Table VIII-3 (page 493), the annual
costs for BPT under this final rule were higher than at proposal;
while the capital costs were lower. For either BAT (PSES;)
option, both annual and capital costs were lower for this finajl
rule. The increase in BPT annual costs are due primarily to
differing assumptions for labor rate, labor requirements, and
contract hauling costs; also, additional analytical data have
been collected since proposal that will result in differing
compliance costs. Further, a 10 percent interest rate for
capital recovery was used for cost estimation at proposal while a
12 percent interest rate was used for this regulation. Each of
these were found to increase annual costs for BPT.
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The decrease in annual costs for the BAT options probably results
from the procedure for estimating flows to the treatment system.
Rather than actual flow reported by each plant, the cost
estimation model discussed in this section calculated flow by
comparing the actual flow for each process element with the
regulatory flow for that element, and then selecting the lower
value as the flow to treatment.
The models also differed in specific assumptions for each module.
The assumptions for the model used at proposal are documented in
a report entitled "Comparison of Cost Methodologies for EGD -
Metals and Machinery Branch." This report is included in the
public record supporting this regulation.
COST ESTIMATION METHODOLOGY; POST-PROPOSAL
The calculation of plant-by-plant costs consists of two steps.
In-plant flow reduction costs are calculated using the in-plant
cost procedures, and treatment system (end-of-pipe) costs are
calculated using the computer model. Sources of cost data,
components of capital and annual costs, and cost update factors
are similar for the two costing procedures. A general discussion
on the sources of cost data, components of costs, and cost update
factors is presented below. Following these discussions the in-
plant cost procedures and computer model are discussed.
Sources of Cost Data
Capital and annual cost data for the selected treatment processes
were obtained from three sources: (1) equipment manufacturers,
(2) literature data, and (3) cost data from existing plants. The
major source of equipment costs was contacts with equipment ven-
dors, while the majority of annual cost information was obtained
from the literature. Additional cost and design data were
obtained from data collection portfolios when possible.
Components of Costs
Capital Costs. Capital costs consist of two components:
equipment capital costs and system capital costs. Equipment
costs include: (1) the purchase price of the manufactured
equipment and any accessories assumed to be necessary; (2)
delivery charges, which account for the cost of shipping the
purchased equipment a distance of 500 miles; and (3)
installation, which includes labor, excavation, site work, and
materials. The correlating equations used to generate equipment
costs are shown in Table VIII-4 (page 494).
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Capital system costs include contingency, engineering, and con-
tractor's fees. These system costs, each expressed as a percen-
tage of the total equipment cost, are combined into a factor
which is multiplied by the total equipment cost to yield the
total . capital investment. The components of the total capital
investment are listed in Table VIII-5 (page 500).
Annual Costs. The total annualized costs also consist of a
direct and " a system component as in the case of total capital
costs. The components of the total annualized costs are listed
in Table VIII-6 (page 501). Direct annual costs include the
following:
o Raw materials - These costs are for chemicals used in the
treatment processes, which include lime, sulfuric acid, alum,
polyelectrolyte, and sulfur dioxide.
o Operating labor and materials - These costs account for the
labor and materials directly associated with operation of the
process equipment. Labor requirements are estimated in terms of
manhours per year. A labor rate of 21 dollars per manhour was
used to convert the manhour requirements into an annual cost.
This composite labor rate included a base labor rate of nine
dollars per hour for skilled labor, 15 percent of the base labor
rate for supervision and plant overhead at 100 percent of the
total labor rate. Nine dollars per hour is the Bureau of Labor
national wage rate for skilled labor during 1982.
o Maintenance and repair - These costs account for the labor and
materials required for repair and routine maintenance of the
equipment.
o Energy - Energy, or power, costs are calculated based on total
nominal horsepower requirements (in kw-hrs), an electricity
charge of $.0483/kilowatt-hour and an operating schedule of 24
hours/day, 250 days/year unless specified otherwise. The
electricity charge rate (March 1982) is based on the industrial
cost derived from the Department of Energy's Monthly Energy
Review.
System annual costs include monitoring, insurance and amortiza-
tion (which is the major component). Monitoring refers to the
periodic sampling analysis of wastewater to ensure that discharge
limitations are being met. The annual cost of monitoring was
calculated using an analytical lab fee of $120 per wastewater
sample and a sampling frequency based on the wastewater discharge
rate, as shown in Table VIIIr7 (page 502).
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Insurance cost is assumed to be one percent of the total depreci-
able capital investment (see Item 23 of Table VIII-6).
Amortization costs, which account for depreciation and the cost
of financing, were calculated using a capital recovery factor
(CRF). A CRF value of 0.177 was used, which is based on an
interest rate of 12 percent, and a taxable lifetime of 10 years.
The CRF is multiplied by the total depreciable investment to
obtain the annual amortization costs (see Item 24 of Table VIII-
6).
Cost Update Factors
All costs are standardized by adjusting^ to June of 1983. This
was done by updating the model costs (which are calculated in
March 1982 dollars) using the EPA-Sewage Treatment Plant
Construction Cost Index. The June 1983 value of this index is
420.6. The cost indices used for particular components of costs
are described below.
Capital Investment - Investment costs were adjusted using the
EPA-Sewage Treatment Plant Construction Cost Index. The value of
this index for March 1982 is 414.0.
Operation and Maintenance Labor - The Engineering News-Record
Skilled Labor Wage Index is used to adjust the portion of Oper-
ation and Maintenance costs attributable to labor. The March
1982 value is 325.0.
Maintenance Materials - The producer price index published by the
Department of Labor, Bureau of Statistics is used. The March
1982 value of this index is 276.5.
Chemicals - The Chemical Engineering Producer Price Index for
industrial chemicals is used. This index is published biweekly
in Chemical Engineering magazine. The March 1982 value of this
index is 362.6.
Energy - Power costs are adjusted by using the price of
electricity on the desired date and multiplying it by the energy
requirements for the treatment module in kwhr equivalents.
In-Plant Costs
In-plant flow reduction cost procedures were developed for the
following lead subcategory process elements and ancillary
activities:
(1) Paste mixing and application area wash water recycle
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(2) Steam curing
(3) Humidity curing water recycle
(4) Slow formation
(5) Open dehydrated formation water
o Countercurrent cascade plate rinsing
o Vacuum pump seal and ejector water recycle
(6) Formation area wet air pollution control (WAPC) water
recycle
(7) Paste mixing WAPC water neutralization
(8) Reuse of battery rinse water in acid cutting
(9) Power floor scrubber water settling
(10) Hose washdown water recycle
(11) Segregation on nonprocess water flows.
Table VII1-8 (page 503) summarizes the number of plants that were
costed using each of the above in-plant technologies. The hose
washdown water recycle costs were estimated by the end-of-pipe
cost estimation model. A brief discussion on the in-plant cost
procedure is presented in this section. A detailed discussion
which includes all design assumptions and a derivation of all in-
plant cost equations is presented in the battery manufacturing
public record.
All in-plant costs were developed in a similar manner. The costs
for implementing each technology were first determined for a
model plant. Using the model plant flow and production,
equipment items required for the in-plant technology were sized.
Equipment costs were then determined using the cost equations
contained in the public record. The model plant production, and
capital and annual operating and maintenance costs (O&M costs)
were then used to develop a general algorithm for determining the
cost for .any size battery manufacturing operation. The general
algorithm was the standard "six-tenths" scaling factor. Figures
VIII-1 to VIII-12 (pages 509 to 520) summarize the equipment
capital and direct annual costs for each in-plant technology. No
credit was given in the in-plant costs for savings due to the
lower water usage that results when the various in-plant
technologies are used.
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The following presents a summary of the development of equipment
capital and direct annual costs for each in-plant technology.
This discussion includes the methodology used to identify the in-
plant technologies applicable for a given plant.
Paste Mixing and Application Area Wash Water Recycle. As
discussed in Section VII, the recycle of pasting area wash water
after settling for suspended solids removal is practiced by a
number of plants in the lead subcategory. Figure VIII-1 shows
the equipment capital and direct annual costs associated with
installing a recycle system for pasting area wash water. The
recycle system costs are based on the cost for installing a three
stage settling system, a holding tank for retaining the settled
water before reuse, piping for segregation, and two pumps.
Pasting area water recycle costs were determined for both BPT and
BAT (PSES). The recycle system costs were estimated for all
plants that discharge pasting area wash except those that had
recycle equipment in place.
Steam Curing. Some plants continuously discharge condensate from
steam curing. As discussed in Section VII, it is feasible to
utilize steam curing without incurring a discharge by
implementing one of a variety of techniques. For plants that
currently discharge this stream, a cost was determined for
converting to zero discharge. The cost model basis selected
includes the addition of pressure relief valves to vent the
steam. Figure VIII-2 shows the equipment capital cost associated
with installing the pressure relief valves. There are no direct
annual costs associated with the zero discharge operation. The
steam curing costs were estimated for both BPT and BAT (PSES).
Humidity Curing Water Recycle. Some plants report a continuous
discharge from humidity curing operations. For plants which
report this discharge, an external water recycle system was
costed for BPT and BAT (PSES). The water recycle system
equipment includes a holding tank, one pump, piping for
segregation, and a collection trench for the curing water.
Figure VIII-3 shows the equipment capital and direct annual costs
for the water recycle system.
Slow Formation. As discussed in Section VII, some plants which
charge batteries at high amperage (fast formation) require the
use of cooling water since they generate significant quantities
of heat. One technology for eliminating the use of cooling which
can be costed is slow formation. Figure VIII-4 shows the
equipment capital costs for converting to slow formation. The
slow formation capital costs are based on the installation of
ratiks for stacking batteries (as opposed to charging on tables)
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and a retrofit cost for converting from fast formation to slow
formation. Direct annual costs are not affected by converting
from fast formation to slow formation.
Slow formation was costed for BAT (PSES) for all plants that
reported a. cooling water discharge from double fill or fill and
dump formation. For plants that report a cooling water discharge
from single fill formation, slow formation was costed for BPT and
BAT (PSES).
Open Dehydrated Formation Water. Wastewater discharge from open
dehydrated formation is associated with rinsing formed plates.
At some plants, wastewater is also discharged from vacuum pump
seals and ejectors used for dehydrating the rinsed plates. The
wastewater discharge from plate rinsing can be greatly reduced if
the plates are rinsed with countercurrent cascade techniques,
with flow controllers and agitation.
Figure VII1-5 shows the equipment capital cost associated with
countercurrent cascade rinsing. These costs are based on
converting from a single stage rinse to a two stage
countercurrent cascade rinse. The countercurrent cascade rinsing
costs include installation of an additional rinse tank, a flow
control system, piping, and air spargers for air agitation. The
rinse tanks are agitated to ensure proper mixing. Air agitation
is accomplished by bubbling compressed air through the air
spargers. The air agitation costs assume that a source of
compressed air is already in-place. The flow control system
consists of a conductivity flow controller and a motorized
butterfly valve.
Figure VIII-5 also shows the incremental labor (direct annual
cost) for using a two stage countercurrent cascade rinse instead
of a single stage rinse. This cost is for the incremental labor
associated with moving the plates from the first stage to the
second stage of the rinse tanks.
Figure VIII-6 shows the equipment capital and direct annual costs
associated with recycling wastewater from vacuum pump seals and
ejectors (sealant water recycle). Since the level of
contamination in waste streams from this source is low, recycle
will drastically reduce the high volume discharges presently
produced at. some facilities. The sealant water recycle costs are
based on the installation of a holding tank, one pump, and piping
for segregation.
Costs for BAT (PSES) only were estimated for countercurrent
cascade rinsing and sealant water recycle. A number of different
costing situations were encountered when estimating these flow
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reduction costs. These situations and the costing procedure
followed for each situation are discussed below:
1. Plant Reports Discharge From Both Plate Rinsing and Sealant
Water Which is Greater than BAT (PSES) Regulatory Flow for
Open Dehydrated Formation — In this situation both
countercurrent cascade rinsing and sealant water recycle
were costed.
2. Plant Reports Discharge from Plate Rinsing Only Which is
Greater Than BAT (PSES) Regulatory Flow for Open Dehydrated
Formation — In this situation only countercurrent cascade
rinsing was costed.
3. Plant Reports Discharges from Both Plate Rinsing and Sealant
Water But Does Not Report Flow — In this situation both
sealant water recycle and countercurrent cascade rinsing
were costed.
4. Plant Reports Discharge from Plate Rinsing Only But Does Not
Report Flow — In this situation countercurrent cascade
rinsing was costed.
5. Plant Reports Discharge Flow from Open Dehydrated Formation
Which is Greater Than BAT (PSES) Regulatory Flow But Does
Not Indicate Where Flow is From — In this situation it was
assumed that the flow was from plate rinsing only and
countercurrent cascade rinsing was costed.
6. Plant Reports Discharge From Open Dehydrated Formation But
Does Not Report the Flow or Where the Flow is From — In
this situation, countercurrent cascade rinsing was costed.
Formation Area Wet Air Pollution Control Water Recycle. Wet air
pollution control (WAPC) scrubbers are used in the formation area
to primarily remove acid fumes generated during formation. The
discharge flow from these scrubbers can be minimized if the
scrubber water is neutralized with caustic and recycled. Figures
VIII-7 and VIII-8 show the equipment capital and direct annual
costs associated with recycle formation area WAPC water. The
recycle system costs include a holding tank, agitator, one pump,
piping for segregation, and a caustic addition system
(instrumentation for pH control, and a caustic storage tank).
The caustic storage tank is mounted on the holding tank so that
caustic can be gravity fed through a small valve into a holding
tank.
Formation area WAPC recycle costs were estimated for BPT and BAT
(PSES) for all plants that reported a discharge from formation
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area WAPC scrubbers in excess of 0.006 I/kg. These costs were
also estinicited for plants which did not report their formation
area WAPC flow.
Paste Mixing WAPC Water Neutralization. An annual cost was
estimated at BPT and BAT (PSES) for any plants which reported a
flow greater than 0.005 I/kg. The model used to establish the
cost basis is a rotoclone-type scrubber. The .flow is based on
semi-annual dumping of the scrubber water. A cost of $100 per
plant per year was assigned to all plants which reported a
discharge flow which exceeded the criterion. This cost was also
assigned to plants which reported a discharge but did not report
the flow value. The cost is for addition of caustic to the
rotoclone tank for acid neutralization to prevent corrosion.
Reuse of Battery Rinse Water in Acid Cutting. Battery rinse
water is used for product rinses in the formation areas and
battery wash with water only.
As discussed in Section VII, all water used in a properly
operated battery rinse can be reused to dilute (cut) acid to the
appropriate specific gravity for battery electrolyte. Proper
operation is where water is recycled at the rinse station and
flows only when batteries are present. Figures VII1-9 and VIII-
10 show the equipment capital and direct annual costs associated
with reusing battery rinse water in acid cutting. The equipment
includes a holding tank, two pumps, piping for segregation, and a
photoelec.tric eye. The photoelectric eye activates the battery
rinse flow when a battery passes beneath it. The eye deactivates
the flow after the last battery is rinsed.
Reuse of battery rinse water in acid cutting costs were estimated
for BAT (PSES). For costing purposes, it was assumed that plants
with formation battery rinses operate a detergent battery wash,
where the final rinse is used as makeup to the detergent recycle.
Several plants had equipment in-place to reuse battery rinse
water; no costs were estimated for these plants.
Power Floor Scrubber Water Settling. Wastewater from power floor
scrubbers contains high concentrations of suspended solids and
should be settled before treatment. Figure VI11-11 shows the
equipment capital and direct annual costs for power floor
scrubber water settling. These settling costs were estimated for
BPT and BAT (PSES) for all plants that discharge wastewater. The
floor scrubbing water settling equipment includes a settling
tank, one pump, and piping. A labor cost for periodic tank
cleaning is included in the O&M costs.
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Segregation. Many plants discharge nonprocess streams to
wastewater treatment. These nonprocess streams are not
contaminated and can be either directly discharged or discharged
to the sanitary sewer. Costs for segregation, or rerouting, of
nonprocess water were estimated for all discharging plants for
both BPT and BAT (PSES). Figure VIII-12 shows the equipment
capital and direct annual costs associated with segregating
nonprocess water.
As with other in-plant costs, the segregation costs were
developed based on a model plant. The following equipment items
were included in the model costs:
o Piping for routing each nonprocess stream to a common sump
o One sump with a level controller
o Piping for routing the combined nonprocess streams from the
sump to the sanitary sewer or direct discharge
o One pump for pumping the water from the sump to the sanitary
sewer or direct discharge.
There are a variety of nonprocess streams present at battery
manufacturing plants. Table VII1-9 presents the disposition of
nonprocess water among the plants visited in the post-proposal
data collection period.
The segregation model costs are based on rerouting deionizer
blowdown water, water softener backflush, and assembly area non-
contact cooling water. The remaining nonprocess streams are
already segregated by most plants.
Cost Estimation Model
Cost estimation was accomplished using a computer model which
accepts inputs specifying the required treatment system chemical
characteristics of the raw waste streams, flow rates and treat-
ment system entry points of these streams, and operating sched-
ules. This model utilizes a computer-aided design of a waste-
water treatment system containing modules that are configured to
reflect the appropriate equipment at an individual plant. The
model designs each treatment module and then executes a costing
routine that contains the cost data for each module. The capital
and annual costs from the costing routine are combined with
capital and annual costs for the other modules to yield the total
costs for that regulatory option. The process is repeated for
each regulatory option.
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Each module was developed by coupling theoretical design informa-
tion from the technical literature with actual design data from
operating plants. This permits the most realistic design
approach possible to be used, which is important to accurately
estimate costs. The fundamental units for design and costing are
not the modules themselves but the components within each module,
e.g., the lime feed system within the chemical precipitation
module. This is a significant for two reasons. First, it does
not limit the model to certain fixed relationships between
various components of each module. For instance, cost data for
chemical precipitation systems are typically presented
graphically as a family of curves with lime (or other alkali)
dosage as a parametric function. The model, however, sizes the
lime feed system as a function of the required mass addition rate
(kg/hr) of lime. The model thus selects a feed system
specifically designed for that plant. Second, this approach more
closely reflects the way a plant would actually design and
purchase its equipment. Thus, resulting costs are close to the
actual costs that would be incurred by the plant.
Overall Structure. The cost estimation model consists of two
main'parts: a design portion and a costing portion. The design
portion uses input provided by the user to calculate design
parameters for each module included in the treatment system. The
design parameters are then used as input to the costing routine,
which contains cost equations for each discrete component in the
system. The structure of the program is such that the entire
system is designed before any costs are estimated.
The pollutants or parameters which are tracked by the model are
shown in Table VIII-10 (page 505).
An overall logic diagram of the computer programs is depicted in
Figure VIII-13 (page 521). First, constants are initialized and
certain variables such as the modules to be included, the system
configuration, plant and wastewater flows, compositions, and
entry points are specified by the user. Each module is designed
utilizing the flow and composition data for influent streams.
The design values are transmitted to the cost routine. The
appropriate cost equations are applied, and the module costs and
system costs are computed. Figures VIII-14 and VIII-15 (pages
522 and 523) depict the logic flow diagrams in more detail for
the two major segments of the program.
Input Data Requirements. Several data inputs are required to run
the computer model. First, the treatment modules to be costed
and their sequence must be specified. Next, information on hours
of operation per day and number of days of operation per year for
the particular plant being costed is required. The flow values
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and characteristics must be specified for each wastewater stream
entering the treatment system, as well as each stream's point of
entry into the wastewater treatment system. These values then
dictate the size and other parameters of equipment for which
costs are to be determined. The derivation of each of these
inputs for costed plants in the lead subcategory are discussed
below.
Choice of the appropriate modules and their sequence for a costed
plant are determined by applying the treatment technology for
each option (see Figures IX-1 and X-l through X-4). These option
diagrams were adjusted to accurately demonstrate the treatment
equipment that the costed plant will actually require. If a
plant has a particular treatment module in place, that cost for
that module will be determined. The information on hours of
operation per day and days of operation per year was obtained
from the data collection portfolio of the costed plant.
The flows used to size the treatment equipment were derived as
follows: production (kg/yr) and flow (1/yr) information was
obtained from dcp, or trip report data where possible, and a
production normalized flow in liters per kilogram was calculated
for each waste stream. This flow was compared to the regulatory
flow, also in liters per kilogram, and the lower of the two flows
was used to size the treatment equipment. Regulatory flow was
also assigned to any stream for which production or flow data was
not reported in the dcp.
The raw waste concentrations of influent waste streams used for
costing were based on sampling data and the assumption that the
total pollutant loading (mg/1) in a particular waste stream is
constant, regardless of flow.
Model Results. For a given plant, the model generates
comprehensive material balances for each parameter (pollutant,
temperature and flowrate) at any point in the system. It also
summarizes design values for key equipment in each treatment
module, and provides a tabulation of costs for each piece of
equipment in each module, module subtotals, total equipment
costs, and system capital and annual costs.
Cost Estimates for Individual Treatment Technologies
Introduction. Treatment technologies have been selected from
among the larger set of available alternatives discussed in
Section VII after considering such factors as raw waste charac-
teristics, typical plant characteristics (e.g., location, produc-
tion schedules, product mix, and land availability), and present
treatment practices. Specific rationale for selection is
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addressed in Sections IX, X, XI, and XII. Cost estimates for
each technology addressed in this section include investment
costs and annual costs for depreciation, capital, operation and
maintenance, and energy.
The specific assumptions for each wastewater treatment module are
listed under the subheadings to follow. Costs are presented as a
function of influent wastewater flow rate except where noted in
the unit process assumptions.
Costs are presented for the following control and treatment
technologies:
Lime Precipitation and Gravity Settling,
Sulfide Precipitation and Gravity Settling,
Vacuum Filtration,
Flow Equalization,
Holding Tank - Recycle,
Multimedia Filtration,
Membrane Filtration,
Reverse Osmosis,
- Oil Skimming,
Contract Hauling. .
Lime Precipitation and Gravity Settling. Precipitation using
lime followed by gravity settling is a fundamental technology for
metals removal. In practice, either quicklime (CaO) or hydrated
lime can be used to precipitate toxic and other metals. Hydrated
lime is more economical for low lime requirements since the use
of slakers, which are necesary for quicklime usage, are practical
only for large-volume applications of lime.
Lime is used to adjust the pH of the influent waste stream to a
value of approximately 9, at which optimum precipitation of the
metals is assumed to occur (see Section VII, page 303), and to
react with the metals to form metal hydroxides. The lime dosage
is calculated as a theoretical stoichiometric requirement based
on the influent metals concentrations and pH. The actual lime
dosage requirement is obtained by assuming an excess of 10
percent of the theoretical lime dosage. The effluent
concentrations are based on the lime precipitation treatment
effectiveness values in Table VII-21 (page 418).
The costs of lime precipitation and gravity settling were based
on one of three operation modes, depending on the influent flow-
rate: continuous, normal batch, and "low flow" batch. The use
of a particular mode for costing purposes was determined on a
least (total annualized) cost basis for.a given flowrate. The
economic breakpoint between continuous and normal batch was esti-
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mated to be 10,600 liters/hour. Below 2,000 liters/hour, it was
found that the "low flow" batch system was most economical.
For a continuous operation, the following equipment were included
in the determination of capital and annual costs:
Lime feed system (continuous)
1. Storage units (sized for 30-day storage)
2. Slurry mix tank (5 minute retention time)
3. Feed pumps
4. Instrumentation (pH control)
Polymer feed system
1. Storage hopper
2. Chemical mix tank
3. Chemical metering pump
pH adjustment system
1. Rapid mix tank, fiberglass (5 minute retention time)
2. Agitator (velocity gradient is 300/second)
3. Control system
- Gravity settling system
1. Clarifier, circular, steel (overflow rate is 0.347
gpm/sq. ft., underflow solids is 3 percent)
2. Sludge pumps (1), (to transfer flow to and from
clarifier)
Ten percent of the clarifier underflow stream is recycled to the
pH adjustment tank to serve as seed material for the incoming
waste stream.
The direct capital costs of the lime and polymer feed were based
on the respective chemical feed rates (dry Ib/hour), which are
dependent on the influent waste stream characteristics. The
flexibility of this feature (i.e., costs are independent of other
module components) was previously noted in the description of the
cost estimation model. The remaining equipment costs (e.g., for
tanks, agitators, pumps) were developed as a function of the
influent flowrate (either directly or indirectly, when coupled
with the design assumptions). A cost curve is presented in
Figure VIII-16 (page 524) for capital costs of the continuous
system.
Direct annual costs for the continuous system include operating
and maintenance labor for the feed systems and the clarifier, the
cost of lime and polymer, maintenance materials and energy costs
required to run the agitators and pumps. A cost curve is
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presented in Figure VIII-16 (page 524) for annual costs of the
countinuous systems.
The normal batch treatment system (used for flows greater than
2,000 liters/hour and less than 10,600 liters/hour) consists of
the following equipment:
Lime feed system (batch)
1. Slurry tank (5 minute retention time)
2. Agitator
3. Feed pump
- Polymer feed system
1. Chemical mix tank
2. Agitator
3. Chemical metering pump
pH adjustment system
1. Reaction tanks (2), (8 hour retention time each)
2. Agitators (2), (velocity gradient is 300/second)
3. Sludge pump (1), (to transfer sludge to dewatering)
4. pH control system
The reaction tanks used in pH adjustment are sized to hold the
wastewater volume accumulated for one batch period (assumed to be
8 hours). The tanks are arranged in a parallel setup so that
treatment occurs in one tank while wastewater is accumulating in
the other tank. A separate gravity settler is not necessary
since settling will occur in the reaction tank after precipita-
tion has taken place. The settled sludge is then pumped to the
dewatering stage.
If additional tank capacity is required in the pH adjustment sys-
tem in excess of 25,000 gallons (largest single fiberglass tank
capacity for which cost data were compiled), additional tanks are
added in pairs. Costs for a sludge pump and agitator are
estimates for each tank. A cost curve is presented in Figure
VIII-16 (page 524) for capital costs of the normal batch system.
The cost of operating labor is the major component of the direct
annual costs for the normal batch system. For operation of the
batch lime feed system, labor requirements range from 15 to 60
minutes per batch, depending on the lime feed rate (5 to 1,000
pounds/batch). This labor is associated with the manual addition
of lime (stored in 50 pound bags). For pH adjustment, required
labor is assumed to be one hour per batch (for pH control,
sampling, valve operation, etc.). Both the pH adjustment tank
and the lime feed system are assumed to require 52 hours per year
(one hour/week) of maintenance labor. Labor requirements for the
475
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polymer feed system are approximately one hour/day, which
accounts for manual addition of dry polymer and maintenance asso-
ciated with the chemical feed pump and agitator.
Direct annual costs also include the cost of chemicals (lime,
polymer) and energy required for the pumps and agitators. The
costs of lime and polymer used in the model are $47.30/kkg of
lime ($43/ton) and $4.96/kg of polymer ($2.25/lb), based on rates
obtained from the Chemical Weekly Reporter (lime) and quotations
from vendors (polymer). A cost curve is presented in Figure
VIII-16 (page 524) for annual costs of the normal batch system.
For small influent flowrates (less than 2,000 liters/hour) it is
more economical on a total annualized cost basis to select the
"low flow" batch treatment system. The lower flowrates allow an
assumption of five days for the batch duration, or holdup, as
opposed to eight hours for the normal batch system. However,
whenever the total batch volume (based on a five day holdup)
exceeds 25,000 gallons, the maximum single batch tank capacity,
the holdup is decreased accordingly to maintain the batch volume
under this level. Capital and annual costs for the low flow
system are based on the following equipment:
- pH adjustment system
1. Rapid mix/holdup tank (5 days or less retention time)
2. Agitator
3. Transfer pump
Only one tank is required for both holdup and treatment because
treatment is assumed to be accomplished during non-operating
hours (since the holdup time is much greater than the time
required for treatment). Costs for a lime feed system are not
estimated since lime addition at low application rates can be
assumed to be done manually by the operator. A common pump is
used for transfer of both the supernatant and sludge through an
appropriate valving arrangement. Addition of polymer was assumed
to be unnecessary due to the extended settling time available. A
cost curve is presented in Figure VIII-16 (page 524), for capital
costs of the "low flow" batch system.
As in the normal batch case, annual costs are comprised mainly of
labor costs for the low flow batch system. Labor requirements
are constant at 1.5 hours per batch for operation (e.g., pH
control, sampling, etc.) and 52 hours per year (one hour per
week) for maintenance. Labor is also required for the manual
addition of lime directly to the batch tank, ranging from 0.25 to
1.5 hours per batch depending on the lime requirement (1 to 500
pounds per batch). Annual costs also include energy costs
associated with the, pump and agitator. A cost curve is presented
476
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in Figure VII1-16 (page 524), for annual costs of the "low flow"
batch system.
Sulfide Precipitation and Gravity Settling. Precipitation using
sulfide precipitants followed by gravity settling is a technology
similar to lime precipitation. In general, sulfide precipitation
removes more metals from wastewater than lime precipitation
because metal sulfides are less soluble than metal hydroxides.
Sulfide precipitants can be either soluble sulfides (such as
sodium sulfide, or sodium bisulfide) or insoluble sulfides (such
as ferrous sulfide). Soluble sulfides generate less sludge than
insoluble sulfides, are less expensive, and are more commonly
used in industry. The sulfide precipitation module is based on
the use of sodium sulfide.
The sulfide precipitation system consists of a pH adjustment step
with lime followed by a sulfide precipitation step. Lime is used
to adjust the pH of the influent waste stream to a value of
approximately 9, at which optimum precipitation of the metals is
assumed to occur, and to react with the metals to form metal
hydroxides. The lime dosage is calculated as a theoretical
stoichiometric requirement based on the influent metals
concentrations, lime precipitation treatment effectiveness
concentration, and pH. The actual lime dosage requirement is
obtained by assuming an excess of 10 percent of the theoretical
lime dosage. The treatment effectiveness concentrations are
based on the lime precipitation treatment effectiveness values in
Table VII-;>1 (page 418).
After pH adjustment, sodium sulfide is added to the wastewater.
The sodium sulfide reacts with the metal hydroxides and forms
metal sulfides. The metal sulfides are less soluble than the
metal hydroxides. Thus, a larger portion of the metals
precipitate (compared to lime precipitation) and metals removal
is enhanced. The sodium sulfide concentration is calculated as
the theoretical stoichiometric requirement based on the influent
metals concentration. The actual sodium sulfide dosage is
obtained by assuming an excess of 25 percent of the theoretical
sodium sulfide dosage. Effluent concentrations are based on
treatment effectiveness values for sulfide precipitation.
As with lime precipitation costs, the costs for pH adjustment
with lime, sulfide precipitation, and gravity settling are based
on one of three operation modes, depending on the influent
flowrate: continuous, normal batch, and "low flow" batch. The
use of a particular mode for costing purposes was determined on a
least (total annualized) cost basis for a given flowrate. The
economic breakpoint between continuous and normal batch is
477
-------
assumed to be 10,600 liters/hour. Below 2,000 liters/hour, it is
assumed that the "low flow" batch system is most economical.
For a continuous operation, the following equipment were included
in the determination of capital and annual costs:
Lime feed system (continuous)
1. Storage units, (sized for 30-day storage)
2. Slurry mix tank (5 minute retention time)
3. Feed pumps
4. Instrumentation (pH control)
- Sodium sulfide feed system (continuous)
1. Storage units (sized for 30-day storage)
2. Mix tank (5 minute retention time)
3. Feed pumps
4. Hood for ventilation
- Polymer feed system
1 . Storage hopper
2. Chemical mix tank
3. Chemical metering pump
- pH adjustment system
1. Rapid mix tank, fiberglass
2. Agitator (velocity gradient is 300/second)
3. Control system,
- Sulfide precipitation system
1. Rapid mix tank, fiberglass
2. Agitator (velocity gradient is 300/second)
3. Hood for ventilation
- Flocculation system
1. Slow mix tank, fiberglass
2. Agitator (velocity gradient is 100/second)
3. 2.0 mg/1 polymer dosage
Gravity settling system
1. Clarifier, circular, steel (overflow rate
is 0.347 gpm/sq. ft., underflow solids is
3 percent)
2. Sludge pumps (1), (to transfer flow to and
from clarifier)
The percent of the clarifier underflow stream is recycled to the
pH adjustment tank to serve as seed material for the incoming
waste stream.
478
-------
An aeration system (tank and spargers) for removing excess
hydrogen sulfide is also included in the costs.
The direct capital costs of the lime, sodium sulfide, and polymer
feed systems were based on the respective chemical feed rates
(dry Ib/hr), which are dependent on the influent waste stream
characteristics. A .cost curve is presented in Figure VIII-17,
(page 525) for capital costs of continuous system.
Direct annual costs for the continuous system include operating
and maintenance labor for the feed systems and the clarifier, the
cost of lime, sodium sulfide, and polymer, maintenance materials
and energy costs required to run the agitators and pumps. A cost
curve is presented in Figure VIII-17 (page 525) for annual costs
of the continuous system.
The normal batch treatment system (used for 2,000 liters/hour <
flow <10,600 liters/hour) consists of the following equipment:
Lime feed system (batch)
1. Slurry tank (5 minute retention time)
2. Agitator
3, Feed pump
Polymer feed system
1. Chemical mix tank
2, Agitator
3. Chemical metering pump
Sodium sulfide feed system
1. Mix tank (5 minute retention time)
2. Agitator
3„ Feed pump
4., Hood for ventilation
pH adjustment and sulfide precipitation system
1. Reaction tanks (8 hour retention time
each)
2. Agitators (Velocity gradient is 300/second)
3. Sludge pump (1), (to transfer sludge to
dewatering)
4. pH control system
5. Hood for ventilation
The batch sulfide precipitation system is similar to the batch
lime precipitation system. An aeration system (tank and air
spargers) for removing excess hydrogen sulfide is included. As
with the continuous sulfide precipitation system, the sodium
sulfide feed system is ventilated. A cost curve is presented in
479
-------
Figure VII1-17 (page 525) for capital costs of the normal batch
system.
Direct annual costs for batch sulfide precipitation include
operating labor costs, the cost of chemicals (lime and sodium
sulfide) and energy required for the pumps and agitators. Lime
costs are discussed in the lime precipitation section. A cost
curve is presented in Figure VII1-17 (page 525) for annual costs
of the normal batch system.
The cost used by the model for sodium sulfide is $517/kkg of
sodium sulfide ($470/ton). This cost is based on rates from the
Chemical Marketing Reporter.
As discussed in the lime precipitation section, for small
influent flowrates (less than 2,000 liters/hour) it is more
economical on a total annualized cost basis to select the "low
flow" batch treatment system. The lower flowrates allow an
assumption of five days for the batch duration, or holdup, as
opposed to eight hours for the normal batch system. However,
whenever the total batch volume (based on a five day holdup)
exceeds 25,000 gallons, the maximum single batch tank capacity,
the holdup is decreased accordingly to maintain the batch volume
under this level. Capital and annual costs for the low flow
system are based on the following equipment:
pH adjustment and sulfide precipitation
system
1. Rapid mix/holdup tank (5 days or less
retention time)
2. Agitator
3. Transfer pump
4. Aeration system (tank and air spargers)
5. Hood for ventilation
Only one tank is required for both holdup and treatment because
treatment is assumed to be accomplished during non-operating
hours (since the holdup time is much greater than the time
required for treatment). Lime and sodium sulfide feed systems
are not costed since lime and sodium-sulfide addition at low
application rates can be assumed to be done manually by the
operator. A common pump is used for transfer of both the
supernatant and sludge through an appropriate valving
arrangement. Addition of polymer was assumed to be unnecessary
due to the extending settling time available. A cost curve is
presented in Figure VIII-17 (page 525) for capital costs of the
"low flow" batch system.
480
-------
As in the normal batch case, annual costs are comprised mainly of
labor costs for the low flow batch system. Labor requirements
are constant at 1 hour per batch for operation (e.g., pH control,
sampling, etc.) and 52 hours per year (one hour per week) for
maintenance. Labor is also required for the manual addition of
lime and sodium sulfide directly to the batch tank. A cost curve
is presented in Figure VIII-17 (page 525) for annual costs of the
"low flow" batch system.
Vacuum Filtration. The underflow from the clarifier is routed to
a rotary pirecoat vacuum filter, which dewaters the hydroxide
sludge (it may also include calcium sulfate and fluoride) to a
cake of 20 percent dry solids. The dewatered sludge is disposed
of by contract hauling and the filtrate is recycled to the rapid
mix tank as seed material for sludge formation.
The capacity of the vacuum filter, expressed as square feet of
filtration area, is based on a yield value of 14.6 kg of dry
solids/hr per square meter of filter area (3 lb/hr/ft2), with a
solids capture of 95 percent. It was assumed that the filter was
operated 8 hours/day.
Cost data were compiled for vacuum filters ranging from 0.9 to
69.7 m2(9.7 to 750 ft2) in filter surface area. Based on a total
annualized cost comparison, it was assumed that it was more
economical to directly contract haul clarifier underflow streams
which were less than 42 1/hr (0.185 gpm), rather than dewater by
vacuum filtration before hauling.
The capital costs for the vacuum filtration include the follow-
ing:
Vacuum filter with precoat but no sludge conditioning,
- Housing, and
Influent transfer pump.
Operating labor cost is the major component of annual costs,
which also include maintenance and energy costs. Cost curves for
capital and annual costs are presented in Figure VIII-18 (page
526) for vacuum filtration.
Flow Equalization. Flow equalization is accomplished through
steel equalization tanks which are sized based .on a retention
time of eight hours or 16 hours and an excess capacity factor of
1.2. Cost data were available .for steel equalization tanks up to
a capacity of 500,000 gallons; multiple units were required for
volumes greater than 500,000 gallons. The tanks are fitted with
agitators with a horsepower requirement of 0.006 kw/1,000 liters
481
-------
(0.03 hp/1,000 gallons) of capacity to prevent sedimentation. An
influent transfer pump is also included in the equalization
system. Cost curves for capital and annual costs are presented
in Figure VIII-19 (page 527) for equalization at 8 hours and 16
hours retention time, respectively.
Holding Tanks Recycle. A holding tank may be used to recycle
water back to a process or for miscellaneous purposes, e.g., hose
washdown for plant equipment. Holding tanks are usually
implemented when the recycled water need not be cooled. The
equipment used to determine capital costs are a fiberglass tank,
pump, and recycle piping. Annual costs are only associated with
the pump. The capital cost of a fiberglass tank is estimated on
the basis of required tank volume. Required tank volume is
calculated on the basis of influent flowrate, 20 percent excess
capacity, and four hour retention time.
When chemical precipitation is operated in a batch mode (less
than 10,600 1/hr), it is assumed that water may be recycled out
of the tank used to operate chemical precipitation. Therefore,
since a separate holding tank is not required, only a pump and
recycle piping are contributors to recycle costs.
Cost curves for capital and annual cost are presented in Figure
VIII-20 (page 528) for flowrates less than 2,000 1/hr and greater
than 10,600 1/hr respectively. In the lead subcategory under BAT
(PSES) water is recycled back to hose washdown after the water is
treated by chemical precipitation and settling.
Multimedia Filtration. Multimedia filtration is used as a
wastewater treatment polishing device to remove suspended solids
not removed in previous treatment processes. The filter beds
consist of graded layers of gravel, coarse anthracite coal, and
fine sand. The equipment used to determine capital and annual
costs are as follows:
Influent storage tank sized for one backwash volume;
- Gravity flow, vertical steel cylindrical filters with
media (anthracite, sand, and garnet);
Backwash tank sized for one backwash volume;
Backwash pump to provide necessary flow and head for
backwash operations;
Influent transfer pump; and
Piping, valves, and a control system.
The hydraulic loading rate is 7,335 lph/m2 (180 gph/ft2) and the
backwash loading rate is 29,340 lph/m2 (720 gph/ft2). The filter
is backwashed once per 24 hours for 10 minutes. The backwash
volume is provided from the stored filtrate.
482
-------
Effluent pollutant concentrations are based on treatability of
pollutants by filtration technology presented in Section VII.
Cost curves for capital and annual costs are presented in Figure
VIII-21 (page 529) for multimedia filtration.
Membrane Filtration. Membrane filtration is used as a wastewater
treatment polishing device f6r suspended solids not removed in
previous treatment processes. Cartridge-type filters are used
instead of multimedia filters to treat small flows (less than
1,150 liters/hour) since they are more economical compared to.
multimedia filters (based on a least total annualized cost
comparison) at these flows. It was assumed that the effluent
quality achieved by these filters was at least the level attained
by multimedia filters. The equipment used to determine capital
and annual costs for membrane filtration are as follows:
Influent holding tank sized for eight hours retention
- Pump
Pirefilter
1, Prefilter cartridges
2. Prefilter housings
Membrane filter
1. Membrane filter cartridges
2* Housing
The majority of annual cost is attributable to replacement of the
spent prefilter and membrane filter cartridges. The maximum
loading for the prefilter and membrane filter cartridges was
assumed to be 0.225 kg per 10 inch length of cartridge. The
annual energy and maintenance costs associated with the pump are
also included in the total annual costs. Cost curves for capital
and annual costs are presented in Figure VIII-21 (page 529) for
membrane filtration.
Reverse Osmosis. Reverse osmosis concentrates the dissolved
organic and inorganic pollutants in wastewater by forcing the
water through semi-permeable membranes which will not pass the
pollutants. The water which permeates the membranes is
relatively free of contaminants and suitable for reuse in most
manufacturing process operations.
Data from several manufacturers of reverse osmosis equipment were
used to determine capital and annual costs. The following
equipment were used in the determination of capital and annual
costs:
483
-------
pH adjustment tank (15 minute retention)
- Cartridge prefilter
1. Cartridges
2. Housing
- Two influent transfer pumps
\
Permeate storage tank (one hour retention)
Brine storage tank (one hour retention)
- Reverse osmosis module
1. Sulfuric acid feed system
2. Inhibitor feed system
3. Conductivity monitor
4. Membrane cleaning system
5. Reverse osmosis membranes and housing
Direct annual costs for reverse osmosis include operating and
maintenance labor for the feed systems, the cost for sulfuric
acid and inhibitor, prefilter cartridge replacement, reverse
osmosis module cartridge replacement, and maintenance materials
and energy costs required for the pumps and air agitation system.
Cost curves for capital and annual costs are presented in Figure
VII1-22 (page 530) for reverse osmosis.
Oil Skimming. Oil skimming' costs apply to the separation of oil-
water mixtures using a coalescent plate-type separator (which is
essentially an enhanced API-type oil-water separator). Although
the required separator capacity is dependent on many factors, the
sizing was based primarily on the influent wastewater flow rate,
with the following design values assumed for the remaining
parameters of importance:
Parameter ' Nominal Design Value
Specific gravity of oil 4 0.85
Operating temperature (°F) 68
Influent oil concentration (mg/1) 30,000
Extreme operating conditions, such as influent oil concentrations
greater than 30,000 mg/1, or temperatures much lower than 68 °F
were accounted for in the sizing of the separator.
The capital and annual costs of oil skimming included the follow-
ing equipment:
- Coalescent plate separator with automatic shutoff
484
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valve and level sensor
t
- Oily waste storage tanks {2-week retention time)
Oily waste discharge pump
Effluent discharge pump
Influent flow rates up to 159,100 1/hr {700 gpm) are costed for a
single unit; flows greater than 700 gpm require multiple units.
The direct annual costs for oil skimming include the cost of
operating and maintenance labor and replacement parts. Annual
costs for the coalescent separators alone are minimal and involve
only periodic clean out and replacement of the coalescent plates.
Cost curves for capital and annual costs are presented in Figure
VIII-23 (page 531) for oil skimming.
Contract Hauling. Concentrated sludge and waste oils are removed
on a contract basis for off-site disposal. The cost of contract
hauling depends on the classification of the waste as being
either hazardous or nonhazardous'. For nonhazardous wastes, a
rate of $0.106/liter ($0.40/gallon) was used in determining
contract hauling costs. The cost for contract hauling hazardous
wastes is determined from the cost equation shown in Table VII1-4
{page 494). This equation was developed from telephone contacts
with waste disposal services. The cost of contract hauling is an
annual cost; no capital costs are associated with it. Annual
cost curves for contract hauling non-hazardous and hazardous
wastes are presented in Figure VIII-24 (page 532).
Compliance Cost Estimation
To calculate the compliance cost estimates, the model was run
using input data as described previously. The actual costs are
stored in a data file, where they are accessed from electronic
spreadsheet software to prepare a cost summary for each plant.
An example of this summary may be found in Table VIII-11 {page
489) .
All options costed are included on one page. Under each option,
there are four columns. The run number refers to which run on
the computer the costs were derived from. The total capital
column includes the capital cost estimate for each piece of
necessary treatment equipment. The required capital column
reflects the estimates of the actual capital cost to the plant to
purchase and install the equipment by accounting for what that
plant has already installed. In other words, the treatment
485
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equipment the plant already has in-place is reflected in the
required capital column.
NORMAL PLANT
In order to estimate costs for new sources, and pollutant
removals and nonwater quality aspects for existing sources, a
normal plant and a normal discharging plant were developed. The
normal plant, an arithmetic average of plants in the subcategory,
is a theoretical plant which contains each process element in the
subcategory. The production level for each process element is
the average process element production in the subcategory. The
flow rates for these process elements are calculated by
multiplying the process element production times the production
normalized flow for the process element at the various options.
In addition, the normal plant was assumed to operate, 16 hours per
day, five days per week, 50 weeks per year.
The normal discharging plant is a theoretical plant which
contains each process element at the average production level for
plants that discharge wastewater. This plant was developed
because plants which discharge wastewater are generally larger
than those which are zero dischargers. The normal discharge
plant costs are used as the basis for estimating new source
costs. Table VII1-12 (page 507) presents the capital and annual
costs for both the normal plant and the normal discharging plant.
NONWATER QUALITY ENVIRONMENTAL ASPECTS
The elimination or reduction of one form of pollution may
aggravate other environmental problems. For this reason
consideration was given to the effect of this regulation on air
pollution, solid waste generation, water scarcity, and energy
consumption. While it is difficult to balance pollution problems
against each other and against energy utilization, the impacts
identified below are justified by the benefits associated with
compliance with the limitations and standards. The following are
the nonwater quality environmental impacts (including energy
requirements) associated with the lead subcategory regulation.
Air Pollution
In general, especially for the lime precipitation systems, none
of the liquid handling processes causes air pollution. With
sulfide precipitation, however the potential exists for -evolution
of hydrogen sulfide, a toxic gas. Proper control of pH in
treatment eliminates this problem. Incineration of sludges or
solids can cause, significant air pollution which must be
controlled by suitable baghouses, scrubbers or stack gas
486
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precipitators as well as proper incinerator operation and
maintenance. Implementation of sulfide technology at existing
plants is costly because of the additional retrofitting a plant
would have to do to create a safe working environment. Due to
their high content of volatile heavy metals/ sludges from battery
manufacturing are not amenable to incineration except in retorts
for metals recovery.
Solid Waste
Costs for treatment sludge handling were included in the computer
cost program already discussed and are included in the compliance
costs. In addition, the cost impact that wastewater treatment
will have on the battery manufacturing category in terms of
satisfying RCRA hazardous waste disposal criteria was analyzed
for lime and settle technology. Battery manufacturing plants
generate an estimated total of 18/960 kkg of solid waste per year
from manufacturing process operations, and an indeterminate
amount of solid waste from wastewater treatment. Wastewater
treatment sludges contain toxic metals including cadmium,
chromium, copper, lead, mercury, nickel, silver, and zinc.
Under the BPT limitations for the lead subcategory, an estimated
4,817 kkg/yr of solid waste will be generated. Solid waste
generation under the BAT limitations and PSES is estimated to be
4,840 kkg/yr and 62,290 kkg/yr respectively. These sludges will
necessarily contain additional quantities (and concentrations) of
toxic metal pollutants.
The solid wastes that would be generated at lead subcategory
battery manufacturing plants by lime and settle treatment
technologies are believed to be not hazardous under Section 3001
of RCRA. This judgement is made based on the recommended
technology of lime precipitation using an excess of lime. By the
addition of a small excess (approximately 10 percent) of lime
during treatment, it is believed that wastewater treatment
sludges will pass the EP toxicity test. Therefore, wastewater
treatment sludge hauling costs for the lead subcategory were
calculated assuming the sludge was nonhazardous. Estimated BPT
wastewater treatment sludge hauling costs for the lead
subcategory are $44,300 per year. Estimated BAT and PSES
wastewater treatment sludge hauling costs are $437,870 per year.
Process sludges such as pasting sludge can be reprocessed to
recover additional lead value. Thus, there is no cost for
disposing process sludge.
If lead subcategory wastewater treatment sludges were considered
to be hazardous, the costs for wastewater treatment sludge
disposal would double. The impact that hazardous waste sludge
487
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hauling costs would have on the lead subcategory was evaluated.
Sludge hauling costs were doubled for eight plants and the total
annual costs for each plant were summed. The total annual costs
($1983) were compared with the proposed costs for Option 4
(proposed costs for Option 4 updated to 1983 dollars) which
projected no plant closures. In all cases, the annual costs for
existing plants at BPT and BAT option levels were less than the
proposed costs for Option 4. Therefore, it can be concluded that
even if individual plants must classify their wastewater
treatment sludges as hazardous, the cost of hazardous waste
disposal would not cause any plant closures.
Consumptive Water Loss
Where evaporative cooling mechanisms are used, water loss may
result and contribute to water scarcity problems, a concern
primarily in arid and semi-arid regions. This regulation does
not require substantial evaporative cooling and recycling which
would cause a significant consumptive water loss.
Energy Aspects
Energy aspects of the wastewater treatment processes are
important because of the impact of energy use on our natural
resources and on the economy. It is estimated that the lead
subcategory consumed 0.77 billion kilowatt hours of electrical
energy in 1982. Table VII1-13 (page 508) shows the total lead
subcategory energy requirement and energy cost for each treatment
option. As shown by Table VIII-13, none of the treatment options
would increase the current electrical energy consumption by more
than one percent.
488
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TABLE VI11-1
BATTERY MANUFACTURING COMPLIANCE COSTS
LEAD SUBCATEGORY
00
VO
Discharge
Status
Direct
Indirect
Total
Discharge
Status
Direct
Indirect
Total
Option BPT (PSES-0)
Option BAT-1
/"* — . — > - 4- - . "! A — *•»•<•« 1 **"*«*«,"«*. ,rv 1
WctpJU t.CtJL fii.HLU.al v^djJJ- C.O.4.
714,843 499,
7,887,805 4,635,
8,602,648 5,134,
Option BAT-^3
Capital
989,487
11,214,186
12,203,673
039
339
378
(PSES
818,501
7,121,534
7,940,035
-3)*
Annual
739
8,381
9,120
,521
,238 1
, 759 1
(PSES-1)
Annual
509,777
4,072,814
4,582,591
Option BAT-
Capital
1,619,406
8,353,268
9,972,674
Option BAT-2
Capital
968,117
8,390,881 4
9,358,998 5
4 (PSES-4)*
Annual
930,465
10,545,270
11,475,735
(PSES-2)
A^«,.,p1
fitiil Clc*. x.
580,626
,723,621
,304,249
*Plant-by-plant costs were not calculated for Options 3 and 4.
based on the normal discharging plant.
All costs are in June, 1983 dollars.
Option 3 and 4 costs are
-------
TABLE VIII-2
IN-PLANT COST PROCEDURE CHANGES
Process
Slow Formation
Final Product Rinse
VO
o
Countercurrent
Rinsing and Sealant
Recycle
Item
Equipment
Retrofit
Equipment
Equipment
Proposal
Buildings, racks and
accessories (undefined)
0
Holding tank
(2 hours retention)
3 rinse tanks
(1/2 hour retention/tank)
Flow controller
2 pumps
1 holding tank for
sealant recycle
(2 hours retention)
Revised
Racks
20% of rack cost
Holding tank (1 week
retention)
Piping for
segregation (to acid
cutting)
2 pumps
Photoelectric eye
Countercurrent rinse:
2 rinse tanks
(1/2 hour retention/
tank)
Air agitation
Flow controller
10 feet of piping to
connect tanks
-------
TABLE VII1-2 (Continued)
IN-PIANT COST
Process
Countercurrent Rinsing
and Sealant Recycle
(Continued)
Item
Proposal
Countercurrent
Rinsing Basis
Labor for
Countercurrent
rinsing
Paste Water Recycle
Equipment
3 stage rinsing
Labor cost = 0.0143
x battery production
(kg/yr)
$6.6/hour-labor rate
3 settling tanks
(1 hour retention/tank)
Piping for segregation
Revised
Sealant recycle:
1 holding tank
(2 hour retention)
100 feet- of piping
for segregation
1 pump
2 stage rinsing and
assumes first stage
Is in place
1.323 x flead usage
(kg/yr))°- 6
$21/hr-labor rate
2.5 ruin, incremental
labor per basket of
plates
Sampling data-
baskets/hr, Pb/hr
3 settling tanks
(1 hour retention/
tank)
-------
TABLE ¥111-2 (Continued)
IN-PIANT COST
Process
Paste Water Recycle
(Continued)
Item
Proposal
Stream Segregation Costs
Five New In-Plant
Technologies
System Parameters
for In-Plant Costs
NOTE:
Annual labor cost
Equipment
General
Engineering
contingency and
contractor's fee
Interest rate
Equipment life
Piping and trench
Not included in
in-plant costs
0%
10%
10 years
Revised
1 holding tank
(1 day retention)
Piping for
segregation
2 pumps
Annual labor cost for
periodically cleaning
out settling tanks is
included
Piping, sump and pump
Included in in-plant
costs
37.5%
12%
10 years
Installation costs are included in revised equipment costs
Revised equipment costs from end-of-pipe treatment equipment costs, literature, and vendor quotes
System parameters (e.g., interest rate) are consistent with end-of-pipe treatment module parameters
-------
TABLE VIII-3
COST DIFFERENCE COMPARISON - PROMULGATED VS. PROPOSED
Plant
146
331
382
446
450
462
513
553
815
943
Mean(%)
ABPT (I)
Capital
-38
-10
-38
,
-68
-40
-57
-84
71
-33
Annual
80
122
109
_ —
101
36
59
-42
135
75
ABAT-'
Capital
-80
-46
-88
-71
-85
-78
-85
-45
-72
I (%)
Annual
-32
-4
-9
,
-12
-41
-45
-45
-46
-30
ABAT -2 (%)
Capital
-78
-41
-89
-72
-82
-73
-82
-55
-72
Annual
-35
-15
___ •
-12
-12
-37
-41
-52
-46
-31
NOTES;
% = [(Promulgation Cost - Proposal Cost)/(Proposal Cost)] x 100
n = 8
493
-------
TABLE VEII-4
COST EQUATIONS FOR RECOMMENDED TREATMENT
AND CONTROL TECHNOLOGIES
NO
Equipment
Agitator, C-clamp
Agitator, Top Entry
Clarifier, Concrete
Clarifier, Steel
Contract Hauling
Equalization Tank, Steel
Equation
C = 839.1 + 587.5 (HP)
A - 0.746 (HPY) (HP) (0.0483) + 0.05 (C)
C = 1,585.55 + 125.302 (HP) - 3.27437 (HP)2
A= 0.746 (HPY) (HP) (0.0483) + 0.05 (C)
C = 78,400 + 32.65 (S) - 7.5357 x 10~4 (S)2
A = exp[8.22809 - 0.224781 (InS)
+ 0.0563252 (InS)2]
C = 41,197.1 + 72.0979(5) + 0.0106542(S)2
A = exp[8.22809 - 0.224781 (InS)
+ 0.0563252 (InS)2]
C = 0
A = 0.40 (G)(HPY)
C = 0
A = exp[-0.0240857 + 1.02731 (InG)
- 0.0196787 (InG)2](HPY)
C - 14,759.8 + 0.170817 (V) - 8.44271
x ID"8 (V)2
C = 3,100.44 + 1.19041 (V) - 1.7288
x ID"5 (V)2
C = exp[4.73808 - 0.0628537 (InV)
+ 0.0754345 (InV)2]
A = 0.05 (C)
Range of Validity
0.25 < HP < 0.33
0.33 < HP '< 5.0
500 < S < 12,000
300 < S < 2,800
Non Hazardous
Hazardous
24,000 < V < 500,000
1,000 < V < 24,000
V < 1,000
-------
TABLE ¥111-4 (Continued)
COST EQUATIONS FOR RECOMMENDED TREATMENT
AND CONTROL TECHNOLOGIES
Equipment.
Feed System, Caustic
VO
Ul
Feed System, Itaual lime
Addition
Feed System, Batch lime
Equation
Continuous feed:
C = exp[9.63461 + 8.36122 x 1CT3 (InF)
+ 0.0241809 (InF)2]
Batch feed:
C = exp[7.50026 + 0.199364 (InF)
+ 0.0416602 (InF)2]
Low Flow Batch:
C = 250
Annual Costs:
Continuous feed:
A = exp[7.9707 - 4.45846 x 10~3 (InF)
+ 0.0225972 (InF)2] +0.183 (HPY)(F)
Batch feed:
A = (21) [16 + 0.5 (BPY)] + 0.131 (F) (HPY) (HPB)
Low Flow Batch:
A= (21) (0.5) (BPY) +0.131 (F) (HPY) (HPB)
C = 0
A = (DPY)[ 0.074 (B) + 5.25 (NB)]
C = 1,697.79 + 19.489 (B) - 0.036824 (B)2
C = 16,149.2 + 10.2512 (B) - 1.65864
x 10-3(B)2
A = (BPY)[5.01989 + 0.0551812 (B)
- 1.79331 x 10-5 (B)2] + 545
Range of Validity
0.4 < F < 417
1.5 < F < 1,500
X < 100
0.4 < F < 417
1.5 < F < 1,500
X< 100
X < 2,200
1 < B < 200
B > 200
-------
TABLE VIII-4 (Continued)
COST EQUATIONS FOR RECOMMENDED TREATMENT
AND CONTROL TECHNOLOGIES .
Equipment
Feed System, lime
(Continuous)
Feed System, Sodium Sulfide
Feed System, Polymer
Feed System, Sulfuric Acid
Filter, Multimedia
Filter, Membrane
Equation
C - exp[6.32249 + 1.70246 (InF)
- 0.137186 (InF)2]
A = exp[4.87322 + 1.78557 (InF)
4- 0.136732 (InF)2] + (F) (HPY) (LC)
C = 13,953.3 4- 117.18 (F) - 0.069117 (F)2
A- [0.758002 4-0.140318 (F) - 8.6493
x 10-8 (F)2](HPY)
C = exp[9.83111 + 0.663271 (InF)
4- 0.0557039 (InF)2]
C = 13,150 4- 2515.2 (F)
A » (HPY)[0.42 4-F] 4- 1,050
A = exp[8.60954 + 0.04109 (InF)
4- 0.0109397 (InF)2] 4- 2.25 (F)(HFY)
C = exp[8.1441 4- 0.23345 (InF)
4- 0.0180092 (InF)2]
A = exp[7.36913 4- 0.0133111 (InF)
4- 0.029219 (InF)2] 4- 0.03743 (F)(HPY)
C = 10,888 4- 277.85 (SA) - 0.154337 (SA)2
A = exp[8.20771 + 0.275272 (InSA)
4- 0.0323124 (lnSA>2]
C - 290.48 + 31.441 (Y) - 0.050717 (Y)2
A = [8.34253 x 10'3 4- 0.173683 (SR)
- 4.1435 x 10'5 (SR)2](HPY)
C - -2,922.48 4- 60.6411 (Y) - 0.065206 (Y)2
A•- [-0.0152849 + 0.172153 (SR) - 3.46041
x 10"6 (SR)2](HPY)
Range of Validity
10
-------
Equipment
Prefliter, Cartridge
Oil-Water Separator
Piping, Recycle
Pump, Centrifugal
Pump, Sludge
Reverse Osmosis System
TABIE VLII-4 (Continued)
COST EQUATIONS FOR RBCOMENEED TREATMENT
AND CONTROL TBCHNOIDGIES
Equation
C,= 283.353 + 25.91.11 (Y) - 0.058203 (Y)2
A= [0.118985 + 0.0803004 (SR) - 1.66003
x 10~5 (SR)2](HPY)
C = -2,612.73 + 51.568 (Y) - 0.059361 (Y)2
A- [-3.82339 + 0.0937196 (SR) - 1.7736
x 10~5 (SR)2](HPY)
C = 5,542.07 + 65.7158 (Y) - 0.029627 (Y)2
A = 783.04 + 6.3616 (Y) - 0.001736 (Y)2
C = exp[6.55278 + 0.382166 (InD)
+ 0.133144 (InD) 2] (0.01)(L)
A= 0
C = exp[6.31076 +0.228887 (InY)
+ 0.0206172 (InY)2]
A - exp[6.67588 + 0.031335 (MY)
+ 0.062016 (InY) 2]
C = 2,264.31 + 21.0097 (Y) - 0.0037265 (Y)2
A = exp[7. 64414 + 0.192172 (IriX)
+ 0.0202428 (InY)2] (HPB)
C - exp[6.82042 + 0.505285 (InX) + 4.77736
x 10-3 (InX)2]
A = [1.39054 + 3.54401 x 1(H (X)
+ 1.0307 x 10-10 (X)2](HPY)
Range of Validity
2 < Y < 140
140 < Y < 336
0 < Y < 700
D> 1
3 < Y < 3,500
5 < Y < 500
16 < X < 120,000
-------
TABLE VIII-4 (Continued)
COST EQUATIONS FOR RECOMMENDED TREATMENT
AND CONTROL TECHNOLOGIES
Equipment
Tank, Batch Reactor
oo
Tank, Concrete
Tank, large Fiberglass
Tank, Small Fiberglass
Tank, large Steel
Tank, Snail Steel
Equation
C - exp[4.73808 - 0.0628537 (InV)
+ 0.0754345 (InV)2]
A - 1,091 + 21 (BPY)
C = 3,100.44 + 1.19041 (V) - 1.7288
x 10-5(7)2
A = exp[8.65018 - 0.0558684 (InX)
+ 0.0145276 (InX)2]
C = 5,800 + 0.8V
A = 0.02 (C)
C = 3,100.44 + 1.19041 (V) - 1.7288
x 10-5(7)2
A = 0.02 (C)
C = exp[4.73808 - 0.0628537 (InV)
+ 0.0754345 (InV)2]
A = 0.02 (C)
C - 3,128.83 + 2.37281 (V) - 7.10689
x 10-5(V)2
C = 14,759.8 + 0.170817 (V)
- 8.44271 x 10~8 (V)2
A = 0.02 (C)
C = 692.82*4 + 6.16706 (V) - 3.95367
x 10~3(V)2
A = 0.02 (C)
Range of Validity
57 < V < 1,000
X < 2,200
1,000 < V < 24,000
2,200 < X < 11,600
24,000 < V < 500,000
1,000 < V < 24,000
V < 1,000
500 < V < 12,000
V > 25,000
100 < V < 500
-------
TABLE VIII-4 (Continued)
COST EQUATIONS FOR
AND CONTROL TECHNOLOGIES
Equipment Equation Range of Validity
Vacuum Filter C - 71,083.7 + 442.3 (SA) - 0.233807 (SA)2 9.4 < SA < 750
A = 17,471.4 + 677.408 (SA) - 0.484647 (SA)2
Vacuum Filter Housing C = (45) [308.253 + 0.836592 (SA)] 9.4 < SA < 750
A = (4.96)[308.253 + 0.836592 (SA)]
A = Direct annual costs (1982 dollars/year)
B = Batch chemical feed rate (pounds/batch)
BPY = Number of batches per year
C = Direct capital, or equipment costs (1982 dollars)
D = Inner diameter of pipe (inches)
F = Chemical feed rate (pounds/hour)
G = Sludge disposal rate (galIons/hour)
HP = Power requirement (horsepower)
HEE = Fraction of time equipment is in operation
HPY = Plant operating hours (hours/year)
L = Length of piping (feet)
LC = lime cost ($/lb, March 1982)
S = Clarifier surface area (square feet)
SA = Filter surface area (square feet)
SR = Solids removed by filter (grams/hour)
V = Tank capacity (gallons)
X = Wastewater flowrate (liters/hour)
Y = Wastewater flowrate (gallons/minute)
-------
TABLE VIII-5
COMPONENTS OF TOTAL CAPITAL INVESTMENT
ui
o
o
Item
Number Item
1 Bare Module Capital Costs
2 Electrical & instrumentation
3 Yard piping
4 Enclosure
5 •• Pumping
6 Retrofit allowance
7 Total Module Cost
8 Engineering/admin. & legal
9 Construction/yardwork
10 Monitoring
t1 Total Plant Cost
12 Contingency
13 Contractor's fee
14 Total Construction Cost
15 Interest during construction
16 Total Depreciable Investment
17 Land
1 8 Working capital
Cost
Direct capital costs from modela
01 of item 1
0% of item 2
Included in item 1
Included in item 1
Included in item 1
Item 1 + items 2 through 6
10.0% of item 7
0% of item 7
0% of item 7
Item 7 + items 8 through 10
15% of item 11
10% of item 11
Item 11 + items 12 through 13
0% of item 14
Item 14 + item 15
0% of item 16
0% of item 16
19
Total Capital Investment
Item 16 + items 17 through 18
aDirect capital costs include costs of equipment and required accessories,
installation, and delivery.
-------
TABLE VIII-6
COMPONENTS OF TOTAL ANNUALIZED COSTS
Item
Number
20
21
22
23
24
Item
Bare Module Annual Costs
Overhead
Monitoring
Insurance
Amortization
Cost
Direct annual costs
0% of item 1 6b
See footnote c
1% of item 1 6
CRF x item 1 6d
from modela
25
Total Annualized Costs
Item 20 + items 21 through 24
aDirect annual costs include costs of raw materials, energy, operating labor,
maintenance and repair. ;
16 is the total depreciable investment obtained from Table 1.
GSee page 463 for an explanation of the determination of monitoring costs.
capital recovery factor (CRF) was used to account for depreciation and
the cost of financing.
-------
TABLE VIII-7
WASTEWATER SAMPLING FREQUENCY
Wastewater Discharge
(LitersPer Day)
0 - 37,850
37,851 - 139,250
189,251 - 378,500
378,501 - 946,250
946,250+
Sampllng Frequency
Once per month
Twice per month
Once per week
Twice per week
Three times per week
502
-------
TABLE VIII-8
IN-PLANT COST FREQUENCY SUMMARY
Technology BPT-PSES 0 BPT-PSES 1
Paste Mixing and Application Area 28 28
Wash Water Recycle
Steam Curing 6 6
Humidity Curing Water Recycle 13 13
Slow Formation 8 10
Plate Countercurrent Rinsing 0 34
Sealant Water Recycle 0 5
Formation Area WAPC Water Recycle 25 25
Paste Mixing WAPC Water Neutralization 31 31
Reuse of Battery Rinse Water in 1 50*
Acid Cutting
Power Floor Scrubber Water Settling 85 85
Hose Washdown Water Recycle 85 85
Segregation of Nonproeess 85 85
Water Flows
*Reuse of battery rinse water in acid cutting was costed for 16
plants to eliminate discharges from formation battery rinsing.
503
-------
TABIE VIII-9
NONPROCESS WATER DISPOSITION MONG HANTS VISITED IN POST-PROPOSAL
Stream
Deionizer Blowdown*
and Water Softener
Baekflush
Assembly Noncontact*
Cooling
laady Oxide
Production Cooling
Grid Mold Cooling
Operations
Air Compressor
Cooling
Boiler Water!
Slowdown
%
Cooling Tower Blowdown
Shower Water
Number of
Plants With
Total Recycle
1 (5)
1 (5)
Number of
Plants That
Already Segregate
1
Number of Plants That
Discharge Stream To
Wastewater Treatment
Number of Plants
Which Do Not Have
Stream
2 (5)
1 (5)
11
*Selected for segregation modeling
^ Associated with curing operation
( ) Plants visited represents a model for five plants
-------
TABLE VIII-10
COST PROGRAM POLLUTANT PARAMETERS
Parameter
Flowrate
pH
Temperature
Total Suspended Solids
*Acidity (as CaC03>
Aluminum
*Ammonia
Antimony
Arsenic
Cadmium
**Ghromium (trivalent)
**Chromium (hexavalent)
Cobalt
Copper
*Cyanide (free)
*Cyanide (total)
*Fluoride
Iron
Lead
Manganese
Nickel
Oil and Grease
*Phosphorous
*Selenium
*Silver
*Thallium
Zinc
Units
liters/hour
pH units
SF
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
*Not analyzed for lead subcategory of battery manufacturing
**Assume chromium is in trivalent form for lead subcategory of
battery manufacturing ,
505
-------
Ol
o
EQUIPMENT
TABLE VIII-11
EXAMPLE PLANT SUMMARY
OPTION DPT
TOTAL REQUIRED
RUN CAPITAL CAPITAL ANNUM.
OPTION BAM
TOTAL REQUIRED
RUN CAPITAL CAPITAL ANNUAL
OPTION BAT-2
TOTAL REQUIRED
RUN CAPITAL CAPITAL ANNUAL
EHUALIZATION
OIL SKINHIN6
CHEM PRECIPITATION
GRAVITY SETTLING
VACUUM FILTRATION
MULTIMED FILTRATION
CONTRACT HAULING
HOLD TftfStS, RECYCLE
IN-PLANT COSTS
SUBTOTAL
SYSTEM CAP COSTS
ENCLOSURE
INSURANCE t TAXES
AMORTIZATION
NONITORING
TOTAL
TOTAL (JUNE 1983)
1 38508
1 2600
1 24300
1 67308
(5)
i e
8600
135300
50737
0
166937
189014
Ctttt
DOlw
2600
0
0
0
8600
17800
6675
0
24475
24867
5300
1380
13308
9600
11300
1600
42400
0
I860
4332
£880
51472
52296
2 20200
2 2600
2 32100
(4)
(5)
2 0
2 2399
8600
65800
24675
0
99475
91923
6600
2600
8
0
2339
8600
20100
7537
0
27637
28079
3208
1300
16400
4290
999
1600
27600
8
904
4891
IVA
34B3S
35392
2 20200
2 2600
2 32100
(4)
(5)
2 18000
2 0
2 2389
A£OA
UUiW
83800
31425
0
115225
117069
6600
2600
0
18000
0
2399
A£M
oow
38100
14287
0
52387
53225
3200
1300
16400
7600
4200
399
;ri«0
35200
0
1152
9272
1440
47064
47817
UBS OF BATTERIES/YR: 8,500,000
NQRHALIZED COST (JUNE 83 t/U):
FOOTNOTES:
.0061524
.8041638
.0056255
1. All costs are in March,1962 dollars except where indicated.
2. Systei capital costs are calculated as 37.5* of the total direct capital costs (capital subtotal).
1 Amortization is calculated as 17.7* of the total required capital costs.
4. Chnical precipitation operated in batch wide; gravity settling not costed.
5. Flow to vacua* filter is less than nniwm for sizing (42 1/hr). StrtM is contract hauled.
1/11/84
-------
TABLE VIII-12
NORMAL PLANT CAPITAL AND ANNUAL COSTS
Normal Plant Costs;
Op 11on
BPT (PSES 0)
BAT 1 (PSES 1)
BAT 2 (PSES 2)
BAT 3 (PSES 3)
BAT 4 (PSES 4)
BDT 5 (PSNS 5)
Capital Cost
107,708
91,782
111,760
100,025
149,339
111,760
Annual Cost
67,263
46,159
54,976
64,787
88,316
54,976
Normal Discharging Plant Costs:
Option
BPT (PSES 0)
BAT 1 (PSES 1)
BAT 2 (PSES 2)
BAT 3 (PSES 3)
BAT 4 (PSES 4)
BDT 5 (PSNS 5)
Capital Cost
122,377
98,628
119,443
109,943
179,934
119,443
Annual Cost
75,085
59,529
69,010
82,169
103,385
69,010
All costs are based on June 1983 dollars.
507
-------
Option
BPT (PSES-0)
BAT-1 (PSES-1)
BAT-2 (PSES-2)
BAT-3 (PSES-3)
BAT-4 (PSES-4)
Costs $/yr
263,000
206,000
222,000
222,000
309,000
TABLE VIII-13
ENERGY COSTS AND REQUIREMENTS
Energy Requirement kwh/yr
5,360,000 (386,540)
4,200,000 (302,576)
4,400,000 (327,184)
v
4,400,000 (327,184)
6,320,000 (454,912)
Percent Increase 'Over
Current Energy Consumption
0.70
0.55
0.57
0.57
0.82
o
oo
( ) - Indicates energy requirement for direct dischargers.
-------
°
u\
o
VO
JUNE -83
TOTAL DIRECT COSTS
°
X
X
CAPITAL
ANNUAL
101
10-*
10J
104
TOTAL PLANT LEAD USAGE (KG/HR)
FIGURE VIII-1
COSTS FOR PASTE MIXING AND APPLICATION AREA WASH WATER RECYCLE
-------
TOTAL DIRECT CAPITAL COSTS {$ - JUNE '83)
-» -* -* ~
00 0 O
-» -» N) U *
X
X
x
'
x
/
v
s'
}f
s
•*"
^r
f
4 105 106
X
x
x
x
'
107
^
108
TOTAL PLANT LEAD USAGE (KG/YR)
FIGURE VIII-2
COSTS FOR STEAM CURING
-------
TOTAL DIRECT COSTS (S - JUNE '83)
-» -» -»
0 0 0
-• ro u
x
X
X
X
X
^
/
/
S
S
S
S
s
jf*
^^^
^
, '
^
^
t
/
.^
S
/
S^
S
/
S
S
^
/•
t
4
t
j
X
X
' CAPIT/
x^
^
/
a
^
^^
,NNL
^
X1
AL
'
X
^
^
/
/
10"
10s
10°
TOTAL PLANT LEAD USAGE (KG/YR(
10b
FIGURE VIII-3
COSTS FOR HUMIDITY CURING WATER RECYCLE
-------
Ln
10°
n
n
UJ
z
10
w
o
o
O
o
UI
cc
a
10J
101
102
10"
CLOSED FORMATION LEAD USAGE (KG/HR)
FIGURE VIII-4
COSTS FOR SLOW FORMATION
-------
Ul
CO
OTAL DIRECT COSTS (» - JUNE '83)
^ «*
3 O <
W 4k
102
^
_sf
*
-------
Cn
P)
00
UJ
z
D
-J
(0
H
(0
o
o
o
UJ
K
<
i
104
103
102
1(
X
X
X
.
X
x
"
,
'
'
f
t
*
^
,'
^
_/"
%
_x
^
s
^~
^
/
s
'
'•
x
^xX
^
^.
VNNl
^
API
x'
JAL
^
TA
^1
^
L
I <" '
)4 105 106 107
> '
< '
108
OPEN DEHYDRATED FORMATION LEAD USAGE (KG/YR)
FIGURE VIII-6
COSTS FOR SEALANT WATER RECYCLE
-------
10°
Ol
Ill
z
D
w
05
05
O
O
tu
ce
Q
<
O
.
10
CAPITAL
10
10
10"
10°
10°
10'
10a
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COSTS FOR SEGREGATION OF NON-PROCESS WATER FLOWS
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FIGURE VIII-13
GENERAL LOGIC DIAGRAM OF COMPUTER COST MODEL
521
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FIGURE YUM4;
LOGIC DIAGRAM OF MODULE DESIGN PROCEDURE
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LOGIC DIAGRAM OF THE GQSTING RQUTINE
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FIGURE VIII-24
COSTS FOR CONTRACT HAULING
532
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through application of the best practicable control technology
currently available"(BPT), Section 301(b)(1)(A), for the lead
subcategory of the battery manufacturing category. BPT reflects
the performance of existing treatment and control practices at
manufacturing plants of various sizes, ages, and manufacturing
processes. Particular consideration is given to the treatment
in-place at plants within the subcategory.
The factors considered in defining BPT include the total cost of
the application of technology in relation to the effluent
reduction benefits from such application, the age of equipment
and facilities involved, the processes employed, non-water
quality environmental impacts (including energy requirements),
and other factors considered appropriate by the Administrator.
In general, the BPT technology level represents the average of
the best existing practices at plants of various ages, sizes,
processes or other common characteristics. Where existing
practice is universally inadequate, BPT may be transferred from a
different subcategory or category. Limitations based on transfer
of technology must be supported by a conclusion that the
technology is transferrable and by a reasonable prediction that
the technology will be capable of achieving the prescribed
effluent limits. See Tanner's Council of America v. Train, 540
F.2d 1188 (4th Cir. 1976). BPT focuses on end-of-pipe treatment
rather than process changes or internal controls, except where
such practices are common throughout the category or subcategory.
TECHNICAL APPROACH TO BPT
The entire battery manufacturing category was examined to
identify the processes used, wastewater generated, and treatment
practices employed in battery manufacturing operations. After
preliminary subcategorization and collection of additional
information using both dcp forms and specific plant sampling and
analysis, the total information about the category was evaluated.
On the basis of this evaluation, the subcategori'zation was
revised as described in Section IV to reflect primarily the anode
materials. The lead subcategory, encompassing lead acid reserve
cells and lead acid storage batteries, is the largest
subcategory. The lead subcategory was further subdivided into
discrete manufacturing process elements as shown in Table IV-1.
These process elements are the basis for defining production
normalized flows and pollutant raw waste concentrations. All
533
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information was then evaluated to determine an appropriate BPT.
Specific factors considered for BPT are:
• The lead subcategory encompasses several manufacturing
process elements each of which may or may not generate
process wastewater. These elements are divided into
groups for anode manufacture, cathode manufacture, and
ancillary (or all other) operations considered to be
part of battery manufacturing. A plant usually is
active in one or more anode process elements, one or
more cathode process elements, and in one or more
ancillary .operations. Process elements within the
subcategory are combined in a variety of ways at
battery manufacturing plants.
• Wastewater streams from different elements within the
subcategory usually share similar pollutant
characteristics, have similar treatment requirements
and are usually treated in combined systems.
• Most wastewater streams generated in the lead
subcategory are characterized by high concentrations of
toxic metals.
• Treatment practices vary extensively within the
subcategory. Observed subcategory practices include:
chemical precipitation of metals as hydroxides,
carbonates, and sulfides; sedimentation; and
filtration.
Other factors which must be considered for establishing effluent
limitations based on BPT have already been addressed by this
document. The age of equipment and plants involved and the
processes employed are taken into account and discussed in
Section IV. Nonwater quality impacts and energy requirements are
discussed in Section VIII.
In making technical assessments of data, EPA considered the
processes and treatment technology of both indirect and direct
dischargers as a single group. An examination of plants and
processes did not indicate any process or product differences
based on wastewater destination. Hence, descriptions of
applicable technology options for direct dischargers, are
referred to when describing indirect discharger applications.
The development of BPT mass limitations for the lead subcategory
was designed to account for production and flow variability from
plant to plant. The production normalizing parameter (pnp) for
the lead subcategory was determined to be the weight of lead used
534
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for all processes except truck wash where weight of lead in
trucked batteries was selected as is discussed in Section IV.
Each process element within the subcategory was then analyzed,
(1) to determine whether or not operations included in the
element generated wastewater, (2) to determine specific flow
rates generated, and (3) to determine the specific production
normalized flows (mean, median or weighted average) for the
process element. This analysis is discussed and summarized in
Section V.
Normalized flows were analyzed to determine which flow was to be
used as part of the basis for BPT mass limitations. The selected
flow (sometimes referred to as a BPT regulatory flow or BPT flow)
reflects the water use controls which are common practices within
the subcategory based upon dcp, industry survey and plant visit
data. All of the flow data used in establishing this regulation
for each process element are presented in Section V.
Significant differences between the mean and median reflect a
data set which has skewed or biased a wide range of points. When
even one data point (for a small data set) or several data points
(for a large uniform data set) have an abnormally high flow
(improper water control) or unusually low flow (extensive in-
process control or process variation), the average or mean may
not represent subcategory practice. In cases where there was
evidence that data were atypical, use of the median value was
considered as a means of minimizing the impact of one point (on a
small data base).or several points (on the larger data base). In
general, the median is used as a part of the basis for BPT mass
limitations. In those cases where a method other than the median
was used as the BPT flow, specific rationale for its use is
presented in the discussion. Factors considered in using the
median values include: numerical variations between the mean and
median, absolute size of mean and median value within a process
element, relative importance of the size of an element to the
total subcategory, and an analysis of specific atypical numbers.
Some elements were limited in the amount of flow data available
for BPT flow analysis. These elements are characteristically
those where a large fraction of the subcategory is involved in
the activity but flow values are available for only a few sites.
These elements are mold release formulation equipment wash,
laboratory, handwash, respirator wash, laundry, and wet air
pollution control. Flows for these elements were obtained from
site visits and equipment vendor information as they were
generally not reported in the dcp's or industry surveys. To
obtain the BPT flow, the general procedure was to calculate the
average flow per site for sites where flow information was
available; the average flow per site was converted to an annual
535
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basis; the annual flow per site was converted to total annual
flow using the number of sites reporting the element; the total
annual flow was then divided by the sum of individual site lead
use values using the most updated values available, 1982 or dcp
(1976). In some cases, flows were first normalized on the basis
of plant personnel for handwash, or respirators for respirator
wash. These average flows were then converted to the total site
flow using the appropriate industry survey data, prior to
conversion to annual flow. In this way, all information provided
was used.
Plants with existing flows above the BPT regulatory flow may have
to implement some method of flow reduction in order to achieve
the BPT limitations. In many cases this will involve improving
housekeeping practices, better maintenance to limit water
leakage, or reducing excess flow by turning down a flow valve.
In other cases, the plant may need to install systems to
recirculate water. As discussed in Section VIII, costs for this
subcategory include recycle systems for a number of process
operations.
The BPT model treatment technology assumes that all
(nonsegregated or nonrecycled) wastewaters generated within the
subcategory are combined for .treatment in a single or common
treatment system for that subcategory even though flow and
sometimes pollutant characteristics of process wastewater streams
varied within the subcategory. A disadvantage of common
treatment is that some loss in pollutant removal effectiveness
will result where waste streams containing specific pollutants at
treatable levels are combined with other streams in which these
same pollutants are absent or present at very low concentrations.
Since treatment systems considered at BPT were primarily for
metals and suspended solids removal, and existing plants usually
had one common treatment system in-place, a common treatment
system for this subcategory is reasonable in terms of cost and
effectiveness. Both treatment in-place at battery plants and
treatment in other categories having similar wastewaters were
evaluated. The BPT treatment systems considered consisted of oil
skimming, chemical precipitation, and settling. These treatment
systems when properly operated and maintained, can reduce various
pollutant concentrations to specific levels for each pollutant
parameter. Derivation of .these concentrations achievable by
specific treatment systems are discussed in Section VII and
summarized in Table VI1-21 (page 418).
The overall effectiveness of end-of-pipe treatment for the
removal of wastewater pollutants is improved by the application
of water flow controls within the process to limit the volume of
wastewater requiring treatment. The controls or in-process
536
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technologies recommended at BPT include only those measures which
are commonly practiced within this subcategory and which reduce
flows to meet the production normalized flow for each process
element.
Mass-based limitations have been determined to be the most
appropriate approach for regulating the lead subcategory.
Concentration-based limitations limit only the concentration of
pollutants in the effluent from the model treatment technology,
whereas mass-based limitations limit the total mass of pollutants
discharged (the product of achievable concentration and flow).
Significant reductions in pollutant discharge can be achieved in
this subcategory by the establishment of regulatory flows. The
concentrations achievable by the model treatment technology are
achievable over a wide range of influent concentrations.
Therefore, even in situations where decreased water discharge is
achieved by recycle (potentially resulting in more concentrated
pollutant levels in the wastestream), the effluent concentrations
will still be low. The resulting mass discharge of pollutants
will be much lower than those which would be achieved by only
concentration based limitations, the achievement of which does
not require flow reduction.
For the development of effluent limitations, mass loadings were
calculated for the process elements within the lead subcategory.
This calculation was made on an element by element basis because
plants in this subcategory are typically active in multiple
wastewater producing process elements; pollutants generated and
flow rates can vary for each process element. The mass loadings
(milligrams of pollutant per kilogram of pnp - mg/kg) were
calculated by multiplying the BPT normalized flow (I/kg) by the
concentration achievable using the BPT model treatment (mg/1) for
each pollutant parameter considered for regulation at BPT. The
BPT normalized flow for the lead subcategory is based on the
median of all applicable data (except for elements with limited
flow data) rather than the average of the best plants.
The following method is used to calculate compliance with the BPT
limitation. The allowable mass discharge for each process
element is determined by multiplying the allowable mass discharge
limitation (mg/kg) for that process element by its level of
production (in kg of production normalizing parameter). The
allowable mass, discharge for a plant is then calculated by
summing the individual mass discharge allowances of the process
elements performed at the plant. The actual mass discharge of
the plant is calculated by multiplying the effluent concentration
of the regulated pollutant parameters by the total plant effluent
flow. The actual mass discharge can then be compared against the
allowable mass discharge.
537
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SELECTION OF POLLUTANT PARAMETERS FOR REGULATION
The pollutant parameters selected for regulation in the lead sub-
category were selected because of their frequent presence at
treatable concentrations in raw wastewater. Specific raw waste
characteristics from the process elements are described in
Section V and are displayed in Tables V-5 to V-31 (pages 178 to
210). Total raw waste characteristics for all of the plants
sampled in this subcategory are presented in Table V-34. Tables
VI-1 and VI-2 (page 296 and 301) summarize the pollutants which
were considered for regulation. The pollutants which are present
at treatable concentrations in lead subcategory raw wastewaters
include antimony, cadmium, chromium, copper, lead, mercury,
silver, nickel, zinc, aluminum, iron, manganese, oil and grease,
and TSS. However, because antimony, cadmium, chromium, mercury,
silver, nickel, zinc, aluminum, and manganese are found in
smaller quantities and will be removed by lime and settle
treatment simultaneously with removal of tne regulated
pollutants, they are not regulated at BPT.
The pollutant parameters .selected are toxic metals (copper and
lead), iron, suspended solids, and oil and grease. pH is
selected as a treatment control parameter. As discussed in
Section VII, the importance of pH control for metals removal
cannot be overemphasized. Even small excursions away from the
optimum pH range (in most cases 8.8 - 9.3) can result in less
than optimum functioning of the system. To accommodate this
operating pH range (8.8 - 9.3) without requiring a final pH
adjustment the effluent pH range is shifted from the commonly
required 6.0 - 9.0 to 7.5 to 10.0. With the application of lime
and settle technology,' the concentration of regulated pollutants
will be reduced .to the concentration levels presented in Table
VII-21.
Total suspended solids, in addition to being present at high
concentrations in the raw wastewater is an important control
parameter for metals removal in chemical precipitation and
settling treatment systems. The metals are precipitated as
insoluble metal hydroxides, and effective solids removal is
required in order to ensure reduced concentrations of toxic
metals in the treatment system effluent. Total suspended solids
are also regulated as a conventional pollutant to be removed from
the wastewater prior to discharge. Oil and grease is regulated
under BPT since some wastestreams generated at lead battery
plants contain high concentrations of oil and grease (as shown in
Section V).
Lead has been selected for regulation under BPT since it is found
at high concentrations in process wastestreams.
538
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Copper has been selected for regulation under BPT since it and
lead are the predominant toxic metals present in lead battery
manufacturing wastewaters. Copper may be introduced into battery
manufacturing wastewaters by corrosion of process equipment
containing copper, such as cables and leads used in charging
operations.
Iron is being regulated because it was found in treatable
concentrations in all total raw wastewater streams. These high
concentrations are attributable to corrosion of process equipment
and charging racks by sulfuric acid.
PRODUCTION OPERATIONS AND DISCHARGE FLOWS
The lead subcategory includes the manufacture of a variety of
battery types, almost all of which are made of the same principal
raw materials: lead, lead oxides, and sulfuric acid electrolyte.
The plants within the subcategory vary widely in their wastewater
discharge volumes, reflecting process variations and a variety of
water use controls and water management practices. All lead
subcategory process elements identified in Table IV-1 (page 105)
generate process wastewater. Specific wastewater sources are
identified in Figure V-2 (page 170). Production normalized flow
data for all of these process elements are presented in Section
V. The same production normalizing parameter (total lead use)
can generally be used for all process elements in this
subcategory except truck wash since water use is related to lead
use.
Table IX-1 {page 557) presents the normalized discharge flows
that form part of the basis for the pollutant mass discharge
limitations for each process element. These normalized flows -are
generally equal to the median normalized flows presented in Table
V-3 (page 174) {except for elements with limited flow data) and
are indicative of half of the plants active in a particular
process element. Median statistical analysis was used for this
subcategory because of the nature of the data base. For the lead
subcategory, which is a large data base, the use of the median
values more realistically reflects where zeroes are in fact,
representative of common industry practice. Table IX-2 (page
559) summarizes the number of plants included in each process
element, the number which have zero discharge, and how zero
discharge is achieved. Therefore the use of the median in this
subcategory is reasonable.
Anode and Cathode Process Elements
All anode and cathode process element BPT regulatory flows
(except grid manufacturing regulatory flows) were calculated by
539
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using the median of plant-reported site specific flow rates which
were individually normalized by the site's lead use. The lead
use value chosen was the most up to date value available, i.e.,
1982 or dcp (1976). Plant-reported flow rates were obtained from
dcp data for all anode and cathode process elements except where
more recent data were available. Certain dcp values were updated
from information ,obtained from trip reports (before and after
proposal), plant contacts, and plant comment information. The
number of production normalized flows (I/kg) varied among these
process elements; the specific supporting data are reported in
Section V.
Leady Oxide Production. Information on water use in leady oxide
production was reported by 41 plants of which 29 plants reported
zero discharge for this process element. Wastewater was reported
to originate from leakage in ball mills, shell cooling contact
cooling, and wet scrubbers for air pollution control. (Scrubbers
are considered under the wet air pollution control process
element). Many plants generating leady oxide using balls mills
or Barton processes use only non-contact cooling water for
bearings, extensive recycle, and dry bag houses for pollution
control and therefore produce no process wastewater. A zero
discharge allowance has been established for this process element
at BPT based upon the fact that 70.7 percent of the plants which
reported data for this.process element discharge no wastewater.
Grid Manufacture. Process wastewater is generated from four grid
manufacturing operations: direct chill casting (continuous strip
casting), lead rolling, mold release formulation, and grid
casting. In direct chill casting, contact cooling water is used
to quickly cool the cast lead strip. The contact cooling water
is collected and continually recirculated. The water in this
system is generally batch dumped. Five plants report the use of
this casting technique and one plant provided flow information
for this wastestream. This plant was presented as the model to
be used for all five plants. The BPT regulatory flow has been
established as 0.0002 I/kg, the production normalized flow for
this one plant.
In lead rolling, an emulsion is used to lubricate the rolling
mills. This emulsion is contract hauled to land disposal off-
site by all five lead battery plants which report this activity.
Lead rolling is included under the battery manufacturing category
but is not specifically regulated because there are no known
dischargers. Guidance is provided in the event that plants which
perform lead rolling find the need to discharge this wastewater.
A regulatory flow of 0.006 I/kg of lead used in batteries (0.0233
I/kg lead rolled) has been established for guidance should plants
540
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find the need to discharge this wastewater. This flow is based
on sampling data from one plant.
Process wastewater from grid casting originates from mold release
formulation and wet air pollution control in some plants. The
wet air pollution control operation is addressed under that
respective process element. The formulation of mold release
agents can generate process wastewaters by cleaning equipment
after mixing batches of the release material. Flow data (average
flow per plant) for the mold release formulation process were
obtained from two companies that reported discharge of this
wastewater at their plants. This represents data on 29 plants
all of which reported a discharge of wastewater. The BPT
regulatory flow for mold release formulation has been established
at 0.006 I/kg. This was obtained by: (1) multiplying the
company specific flow by the number of respective plants in the
company and (2) dividing this total flow by the sum of the
company-specific productions to obtain a company-specific
production normalized flow. The two resulting company-specific
PNFs were then averaged to obtain the BPT flow.
Paste Preparation and Application. Information on water use for
the paste preparation and application process element was
reported by 100 plants, of which 57 reported zero discharge of
wastewater. The establishment of a closed loop system for the
paste processing and area washdown wastewater is a common
practice among lead subcategory plants. Settling the wastewater
allows for the removal of solids which can be either re-
introduced into the paste formulation process or sent to a
smelter for the recovery of lead. After settling, the wastewater
can be used either in paste formulation or pasting area floor and
equipment washdown. A zero discharge allowance has been
established for this process element at BPT because the
elimination of process wastewater discharge from paste
preparation and application areas by collection, settling, and
reuse is commonly practiced by plants in the lead subcategory.
Discharges from wet scrubbers used to control fumes from paste
mixing at some plants are included in the wet air pollution
control process element.
Curing. Eighty-seven of the 97 plants supplying data reported
zero discharge of wastewater from plate curing. Wastewater
generated by the other ten plants was a result of steam or
controlled humidity curing with discharge. Steam curing and
humidity curing processes were observed at existing plants which
currently achieve zero discharge from this process element. This
is achieved by collection and recirculation methods for the
wastewater, as described in Section VII. Therefore, a zero
541
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discharge allowance has been established for this process
element.
Closed Formation. The closed formation process includes three
distinct elements? single fill formation and double fill
formation (which are collectively known as closed formation of
wet batteries), and fill and dump formation (also known as closed
case formation of damp batteries). The closed formation process
generates wastewater from a variety of sources as discussed in
Section V but primarily from the rinsing of battery cases. A few
plants in the subcategory reported and were observed to use large
amounts of cooling water. The use of contact cooling water
results from the implementation of rapid charging rates, as
discussed in Section VII. As discussed in Section V, wet
scrubbers used to control fumes from closed formation are
included in the wet air pollution control process element.
In the single fill operation, the battery is filled with acid of
such specific gravity that, after formation, the electrolyte will
be suitable for shipment and operation of the battery. For this
process element, 31 of the 43 plants supplying data reported no
discharge. Zero discharge is achieved by using low-rate or
controlled charging techniques which do not require the use of
contact cooling water to dissipate heat generated during battery
charging. Effective battery filling techniques are also used to
control spills and eliminate the need for battery rinsing prior
to charging. A zero discharge allowance has been established for
single fill closed formation since zero discharge is indicative
of common industry practice for the single fill process.
Even though the final shipping status is different for the double
fill and fill and dump processes (wet—with electrolyte vs. damp-
without electrolyte), the generation of process wastewater and
the pollutant characteristics are essentially similar. In the
double fill formation process, the batteries are filled with a
low specific gravity electrolyte, charged, and the electrolyte
dumped. The batteries are then filled with a higher specific
gravity electrolyte for shipping. The reuse of dumped formation
acid is a common practice among the lead subcategory plants and
is economically beneficial. Contamination of the electrolyte is
minimized by limiting spillage and implementing effective acid
collection techniques during post-formation dumping. Once the
waste electrolyte solution is collected, it is combined with
fresh sulfuric acid and water to achieve the acid quality
required for process reuse. Of the 35 plants providing data on
the double fill process, seven reported zero discharge of
wastewater.
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The fill and dump formation process is the same as the double
fill process except that a second electrolyte fill is not
performed before shipment. Thirteen plants provided information
on the fill and dump formation process, of which 12 reported
discharge of wastewater.
Because the processes are essentially identical, a BPT regulatory
flow has been established for double fill and fill and dump
formation combined. The BPT flow, is based on the median of all
of the data for the two processes and is 0.45 I/kg lead used.
Open Formation. The open case formation process includes open
formation for wet plates and open formation for dehydrated
plates.
In the case of open formation for dehydrated plates, the primary
source of wastewater is from the rinsing and dehydration of
plates. Of the 42 sites which provided information on open
dehydrated formation, 40 reported a discharge of wastewater.
The median normalized discharge flow of 11.05 I/kg was selected
as the BPT regulatory flow for open case formation for dehydrated
plates. The median flow was selected because it is considered to
be common industry practice with 50 percent of the plants
currently discharging at or below this level.
Open formation for wet plates is frequently used for the
manufacture of industrial batteries with large electrodes.
Wastewater from this operation is sometimes generated from
dumping and not reusing electrolyte after a certain number of
formation cycles. Some plants reuse this electrolyte in final
battery products/ others send it to treatment. Plants also
reported area washdown, and rinsing of formed plates as
contributing to the discharge from this operation. Of the 16
plants providing information on this process element, ten
reported zero discharge of process wastewater. Five of the six
discharging plants discharge plate rinsing wastewater, spent
electrolyte or both. These plants contend that a discharge of
these wastewaters is unavoidable because there is no
opportunities in the plant for reuse of the acid or rinse water.
Therefore, a BPT regulatory flow of 0.053 I/kg has been
established for these waste streams based on the median discharge
flow from these five plants. The sixth plant which discharges
wastewater from open wet formation was not used to calculate the
regulatory flow. This plant reuses spent electrolyte but
discharges wastewater from formation area equipment washdown.
None of the other plants with open wet formation reported a
discharge from equipment washdown. Therefore, flow data from
this plant was not used to determine a regulatory flow.
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Four of the five plants used to determine the regulatory flow, are
operated by one company. The frequency of batch electrolyte
discharges at these four plants varies from daily discharges to
semi-annual discharges. This indicates that the number of
formation cycles that electrolyte can be used before dumping is
not well defined at this company. To calculate the regulatory
flow for open wet formation, it was assumed that electrolyte is
batch dumped once per month at these four plants.
Wastewater discharges associated with wet scrubbers used to
control fumes generated from open wet formation are included in
the wet air pollution control process element.
Plate Soak. Based on data collected in dcps, industry surveys,
from site visits and in plant comments received, some plants soak
plates usually for heavy industrial batteries in sulfuric acid
prior to formation. The plates soaked are relatively thick 0.25
cm (0.10 inch or greater). Occasional dumping of this acid is
required generating a small waste stream which must be treated.
The BPT regulatory flow for this stream is calculated to be 0.021
I/kg of lead used in batteries that are plate soaked. This
number is based on the median of data reported by three plants on
the amount of electrolyte dumped.
Ancillary Operations
Regulatory flows for ancillary operations were calculated using
either medians of individual plant production normalized flows or
a weighted average of flow data available followed by production
normalization. The method which was used was dictated by the
amount of flow data which were available from lead subcategory
plants. Where a few flow rates were measured or reported by
plants but the participation by plants in the element is
significant, a weighted average was used. This averaging
technique varied in accordance with the type of data being used
and is discussed for each applicable element. The plants which
reported flow data as well as those which reported the process
element are presented in Table IX-1. As in the case of the
anodes and cathode elements, the production normalized flow data
base included dcp data which were updated with data obtained from
site visits, plant contacts, and plant comments.
Battery Wash. Battery wash operations produce wastewater as a
result of two different process elements - washing with detergent
and washing with water only. Nearly all of the plants active in
these process elements reported wastewater discharge. Sixty-six
plants provided flow data on battery wash of which 44 reported
the use of water and 22 reported the use of detergent. Of the
plants reporting the use of a detergent wash system, none
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reported zero discharge of wastewater. The median production
normalized discharge flow, 0.90 I/kg, is used as the flow basis
for determining the BPT flow for detergent washing of batteries.
The median was chosen because 50 percent of the plants are
currently maintaining this flow which is considered to be common
industry practice. Those plants currently discharging at a flow
greater than the median could reduce their flows by additional
recirculation of wash solution and rinse water, and by reusing
the final rinse as make-up to the detergent portion of the system
resulting in discharge from only the detergent wash step. <'
Of the 44 plants reporting the use of water battery wash systems,
43 reported a discharge of wastewater. The BPT regulatory flow
for water washing has been established at the median production
normalized flow of 0.59 I/kg. Those plants currently discharging
at a flow greater than the median could reduce their flows by
either reducing the amount of water per battery directly, or
using efficient methods described in Section VII.
Truck Wash. Sampling and industry survey data support a
discharge allowance for truck wash wastewater in both the battery
manufacturing and nonferrous metals manufacturing categories.
EPA observed that trucks are used to transport used batteries in
connection with battery cracking (secondary lead subcategory of
the nonferrous metals manufacturing category) processes. Trucks
are also used to transport batteries for various purposes related
to battery manufacturing, operations. The truck wash regulatory
flow for the lead subcategory of battery manufacturing applies
only to those sites without an associated on-site secondary lead
smelting plant. Truck washing at sites that have battery
cracking or secondary lead smelting will be regulated under the
nonferrous metals manufacturing regulation. Equivalent
regulatory flows for truck wash are promulgated under the two
regulations.
Flow data to calculate the BPT flow for battery manufacturing
truck wash operations were obtained from two sampling visits
after proposal. For each site, a daily truck wash flow was
calculated using the highest measured flow per truck (150 liters)
from the two sites measured. Assuming 250 operating days per
year, these flows were converted to annual flows. Production
data from 1982 was used for both plants to obtain two production
normalized flows which were then averaged to obtain the BPT flow
of 0.014 I/kg of batteries trucked.
Laundry. Eleven sites in the subcategory reported on-site
laundering of work clothing based on industry survey data. Flow
data were obtained during 2 sampling visits for 2 laundry
operations. Both of these plants reported discharge of laundry
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wastewater. Although information of laundry activities indicates
that most plants do not have on-site laundries, those plants
which do will have a discharge of laundry wastewater; therefore,
a BPT regulatory flow for on-site laundering of work uniforms is
appropriate. Laundry discharge flows were normalized by work
uniform using measured flow rates obtained at both sites. These
flows were average^ to obtain 21.4 liters per uniform. The
number of uniforms ' washed per day at each plant reporting this
element was obtained from the industry survey. Using the average
liters per uniform, number of uniforms per day, and an assumed
250 days per year, an annual flow from the laundry operation was
estimated for each of the 11 plants. The total laundry flow from
all eleven plants was divided by the total of their respective
annual production values (the most recently available data) to
determine the BPT regulatory flow of 0.109 I/kg.
Miscellaneous. A BPT regulatory flow of 0.427 I/kg has been
established to cover a miscellaneous group of wastestreams.
These wastestreams are associated with the following process
elements: floor wash, wet air pollution control, battery repair,
laboratories, hand wash, and respirator wash. Discharge
allowances for these six streams are combined together because
all of those activities occur at almost all lead plants, and
combining them into a single group, facilitates administration.
If a plant has any one of these streams, then the plant receives
the entire miscellaneous wastewater discharge allowance. The
miscellaneous regulatory flow is the arithmetic sum of the
regulatory flows established for each process element of the
miscellaneous group. Each individual process element and its
associated regulatory flow is discussed below.
Floor Wash - Information provided in the dcp, industry survey
responses, and from site visits were considered in establishing
the regulatory flow for floor wash. Data were available from 13
plants, of which two reported zero discharge. A variety of
cleaning methods are used including buckets, mops, hoses, and
other manual methods, as well as wet power (vacuum) floor
scrubbers. A normalized flow of 0.13 I/kg has been calculated
based on the median of production normalized flow data reported
and measured. This regulatory flow applies to floor wash outside
of the pasting area.
Wet Air Pollution Control - The established regulatory flow for
wet air pollution control scrubber blowdown is based on model
technologies typical of those used for wet scrubbing of pasting
areas and wet scrubbing of formation areas (See Sections V and
VII). These models incorporate data obtained from on-site plant
visits and vendor information for the two scrubber types
typically used. Observations made during plant visits indicated
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that most plants have no more than two wet scrubber operations
on-site; therefore, a regulatory flow which sums both wet
scrubber model flows has been established. The BPT regulatory
flow is based on the sum of two model technology flows instead of
the average normalized flow shown in Table V-3. As discussed in
Section V, a wide range of discharge flows were reported from wet
air pollution control activities even though only two different
scrubbers designs are used in this subcategory. The two model
technologies accurately reflect the discharge flows which can be
achieved from the two types of wet air pollution control devices
used in this subcategory.
The information reported in the battery manufacturing and casting
dcp, site visits, plant contacts, and vendor contacts were used
to identify the types of scrubbers used at lead subcategory
plants. As discussed in Section V, these were identified as two
design types which are used in two groups of process elements:
group I consists of leady oxide production, pasting, grid
manufacture and assembly, and group II consists of the formation
elements. Each design has a characteristic discharge mode of
operation and flow rate. The group I design incurs infrequent
(semi-annual) batch dumping provided that proper corrosion
protection measures are taken, such as the addition of alkali
into the holding tank. The type of discharge mode is supported
by plant visits and dcp flow data. The actual flow used for the
group I model was obtained from equipment vendor information for
a conservatively large scrubber: accomodates 50,000 SCFM with a
water capacity of 3,000 gallons. (Typically reported sizes in
group I accommodate 6-14,000 SCFM with a capacity of 220-1330
gallons.) This volume (3000 gallons) is assumed to be dumped
semi-annually. Pasting area scrubbing represents the most common
group I scrubbing activity. The BPT regulatory flow for group I
scrubbing was calculated by multiplying the annual model
discharge volume by the number of sites reporting pasting area
scrubbers and dividing by the total production from these sites.
A 0.005 I/kg normalized flow was obtained using this procedure.
In a similar manner to the approach used to obtain a normalized
flow for group I scrubbers, a group II scrubber normalized flow
was obtained. One of the sampled plants was used as a model for
the scrubber design and operating mode. Equipment was added (in
the model) to accommodate recycle of the existing model plant
washdown water as well as for caustic addition to allow for more
extensive recycle. A vendor-recommended blowdown rate was used
(1.5 x (0.005 gpm per 1000 cfm of air)). This factor was
multiplied by the flow rate of air through each scrubber in the
model plant and then multiplied by the number of scrubbers used
at the model plant. This resulting flow was then converted to an
annual • flow based on the operation of the model plant system.
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The normalized flow for formation scrubbing was calculated for
the model plant using the 1982 production for the model plant.
This normalized flow is 0.006 I/kg.
The complete wet scrubber regulatory flow of 0.011 I/kg was
calculated by adding group I and group II normalized flows.
Battery Repair - Thirty plants which returned industry survey
information indicated some type of battery repair operation.
However, flow data is available from only three plants from which
a normalized flow can be calculated. The BPT regulatory flow has
been established at the median flow of 0.25 I/kg. Contributing
wastewater sources include dumped electrolyte, repair area
washdown, and contact cooling water.
Laboratory - Site visit data were used to determine a regulatory
flow for wastewater discharged from on-site laboratory
facilities. The laboratory tests performed at the battery plants
which generate wastewater were found to be very similar from
plant to plant; there were no differences which justified
significant flow differences between plants. Observations made
indicated that some plants reclaim quality control lead samples
taken for their lead value. Based on this practice, lead
loadings in the discharge water to treatment should mostly be due
to lab instrument washing, dumped electrolyte from battery
teardown and wet air pollution control scrubbers used to control
fumes from various tests; also some tests require plate rinsing
before chemical assay. These wastewater sources are included in
the process water flow for the laboratory process element. Other
flows such as noncontact cooling water for graphite furnaces and
other instrumentation are not included.
Discharge information was obtained for all sites visited, and
flow data were obtained from five sites; two were measured and
three flows were plant-reported. Data from four of these sites
were used in the normalized flow calculation; one value was more
than an order of magnitude above the others without any
associated justification. The normalized flow was calculated by
adding the daily flows from the four sites, converting the total
daily flow to an annual flow assuming 250 days of operation per
year, and dividing the total annual flow by the total production
from the four sites. A normalized flow of 0.003 I/kg was
calculated from the above procedure.
Hand Wash - Data were collected from site visits and industry
surveys on hand wash operations; these data support a regulatory
flow for employee hand wash within the production areas of the
plant. Hand wash is assumed to be practiced at all sites. Of
the sites visited, most discharge hand wash water to a sanitary
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sewer without treatment while a few sites treat hand wash water
before discharge. Hand wash flows were measured at two sites
yielding the same flow values (1.5 I/person). This flow (1.5
I/person) was used to obtain individual site flow rates by using
the number of employees in required washup at the site. The
number of employees were reported in the industry survey
responses. This daily flow for each site was converted to an
annual flow using 250 days per year. The 63 annual flows were
added and divided by the 63 plants' associated total production.
A normalized flow of 0.027 I/kg of total lead used was
established for hand wash.
Respirator Wash - Sampling data and industry survey data were
used to determine a normalized flow of 0.006 I/kg for respirator
wash water. Fifty-one plants reported on-site respirator wash
activities. Flow data were available for six plants, all of
which reported the discharge of this wastewater. Flow values
from the six plants were normalized by the number of respirators
washed and averaged to obtain an average flow of 4.6 liters per
respirator washed. For those sites reporting the number of
respirators washed per day in the industry survey responses, the
average flow per respirator was used to^determine a daily flow at
each site. These daily flows were added and the sum was
converted to an annual flow assuming 250 operating days per year.
The total annual flow was then divided by the sum of the
respective productions to obtain the regulatory flow. The most
updated production values were used.
MODEL TREATMENT TECHNOLOGY
BPT end-of-pipe technology for the lead subcategory is
illustrated in Figure IX-1 (page 583). The BPT treatment scheme
consists of oil and grease removal by oil skimming, and end-of-
pipe lime and settle treatment applied to all combined
wastewater. The end-of-pipe model technology of lime and settle
treatment is intended to be state of the art lime and settle
technology which is properly designed and carefully operated.
Caustic, sodium carbonate, or lime is added to adjust the pH to a
level that promotes adequate precipitation. The optimum pH range
for precipitation of metals, especially lead, from lead
subcategory waste streams is 8.8-9.3. Carbonate ion in addition
to hydroxide may be required to promote the effective
precipitation of lead. Carbonate precipitation is similar to
hydroxide precipitation in terms of metals removal, and the
treated effluent from carbonate precipitation is compatible for
use in lead recovery processes. Alternatively, treatment system
performance can be improved by evaluating other precipitation
technologies. Sulfide precipitation is more effective than
hydroxide precipitation at removing lead because of the lower
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solubility of lead sulfide. Also, iron coprecipitation, which
involves the addition of iron salts to a precipitation and
settling system, can enhance the removal efficiency of the
system. However, since the presence of iron salts in recycled
waters could be detrimental to lead subcategory processes, the
use of iron coprecipitaton would most likely be limited to the
treatment of waste streams which are to be discharged. Proper pH
control will enhance the settling of both metal precipitates and
suspended solids. Clarifiers can achieve required effluent
concentrations; however, comparable effluent concentrations can
be achieved in tanks or lagoons or by filtration. In some cases,
provisions of an oil skimmer may also be required to achieve
acceptable effluent quality.
The sludge which accumulates during settling must be removed to
ensure continued effective operation of the settling device. A
vacuum filter is included in the BPT system to reduce the water
content of the sludge and minimize the quantity of material
requiring disposal. The resulting filtrate is returned for
further treatment, and the sludge should be sent to metal
recovery or to a secure landfill. It is not anticipated that
such sludges will be hazardous wastes.
Lime and settle (chemical precipitation) technology was con-
sidered as BPT following a careful review of collected
information characterizing process wastewater, present treatment
practices, and present manufacturing practice. Removal of
metals, the primary requirement in treating lead subcategory
process wastewater, can be achieved by chemical precipitation and
settling. This technology is similar to that presently in-place
at plants which treat their wastewaters. As summarized in Table
IX-3 (page 561) the most frequently reported end-of-pipe systems
in this subcategory were equivalent to pH adjustment and settling
or pH adjustment and filtration (53 plants); ten others reported
the use of filtration following pH adjustment and settling. pH
adjustment only or no pH adjustment with treatment was practiced
at 46 plants, and 74 plants reported no treatment in-place.
On the basis of 33 plant visits and an evaluation of effluent
data submitted, which was discussed in Section V, it was
concluded that existing treatment facilities in the subcategory
generally were improperly designed, maintained, or operated. In
fact, those plants which had filtration units in place, used them
generally as primary solids removal units and not as polishing
filters designed to achieve low effluent pollutant
concentrations. Based on the observation that most plants
already have BPT end-of--pipe systems in-place, the selected BPT
is judged to be reasonable. A discussion of the reasonableness
of the BPT limitations is presented later in this section. As an
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alternative to reducing effluent concentrations to meet discharge
limitations, the discharge flow can be reduced by either
substitution of dry processes or by the reuse of treated or
untreated wastewater.
EFFLUENT LIMITATIONS
The pollutant mass discharge limitations (milligrams of pollutant
per kilogram of pnp) were calculated by multiplying the BPT
regulatory flows summarized in Table IX-1 (I/kg) by the
concentration achievable by the BPT model treatment system
summarized in Table VI1-21 (mg/1) for each pollutant parameter
considered for regulation at BPT (I/kg x mg/1 = mg/kg). The
results of this computation for all process elements and
regulated pollutants in the lead subcategory are summarized in
Tables IX-4 to IX-16 (pages 562 to 574). These limitation tables
list all the pollutants which were considered for regulation and
those specifically regulated are marked with an asterisk.
POLLUTANT REMOVALS AND COSTS
In the establishment of BPT, the cost of application of tech-
nology must be considered in relation to the effluent reduction
benefits from such application. The quantity of pollutant re-
moval by BPT is displayed in Table X-6 (page 604) for the total
subcategory and Table X-7 (page 605) for direct dischargers only.
Treatment costs are shown in Table X-8 (page 606). The capital
cost of BPT as an increment'above the cost of in-place treatment
equipment is estimated to be $8.60 million ($1983) ($0.715
million for direct dischargers) for the lead subcategory. Annual
costs of BPT for the lead subcategory are.estimated to be $5.13
million ($1983) ($0.499 million for direct dischargers). The
quantity of pollutants removed from estimated raw waste by the
BPT model technology for this subcategory is estimated to be
10,978,344 kg/yr (791,232 kg/yr for direct dischargers) including
1,601,278 kg/yr (115,407 kg/yr for direct dischargers) of toxic
metals. The pollutant removals justify the costs incurred by the
plants in the lead subcategory.
REASONABLENESS OF THE LIMITATIONS
To confirm the reasonableness of these limitations for this
subcategory, limitations were compared to actual performance at
lead subcategory plants by first looking at plant flows. Because
BPT is common end-of-pipe treatment from multiple process
elements, and because compliance with the regulation will be
judged on a total plant basis, total plant performance is
compared rather than performance from each process element. This
was accomplished by calculating total process wastewater BPT
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regulatory flow rates for each plant in the subcategory1based on
available production information and on the normalized process
element BPT flows shown in Table IX-1. These calculated BPT flow
rates were then compared to effluent flow rates actually reported
or measured. Effluent concentrations were also compared to those
attainable by lime and settle (L&S) technology as presented in
Table VII-21. Finally total plant pollutant mass discharges were
compared to BPT limitations for plants which, on the basis of
effluent flow rates and concentrations, were potentially meeting
BPT mass discharge limitations.
As a first step in this comparison, lead subcategory process
wastewater flow rates from each plant were compared to the flow
rates upon which mass limitations for the plant would be based.
Since operating schedules are generally regular in this
subcategory, this comparison was made on the basis of hourly
flows. To calculate actual process wastewater discharge flows,
the discharge flow rate (1/hr) from each process element at the
plant were added. The total process wastewater flow from this
procedure represents the sum of reported process element flows
from the plant. Process elements for which flow data were not
reported are not included in the total flow. In general, flow
data from the ancillary streams added after proposal (laboratory,
truck wash, handwash, respirator wash, and laundry) are not
included in the total reported process element flows, since flow
data was only available from a few plants for these process
elements. (Flows from these process elements are included when
available.) At some plants, individual process element flows
were either not available, or only available for a few of the
process elements that the plant reported. However, most of these
plants reported a total process wastewater flow in their dcps.
For these plants, the total process wastewater flow was assumed
to be equal to the combined flow from process elements reported
in the dcp. It was assumed that discharges from process elements
not reported in the dcps (such as laboratory, truck wash,
handwash, respirator wash, and laundry) were not included in the
total process wastewater flow. For all plants, the total process
wastewater flow was compared to the sum of corresponding BPT
flows for each process element included in the total flow.
Production information was used to determine the hourly BPT
process element flows. The annual pnp was divided by the plants
operating time to determine an hourly pnp. This hourly pnp was
multiplied by the normalized flow shown for the process element
in Table IX-1. The hourly BPT process element flows were then
added to determine the total BPT flow. This BPT flow was then
compared to the total process wastewater flow. Table IX-17 (page
575) presents a comparison of these flows.
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Fifty-seven plants reported zero discharge of process wastewater
from the lead subcategory and were, therefore, complying with the
BPT flow and limitations. Twenty-eight additional plants were
identified that produce total wastewater discharge flows less
than those used in calculating BPT mass discharge limitations.
Fourteen of the twenty-eight have BPT treatment systems (L&S
technology) in-place, and 13 of these 14 submitted effluent data
which is summarized in Table IX-18 (page 580). Plants which had
pH adjustment and filtration were considered to have treatment
equipment in-place that is equivalent to BPT (lime and settle).
However, the filtration systems were usually used only for
primary solids removal. Only one plant submitted data indicating
that it would comply with the average lead concentration values
shown in Table VII-21; however, its TSS concentration was
significantly high, indicating a poorly maintained settling
system. On the basis of the data submitted, operational factors
which influence treatment performance could only be evaluated for
the plants submitting pH data. As discussed in Section VII, pH
should be maintained at 8.8-9.3 for the most efficient removal of
pollutants. Only one plant (Plant J) reported a pH which was in
the 8.8-9.3 range. However, this plant has other operational
problems (these problems are discussed later) which result in a
high effluent lead concentration.
Lead subcategory treated wastewater values (pH, lead and TSS)
vary considerably among plants indicating that treatment systems
vary in design and operating practices. This was also evident at
plants that were sampled. Six of the sampled plants discharge
process wastewater and have BPT equivalent treatment syterns in-
place. Sampling data from these six plants are also summarized
in Table IX-17. Three of the six plants (Plants A, J and M) were
maintaining flows in compliance with BPT, and three (Plants N, 0,
and P) were not. As shown in Table IX-17, plant A was not
maintaining pH within an acceptable range, and consequently was
not meeting lead concentrations for BPT technology. The
filtration system at this plant was used as a primary solids
removal device and was not operating effectively at the time of
sampling, resulting in high TSS concentrations. Sampling data at
this plant did not support the plant's dcp data for lead
concentration and showed that the plant was not complying with
its permit which allowed a maximum of 1.0 mg/1 of lead to be
discharged. With proper pH control and the addition of settling
tanks with adequate retention time, this plant would be expected
to comply with its permit and BPT limitations. Plant J not only
had the same operational problems as plant A (improper pH control
and no settling with filtration), but also the treatment system
was being overloaded to almost triple its design capacity, due to
increased production. This plant could readily comply with BPT
limitations by maintaining proper pH control and by either
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limiting flows to the treatment system to design levels only, or
enlarging the treatment system. The industry survey data from
Plant J was submitted after the plant was sampled. These data
indicate that the plant now operates at an average pH level of 9.
However, the effluent lead concentration reported in the industry
survey indicates that the plant has not solved its other
operational problems. It was observed during the visit to Plant
M that a pH of 7.5 was used to precipitate metals. This is well
below the effective removal range of 8.8 to 9.3. Despite this
low pH, lead was not detected in the effluent from this plant
during sampling. Industry survey data from Plant M (which
represents wastewater treatment performance over a longer time
period than sampling) indicate that an average effluent lead
concentration of 0.25 mg/1 is achieved. Thus, it appears that
Plant M does not achieve the effluent lead concentrations
achieved during sampling on a regular basis. This is probably
due to the low operating pH. If the operating pH is maintained
within the 8.8 to 9.3 range, this plant would be expected to
achieve effluent concentrations similar to those achieved during
sampling on a regular basis.
Three of the sampled plants with BPT equivalent treatment systems
in-place do not comply with the BPT flows. Two of these plants
(Plants N and O) maintain pH within the effective removal range.
This enables these two plants to achieve effluent lead
concentrations comparable to the average lead concentration shown
in Table VII-21. Several operational problems were observed at
Plant P. Plant P uses a clarifier with tube settlers to remove
precipitated solids. As with Plant M, an operating pH of 7.5 was
observed to be used to precipitate metals. In addition, the tube
settler used for primary solids removal was observed to be laden
with solids. This impedes the manner in which the tube settler
removes solids. Also, the clarifier at this plant is designed
for continuous operation, but was operated intermittantly during
the visit. A lead concentration of 0.100 mg/1 was observed in
the effluent lead sample taken during the visit to this plant.
As shown by the industry survey data from Plant P, this
concentration is not achieved on a regular basis. If the
operational problems of the wastewater treatment system are
corrected, this plant would be expected to achieve the
concentrations observed during sampling on a regular basis.
Other lead plants which were visited, but not sampled supported
the conclusions reached from evaluation of submitted data and
sampling data. Several plants were maintaining the BPT process
flows and also had BPT or better end-of-pipe treatment systems
in-place which allowed the plants to reuse the water and thus
achieve zero discharge of wastewater pollutants. Other plants
appeared to have the same operational problems (no pH control and
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overloaded treatment systems) as some of the sampled plants
previously mentioned. Four additional plants in the lead
subcategory were sampled. Three of these plants achieve zero
discharge of wastewater pollutants by methods other than BPT
technology such as treated wastewater reuse, contract hauling and
evaporation, or land application. Process wastewater was sampled
at each of these three plants and sampling results are shown in
Section V. The effluent from wastewater treatment (which is
reused or land applied) at one of these plants was also sampled.
Sampling results and an evaluation of the plants' treatment
system are presented in Section V. The other sampled plant uses
a lime, settle, and filter wastewater treatment system. This
system was characterized during sampling and is discussed in
Section V.
In summary, the above discussion shows that 85 plants currently
comply with BPT flows, and that of the 112 plants with treatment
in-place, the most common treatment system was based on lime and
settle technology. Most plants did not indicate the presence of
ancillary streams added after proposal. If these 'streams are
assumed to be present in the total process flow from these plants
and the added flow allowance added, two additional plants would
meet the BPT flows. When EPA evaluated treatment system
performance at plants with BPT treatment and BPT flow, the data
indicated that treatment system design and operating practices at
most plants were inadequate. In particular, close pH control was
not practiced at BPT lead subcategory plants. Because lime and
settle treatment practices in the lead subcategory are generally
inadequate the effectiveness of lime and settle technology must
be transferred from other industrial categories with similar
wastewaters. From the data and information collected, it appears
that most lead subcategory plants can comply with BPT with only
minimal changes in their present practices, such as wastewater
flow control, pH control, and better control of operating
parameters. Therefore, the selected BPT level has been
determined to be reasonable.
APPLICATION OF REGULATIONS IN. PERMITS
The purpose of these limitations (and standards) is to form a
uniform national basis for regulating wastewater effluent from
the battery manufacturing category. For direct dischargers, th-e
regulations are implemented through NPDES permits. Because of
the many elements found in lead battery manufacturing and the
apparent complexity of the regulation, an example of applying
these limitations to determine the allowable discharge from
battery manufacturing is included. The lead subcategory battery
manufacturing category is regulated on an individual wastestream
"building block" approach as shown below.
555
-------
Example A. Plant X manufactures lead acid batteries using 5.2 x
10* kg lead/yr. The plant operates for 250 days during the year.
Leady oxide is purchased; paste is mixed in the plant and applied
to casted grids; plates are cured in stacks; 80% of the batteries
are charged using closed, single-fill formation; 20% are formed
using open formation and dehydration for dehydrated batteries;
all batteries are detergent washed. The plant provides hand wash
for their employees, routinely washes floors in process areas,
and has respirator wash.
Table IX-19 (page 582) illustrates the calculation of allowable
daily discharge of lead for this plant.
. 556
-------
TABLE IX-1
FLOW BASIS FOR BPT MASS DISCHARGE LIMITATIONS
LEAD SUBCATEGORY
Ul
Ol
Process Element
Anodes and Cathodes
Leady Oxide Production
Grid Manufacture
Mold Release Formulation
Direct Chill Casting
Lead .Rolling
Paste Preparation and Application
Curing
Closed Formation (in case)
Single Fill
Double Fill
Fill and Dump
Open Formation (out of case)
Dehydrated
Wet
Plate Soak
Ancillary Operations^
Battery Wash
Detergent
Water Only
Median
Flow
(I/kg)
0.00
*
\
0.0002
0.006
0.00
0.00
0.00
0.451/
0.45V
11.05
0.00
Mean
Flow
(I/kg)
0.37
0.006
0.0002
0.006
0.49
0.03
0.28
0.92
1.83
28.26
0.36
BPT
Flow
(I/kg)
0.00
0.006
0.0002
0.006
0.00
0.00
0.00
0.45
0.45
11 .05
0.0532/
0.021
0,026
0.021
0.90
0.59
1 .70
3.47
0.90
0.59
-------
Ul
Ul
00
TABLE IX-1 (continued)
FLOW BASIS FOR BPT MASS DISCHARGE LIMITATIONS
LEAD SUBCATEGORY
Process Element
Anodes and Cathodes
Truck Wash
Laundry
MiscellaneousGroup
Floor Wash
Wet Air Pollution Control
Battery Repair
Laboratory
Hand Wash
Respirator Wash
-Total Miscellaneous Group
Median
Flow
(I/kg)
'0.014
*
0.13
0.00
0.25
*
*
*
Mean
Flow
(I/kg)
0.014
0.109
0.11
0.26
0.20
0.003
0.027
0.006
BPT
Flow
0.014
0.109
0.13
0.0113/
0.25
0.003
0.027
0.006
0.427
/ Based on combined data for double fill and fill and dump formation.
/ Based on subset of plants which discharge open wet formation wastewater
/ Based on sum of model flows for pasting and formation area scrubbers.
*Calculated as a flow weighted average - no median available
-------
TABUE IX-2
SUMMARY OF ZERO DISCHARGE FOR LEAD SUBCAHQQRY PROCESS ELEMENTS
Process Element
No, of Plants
Reporting Flow Efata
For Process Element
ND. of Plants Reporting
Zero Discharge in
Process Element
ttathod of Attaining
Zero Discharge
Leady Qcide Production
41
29
Use of non-contact cooling water on
ball mills.
Grid Manufacture
M3ld Release Formulation
Direct Chill Casting
Lead Rolling
2(29)
US)'/
K5)1/
Use commercially available mold-release
formulations.
Ifone reported.
Contract hauling.
Ui
Oi
teste Preparation and
Application
Curing
100
97
57
87
Recycle of wastewater after settling
(common practice).
Curing In covered stacks; in humidity
controlled rooms; internal reeireulation.
Closed Formation—
Single Fill
touble Fill
Fill and Dump
43
35
13
31
7
1
low rate and controlled formation and reuse
battery case rinsewater in acid cutting.
low rate and controlled formation and reuse
battery case rinsewater in acid cutting.
Low rate and controlled formation and reuse
battery case rinsewater in acid cutting.
Open Forraation-
ttehydrated
Wet
42
16
2
10
Water recycled after treatment.
Reuse formation acid.
Plate Soak
Reuse plate soak acid.
-------
WIE IX-2 (continued)
SUWARY OF ZERO DISCHARGE FOR LEAD SUBQVTEQORY PROCESS EUJMENTS
Process Elesnent
Na, of Hants
Reporting Flow
For Process Element
Ifo. of Hants Reporting
Zero Discharge In
Process Element
Battery Wash
Datergent
Water Only
Truck Wash
Laundry
Floor Wash
Wet "Air ibllution Control 2/
Battery Bepair
laboratory
Hand Wash
Respirator 'Wash
22
44
2 (18)1/
2 (11)1/
13
56 (80)
3 .
4 (57) 1/
2 (63) V
6 (51)1/
0
1
0
0
2
32
0
0
0
0
Ifethod of Attaining
Zero Discharge
Reuse battery case rlnsewater in acid
cutting.
Reuse lattery case rinsewater in acid
cutting.
bbne reported.
Use offsite commercial services.
Use of dry floor cleaning procedures.
Use of dry baghouses; reuse group I
scrubber water in paste washdowi;
eliminate overflow from group 1 scrubbers;
no washdown of demlster mesh in formation
scrubbers.
Rjne reported,
Ifene reported.
Nane reported.
Reclaim disposable respirators at
a smelter.
'' The number in parenthesis is the number of plants which reported being active for these process elements,
2/ Based on number of scrubbers from all process areas but laboratory. The number in parenthesis is number of plants reporting scrubber usage.
-------
TABLE IX-3
SUMMARY OF TREATMENT IN-PLACE
AT LEAD SUBCATEGORY PLANTS
ut
OS
Treatment
In-PIace
None
Number of
Plants
Less than BPT
(pH adjust only or no pH
adjust with treatment)
BPT Treatment
(L&S, or pH adj.ust,
filter)
BAT Treatment
(L,S & F)
Not Classified
74
46
53
10
Discharge Status
Direct IndirectZero
1
1 (D
8 (2)
2 (1)
0
12
40 (9)
40 (5)
42 I/
5 (1)
_!_/ Discharge status is unknown for 19 plants, which are included in the total
number of plants with no treatment, but not under discharge status. Fifteen
of these plants are not full line manufacturers. Based on the observations
that most non-full line manufacturers are zero dischargers, and that permit
information was not found on these plants, they are considered as indirect or
zero dischargers with no reported treatment in-place.
( ) Indicates number of plants that are closed.
-------
TABLE IX-4
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Mold Release Formulation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.01
0.002
0.003
0.011
0.002
0.002
0.01
0.0025
0.009
0.04
0.007
0.004
0.120
0.246
the range of 7.5 to
0.008
0.0009
0.001
0.006
0.001
0.0006
0.0076
0.001
0.004
0.02
0.004
0.002
0.072
0.117
10.0 at all times
*Regulated Pollutant
562
-------
TABLE IX-5
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Direct Chill Lead Casting
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - rag/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.00057
0.00007
0,000088
0.0004
0.00008
0.00005
0.00038
0.000082
0.00029
0.0013
0.0002
0.0001
0.004
0.008
the range of 7. 5 t o
0.00026
0.00003
0.000036
0.0002
0.00004
0.00002
0.00025
0.000034
0.00012
0.0006
0.0001
0.00006
0.002
0.003
10.0 at all times
^Regulated Pollutant
563
-------
TABLE IX-6
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Lead Rolling
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.017
0.002
0.003
0.011
0.003
0.002
0.012
0.002
0.009
0.039
0.007
0. 004
0.120
0.246
the range of 7.5 to
0.008
0.0009
0.001
0.006
0.001
0.0006
0.008
0.001
0.004
0.019
0.004
0.002
0.072
0.117
10.0 at all times
*Regulated Pollutant
564
-------
TABLE IX-7
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Lead Rolling
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead rolled
English Units - lb/1,000,000 Ib of lead rolled
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.07
0.008
0.01
0.04
0.01
0.006
0.04
0.01
0.03
0.15
0.03
0.02
0.47
0.96
the range of 7.5 to
0.03
0.004
0.004
0.02
0.005
0.002
0.03
0.004
0.01
0.07
0.01
0.007
0.28
0.45
10.0 at all times
*Regulated Pollutant
565
-------
TABLE IX-8
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Closed Formation - Double Fill, or Fill & Dump
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
* Copper
*Lead
Mercury
Nickel
Silver *
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
1.29
0.15
0.20
0.86
0.19
0.11
0.86
0.18
0.66
2.89
0.54
0.31
9.00
18.45
the range of 7.5 to
0.58
0.07
0.08
0.45
0.09
0.05
0.57
0.08
0.27
1.44
0.27
0.13
5.40
8.78
10.0 at all times
*Regulated Pollutant
566
-------
TABLE IX-9
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Open Formation - Dehydrated
Pollutant or
Pollutant
Property
Maximum for
anyone day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Alum inum
* Iron
Manganese
*0il and Grease
*TSS
*pH Within
31.71
3.75
4.86
20.99
4.64
2.76
21.21
4.53
16.13
71.05
13.26
7.51
221.00
453.05
the range of 7.5 to
14.14
1.65
1.98
11.05
2.21
1.10
14.03
1.87
6.74
35.36
6.74
3.20
132.60
215.47
10.0 at all times
*Regulated Pollutant
567
-------
TABLE IX-10
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Open Formation - Wet
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony 0.15 0.07
Cadmium 0.02 0.007
Chromium 0.02 0.009
*Copper 0.10 0.05
*Lead 0.02 0.01
Mercury 0.01 0.005
Nickel 0.10 0.07
Silver 0.02 0.009
Zinc 0.08 0.03
Aluminum 0.34 0.17
*Iron 0.06 0.03
Manganese 0.04 0.02
*0il and Grease 1.06 0.64
*TSS 2.17 1.03
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
568
-------
TABLE IX-11
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Plate Soak
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead-used
English Units - lb/T,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.06
0.007
0.009
0.04
0.009
0.005
0.04
0.008
0.03
0.14
0.03
0.01
0.42
0.86
the range of 7.5 to
0.03
0.003
0.003
0.02
0.004
0.002
0.03
0.003
0.01
0.07
0.01
0.01
0.25
0.41
10.0 at all. times
*Regulated Pollutant
569
-------
TABLE IX-12
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Battery Wash (Detergent)
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
2.58
0.31
0.396
1.71
0.38
0.23
1.73
0.37
1.31
5.79
1.08
0.61
18.00
36.90
the range of 7.5 to
1,15
0.14
0.162
0.90
0.18
0.09
1.14
0.15
0.55
2.88
0.55
0.26
10.80
17.55
10.0 at all times
*Regulated Pollutant
570
-------
TABLE, IX-13
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Battery Wash (Water Only)
Pollutant or
Pollutant- Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
* Iron
Manganese
*0il and Grease
*TSS
*pH Within
1,69
0.20
0.26
1.12
0.25
0.15
1.13
0.24
0.86
3.79
0.71
0.40
11.80
24.19
the range of 7.5 to
0.76
0.09
0.11
0.59
0.12
0.06
0.75
0.10
0.36
1.89
0.36
0.17
7.08
11.51
10.0 at all times
*Regulated Pollutant
571
-------
TABLE IX-14
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Truck Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked batteries
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.040
0.004
0.006
0.026
0.005
0.003
0.026
0.005
0.020
0.09
0.016
0.01
0.280
0.574
the range of 7.5 to
0.017
0.002
0.002
0.014
0.002
0.001
0.017
0.002
0.008
0.04
0.008
0.004
0.168
0.273
10.0 at all times
*Regulated Pollutant
572
-------
TABLE IX-1 5
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Laundry
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
* Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.31
0.037
0.05
0.21
0.05
0.027
0.209
0.045
0.16
0.70
0.13
0.07
2.18
4.47
the range of 7.5 to
0.14
0.016
0.02
0.11
0.02
0.011
0.138
0.019
0.07
0.35
0.07
0.03
1.31
2.13
10.0 at all times
*Regulated Pollutant
573
-------
TABLE IX-1 6
LEAD SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - rag/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
1.23
0.15
0.19
0.81
0.18
0.11
0.82
0.18
0.62
2.75
0.51
0.29
8.54
17.51
the range of 7.5 to
0.55
0.06
0.08
0.43
0.09
0.04
0.54
0.07
0.26
1.37
0.26
0. 12
5.12
8.33
10.0 at all times
*Regulated Pollutant
574
-------
TABLE 1X-17
COMPARISON OF ACTUAL TOTAL FLOW RATES
TO BPT HOURLY FLOW RATES
Ui
-si
Ui
Plant ID
107
110
112
122
132
133
135
138
144
146
147
152
155
158
170
173
178
179
182
184
190
191
198
207
208
212
213
226
233
237
239
242
255
261
269
277
278
280
288
295
Actual Flow
Meets BPT
Actual Flow
(1/hr)
1503
NA
3108
11 706
NA
NA
0
NA
0
6815
0
9280
NA
0
0
0
0
7.57
NA
0
0
37325
10266
18851
NA
7041
454
9312
9375
11129
6106
NA.
NA
2271
12212
-NA
5770
NA
NA
0
BPT Hourly Flow
(1/hr)
11475
NA
621
5091
NA
NA
NA
NA
2650
4000
6.0
6850
NA
NA
NA
0
2143
20
NA
1632
NA
105
591
5685
NA
2966
0
13200
8070
16775
2255
NA
NA
1019
20615
96
5.1
NA
NA
NA
-------
TABLE IX-t? (Continued)
COMPARISON OF ACTUAL TOTAL FLOW RATES
TO BPT HOURLY FLOW RAXES
Oi
Plant ID
299
311
320
321
331
342
346
349
350
356
358
361
366
370
371
372
374
377
382
386
387
400
402
403
406
421
429
430
436
439
444
446
448
450
462
463
466
467
469
472
Actual Flow
Meets BPT
x
x
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Actual Flow
(1/hr)
0
20895
34450 -
0
2498
61920
0
7845
NA
0
7041
NA
0
NA
3390
0
3861
0
1197
7950
2006
3835
NA
NA
NA
0
0
0
0
29000
0
2063
14645
27252
2574
NA
0
0
15
0
BPT Hourly Flow
(1/hr)
NA
13496
17065
NA
2200
31635
NA
16150
NA
NA
3643
NA
NA
NA
7385
NA
0
NA
3160
10083
2825
1949
NA
NA
NA
1.3
NA
0
0
4107
NA
4015
3525
8190
2614
NA
330
NA
1350
1900
-------
TABLE IX-17 (Continued)
COMPARISON OF ACTUAL TOTAL FLOW RATES
TO BPT HOURLY FLOW RATES
Ul
«-J
•-J
Plant ID
480
486
491
493
494
495
501 .
503
504
513
517
520
521
522
526
529
536
543
549
553
572
575
594
620
623
634
635
640
646
652
656
668
672
677
680
681
682
683
685
686
690
Actual Flow
Meets BPT
x
x
X
X
X
X
X
X
X
X
X
X
X
X
Actual Flow
(1/hr)
30610
NA'
NA
NA
3110
0
12624
0
0
1363
0
4542
0
0
18170
570
NA
0
47470
3449
2275
3634
0
NA
NA
1590
1685
25196
476
12705
NA
0
52950
0
1534
4542
6814
0
6359
8404
0
BPT Hourly Flow
(1/hr)
19680
NA
NA
605
3735
NA
4620
35185
NA
3895
NA
1205
NA
NA
2563
700
NA
23
645
1318
1196
2000
NA
NA
480
1535
4915
16648
555
2080
NA
0
9908
NA
1105
492
3925
NA
4230
3960
815
-------
TABLE IX-17 (Continued)
COMPARISON OF ACTUAL TOTAL FLOW RATES
TO BPT HOURLY FLOW RATES
00
Plant ID
704
705
706
708
714
716
717
721
722
725
730
731
732
733
738
740
746
765
768
771
772
775
777
781
785
786
790
796
811
814
815
817
820
828
832
844
852
854
857
863
866
Actual Flow
Meets BPT
x
X
X
X
X
X
X
X
X
X
X
Actual Flow
(1/hc)
27125
3180
0
NA
1590
NA
6490
0
NA
0
443
2858
3607
NA
29080
NA
0
11690
7881
1363
11500
4088
4325
NA
41660
5120
0
0
HA
13130
598
0
3407
40
10520
NA
16070
0
0
11055
0
BPT Hourly Flow
(1/hr)
3260
2115
0
3635
2025
200
4350
1265
NA
NA
2184
974
2230
NA
24815
NA
NA
10051
11205
NA
30
2895
2785
NA
10190
1790
0
NA
NA
2830
141
0
3900
90
7281
1810
15055
NA
4730
6350
NA
-------
TABLE IX-17 (ConCinued)
COMPARISON OF ACTUAL TOTAL FLOW RATES
TO BPT HOURLY FLOW RATES
Ui
PlantID
877.
880
883
893
901
917
920
927'
936
939
942
943
947
951
963
964
968
971
972
976
978
982
979
990
Actual Flow
Meets BPT
Actual Flow
(1/hr)
46165
0
0
2470
0
18851
NA
0
3706
NA
0
17261
18397
1135
0
0
0
0
23837
26801
1840
10540
0
3180
BPT Hourly Flow
(1/hr)
4615
NA
100
2865
580
11785
NA
NA
2750
NA
NA
26595
16094
NA
0
NA
NA
5026
4520
33845
7199
12340
0
2389
-------
TABLE IX-18
SUMMARY OF BPT TREATMENT EFFECTIVENESS
AT LEAD SUBCATEGORY PLANTS
PGP Data - Plants Meeting BPT Flow
Ul
00
0
ID
A
B
C
D
E
F
ID
G
H
I
J
K
L
M
D/I*
D
I
I
I
D
I
D/I*
I
I
I
I
D
I
I
Cr Cu Pb
0.1 0.05
1.0
3.5
1
0.28
1
Industry Survey Data
Cr Cu Pb
3.36
0.5
2.3
1.1
.24
0.25
Ni Zn Fe O&G
0.3
23.4
1.5
- Plants Meeting BPT Flow
Ni Zn Fe O&G
TSS
5548
26
150
20
46
TSS
4810
29
90
pH
7.8
6.5
7.28
pH
7.41
8
8.2
9.0
7.67
7.5
6.92
*D/I - Direct or Indirect Discharge
-------
Ut
00
TABLE IX-18 (Continued)
SUMMARY OF BPT TREATMENT EFFECTIVENESS
AT LEAD SUBCATEGORY PLANTS
Sampled Plants With BPT Treatment
ID
A
J
M
N1/
oV
pi/
Sampling
Day Cr
1
2
3
1
2
3
1
2
1
2
3
(Industry
1
2
3
(Industry
( Industry
0
0
0
0
0
0
0
0
0
0
0
Survey
0
0
0
Survey
0
Survey
.000
.010
.005
.010
.010
.059
.000
.000
.000
.005
.005
Data)
.000
.000
.000
Data)
.00
Data)
Cu
0.000
0.040
0.034
0.059
0.050
0.090
0.023
0.012
0.018
0.014
0.019
0.05
0. 000
0.000
0.000
Pb
1.350
4.050
3.580
6.06
3.880
13.30
0.000
0.000
0.110
0.130
0.110
0.09
0.1
0.07
0.19
0.14
6.100
13.2
Ni
0.000
0.000
0.012
0.110
0.068
0.046
vO. 31
0.35
0.011
0.009
0.011
0.000
0.000
0.000
0.000
Zn
0.000
0.710
0.590
0.165
0.000
0.105
0.15
0.000
0.000
0.000
0.037
0.000
0.000
0.000
0.080
• Fe
0.000
0.000
0.000
0.420
0.280
3.380
0.000
0.000
0.760
0.920
0.950
0.1
0.000
0.000
0.200
O&G
10.0
9.9
5.0
2.3
1.7
3.7
0.000
0.000
1.4
2.7
2.2
9.0
0.000
2.0
NA
TSS
90.6
76.0
39.8
3.5
11.0
66.0
33.0
25.0
13.0
11.0
11.0
30.0
140.0
46.0
25.0
7
NA
67
El
6.5-8.5
7.2-8.8
6.6-7.9
6.0-10.4
7.7-9.2
7.0-9.0
NA
7.11
9.0-9.3
8.7-9.1
8.6-9.1
7.6
9.0
9.0
9.0
8.76
NA
6.6
1/ These plants did not meet the BPT Flow.
NA - Not Available
-------
TABLE IX-19
SAMPLE DERIVATION OF THE BPT 1-DAY LEAD LIMITATION
Ul
oo
PNP
Process Elements kg/yr (10°)
1.
2.
3.
4.
5.
6.
7.
Leady Oxide
Purchased
Paste Prep. &
Application
Curing - Stacked
Formation -
Closed, Single
Formation -
Open, Dehydrated
Battery Wash -
With Detergent
Miscellaneous
2.6
5.2
5.2
4.16
1.04
5.2
5.2
Avg. PNP
(kg/day)
10400
20800
20800
16640
4160
20800
20800
1 -Day Limits
(mg/kg)1/
0.0
0.0
0.0
0.0
4.64
0.38
0.18
Lead Mass
Discharge (mg/day)5
0.0
0.0
0.0
0.0
19,302
7,904
3,744
(Hand Wash,
Respirator Wash,
and Floor Wash) 3/
TOTAL Plant X Discharge (1-Day Value for Lead): 30,950 rag/day (0.68 Ib/day)
jy I/kg of lead used from Table IX-1 multiplied by lime and settle treatment
concentrations (mg/1) from Table VII-21.
21 Average PNP multiplied by the 1-day limits in Tables IX-9, IX-12, and
IX-16, then each process summed for the plant's daily discharge limit.
37 Plant indicates hand wash, respirator wash, and floor wash; therefore, plant
receives total miscellaneous wastewater allowance.
-------
oo
to
PROCESS WASTEWATER FROM:
GBID MANUFACTURE
DIRECT CHILL CASTING
MOLD RELEASE FORMULATION
PLATE SOAK
CLOSED FORMATION
DOUBLE FILL (WET BATTERY)
FILL AND DUMP (DAMP BATTERY)
OPEN FORMATION
DEHYDRATED
WET
BATTERY WASH
DETERGENT
WATER ONLY
• TRUCK WASH
LAUNDRY
MISCELLANEOUS WASTEWATER
LIME AND
CARBONATE
ADDITION
t / I I
DISCHARGE
REMOVAL OF
OIL AND CREASE
SLUDEE TO
RECLAIM OR
DISPOSAL
SLUDGE
QEWATHIHG
MECOMMENDEO IN-PROCESS TECHNOLOGY:
•CONTROL SPILLS
•LOW-RATE OR CONTROLLED CHARGING IN CASE
•SPENT FORMATION ACID IS REUSED
•DIRECT CHILL CASTING WATER IS RECYCLED
•FORMATION AREA SCRUBBER WATER IS RECYCLED
•BATCH AIR SCRUBBER WATER IS NEUTRALIZED
•PASTING OPERATION WASTEWATER IS RECYCLED OR REUSED
PASTE FORMULATION '
AMD APPLICATION AREA
WJISNODWH WASTEWATER
RECYCLE OR REUSE
MULTISTAGE SETTLIN6
LEAD OXIDES
RETURN TO PflOCESS
FIGURE IX-1. LEAD SUBCATEGORY BPT TREATMENT
-------
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
The effluent limitations presented in this section apply to
existing direct dischargers. A direct discharger is a site which
discharges or may discharge pollutants into waters of the United
States. These effluent limitations which were to be achieved by
July 1, 1984, are based on the best available control and
treatment technology employed by a specific point source within
the industrial category or subcategory, or by another industry
where it is readily transferrable. Emphasis is placed on
additional treatment techniques applied at the end of the
treatment systems currently employed for BPT, as well as
improvements in reagent control, process control, and treatment
technology optimization.
The factors considered in assessing the best available technology
economically achievable (BAT) include the age of equipment and
plants involved, the processes employed, process changes, non-
water quality environmental impacts (including energy
requirements), and the costs of application of such technology
(Section 304 (b) (2) (B)). In general, the BAT technology level
represents, at a minimum, the best existing economically
achievable performance of plants of various ages, sizes,
processes or other shared characteristics. As with BPT, in those
subcategories where existing performance is universally
inadequate, BAT may be transferred from a different subcategory
or category. BAT may . include process changes or internal
controls, even when not common industry practice. This level of
technology also considers those plant processes and control and
treatment technologies which at pilot plant and other levels have
demonstrated both technological performance and economic
viability at a level sufficient to justify investigation.
TECHNICAL APPROACH TO BAT
In pursuing effluent limitations for the battery manufacturing
category, the. Agency desired to review a wide range of BAT
technology options. To accomplish this, the Agency elected to
develop significant technology options which might be applied to
battery manufacturing wastewater as BAT. These options were to
consider the range of technologies which were available and
applicable to the battery manufacturing subcategories, and to
suggest technology trains which would reduce the discharge of
toxic pollutants remaining after application of BPT. The
statutory assessment of BAT considers costs, but does not require
a balancing of costs against effluent reduction benefits [see
Weyerhaeyser v. Costle, 11 ERG 2149 (D.C. Cir. 1978)].
585
-------
In a draft development document that was given limited
circulation in September, 1980 to battery manufacturers and
others who requested to receive a copy, a number of alternative
BAT systems were described for the lead subcategory. Comments
from this limited, but technically knowledgeable audience were
used, together with further review and analysis of available
data, in refining these alternatives and in making the selection
of a specific BAT option for the lead subcategory. Some options
originally presented in the draft development document were
eliminated from consideration, and others were modified on the
basis of comments received and other reevaluation.
At proposal, four technology options were considered as a basis
for development of BAT limitations for this subcategory. These
options are built incrementally upon BPT (option 0) and achieve
either reduced process wastewater volume or reduced effluent
pollutant concentrations in comparison with the previous option.
All of the in-process controls included in these options were
observed in practice within the lead subcategory. Some end-of-
pipe technologies transferred from other industrial categories
were considered as well as those that were practiced at lead
subcategory plants.
For promulgation, four technology options were considered as a
basis for development of BAT limitations. BAT options 1 to 3
remain unchanged from proposal except reuse of treated water for
hose washdown is added as an in-process technology. The
treatment scheme for BAT option 4 was revised, and an additional
in-process technology, reuse of treated water for truck washing
activities, was added. The revised option 4 treatment scheme was
determined after carefully reviewing comments received on the
proposed regulation.
BAT Options Summary
In summary form, the treatment technologies which were considered
for the lead subcategory of the battery manufacturing category
are:
Option 0 for this subcategory (Figure IX-1, page 583) consists of
the following technologies:
a) In-process technology:
control spills
low-rate or controlled charging in case
reuse of spent formation acid in all but open
wet formation
- multiple stage settling and tptal recycle
586
-------
or reuse of pasting operations wastewater
direct chill casting water recycle
recycle of formation area scrubber water
Neutralize batch air scrubber water
b) End-of-pipe treatment:
oil skimming
lime precipitation augmented with carbonate
sedimentation
sludge dewatering
Option 1 (Figure X-l, page 616) includes all aspects of option 0
and builds on it by adding the following:
a) In-process technology:
- countercurrent rinse of electrodes after open
case formation
eliminate or recycle process water for plate
dehydration
reuse of treated water for hose washdown activity
water rinse for batteries prior to deter-
gent wash
reuse of detergent rinse as makeup to
detergent tank
countercurrent rinse of batteries
reuse of battery rinse water from battery wash
with water only or closed formation case rinsing
b) End-of-pipe treatment for this option is unchanged from
option 0.
Option 2 (Figure X-2, page 617) builds on option 1 with improved
end-of-pipe treatment.
a) In-process technology is unchanged from option 1 .
b) End-of-pipe treatment in addition to option 1:
polishing filtration (multimedia filter)
Option 3 (Figure X-3, page 618) builds on option 2 with revision
of end-of-pipe treatment.
a) In-process technology is unchanged from option 1.
b) End-of-pipe treatment consist of the following
treatment steps:
oil skimming
chemical precipitation using sulfide
sedimentation
- polishing filtration using membrane filters
- sludge dewatering
587
-------
Option 4 (Figure X-4, page 619) provides improved end-of-pipe
treatment and additional in-process technology.
a) In-process technology
all in-process technologies of option 1
recycle of permeate from reverse osmosis
to the manufacturing process
reuse of treated water for truck washing activites
b) End-of-pipe treatment consists of the following
treatment steps:
oil skimming
- filtration (mixed media or membrane) of selected
streams
reverse osmosis of selected streams
lime precipitation of brine and remaining
streams augmented with carbonate
sedimentation of treated brine
- filtration (membrane type) of treated brine
sludge dewatering.
Option 1
Option 1 continues the end-of-pipe treatment of option O (BPT)
and adds improved in-process controls to reduce the amount of
wastewater treated and discharged. The in-process flows for each
process element for option 1 (and also options 2 and 3) are
presented in Table X-l (page 598). All in-process control
techniques included in option 0 are continued as part of this
treatment and control option. As described in Section IX, the
following process elements have a zero discharge allowance at
option 0: leady oxide production; paste preparation and
application; curing; and closed formation of single-fill
batteries. Under option 1, zero discharge allowances are also
established for closed formation of double fill and fill and dump
batteries, and water only battery wash. Decreased regulatory
flows are established at option 1 for open formation dehydrated
plates, detergent battery wash and miscellaneous wastewaters
(specifically the floor wash flow). The in-process controls used
as the basis of these option 1 flows are discussed below:
Closed Formation - All wastewater discharges from closed
formation processes are eliminated by application of one or more
of the in-process controls included under the option 1
technology. All of these controls are presently observed within
the subcategory. Specific in-process controls included are:
• Low rate or controlled charging (from Option 0) or
recycle of contact cooling water with reuse of overflow
• Control of spillage in electrolyte filling and
588
-------
and dumping to reduce case contamination and
eliminate battery rinsing; or recirculation
of rinse water with reuse of overflow .
Slow charging' or controlled charging rates used in closed
formation eliminate the use of contact cooling water and the
resultant process wastewater discharge. Contact cooling water
used in higher rate formation processes may be recycled through a
cooling tower and neutralized as required. Widespread practice
of these techniques is illustrated in Table X-1; 31 of 43
reporting plants report no process wastewater discharge from
closed case single fill formation processes.
Appropriate care and technology in filling batteries with acid
electrolyte prior to formation, limits or eliminates acid
contamination of the battery cases and of production equipment
and work areas. If double fill or fill and dump processes are
employed, similar control during the removal or refill of the
electrolyte is also required. Production by single fill
techniques simplifies the controls which must be employed , since
only the single-filling operation (there is no acid removal
operation) must be controlled. Effective control of overflows
and acid spillage in filling batteries has been demonstrated,
both by manufacturers employing automatic filling equipment (with
acid level sensing provisions and special design features to
avoid drips and spills) and by manufacturers employing careful
manual battery filling procedures. These practices limit or
eliminate the requirement for battery rinsing or washing prior to
further handling or shipment, reducing or eliminating the
quantity of wastewater which must be treated. As an alternative
to this level of control in filling and acid removal, equivalent
pollution reduction may be achieved by recycle of the battery
rinse water and reuse of the overflow in acid cutting.
Where recycle is used to reduce or eliminate wastewater
discharges associated with closed formation processes, some
blowdown or a bleed from the system may be needed. The overflow,
or blowdown, streams discussed above may be directed to either
the acid cutting or paste preparation processes. Both of these
operations have negative water balances and together require
about 0.4 I/kg of makeup water. These reuse practices have been
observed at existing plants.
Combinations of these spill control and water reuse technologies
can be employed to reduce wastewater discharge to zero from
closed case formation. As shown in Table X-1, some plants are
now achieving this wastewater control level; 39 of 91 plants
report no process wastewater discharge from closed formation.
589
-------
For double fill operations, seven of the 35 plants active in this
operation reported attaining zero discharge. For fill and dump
operations, one of the 13 plants active in this operation
reported zero discharge. These plants demonstrate that spill
control and water reuse practices can be used to reduce the
option 0 wastewater discharge flow from these closed formation
processes (0.45 I/kg-) to zero. Therefore, a zero discharge
allowance is established for option 1 for these process elements.
Open Formation - Dehydrated Batteries - Significant reductions in
process wastewater discharges from the formation and dehydration
of plates for dehydrated batteries are achieved by several in-
process control techniques, including:
0 Use of countercurrent rinsing and rinse flow control or
recycle of wastewater from post-formation plate rinses
0 Elimination or recycle of process water used in plate
dehydration
Countercurrent cascade rinsing and rinse flow control can provide
significant reductions in wastewater discharge from rinsing
electrodes after open formation. The achievable reduction is
discussed in Section VII. Although countercurrent and multi-
stage rinses after open formation are reported by a number of
plants in this subcategory, these techniques are not coupled with
effective rinse flow control. Consequently, they may not achieve
substantially reduced wastewater discharge volumes compared to
single-stage rinses. As an alternative to countercurrent rinsing
and strict rinse flow control, rinse wastewater may be recycled
for reuse in plate rinsing either before or after treatment.
Because this technique affords lower rinsing efficiency than
countercurrent cascade rinsing, it may not be compatible with
both acceptable product quality and wastewater flow rates at some
sites. Also, where wastewater is recycled after treatment,
higher treatment costs may be incurred.
Process water used in dehydrating electrodes is from seal water
on the vacuum pumps or ejectors used in vacuum drying of elec-
trodes. This water becomes contaminated with acid and lead from
the electrodes and consequently requires treatment prior to
discharge. The volume of this wastewater may be greatly reduced
by recycle, or eliminated entirely by the use of other
dehydrating techniques such as steam dehydrating or the use of
inert gas. These results are achieved by many plants producing
dehydrated batteries, although most plants did not specifically
identify the techniques employed.
Two of the 42 plants reporting open formation of dehydrated
plates also reported zero discharge from this operation. As
590
-------
discussed above, significant reductions in process wastewater
discharge from the formation and dehydration of plates for
dehydrated batteries can be achieved by several in-process
control techniques including; countercurrent cascade rinsing and
rinse flow control; recycle of treated wastewater for plate
rinses; and elimination or recycle of process water used in plate
dehydration. The regulatory flow at option 1 for open formation
of dehydrated batteries was calculated in the following manner.
As described in Section IX, the flow used for determining BPT
mass discharge limitations for this subcategory is 11.05 I/kg.
This consists of water from the plate dehydration area and from
the plate washing area. The application of two-stage
countercurrent cascade rinsing to plate washing will achieve a
water reduction factor of 6.6 (see Section VII). Treatment and
reuse of water in the plate dehydration area will achieve an
equivalent water use reduction. The option 1 flow of 1.68 I/kg
is derived by applying the water reduction factor of 6.6 to the
BPT flow of 11.05 I/kg. This flow appears to be reasonable
because some plants have eliminated plate dehydration wastewater,
and additional stages of countercurrent rinsing could further
reduce rinse water flow.
Battery Wash - At Option 1, water only washing of batteries has
been limited to a zero discharge allowance and the regulatory
flow for detergent washing of batteries has been reduced. In-
process control techniques for the reduction of wastewater
discharges from battery washing with detergent operations include.
use of efficient acid addition and removal techniques as
discussed previously. Also, water used for prerinsing, reducing
the need for detergent water, removes electrolyte splashes from
battery cases and may be recycled. Slowdown from this recycle
can be used in some cases in paste formulating, or primarily in
acid cutting. As discussed in Section VII, many plants visited
demonstrated significant overuse of water in these battery wash
operations. Simple cutback in the water used per battery by flow
reduction through the nozzles is feasible. Use of mechanical
switching devices to prevent water flow when batteries are not
present has a significant impact on water use. The use of
automatic washers typically includes a final water only rinse
after the detergent wash. This final rinse water may be reused
as makeup for the detergent wash cycle since it already contains
detergent and it would also be more economical for the plant.
Wastewater from rinses of detergent at this final product stage
may not be amenable to reuse in other battery manufacturing
operations and therefore requires a discharge allowance. The
option 1 regulatory flow for detergent battery wash has been
reduced to half of the BPT flow or 0.45 I/kg. This flow is based
on the reuse of final rinse water as makeup to the detergent
portion of the battery wash, system. Non-detergent (initial)
591
-------
rinse water can be reused in detergent wash or can be rerouted to
acid cutting operations.
Nondetergent rinses (battery wash with water only) seen
frequently in battery manufacturing operations (44 of 66 plants)
can be recycled and reused, eliminating a wastewater discharge
from this type of battery wash. Techniques for reducing flow,
segregating by recycle, and reuse possibilities are discussed in
Section VII and above under closed formation and battery wash
with detergent. Wash water removes water soluble components such
as acid and lead which do not preclude reuse of the water in
electrolyte. A discussed in Section VII, the buildup of key
contaminants can be monitored to allow the reuse of this water
without infringing on established engineering specifications for
product purity. A zero discharge allowance has been established
for water only battery wash at option 1 based on reuse of this
water in acid cutting.
M is eel1anepug Wastewater - The miscellaneous regulatory flow for
option 1 is decreased from the option 0 (BPT) flow to 0.307 I/kg
due to a reduction in the normalized flow for the floor wash
operation. From site visits, primarily after proposal, it was
found that a number of plants use wet floor scrubbing techniques
and extensively use power floor scrubbers for efficient cleanup.
In order to protect the power scrubbers from contamination or
corrosion, these machines should use fresh water only. For hoses
and bucket and mop operations, however, the use of treated
wastewater is feasible and is recommended as the flow reduction
technique for this process element at option 1.
The floor wash normalized flow has been reduced to 0.01 I/kg.
This is based on a flow weighted average of data from plants
using advanced floor washing techniques. This regulatory flow
can easily be achieved by the use of commercial floor washing
machines, careful spill maintenance, dry floor cleaning
techniques, and recycle of treated water for reuse in hoses.
Option ,2
Option 2 consists of the in-process technologies set forth in
option 1 plus end-of-pipe treatment consisting of oil skimming,
pH adjustment using lime augmented by carbonate precipitation,
settling, and mixed media filtration. This is a conventional
system which should be almost as effective in lead removal as
option 3.
Option 3
592
-------
Option 3 continues all of the in-process control technologies
included inception 1 and adds improved end-of-pipe treatment.
For this option the end-of-pipe treatment consists of oil
skimming, pH adjustment with lime, chemical precipitation with
sulfide, sedimentation, and polishing filtration. A membrane
filter was included to achieve maximum reduction of suspended
solids. A membrane filter has been demonstrated in treating lead
subcategory process wastewater on a pilot scale, although it was
not used .in conjunction with sulfide precipitation in that
instance. .
Option 4
The treatment technologies included in option 4 are oil skimming,
membrane filtrati.on, reverse osmosis, lime precipitation, and
sludge dewatering. As discussed earlier, option 4 has been
revised for the promulgated regulation. In the revised option 4
treatment scheme, process water is segregated such that certain
less concentrated streams are directed through filtration and
subsequently reverse osmosis. The reverse osmosis brine and the
remaining process water streams are commingled for treatment by
lime precipitation and the treated water is filtered and
discharged. Both sets of streams are initially treated by oil
skimming and the permeate from reverse osmosis (50 percent of
reverse osmosis influent) is recycled after treatment back to the
manufacturing process.
In addition, treated water is reused for truck washing
activities.
BAT OPTION SELECTION
The BAT options were carefully evaluated, and the technical
merits and disadvantages of each were compared. Quantitative
estimates were prepared using all available data for each plant
in the subcategory. As a part of this evalution, a theoretical
"normal" plant was developed. This normal plant is defined as a
theoretical plant which has each of the manufacturing process
elements covered by the subcategory at a production level that is
the average level of all plants in the subcategory. While no
such entity is known to. exist, it is a useful concept in
evaluating the pollutant reduction benefits of various options,
and appraising the importance of toxic and other pollutant
discharges.
The EPA data base was used as a basis for generating the normal
plant profile and data. All 186 plants in the data base supplied
some data. Where data was lacking, the nonresponding plants were
presumed to be similiar to the average of those that supplied
593
-------
information. Normal plant production normalizing parameter
equivalents (million kg/yr of lead) and flow (million 1/yr) are
displayed for each lead subcategory process in Table X-2 (page
599).
An evaluation of the lead subcategory indicates that plants which
discharge process wastewater tend to have higher productions than
those which achieve zero discharge. As discussed earlier, data
from all plants (both dischargers and zero dischargers) were used
to develop the normal plant. Therefore, productions and flows at
a typical discharging plant will be higher than those at the
normal plant. In order to determine pollutant reduction benefits
for plants which discharge wastewater, the normal plant was used
to develop a normal discharging plant. This plant is a
theoretical plant which has each of the manufacturing process
elements at a production level that is the average level of
direct and indirect dischargers in the subcategory. The
productions and flows of the normal discharging plant are
approximately 1.3 times the normal plant values shown in Table X-
2. The normal discharging plant was used to estimate pollutant
removal benefits for all discharging plants, direct dischargers,
and indirect dischargers.
In Section V the average pollutant concentrations in lead
subcategory process elements were described and -displayed in
Table V-5 (page 178). These raw waste concentrations are used as
the basis for calculating treatment effectiveness and pollutant
removal benefits of the several technology options. Treatment
effectiveness is based on both in-process controls and end-of-
pipe treatment. Treatment effectiveness calculations are
summarized in Table X-3 (page 601), benefits are displayed in
Tables X-4 (for the normal plant) (page 602), X-5 (for the normal
discharging plant) (page 603), X-6 (for all discharging plants)
(page 604), and X-7 (for direct discharging plants) (page 605).
The first step involved in calculating pollutant reduction
benefits for the normal plant was to estimate raw waste
generation. To calculate normal plant raw waste generation, the
raw normal plant flow (1/yr MO6)) shown in Table X-2 for each
process element was multiplied by the corresponding process
element pollutant concentrations (mg/1) shown in Table V-5 (page
178). The raw waste generation (kg/yr) for the individual
process elements were then summed to determine the total raw
waste generated by the normal plant. Pollutant reduction
benefits of each treatment and control alternative were
calculated using the raw waste generation, the normal plant
effluent discharge flow for the option (see Table X-2), and the
treatment effectiveness concentrations. The normal plant
effluent discharge flow (1/yr (10*)) was multiplied by the
treatment effectiveness concentrations (mg/1) (Table VII-21, page
594
-------
418) to determine the total mass of pollutants discharged
annually (kg/yr) with the control and treatment alternative. The
mass of pollutants removed by the control and treatment
alternative-is the difference between raw waste and pollutants
discharged.
Pollutant reduction benefits for the normal discharging plant
were determined in a similar manner to those for the normal
plant. Total discharging plant benefits were calculated by
multiplying the normal discharging plant benefits by 111 (there
are 111 plants which currently discharge wastewater in the lead
subcategory). The 19 plants in the subcategory which have closed
were not included in the total discharging plant benefits.
Benefits for direct dischargers were determined by multiplying
the normal discharging plant benefits by eight (there are eight
active direct dischargers in the subcategory).
The Agency proposed Option 1 as the basis for BAT but also stated
that consideration would be given to establishing Option 2 as BAT
at promulgation. Both of these options were carefully evaluated
since proposal. As part of this evaluation after proposal,
required capital and total annual compliance costs for technology
options 1 and 2 for the lead subcategory were estimated. These
estimates were developed by estimating costs for each active
discharging plant (85 plants) in the subcategory based on
reported production and wastewater flows, and summing the costs
for each level of treatment and control. Compliance costs were
not estimated for closed plants; there are no compliance costs
for the 57 zero dischargers in the subcategory. Twenty-six
plants in the lead subcategory did not report sufficient
production or flow data to be costed. In order to include these
plants in the subcategory total of 186, the characteristics
available in the data base were used, primarily number of
employees, to establish general plant size. The average plant
cost for those analogous plants which had been costed was
assigned to each of those plants with insufficient data to
establish a cost for this group of plants. The results of these
lead subcategory cost calculations are shown in Table X-8. An
economic impact analysis based on estimated costs indicates that
there are no potential plant closures projected for these
options.
EPA has selected option 1, presented in Figure X-l (page 616), as
the basis for BAT effluent limitations because it removes over
99.9 percent of the toxic metals and other pollutants from
estimated raw waste and is economically achievable. The Agency
has decided not to include filtration as part of the model BAT
treatment technology (Option 2). EPA has concluded that
compliance with promulgated limitations based on option 1 will
595
-------
remove practically all the toxic and other pollutants from lead
battery manufacturing wastewater discharges. Further treatment
would result only in insignificant reductions in annual national
discharges.
REGULATED PQLLUTAN31 PARAMETERS
The pollutant parameters listed in Tables VI-} and VI-2 (pages
296 and 301) as being considered for regulation were used to
select the specific pollutants to be regulated in the lead
subcategory. The selection of toxic pollutants for regulation
was based primarily upon the presence of the pollutant at
treatable concentrations in lead subcategory raw waste streams.
Plants in the lead subcategory have a variety of different
combinations of process elements, but, in general, the same
pollutants are detected in significant concentrations for all
processes. Other pollutants, not specifically regulated, would
also be controlled by the removal of the selected pollutants.
The overall costs for monitoring and.analysis would "therefore be
reduced. Nonconventional pollutants are regulated as appropriate
when found at treatable concentrations. Conventional pollutants
(pH, TSS and O&G) are not regulated under BAT, except where one
might be used as an indicator, but are generally considered under
BCT.
Pollutant parameters regulated at.BAT for this subcategory are
lead, copper and iron. Antimony, cadmium, chromium, mercury,
nickel, silver, zinc, aluminum, and manganese which appeared at
lower concentrations and were considered, but not selected for
regulation at BAT, are expected to be'adequately removed by the
application of the selected technology.
The conventional pollutant .parameters, oil and grease, total
suspended solids and pH .are not .regulated under BAT, but are
considered under BCT.
POLLUTANT REMOVALS AND COSTS
In establishing BAT, EPA considered the cost of treatment and
control and the pollutant reduction benefits to evaluate economic
achievability. The application of BAT to the lead subcategory
will remove 115,604 kilograms (254,330 pounds) per year of toxic
metals and 679,114 kilograms (1,494,050 pounds) per year of other
pollutants from the estimated raw waste of direct dischargers.
The associated capital cost, above equipment in place is $0.819
million ($1983) and the total annual cost is $0.510 million
($1983). These costs assume that plants will install BAT
59-6
-------
treatment at the BAT regulatory flow. The Agency has determined
that the BAT limitations are economically achievable.
EFFLUENT LIMITATIONS
The effluent concentrations attainable through the application of
BAT technology are displayed in Table VI1-21 under L&S
technology. The BAT mass discharge limitations can be calculated
by multiplying these concentrations by the applicable BAT
regulatory flows listed in Table X-l. These limitations are
expressed in terms of mg of pollutant per kg of lead used in the
product and are presented in Tables X-9 to X-l7 (pages 607 to
615). By multiplying these limitations by the actual production
within a process element, the allowable mass discharge for that
process element can be calculated. The allowable pollutant
discharge for the different process elements can be summed to
determine the total allowable mass discharge for the plant. In
the limitation tables, all the pollutants which were considered
for regulation are listed and those selected for regulation are
*'d.
The reasonableness of these BAT limitations is based upon two
premises - the demonstrated ability to achieve the flow levels
and the proven ability of the lime and settle technology to
achieve the designated effluent concentrations. The flows used
as a basis to calculate BAT mass discharge limitations are based
upon demonstrated performance at lead subcategory plants. By
process substitution or in-process controls, lead battery
manufacturing plants can meet the option 1 based flow levels.
Every process element within the lead subcategory for which a
zero regulatory flow has been established is known to be
performed without wastewater discharge in at least one plant.
Table X-l includes a summary of the number of plants which are
active in each process element.but do not discharge wastewater as
a result of these process elements.
597
-------
x-i
P80CBJS ELEMENT FLOW SUMMARY
Li&D SUBCA'IEGORY
U1
VD
00
No. Plants
Reporting
PROCESS ELEMENT Flow Data
ANODES AND CATHODES
Leady Oxide Production 41
Grid Manufacture
ttold Release Formulation 2 (29)
Direct Chill Casting 1
Lead Rolling 1
Paste Preparation and
Application 100
Curing 97
Closed Formation (In Case)
Single Fill 43
Double Fill 35
Fill and Dump 13
Open Formation (Out of Case)
Dehydrated 42
Wet 16
Plate Soak 3
AKCILLARY OPERATIONS
Battery Wash
Detergent 22
Water Only 44
Floor Wash +
Wet Air dilution Control +
Battery Repair + 3
Laboratory + 4
Truck Wash 2
PERSONAL HYGIENE
Hand Wash + 2 (63)
Respirator Wash + 6 (51)
Laundry 2 (11)
tb. Plants
Reporting
Zero
Discharge
29
0
57
87
31
7
1
2
10
0
32'/
0
0
0
0
0
0
0.00
0.90
0.59
0.13
0.00
0.25
*
0.014
Mean BPT (PSES 0)
Flow Flow
I/kg I/kg
0.37
1.70
3.47
0.11
0.26
0.20
0.003
0.014
0.027
0.006
0.109
0.00
*
0.0002
0,006
0.00
0.00
0.00
0.45
0.45
1.05
0.00
0.021
0.006
0.0002
0.006
0.49
0.03
0.28
0.92
1.83
28.26
0.36
0.026
0.006
0.0002
0.006
0.00
0.00
0.00
0.45
0.45
11.05
0.053
0.021
0.90
0.59
0.13
0.011
0.25
0.003
0.014
0.027
0.006
0.109
BAT (PSES)
I/kg
0.00
0.006
0.0002
0.006
0.00
0.00
0.00
0.00
0.00
1.68
0.053
0.021
0.45
0.00
0.01
0.011
0.25
0,003
0.014
0.027
0.006
0.109
ME (PSES 4)
Flow
1/kR
0.00
0.003t
0.0001t
0.006
0.00
0.00
0.00
0.00
0.00
0.84t
0.053
0.021
0.23t
0.00
0.01
0.011
0.25
0.003
0.005
0.027
0.006
0.109
MISCELLAKEDIS (Elements marked "+" are included)
0.427
0.307
I/ Based on number of scrubbers from all process areas but laboratories.
"II Lead rolling spent emulsion is contract hauled by five plants; flow data is available from one of these plants.
( ) Number of plants used to calculate I/kg f},aw per unit operation
t Flow reduction at this option based on 50% water reuse using reverse osmosis.
* Calculated as flow weighted average - no median available
0.307
-------
TABLE X-2
NORMAL PIANT ELEMENT FLOWS
LBU) 8UBCATEGORY
Normal Plant Flow. 1/yr (106)
Ui
*O
vo
Process Element
Leady Oxide
Produced On Site
Purchased
Grid Manufacture
Direct Chill Casting
Mold Release Formulation
Paste Preparation & Application
Curing
Stacked
Controlled Room
Steam Cure
Formation
Closed Formation
' • Single Fill
•' - Double Fill
Fill and Dump
Open Formation
Dehydrated
Wet
Plate Soak
Battery Wash
With Detergent
Water Only
Wet Air Pollution Control
Floor Wash
Battery Repair
Laboratory
Truck Wash
• PNP Equivalent
kg/yr lead (106)
5.440
2.928
2.512
0.648
4.792
5.440
5.440
4.074
0.718
0.648
5.440
4.301
1.684
2.078
0.539
1.139
0.973
0.166
0.071
0.289
4.678
5.440
5.440
0.127
5.440
.1.422
MW
1.083
0.0001
0.034
2.666
0
0
1.24
0.472
1.912
0.986
27.497
0.060
0.002
0.491
16.233
0.059
0.707
0.032
0.016
0.020
BPT
(PSES 0)
0
0.0001
0.029
0
0
0
0
0
0.935
0.243
10.752
0.009
0.002
0.26
2.70
0.059
0.707
0.032
0.01
0.020
BAT 1,2,3
(ESES 1,2,3)
0
0.0001
0.029
0
0
0
0
0
0
0
1.635
0.009
0.002
0.13
0
0.059
0.05
0.032
0.01
0.020 (0.007)*
BAI 4
(PSES 4)
0
0.00005
0.014
0
0
0
0
0
0
0
0.817
0.009
0.002
0.066
0
0.059
0.05
0.032
0.01
0.007
-------
TABLE X-2 (continued)
NO»WL PLANE ELEMENT FMMS
LEAD SUBCATEQQRY
Process Element
Personal Hygiene
Hand Wash
Respirator Wash
Laundry
Total Normal Plant
5.440
5.440
0.837
5.440
0.147
0.033
0.091
53.7361
Normal Plant Flow, 1/yr (106)
PHP Equivalent
kg/yr lead (106)
RAH
BPT
(PSES 0)
BAT 1,2,3
(PSES 1,2,3)
BAT 4-
(PSES 4)
0.14
0.03
0.09
16.018
0.14
0.03
0.09
2.236 (2.223)*
0.14
0.03
0.09
1.327
O
O
*Elows used foe selected new source option.
-------
TABLE X-3
SIMWRY OF TREMMBir EFFECTIVENESS
U3M) SUBCATEOTW
PARAMETER
Flow
114.
118.
119.
120.
122.
123.
124.
2 126.
128.
(I/kg)*
Antimony
Cadrolm
Chromiun
Gbpper
lead
Mercury 1/
tickel -'•••
Silver \J
Zinc
Aitminum
Iron
Manganese
Oil&Grease
TSS
RAW
BJg/1
WASTE
mg/kg
9.886
0.146
0.005
0.076
0.175
205.822
80.0
0.073
190.0
0.487
0.287
4.566
0.038
54.605
.'1154.747
1.44
0.04
0.75
1.73
2034.84
800.0
0.72
1800.0
4.8t
2.83
45.14
0.37
539.84
11416.32
BPT (PSES 0)
mg/1 mg/kg
2
0.28
0.009
0.08
0.50
0.12
200.-0
0.23
3.00
0.33
0.68
0.41
0.12
10.00
12.00
.94
0.82
0.02
0.24
1.47
0.35
760.0
0.69
8.82
0.97
2.00
1.20
0.36
29.42
35.31
BAT 1 (PSES 1)
mg/1 rag/kg
0.40
0.70
0.05
0.08
0.58^
0.12
0.584
0.74
2.24
0.33
2.24
0.41
0.16
10.00
12.00
0.28
0.02
0.03
0.23
0.04
0.234
0.30
0.919
0.13
0.91
0.16
0.06
4.09
4.91
BAT 2 (PSES 2)
mg/1 mg/kg
0.
0.47
0.04
0.07
0.39
0.08
0.584
0.22
2.24
0.23
1.49
0.28
0.14
10.00
2.60
,40
0.19
0.02
0.02
0.15
0.03
0.234
0.09
0.919
0.09
0.60
0.11
0.05
4.09
1.06
BAT 3 (PSES 3)
mg/1 rag/kg
0.
0.47
0.01
0.08
0.05
0.01
0.584
0.05
2.24
0.01
1.49
0.28
0.14
10.00
2.60
40
0.19
0.004
0.03
0.02
0.004
0.234
0.02
0.919
0.004
0.60
0.11
0.05
4.09
1.06
BAT 4 (PSES •
mg/1 mg/kj
0,
0.47
0.04
0.07
0.39
0.08
0.986
0.22
3.79
0.23
1.49
0.28
0.14
10.00
2.60
,24
0.11
0.01
0.01
6.09
0,01
0.23;
0.05
0.911
0.05
0.36
0.06
0.03
2.42
0.62
*tfcrmalized flow based on total subcategory lead weight.
_1/ Mercury and silver units are ng/1 x 10"^ and tag/kg.x
-------
TABLE X-4
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LEAD SUBCATEGORY - NORMAL PLANT
ON
O
PARAMETER
FLOW 1/yr (10&)
1 14 Antimony
118 Cadmium
1 1 9 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Oil & Grease
TSS
Total Toxics
Total Nonconv.
Total Gonv.
Total Pollu.
RAW WASTE
kg/yr
53.78
7.85
0.29
4.08
9.46
11068.96
0.44
3.92
1.02
26.19
16.02
261.97
2.15
2936.66
62137.96
11122.21
280.14
65074.62
76476.97
BPT &
removed
kg/yr
3.38
0.16
2.74
1.45
11067.04
0.03
0.14
1.02
20.91
5.12
255.41
0.18
2776.57
61945.85
11096.86
260.70
64722.42
76079.99
PSES 0
discharged
kg/yr
16.009
4.474
0.127
1.344
8.006
1.921
0.411
3.782
0.000
5.282
10.904
6.563
1.973
160.090
192.108
25.347
19.440
352.198
396.985
BAT 1
removed
kg/yr
6.29
0.20
3.89
7.51
11068.69
0.44
2.27
1.02
25.46
11.03
261.06
2.15
2914.39
62111.24
11115.77
274.24
65025.63
76415.63
& PSES 1
discharged
kg/yr
2.227
1.558
0.094
0.187
1.955
0.267
0.000
1.647
0.000
0.734
4.988
0.913
0.000
22.270
26.724
6.442
5.901
48.994
61.337
BAT 2
removed
kg/yr
6.80
0.20
3.93
8.59
11068.78
0.44
3.43
1.02
25.68
12.70
261.35
1.84
2914.39
62132.17
11118.87
275.89
65046.56
76441.32
& PSES 2
discharged
kg/yr
2.227
1.046
0.094
0.155
0.868
0.178
0.000
0.489
0.000
0.512
3.318
0.623
0.311
22.270
5.790
3.342
4.252
28.060
35.654
BAT 3
removed
kg/yr
. 6.80
0.27
3.90
9.35
11068.94
0.44
3.81
1.02
26.17
12.70
261.35
1.84
2914.39
62132.17
11120.70
275.89
65046.56
76443.15
& PSES 3
discharged
kg/yr
2.227
1.046
0.022
0.178
0.111
0.022
0.000
0.111
0.000
0.022
3.318
0.623
0.311
22.270
5.790
1.512
4.252
28.060
33.824
BAT 4
removed
kg/yr
7.23
0.23
3.99
8.95
11068.86
0.44
3.63
1.02
25.89
14.06
261.60
1.97
2923.48
62134.53
11120.22
277.62
65058.01
76455.86
& PSES 4
discharg'
kg/yr
1.318
0.619
0.064
0.092
0.514
0.105
0.000
0.289
0.000
0.303
1.963
0.369
0.184
13.180
3.426
1.986
2.516
16.606
21.108
Sludge kg/yr
463185
465199
465418
465445
465538
-------
TABLE X-5
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LEAD SUBCATEGORY - NORMAL DISCHARGING PLANT
O
LO
PARAMETER
FLOW 1/yr (106)
1 14 Antimony
1 18 Cadmium
1 1 9 Chromium
1 20 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron '
Manganese
Oil & Grease
TSS :
Total Toxics
Total Nonconv.
Total Conv.
Total Pollu.
RAW WASTE
kg/yr
69.91
10.20
0.37
5.30
12.29
14389.65
0.57
5.09
1.32
34.04
20.82
340.56
2.79
3817.66
80779.35
14458.83
364.17
84597.01
99420.01
BPT &
removed
kg/yr
4.39
0.21
3.56
1.89
14387.16
0.04
0.18
1.32
27.18
6.65
332.03
,0.23
3609.55
80529.61
14425.93
338.91
84139.16
98904.00
PSES 0
BAT 1 &
PSES 1
BAT 2 &
PSES 2
BAT 3
discharged removed discharged removed discharged removed
kg/yr kg/yr kg/yr kg/yr kg/yr kg/yr
20.81
5.81
0.16
1.74
10.40
2.49
0.53
4.91
0.00
6.86
14.17
8.53
2.56
208.11
249.74
32.90
25.26
457.85
516.01
8.18
0.25
5.06
9.75
14389.31
0.57
2.95
1.32
33.09
14.34
339.38
2.19
3788.71
80744.61
14450.48
355.91
. 84533.32
99339.71
2.89
2.02
0.12
0.24
2.54
0.34
0.00
2.14
0.00
0.95
6.48
1.18
0.60
28.95
34.74
8.35
8.26
63.69
80.30
8.84
0.25
5.10
11.17
14389.42
0.57
4.46
1.32
33.38
16.51
339.75
2.39
3788.71
80771.83
14454.51
358.65
84560.54
99373.70
2.89
1.36
0.12
0.20
1.12
0.23
0.00
0.63
0.00
0.66
4.31
0.81
0.40
28.95
7.52
4.32
5.52
36.47
. 46.31
8.84
0.34
5.07
12.15
14389.62
0.57
4.95
1.32
34.01
16.51
339.75
2.39
3788.71
80771.83
14456.87
358.65
84560.54
99376.06
& PSES 3
BAT 4
discharged removed
kg/yr kg/yr
2.89
1.36
0.03
0.23
0.14
0.03
0.00
0.14
0.00
0.03
4.31
0.81
0.40
28.95
7.52
1.96
5.52
36.47
43.95
9.40
0.29
5.19
11.63
14389.52
0.57
4.72
1.32
33.65
18.27
340.09
2.56
3800.53
80774.90
14456.29
360.92
84575.43
99392.64
& PSES 4
discharged
kg/yr
1.72
0.80
0.08
0.11
0.66
0.13
0.00
0.37
0.00
0.39
2.55
0.47
0.23
17.13
4.45
2.54
3.25
21.58
27.37
Sludge kg/yr
602141
604759
605044
605078
605200
-------
TABLE X-6
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LEAD SUBCATEGORY - TOTAL DISCHARGERS
O
PARAMETER
RAW WASTE BPT &
kg/yr _
removed
FLOW 1/yr (106) 7760.01
1 14 Antimony
118 Cadmium
1 19 .Chromium
1 20 Copper
122 Lead •
1 23 Mercury
1 •
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Oil & Grease
TSS
Total Toxics
Total Noriconv.
Total Conv.
Total -Pollu. 1
1132.20
41.07
588. 30
1 364. 1 9
1597251.15
63.27
564. 99
146.52
3778.44
2311.02
37802.16
309. 69
423760.26
8966507.85
1604930.13
40422, 87
9390268.11
1035621.11
487.29
23.31
395.16
209. 79
1596974.76
4.44
19.98
146.52
3016.98
738.15
36855.33
25.53
400660.05
8938786.71
'1601278.23
37619.01
9339446.76
10978344.00
PSES 0
BAT 1 & PSES 1
discharged removed discharged
kg/yr kg/yr kg/yr
2309.91
644.91
17.76
193.14
1154.40
276.39
58.83
545.01
0.00
761.46
1572.87
946.83
284. 16
23100.21
27721.14
3651.90
2803. 86
50821.35
57277. 1 1
907.98
27.75
561 . 66
1082.25
1597213.41
63.27
327.45
146.52
3672.99
1591.74
37671,18
243. 09
420546.81
8962651.71
1604003.28
39506.01
9383198.52
•11026707.81
320. 79
224. 22
13.32
26.64
281.94
37.74
0.00
237. 54
0.00
105.45
719.28
1 30. 98
66.60
3213.45
3856.14
926.85
916.86
7069.59
8913.30
BAT 2 & PSES 2
removed discharged
kg/yr kg/yr
981.24
27.75
566.10
1239.87
1597225.62
63.27
495.06
146.52
3705.18
1832.61
37712.25
265.29
420546.81
8965673.13
1604450.61
39810.15
9386219.94
11030480.70
320.79
150.96
13.32
22.20
124.32
25.53
0.00
69.93
0.00
73.26
478.41
89.91
44.40
3213.45
834.72
479.52
612.72
4048.17
5140.41
BAT 3 & PSES 3
removed discharged
kg/yr kg/yr
981.24
37.74
562. 77
1348.65
1597247.82
63.27
549.45
146.52
3775.11
1832.61
37712.25
265.29
420546.81
8965673.13
1604712.57
39810.15
9386219.94
11030742.66
320.79
150.96
3.33
25.53
15.54
3.33
0.00
15.54
0.00
3.33
478.41
89.91
44.40
3213.45
834.72
217.56
612.72
4048.17
4878.45
BAT 4 & PSES 4
removed discharged
kg/yr kg/yr
1043.40
32.19
576.09
1290.93
1597236.72
63.27
523.92
146.52
3735.15
2027.97
37749.99
284.16
421858.83
8966013.90
1604648.19
40062.12
9387872.73
11032583.04
190.92
88.80
8.88
12.21
73.26
14.43
0.00
41.07
0.00
43.29
283. 05
52.17
25. 53_
1901.43
493.95
281.94
360.75
2395.38
3038.07
Sludge kg/yr
66837651
67128249
67159884
67163658
67177200
-------
TABLE X-7
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LEAD SUBCATEGORY - DIRECT DISCHARGERS
O
tn
PARAMETER
FLOW 1/yr (106)
1 14 Antimony
118 Cadmium
1 1 9 Chromium
1 20 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
V28 Zinc
Aluminum
Iron
.Manganese
Oil & Grease
TSS
Total Toxics
•Total Nonconv.
Total Conv.
•Total Pollu,
RAW WASTE
kg/yr
559.28
81.60
2.96
42.40
98.32
115117.20
4.56
40.72
10.56
272.32
166.56
2724.48
22.32
30541.28
646234.80
115670.64
.2913.36
676776.08
795360. 08
BPT
removed
kg/yr
35.12
1.68
28.48
15.12
115097.28
0.32
1.44
10.56
217.44
53.20
2656.24
1.84
28876.40
644236.88
115407.44
2711.28
673113.28
791232.00
discharged
kg/yr
166.48
46.48
1.28
13.92
83.20
19.92
4.24
39.28
0.00
54.88
113.36
68.24
20.48
1664.88
1 99-7-92
263.20
202.08
3662.80
4128.08
BAT
1
removed discharged
kg/yr kg/yr
65.44
2.00
40.48
78.00
115114.48
4.56
23. 60
10.56
264. 72
114.72
2715.04
17.52
30309.68
645956.88
115603.84
2847. 28
676266.56
794717.68
23.12
16.16
0.96
1.92
20.32
2.72
0.00
17.12
0.00
7.60
51.84
9.44
4.80
231.60
277.92
66.80
66.08
509. 52
642.40
BAT
2
removed discharged
kg/yr kg/yr
70.72
2.00
40.80
89.36
115115.36
4.56
35. 68
10.56
267.04
132.08
2718.00
19. 12
30309.68
646174.64
115636.08
2869. 20
676484.32
794989.60
23.12
10.88
0.96
1.60
8.96
1.84
0.00
5.04
0.00
5.28
34.48
6,48
3.20
231.60
60,16
34.56
44.16
291.76
370.48
BAT 3
removed
„- k«/yr
70.72
2.72
40.56
97.20
115116.96
4.56
39.60
10.56
272.08
132.08
2718.00
19.12
30309. 68
646174.64
115654,96
2869.20
676484. 32
795008.48
BAT 4
discharged removed discharge*
kg/yr kg/yr kg/yr
23.12
10.88
0.24
1.84
1.12
0.24
0.00
1.12
0.00
0.24
34.48
6.48
3.20
231.60
60.16
15.68
44.16
291.76
351.60
75.20
2.32
41.52
93.04
115116.16
4.56
37.76
10.56
269,20
146.16
2720.72
20.48
30404. 24
646199.20
115650.32
2887.36
676603.44
795141.12
13.76
6.40
0.64
0.88
5.28
1.04
0.00
2.96
0.00
3.12
20.40
3.76
1.84
137.04
35.60
20.32
26.00
172.64
218,96
Sludge kg/yr
4817128
4838072
4840352
4840624
4841600
-------
TABLE X-8
BATTERY MANUFACTURING COMPLIANCE COSTS
LEAD SUBCATEGORY
o
Ov
Discharge
Status
Direct
Indirect
Total
Discharge
Status
Direct
Indirect
Total
Option BPT (PSES-0) Option BAT-1
Capital Annual Capital
714,843 499,039 818,501
7,887,805 4,635,339 7,121,534
8,602,648 5,134,378 7,940,035
Option BAT-3 (PSES-3)*
Capital Annual"
989,487 739,521
11,214,186 8,381,238 1
12,203,673 9,120,759 1
(PSES-1)
Annual
509,777
4,072,814
4,582,591
Option BAT-
Capital
1,619,406
8,353,268
9,972,674
Option BAT-2
Capital
968,117
8,390,881
9,358,998
4 (PSES-4)*
Annual
930,465
10,545,270
11,475,735
(PSES-2
Annual
580,62
4,723,62
5,304,24
* Plant-by-plant costs were not calculated for Options 3 and 4.
based on the normal discharging plant.
All costs are in June, 1983 dollars.
Option 3 and 4 costs are
-------
TABLE X-9
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Mold Release Formulation
Pollutant or
Pollutant
Property
Maximum for
any one day
.Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
* Iron
Manganese
0.01
0.002
0.003
0.011
0.002
0.002
0.01
0.0025
0.009
0.04
0.007
0.004
0.008
0.0009
0.001
0.006
0.001
0.0006
0.008
0.0010
0.004
0.02
0.003
0.002
*Regulated Pollutant
607
-------
TABLE X-10
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Direct Chill Lead Casting
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Si Iver
Zinc
Aluminum
*Iron
Manganese
0.00057
0.00007
0.00009
0. 0004
0. 00008
0.00005
0.00038
0. 00008
0. 00029
0.0013
0.0002
0.0001
0.00026
0.00003
0.00004
0. 0002
0.00004
0.00002
0.00025
0. 00003
0.00012
0.0006
0.0001
0.00006
*Regulated Pollutant
608
-------
TABLE X-1 1
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Open Formation - Dehydrated
Pollutant or
Pollutant Maximum fo.r Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units '- lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
* Iron.
Manganese
4.82
0, 57
0.73
3.19
0.71
0.42 ;
3.22
0.68
2.45
10.80
2.02
1.14
2.15
0.25
0.30
1.68
0.34
0.16
2.13
0.28
1.02
5.38
1.02
.0.49
*Regulated Pollutant
609
-------
TABLE X-12
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Open Formation - Wet
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
0.152
0.018
0.023
0.100
0.022
0.013
0.101
0.021
0.077
0.34
0.06
0.04
0.067
0.007
0.009
0.053
0.010
0.005
0.067
0.009
0.032
0.17
0.03
0.02
*Regulated Pollutant
610
-------
TABLE X-13
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Plate Soak
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
0.060
0.007
0.009
0.039
0.008
0.005
0.040
0.008
0.030
0.135
0.030
'0.014
0.026
0.003
0.003
0.021
0.004
0.002
0.026
0.003
0.012
0.067
0.010
0.006
*Regulated Pollutant
611
-------
TABLE X-14
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Battery Wash (Detergent)
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
1.29
0.15
0.20
0.86
0.19
0.11
0.86
0.18
0.66
2.89
0.54
0.31
0.58
0.07
0.08
0.45
0.09
0.05
0.57
0.08
0.27
1.44
0.27
0.13
*Regulated Pollutant
612
-------
TABLE X-15
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Truck Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked batteries
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
0.040
0.004
0.006
0.026
0.005
0.003
0.026
0.005
0.020
0.09
0.016
0.01
0.017
0.002
0.002
0.014
0.002
0.001
0.017
0.002
0.008
0.04
0.008
0.004
*Regulated Pollutant
613
-------
TABLE X-16
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Laundry
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
0.31
0.037
0.05
0.21
0.05
0.027
0.209
0.045
0.16
0.70
0.13
0.07
0.14
0.016
0.02
0.11
0.02
0. 01 1
0.138
0.019
0.07
0.35
0.07
0.03
*Regulated Pollutant
614
-------
TABLE X-17
LEAD SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
0.88
0. 10
0.14
0.58
0.13
0.08
0.59
0.13
0.45
1.97
0.37
0.21
0.39
0.05
0.06
0.31
0.06
0.03
0.39
0.05
0.19
0.98
0.19
0.09
^Regulated Pollutant
615
-------
PRDCESS WftSTEWATEB FBOM:
GRID MANUFACTURE
DIRECT CHILL CASTING
MOLD RELEASE FORMULATION
PLATE SOAK
OPEN FORMATION
DEHYDRATED
WET
BATTERY WASH
DETERGENT
TRUCK WASH
LAUNDRY
MISCELLANEOUS WASTIWATER
LIME AND
CARBONATE
ADDITION
l/s
RECYCLE HOSE WASHDOWN WATER
/ / } *
OIL
SKIMMING
1
REMOVAL OF
OIL AND GREASE
•X«-S*«_-»rf-^jC''_Xv->«— •»•"•
CHBIOI
mammon
-*•
fllTRATS
SEDIMENTATION
SLUDGE
\\
HOLDING
TANK
DISCHARGE
SlUOBE TO
DECLAIM Ofl
DISPOSAL
SLUDGE
DEWATERIHG
ADDITIONAL RECOMMENDED IN-PROCESS TECHNOLOGY:
•COUNTERCURRENT RINSE ELECTRODES AFTER OPEN FORMATION
•ELIMINATE OR RECYCLE PROCESS WATER FOR PLATE DEHYDRATION
•WATER RINSE OF BATTERIES PRIOR TO DETERGENT WASH
•COUNTERCUBRENT RINSE BATTERIES
•REUSE BATTERY WATER
•REUSE TREATED WATER FOR HOSE WASHDOWN
FIGURE X-1. LEAD SUBCATEGORY BAT OPTION 1 TREATMENT
-------
PROCESS WASTEWATER FROM:
GRID MANUFACTURE
DIRECT CHILL CASTING
MOLD RELEASE FORMULATION
PLATE SOAK
OPEN FORMATION
DEHYDRATED
WET
BATTERY WASH
DETERGENT
TRUCK WASH
LAUNDRY
MISCELLANEOUS WASTEWATER
V / / /
Yl' 'IV
/ / / ^
OIL
SKIMMING
1
REMOVAL OF
OIL AND GREASE
_, BACKWASH
LIME AND
CARBONATE
ADDITION
IP -
^ -~~~~f* — ~— - A \ ^^^^^^
t££%m^ SEDIMENTATION
^ r*,m^ | ^"*22S^-Aiiv;j3-?niB'>^
SLUDGE
FILTRATE ^'A
REUSE FOR
HOSE WASHDOWN
HOLOIIIfi
TANK
a*«W*ir>»--«4:i
§4 POLISHING m
fi'iflLTRATIONi?.
/»:;.-»v».-;?;*?.S-
^\ CjL SLUDGE TO
„. \/J\ RECLAIM OR
j » \ DISPOSAL
• DISCHARGE
SLUDGE
OEWATERING
IN-PROCESS TECHNOLOGIES ARE THE SAME AS OPTION 1
FIGURE X-2. LEAD SUBCATEGORY BAT OPTION 2 TREATMENT
-------
PflflCfSS WASTF.WATER FROM:
GRID MANUFACTURE
DIRECT CHILL CASTING
MOLD RELEASE FORMULATION
PLATE SOAK
OPEN FORMATION
DEHYDRATED
WET
BATTERY WASH
DETERGENT
TRUCK WASH
LAUNDRY
SULFIDE
ADDITION
REUSE FOR
HOSE WASHDOWH
/ / / v
OIL
SKIMMING
CKHCtt
MOTTHTKW
REMOVAL OF
OIL AND CREASE
DISCHARGE
SLUDGE
DEWATERING
IN-PROCESS TECHNOLOGIES ARE THE SAME AS OPTION I
FIGURE X-3. LEAD SUBCATEGORY BAT OPTION 3 TREATMENT
-------
ON
PROCESS WASTEWATER FROM:
GRID MANUFACTURE
DIRECT CHILL CASTING
MOLD RELEASE FORMULATION
OPEN FORMATION
PERMEATE RETURN
TO PROCESS
BATTERY WASH
DETERGENT
i / / /
tv ri
/ / / *
OIL
SKIMMING
1
REMOVAL OF
OIL AND GREASE
8RINE
PROCESS WASTEWATER FROM:
PLATE SOAK
OPEN FORMATION
WET
TRUCK WASH . . ,
MISCELLANEOUS WASTEWATER 7 7V ^ \
OIL
SKIMMING
I
f
REMOVAL OF
Oil AND GREASE
LIME AND
CARBONATE REUSE FOR HOSE WASKDOWN
ADDITION AND TRUCK WASH
\o '
mcmniM j sramiEiimioN j |
"UJs*esSt^j^ J
I
/" "\ _Q SLUD8EIO
» I m lXT| RECLAIM OR
FILTRATE \\T /7 t t 01SPOS*L
SlUDGE l%?«aj.3«®>:
OEUfMTCDIUn t'.-i-Ji'ffiTijrf !!•"'-
•WARS)
ADDITIONAL RECOMMENDED IN-PROCESS TECHNOLOGY: REUSE TREATED WATER FOR TRUCK WASH
FIGURE X-4. LEAD SUBCATEGORY BAT OPTION 4 TREATMENT
-------
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the Clean Water Act is the best available
demonstrated control technology (BDT).
This section presents effluent characteristics attainable by new
sources through the application of the best available
demonstrated control technology (BDT), processes, operating
methods, or other alternatives including, where practicable, a
standard permitting no discharge of pollutants. Five levels of
technology are discussed; cost, performance and pollutant
removals are presented, and the rationale for selection of the
BDT is outlined. The selection of pollutant parameters for
specific regulations is discussed and discharge limitations for
the regulated pollutants are presented for the lead subcategory.
TECHNICAL APPROACH TO NSPS
The technology options considered as possible BDT for the lead
subcategory are similar to the options considered at BAT. BAT
options are discussed in outline form and in detail in Section X
(pages 586-593) and are depicted schematically in Figures X-l to
X-4 (pages 616-619). These options were evaluated for their
applicability, cost, and pollutant reduction benefits. Option 1
was selected as the BAT model technology.
Each of the four BAT options is considered as an option for BDT.
In addition to these four options, the Agency considered another
option, option 5, for BDT. Option 5 is almost identical to
option 2, the only difference being that treated water is reused
for truck washing activities. This results in a reduction of the
truck wash regulatory flow to 0.005 I/kg. The treatment scheme
for option 5 is identical to the scheme shown in Figure X-2.
Both truck wash and floor wash water are recycled from the
holding tank.
As discussed in Section X, EPA revised option 4 between proposal
and promulgation. At proposal, option 4 consisted of oil
skimming, chemical precipitation (with lime and carbonate),
filtration, and reverse osmosis for all process streams. The
permeate from the reverse osmosis unit was returned to the
manufacturing process for use as make up water. The brine
containing essentially all of the process wastewater pollutants,
was treated in a system identical to the end-of-pipe system
621
-------
provided in option 3. This option was selected as the basis for
the proposed NSPS.
Commenters on the proposed NSPS contended that reverse osmosis is
not demonstrated in the subcategory and- is not readily
transferable from other categories or subcategories. Commenters
also pointed out that reverse osmosis technology could not
adequately treat all of the waste streams at a lead battery
plant. They stated that the technology would be plagued by
operational problems due to its sensitivity to temperature, pH,
acidity, chloride concentrations and blinding. EPA agrees with
the Commenters that reverse osmosis may not adequately treat all
lead battery wastewater discharges. However, the Agency believes
that a combination of filtration and reverse osmosis for less
concentrated wastewaters followed by lime, settle, and filter
technology for the reverse osmosis brine and other wastewaters is
an appropriate technology for option 4. Less concentrated
wastewaters which may be treated by reverse osmosis include open
dehydrated formation wastewater, continuous strip casting
wastewater, mold release formulation equipment washdown, and
detergent battery wash wastewater. This new treatment scheme is
the basis for the revised option 4. The Agency carefully
considered this option and has concluded that all of the
technologies included as part of this option have been
demonstrated in industrial situations. This technology has been
used on acid mine drainage which is similar to battery
manufacturing wastes in that it contains high levels of toxic
metals and sulfuric acid.
The Agency has elected to base NSPS on option 5. This option
adds polishing filtration to the BAT end-of-pipe treatment
(chemical precipitation and sedimentation) and increased flow
reduction measures. The increased flow reduction for NSPS is
applied to truck washing. The BAT regulatory flow for truck
washing is reduced from 0.014 I/kg (BPT and BAT) to 0.005 I/kg
for NSPS. This flow reduction measure is based on using two-
stage rinsing for truck washing; 1) a rinse with treated
wastewater, 2) followed by a final fresh water rinses. The
promulgated NSPS will result in the discharge of only a miniscule
amount of pollutants from new plants. EPA has^concluded that a
national standard based on the use of advanced end-of-pipe
treatment technologies beyond the recommended BAT plus filtration
in order to remove the remaining deminimis pollutants is* not
warranted.
Option 5 has been selected as the preferred option because it
improves pollutant removal and the technology is demonstrated.
As an alternative to flow reduction and treatment, new plants can
select dry manufacturing processes and water conservation
622
-------
practices and achieve no discharge of pollutants. No discharge
of wastewater pollutants is practiced by 57 existing plants.
Also, as discussed in the EIA, no entry impacts are projected
with the selection of this option.
POLLUTANT REMOVALS AND COSTS
The Agency used the normal discharging plant to estimate costs
and pollutant reduction benefits associated with the five BDT
treatment options for a new direct discharge lead battery plant.
Pollutant reduction benefits for options 1 to 4 are identical to
those presented for the normal discharging plant in Table X-5
(page 603). Pollutant reduction benefits for option 5 are
presented in Table XI-1 (page 624). Based on the normal
discharging plant, a new direct discharger would generate 14,459
kilograms (31,810 pounds) per year of toxic pollutants. The NSPS
technology (option 5) would reduce toxic pollutant levels to 4.33
kilograms (9.53 pounds) per year and the discharge of other
pollutants to 42 kilograms (92.4 pounds) per year. The capital
investment cost for a new model lead battery manufacturing plant
to install the NSPS technology is estimated to be $0.119 million
with annual costs of $0.069 million (1983).
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in significant quantities for processes within new
sources will be any different than with existing sources.
Consequently, pollutants selected for regulation, in accordance
with the rationale -of Section VI, IX, and X are the same ones
that were selected at BAT with the addition of TSS, oil and
grease, and pH.
NEW SOURCE PERFORMANCE STANDARDS
New source performance standards for this subcategory are based
on the wastewater flow reductions achieved by improved in-process
control and recycle, and the pollutant concentrations achievable
by lime, .settle and filter end-of-pipe treatment. Regulatory
flows used as the basis for new source standards are the same as
those used at BAT (with the exception of truck wash) and can be
found in Table X-l (page 598). The NSPS regulatory flow for
truck wash is 0.005 I/kg. Effluent concentrations achievable by
the application of new source technology are displayed in Table
VII-21 (page 418).
Tables XI.-2 through 10 (pages 625-633) display ,NSPS for the lead
subcategory. ..-..-........ * .
623
-------
TAB IB XI-1
POLLUTANT REDUCTION BENEFITS
OPTION 5
RAW WASTE
PARAMETER
Removed
kg/yr
OPTION 5
Discharged
FLOW 1/yr (106)
114 Antimony
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Oil & Grease
TSS
Total Toxics
Total Nonconv.
Total Conv.
Total Pollutants
69.91
10.20
0.37
5.30
12.29
14389.65
0,57
5.09
1.32
34.04
20.82
340.56
2.79
3817.66
80779.35
14458.83
364.17
84597.01
99420.01
8.85
0.23
5.10
11.17
14389.42
0.57
4.46
1.32
33.38
16.54
339.76
2.39
3788.88
80771.87.
14454.50
358.69
84560.75
99373.94
2.87
1.35
0.14
0.20
1.12
0.23
0.00
0.63
0.00
0.66
4.28
0.80
0.40
28.78
7.48
4.33
5.48
36.26
46.07
Sludge
605046
-------
TABLE XI-2
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Mold Release Formulation
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.01
0.0012
0.0022
0.0077
0.0017
0.0009
0.0033
0.0017
0.0061
0.0367
0.0072
0.0018
0.060
0.090
the range of 7.5 to
0.0052
0.0005
0.0009
0.0037
0.0008
0.0004
0.0022
0.0007
0.0025
0.0163
0.0037
0.0014
0.060
0.072
10.0 at all times
^Regulated Pollutant
625
-------
TABLE XI-3
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Direct Chill Lead Casting
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony •
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.000386
0.000040
0.000074
0.000256
0.000056
0.000030
0.000110
0.000058
0.000204
0.00122
0.000240
0.00006
0.0020
0.0030
the range of 7.5 to
0.000172
0.000016
0.000030
0.000122
0.000026
0.000012
0.000074
0.000024
0.000084
0. 00054
0.000122
0.00005
0.0020
0. 0024
10.0 at all times
*Regulated Pollutant
626
-------
TABLE XI-4
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Open Formation - Dehydrated
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*lron
Manganese
*0il and Grease
*TSS
*pH Within
3.24
0.33
0.62
2. 15
0.47
0.25
0.92
0.48
1.71
10.26
2.01
0.50
16.80
25.20
the range of 7.5 to
1.44
0.13
0.25
1.02
0.21
0.10
0.62
0.20
0.70
4.55
1.02
0.39
16.80
20.16
10.0 at all times
*Regulated Pollutant
627
-------
TABLE XI-5
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Open Formation - Wet
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.102
0.010
0.019
0.067
0.014
0.007
0.029
0.015
0.054
0.324
0.063
0.016
0.53
0.80
the range of
0.045
0.004
0.007
0.032
0.006
0.003
* 0.019
0.006
0.022
0. 1 44
0.032
0.012
0.53
0.64
7.5 to 10.0 at all times
*Regulated Pollutant
628
-------
TABLE XI-6
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Plate Soak
Pollutant or
Pollutant
Proper ty
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
* Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.04
0.004
0.007
0.026
0.005
0.003
0.011
0.006
0.021
0. 128
0.025
0.006
0.21
0.32
the range of 7.5 to
0.018
0.001
0.003
0.012
0.002
0.001
0.007
0.002
0.008
0.057
0.012
0.005
0.21
0.25
10.0 at all times
*Regulated Pollutant
629
-------
TABLE XI-7
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Battery Wash (Detergent)
Pollutant
Pollutant
Property
or
Maximum
any one
for
day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.868
0.090
0.166
0.576
0.126
0.067
0.247
0.130
0.459
2.750
0.540
0.135
4.50
6.75
the range of 7.5 to
0.387
0.036
0.067
0.274
0.058
0.027
0.166
0. 054
0.189
1.22
0.274
0. 104
4.50
5.40
10.0 at all times
*Regulated Pollutant
630
-------
TABLE XI-8
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Truck Wash
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - rag/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked batteries
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.009
0.001
0.001
0.006
0.001
0.0008
0.002
0.001
0.005
0.031
0.006
0.002
0.050
0.075
the range of 7.5 to
0.004
0.0004
0.000
0.003
0.0007
0.0003
0.001
0.0006
0.002
0.014
0.003
0.001
0.050
0.060
10.0 at all times
*Regulated Pollutant
631
-------
TABLE XI-9
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Laundry
Pollutant or
Pollutant Maximum for Maximum for
Property any one day : monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
*Iron
Manganese
*0il and Grease
*TSS
*pH Within the
0.210
0.022
0.040
0.14
0.03
0.016
0.060
0.032
0.111
0.666
0.13
0.030
1.09
1.64
range of 7.5 to
0.094
0.009
0.016
0.07
0.01
0.007
0.040
0.013
0.046
0.295
0.07
0.025
1.09
1.31
10.0 at all times
*Regulated Pollutant
632
-------
TABLE XI-10
LEAD SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum.
*Iron
Manganese
*0il and Grease
*TSS
*pH Within
0.59
0.06
0.11
0.39
0.085
0.05
0.17
0.09
0.31
1.88
0.37
0.09
3.07
4.61
the range of 7.5 to.
0.26
0.02
0.05
0.19
0.039
0.02
0. 11
0.04
0.13
0.83
0.19
0.07
3.07
3.69
10.0. at all times
*Regulated Pollutant
633
-------
-------
SECTION XII
PRETREATMENT
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of Publicly
Owned Treatment Works (POTW). The Clean Water Act of 1977 adds a
new dimension by requiring pretreatment for pollutants, such as
toxic metals, that limit POTW sludge management alternatives,
including the beneficial use of sludges on agricultural lands.
The legislative history of the 1977 Act indicates that
pretreatment standards are to be technology-based, and analogous
to the best, available technology for removal of toxic pollutants.
(Conference Report 95-830 at 87; reprinted in Comm. on
Environment, and Public Works, 95th Cong., 2d Session, A
Legislative History of the Clean Water Act of 1977, Vol. 3 at
272) .
The general pretreatment regulations can be found at 40 CFR Part
403. See 43 FR 27736 June 26, 1978, 46 FR 9404 January 28, 1981,
and 47 FR 4518 February 1, 1982. These regulations describe the
Agency's overall policy for establishing and enforcing
pretreatment standards for new and existing users of a POTW and
delineate the responsibilities and deadlines applicable to each
part in this effort. In addition, 40 CFR Part 403, Section
403.5(b), outlines prohibited discharges which apply to all users
of a POTW.
Section 307(c) of the Act requires EPA to promulgate pretreatment
standards for new sources (PSNS) at the same time that it promul-
gates NSPS. New indirect dischargers, like new direct
dischargers, have the opportunity to incorporate the best
available demonstrated technologies including process changes,
in-plant' controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation.
This section describes the control technology for pretreatment of
process wastewaters from existing sources and new sources. The
concentrations and mass discharge limitations of regulated
pollutants for existing and new sources, based on the described
control technology, are indicted by the data presented in
Sections V and VII.
635
-------
DISCHARGE OF WASTEWATERS TO A POTW
' There are 103 plants in the lead subcategory of the battery
manufacturing category which currently discharge to a POTW.
Pretreatment standards are established to ensure removal of
pollutants discharged by such plants which interfere with, pass
through or are otherwise incompatible with a POTW. A
determination of which pollutants may pass through or be
incompatible with POTW operations, and thus be subject to
pretreatment standards, depends on the level of treatment
employed by the POTW. In general, more pollutants will pass
through a POTW employing primary treatment (usually physical
separation by settling) than one which has installed secondary
treatment (settling plus biological treatment).
Most POTW currently consist of primary or secondary treatment
systems which are designed to treat domestic wastes. Many of the
pollutants contained in battery manufacturing wastes are not
biodegradable and are, therefore, ineffectively treated by such
systems. Furthermore, these wastes have been known to pass
through or interfere with the normal operations of these systems.
Problems associated with the uncontrolled release of pollutant
parameters identified in battery process wastewaters to POTW were
discussed in Section VI. The discussion covered pass-through,
interference, and sludge useability.
The Agency based the selection of pretreatment standards for the
battery category primarily on the minimization of pass through of
toxic pollutants at POTW. The Agency compared the removal rates
for each toxic pollutant limited by the pretreatment options to
the removal rate for that pollutant at a well operated POTW. The
POTW removal rates were determined through a study conducted by
the Agency at over 40 POTW and a statistical analysis of the
data. (See Fate of Priority Pollutants In Publicly Owned
Treatment Works, EPA 440/1-80-301, October, 1980; and Determining
National Removal Credits for Selected Pollutants for Publicly
Owned Treatment Works, EPA 440/82-008, September, 1982). The
POTW removal rates are presented below:
Toxic Pollutant POTW Removal Rate
Cadmium 38%
Chromium 65%
Copper 58%
Cyanide 52%
Lead 48%
Nickel 19%
Silver 66%
Zinc 65%
636
-------
The study did not analyze national POTW removals for mercury.
The range of removal indicated by the data ranged from 19 to 66
percent. However, as discussed in Section VI, mercury has
inhibiting effects upon activated sludge POTW at levels of 0.1
mg/1 and loss of COD removal efficiency of 59 percent is reported
with 10.0 mg/1 of mercury. Therefore, unless treated at the
source, mercury is likely to cause POTW interference. The model
treatment technologies chosen as the basis for PSES and PSNS will
achieve removals of greater than 99.9 percent for toxic metals as
is demonstrated by the pollutant reduction benefits shown in
Table XII-1 (page 640).
The pretreatment options selected provide for significantly more
removal of toxic pollutants than would occur if battery
wastewaters were discharged untreated to the POTW. Thus,
pretreatment standards will control the discharge of toxic
pollutants to the POTW and prevent pass through.
TECHNICAL APPROACH TO PRETREATMENT
The goal of pretreatment is to control pollutants which will pass
through a POTW, interfere with its operation, or interfere with
the use or disposal of POTW sludge. Because battery manufac-
turing wastewater streams characteristically contain toxic metals
which pass through POTW, pretreatment requirements for these
streams do not differ significantly from treatment requirements
for direct discharge. Consequently, the options presented for
PSES and PSNS are identical to treatment and control options
presented for BAT and NSPS, respectively. These options combine
both in-plant technology and wastewater treatment to reduce the
mass of pollutants (especially toxic metals) which will pass
through the POTW or contaminate the POTW sludge.
Factors considered in selecting the specific technology options
presented have been discussed in Sections IX, X and XI. The same
considerations apply to pretreatment prior to introduction of the
wastewater into a POTW.
Option 0 for pretreatment standards for existing sources (PSES)
is identical to BPT (option 0) which is described in Section IX.
PSES options 1-4 are identical to BAT options 1-4 respectively.
End-of-pipe treatment systems for each of these options are
depicted in Sections IX or X as appropriate. PSNS options 1-5
are the same as BDT options 1-5 discussed in Section XI.
Effluent performance achieved by these pretreatment options will
be the same as that provided by the respective BPT, BAT and BDT
options and is indicated by the production normalized flow
information provided in Section V and the technology performance
637
-------
data shown in Section VII. Compliance cost data for all options
are displayed in Table X-8 (page 606). Pollutant removals for
indirect dischargers of the lead subcategory are displayed in
Table XII-1 (page 640).
PSES AND PSNS OPTION SELECTION
Option 1 is selected as the PSES option because standards are
achievable using technologies and practices that are currently in
use at plants in the subcategory. Implementation of this
technology will result in a significant reduction of toxic
pollutant discharges to POTW which would otherwise pass through.
This option is analogous to that chosen for BAT and has been
determined to be economically achievable.
Option 5 is selected as the regulatory approach for pretreatment
standards for new sources (PSNS). This option is analogous to
that chosen for NSPS and has been chosen for the same reasons as
discussed in Section XI.
POLLUTANT REMOVAL BENEFITS AND COST
As a means of evaluating the economic achievability of each of
the options, the'Agency developed cost estimates for existing
plants and used the normal dischargingg plant to estimate costs
and benefits for a new plant. The cost estimates for existing
indirect dischargers are presented in Table X-8.
Implementation of PSES will remove 1,488,399 kilograms (3,274,478
pounds) per year of toxic metals and 8,743,591 kilograms
(19,235,899 pounds) per year of other pollutants from the
estimated raw waste generation for indirect dischargers, at a
capital cost, above -equipment in place, of $7.114 million and a
total annual cost of $4.069 million. These costs assume plants
will install PSES treatment systems at the PSES regulatory flow.
The Agency has determined that these standards are economically
achievable.
New source plant costs were estimated for the lead subcategory
using the normal discharging plant. The total capital investment
cost for a new lead battery manufacturing plant to install PSNS
technology is $0.119 million with corresponding total annual
costs of $0.069 .million. This new lead battery manufacturing
plant would generate a raw waste -load of approxiamtely 14,459
kilograms (31,810 pounds) per year of toxic pollutants and 84,961
kilograms (186,914 pounds) per year of other pollutants.
Application of PSNS technology would reduce the toxic pollutant
discharge to 4.33 kilograms (9.53 pounds) per year and the
638
-------
discharge of other pollutants to 42 kilograms (92.4 pounds) per
year.
POLLUTANT PARAMETERS FOR REGULATION
Pollutant parameters selected for pretreatment regulation in this
subcategory are copper and lead. As discussed in Section X these
pollutants were selected for their toxicity, use within the
subcategory and treatability. For the pretreatment standards,
POTW treatment, incompatability and pass-through of copper and
lead were also considered. Conventional pollutants and iron are
not specifically regulated because a POTW may use iron as a
coagulant in the treatment process and a POTW is specifically
designed to treat the conventional pollutants.
PRETREATMENT STANDARDS
Effluent standards for existing pretreatment sources are
identical to the BAT limitations discussed in Section X. These
standards are expressed in terms of mg of pollutant per kg of
production normalizing parameter for each process element. PSES
are displayed in Tables XII-2 to XII-10 (pages 641-649). These
standard tables list all the pollutants which were considered for
regulation, and those regulated are *'d.
Pretreatment standards for new sources are identical to NSPS
discussed in Section XI except that conventional pollutants and
iron are not regulated. Standards are displayed in Tables XII-11
to XII-19 (pages 650-658).
639
-------
TABLE XII-1
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LEAD SUBCATEGORY - INDIRECT DISCHARGERS
PARAMETER
FLOW 1/yr (1
1 1 4 Antimony
118 Cadmium
119 Chromium
1 20 Copper
122 Lead
1 23 Mercury
124 Nickel
126 Silver
128 Zinc
Aluminum
Iron
Manganese
Oil & Crease
TSS
RAW WASTE
kg/yr
06) 7200.73
1050.60
38.11
545. 90
1265.87
1482133.95
58.71
524.27
135.96
3506.12
2144.46'
35077.68
287.37
393218.98
8320273.05
Total Toxics 1489259.49
Total Nonconv. 37509.51
Total Conv. 8713492.03
Total Pollu. 10240261.03
PSES
0
removed discharged
kg/yr kg/yr
452.17
21.63
366.68
1 94. 67
1481877.48
4.12
18.54
135.96
2799.54
684.95
34199.09
23.69
371783.65
8294549.83
1485870.79
34907.73
8666333.48
10187112.00
2143.43
598.43
16.48
179.22
1071.20
256.47
54.59
505. 73
0.00
706. 58
1459.51
878.59
263.68
21435.33'
25723.22
3388.70
2601.78
47158.55
53149.03
PSES
1
removed discharged
kg/yr kg/yr
842. 54
25.75
521.18
1004.25
1482098.93
58.71
303.85
135.96
3408.27
1477.02
34956.14
225.57
390237.13
8316694.83
1488399.44
36658.73
8706931.96
10231990. 13
297.67
208.06
12.36
24.72
261.62
35.02
0.00
220. 42
0.00
97.85
667.44
121.54
61.80
2981.85
3578.22
860.05
850. 78
6560.07
8270.90
PSES
2
remove'!! discharged
kg/yr kg/yr
910.52
25.75
525.30
1150.51
1482T10.26
58.71
459.38
135.96
3438. 14
1700.53
34994.25
246.17
390237.13
8319498.49
1488814.53
36940. 95
8709735.62
10235491.10
297.67
140.08
12.36
20.60
115.36
23.69
0.00
64.89
0.00
67.98
443.93
83.43
41.20
2981.85
774.56
444. 96
568. 56
3756.41
4769.93
PSES
3
removed discharged
kg/yr kg/yr
910.52
35.02
522.21
1251.45
1482130.86
58.71
509.85
135.96
3503.03
1700.53
34994.25
246.17
390237.13
8319498.49
1489057.61
36940.95
8709735.62
10235734.18
297.67
140.08
3.09
23.69
14.42
3.09
0.00
14.42
0.00
3.09
443.93
83.43
41.20
2981.85
774.56
201.88
568. 56
3756.41
4526.85
PSES
4
removed discharged
kg/yr kg/yr
968.20
29.87
534.57
1197.89
1482120.56
58.71
486.16
135.96
3465.95
1881.81
35029.27
263.68
391454.59
8319814.70
1488997.87
37174.76
8711269.29
102374*1.92
177.16
82.40
8.24
11.33
67.98
13.39
0.00
38.11
0.00
40.17
262.65
48.41
23.69
1764.39
458.35
261.62
334.75
2222.74
2819.11
Sludge kg/yr
62020523
62290177
62319532
62323034
62335600
-------
TABLE XI1-2
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Mold Release Formulation
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - tag/kg of lead used
English Units - lb/1>000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.01
0.002
0,003
0.011
0.002
0.002
0.01
0.0025
0.009 '
0,04
0.007
0.004 .
0.008
0.0009
0.001
0.006
0.001
0.0006
0.008
0.0010
0.004
0.02
0.003
0,002
*Regulated Pollutant
641
-------
TABLE XI1-3
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Direct Chill Lead Casting
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for ,
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.00057
0. 00007
0.00009
0.0004
0.00008
0.00005
0.00038
0.00008
0.00029
0.0013
0.0002
0.0001
0.00026
0. 00003
0.00004
0.0002
0.00004
0. 00002
0.00025
0. 00003
0.00012
0. 0006
0.0001
0.0006
*Regulated Pollutant
642
-------
TABLE XI1-4
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Open Formation - Dehydrated
Pollutant or
Pollutant .
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver .
Zinc . -,
Aluminum
Iron
Manganese :
4.82
0.57
0.73
3.19
0.71
0.42
3.22
0.68
2.45
10.80
2.02
1.14
2.15
0.25
0.30
1.68
0.34
0.16
2.13
0.28
1.02
5.38
1.02
0.49
*Regulated Pollutant
643
-------
TABLE XII-5
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Open Formation - Wet
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.152
0.018
0.023
0.100
0.022
0.013
0.101
0.021
0.077
0.34
0.06
0.04
0.067
0.007
0.009
0.053
0.010
0.005
0.067
0.009
0.032
0. 17
0.03
0.02
*Regulated Pollutant
644
-------
TABLE XI1-6
LEAD SUBCATEGQRY
PR'ETREATMENT STANDARDS FOR EXISTING SOURCES
Plate Soak
Pollutant or
Pollutant Maximum for Maximum for
Property any one day i monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.060
0.007
0.009
0.039
0.008
0. 005
0. 040
0.008
0.030
0.135
0.030
'0.014
0.026
0.003
0.003
0.021
0.004
0.002
0.026
0.003
0.012
0.067
0.010
0.006
*Regulated Pollutant
645
-------
TABLE XI1-7
LEAD SUBGATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Battery Wash. (Detergerit)
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
1.29
0. 15
0.20
0.86
0.19
0.11
0.86
0.18
0.66
2.89
0.54
0.31
0.58
0.07
0.08
; 0.45
0.09
0.05
0.57
0.08
0.27
1.44
0.27
0.13
*Regulated Pollutant
646
-------
TABLE XII-8
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Truck Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked batteries
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.040
0.004
0.006
0.026
0.005
0.003
0.026
0.005
0.020
0.09
0.016
0.01
0.017
0.002
0.002
0.014
0.002
0.001
0.017
0.002
0.008
0.04
0.008
0.004
*Regulated Pollutant
647
-------
TABLE XH-9
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Laundry
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper .
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.31
0.037
0.05
0.21
0.05
0.027
0.209
0.045
0.16
0.70
0.13
0.07
0.14
0.016
0.02
0.11
0.02
o. in
0. .38
0.019
0.07
0.35
0.07
0.03
*Regulated Pollutant
648
-------
TABLE XII-10
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.88
0.10
0.14
0.58
0.13
0.08
0.59
0.13
0.45
1.97
0.37
0.21
0.39
0.05
0.06
0.31
0.06
0.03
0.39
0.05
0.19
0.98
0.19
0.09
*Regulated Pollutant
649
-------
TABLE XII-11
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Mold Release Formulation
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - rag/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Alum inum
Iron
Manganese
0.01
0.0012
0.0022
0.0077
0.0017
0.0009
0.0033
0.0017
0.0061
0.0367
0.0072 \
0.0018 *
0.0052
0.0005
0.0009
0.0037
0.0008
0. 0004
0.0022
0. 0007
0.0025
0.0163
0.0037
0.0014
*Regulated Pollutant
650
-------
TABLE XII-12
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Direct Chill Lead Casting
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium .
*Copper
*Lead
Mercury
Nickel
Silver
Zinc ;•
Aluminum >
Iron
Manganese
0.000386
0.000040
0.000074
0.000256
0.000056
0.000030
0.000.110
0.000058
0.000204
0.00122
0.000240
0.00006
0.000172
0.000016
0.000030
0.000122
0.000026
0.000012
0.000074
0.000024
0.000084
0.00054
0.000122
0.00005
*Regulated Pollutant
651
-------
TABLE XII-13
LEAD SUBCATEGORY
PRETREATMENT STANDARDS .FOR NEW SOURCES
Open Formation - Dehydrated
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
3.24
0.33
0.62
2.15
0.47
0.25
0.92
0.48
1.71
10.26
2.01
0.50
1.44
0.13
0.25
1.02
0.21
0. 10
0.62
0.20
0.70
4.55
1.02
0.39
*Regulated Pollutant
652
-------
TABLE 'XII-14
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Open Formation - Wet
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - rag/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0,102
0.010
0.019
0.067
0.014
0.007
0.029
0.015
0.054
0. 324
0.063
0.016
0.045
0.004
0.007
0.032
0.006
0.003
0.019
0.006
0.022
0.144
0.032
- ^0.012
*Regulated Pollutant
653
-------
TABLE XII-15
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Plate Soak
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.04
0.004
0.007
0.026
0.005
0.003
0.011
0.006
0.021
0.128
0.025
0.006
0.018
0.001
0.003
0.012
0.002
0.001
0.007
0.002
0.008
0.057
0.012
0.005
*Regulated Pollutant
654
-------
TABLE XII-16
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Battery Wash (Detergent)
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - rag/kg of lead used
English Units - lb/1,000,000 Ib of .lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.868
0.090
0.166
0.576
0.126
0.067
0. 247
0.130
0.459
2. 750
0.540
0.135
0.387
0.036
0.067
0.274
0,058
0.027
0.166
0.054
0.189
1.22
0.274
0.104
*Regulated Pollutant
655
-------
TABLE XII-17
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Truck Wash
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - me/kg of lead in trucked batteries
English Units - lb/1,000,000 Ib of lead in trucked batteries
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.009
0.001
0.001
0.006
0.001
0.0008
0.002
0.001
0.005
0.031
0.006
0.002
0.004
0.0004
0.000
0.003
0.0007
0.0003
0.001
0.0006
0.002
0.014
0.003
0.001
*Regulated Pollutant
656
-------
TABLE XII-18
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Laundry
Pollutant or
Pollutant . Maximum for Maximum for
Property . any one day monthly average
Metric Units - mg/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc - ,
Aluminum
Iron
Manganese
0.210
0.022
0.040
0.14
0.03
0.016
0.060
0.032
0.111
0.666
0.13
0.030
0.094
0.009
0.016
0.07
0.01
0.007
0.040
0.013
0.046
0. 295
0.07
0.025
*Regulated Pollutant
657
-------
TABLE XII-19
LEAD SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - tng/kg of lead used
English Units - lb/1,000,000 Ib of lead used
Antimony
Cadmium
Chromium
*Copper
*Lead
Mercury
Nickel
Silver
Zinc
Aluminum
Iron
Manganese
0.59
0.06
0.11
0.39
0.085
0.05
0.17
0.09
0.31
1.88
0.37
0.09
0.26
0.02
0.05
0.19
0.039
0.02
0.11
0.04
0.13
0.83
0.19
0.07
*Regulated Pollutant
658
-------
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
The 1977 amendments to the Clean Water Act added Section
301(b)(2)(E), establishing "best conventional pollutant control
technology" (BCT) for discharge of conventional pollutants from
existing industrial point sources. Conventional pollutants are
those defined in Section 304(a)(4) [biological oxygen-demanding
pollutants (BOD5_), total suspended solids (TSS), fecal coliform,
and pH] and any additional pollutants defined by the
Administrator as "conventional" [oil and grease (O&G) 44 FR
44501, July 30, 1979].
BCT is not an additional limitation but replaces BAT for the
control of conventional pollutants. In addition to other factors
specified in Section 304(b)(4)(B), the Act requires that BCT
Limitations be 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 conventional pollutants with the
costs to publicly owned treatment works 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 published its methodology for carrying out the BCT analysis
on August 29, 1979 (44 FR 50732). In the case mentioned above,
the Court of Appeals ordered EPA to correct data errors
underlying EPA's calculation of the first test, and to apply the
second cost test. (EPA argued that a second cost was not
required.) On October 29, 1982, the Agency proposed a revised
BCT methodology. EPA is deferring proposal of BCT limitations
for the battery manufacturing category until the proposed
methodology is made final.
659
-------
-------
SECTION XIV
ACKNOWLEGEMENTS
This document has been prepared by the staff of the Effluent
Guidelines Division with assistance from technical contractors,
other EPA offices and other persons outside of EPA. This Section
is intended to acknowledge the contribution of the persons who
have contributed to the development of this report.
The initial effort on this project was carried out by Hamilton
Standard Division of United Technologies, under Contract No. 68-
01-4668 and 68-01-5827. They performed data collection, data
compilation, field sampling and analysis, initial wastewater
treatment costing, and made the initial drafts for this project.
Hamilton Standard's effort was managed by Daniel J. Lizdas,
Walter Drake, and Robert W. Blaser. Edward Hodgson directed the
engineering activities and field sampling operations were under
the direction of Richard Kearns.
Assistance with the assembling of the proposed document was done
under Contract 68-01-6469 by Versar Inc. Versar's effort on the
proposed document was managed by Lee McCandless and Jerome
Strauss. Efforts done by Whitescarver Associates, a Versar
subcontractor, were managed by John P. Whitescarver. Lawrence
Davies directed the project activities of the support staff at
Versar Inc. and made contributions to the report. Contributions
to the report were made by Robert W. Hardy of Whitescarver
Associates, and Pamela Hillis, Jean Moore, Gayle Riley and other
technical and support staff at Versar.
In preparation of this final document, the Agency was assisted by
Versar Inc., under contract 68-01-6469, and two subcontractors to
Versar, Radian Corp. and JFA, Inc. Versar's effort was managed
by Lee McCandless. Thomas Wall of JFA and Anna Wojciechowski of
Versar provided assistance in assembly of the administrative
record. Radian technical effort was managed by James Sherman
with technical contributions by Mark Hereth, Robert Curtis, Heidi
Welner and John Cpllins.
Dov Weitman, Ellen Siegler and Mark Greenwood of the Office of
General Counsel provided legal advise to the project. Ellen
Warhit, Debra Maness, Mary Ives, Allen Leduc, Emily Hartnell, and
William Webster were economic project officers; Henry Kahn,
Barnes Johnson, and Richard Kotz provided statistical analysis;
Alexandra Tarney and Eleanor Zimmerman provided environmental
evaluations.
661
-------
Word processing was provided by Pearl Smith, Glenda Nesby, and
Carol Swann.
Technical direction and supervision of the project was provided
by Ernst P. Hall P.E., Chief, Metals and Machinery Branch. The
technical project officer was Mary L. Belefski, with assistance
from Jay von Hemert, and Robert W. Hardy, formerly with the
Agency. It is with special sadness that we note the passing of
Jay von Hemert on January 29, 1984.
Finally appreciation is expressed to the many battery
manufacturing companies who provided detailed information and
explanations of the many and varied battery manufacturing
processes and individuals who contributed comments and data for
the formulation of this document.
662
-------
SECTION XV
BIBLIOGRAPHY
"Antimony" Final Water Quality Criteria, PB117319, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
"Arsenic" Final Water Quality Criteria, FBI 17327, Criteria and
Standards Division, Office of Water Regulations and Standards {45
FR 79318-79379, November 28, 1980).
"Batteries find a niche on the circuit board." Machine Design, L.
Teschler (editor), p. 75-79 (May 10, 1979).
"A big breakthrough in batteries...almost."
Mechanix Illustrated, p. 50-51, 115 (March 1978).
Bellack, Ervin, "Arsenic Removal from Potable Water," Journal
American Water Works Association, July, 1971.
Bhattacharyya, 0., Jumawan, Jr., A.B. and Grieves, R.B.,
"Separation of Toxic Heavy Metals by Sulfide Precipitation,"
Separation Science and Technology, 14(5), 1979, pp. 441-452.
Brown, H.G., Hensley, C.P., McKinney, G.L. and Robinson, J.L.,
"Efficiency of Heavy Metals Removal in Municipal Sewage Treatment
Plants, "Environmental Letters, 5 (2), 1973, pp. 103-114.
"Cadmium" Final Water Quality Criteria, PB117368, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980.
Chamberlin, N.S. and Snyder, Jr., H.B., "Technology of Treating
Plating Waste," 10th Industrial Waste Conference.
Chen, K.Y. , Young, C.S., Jan, T.K. and Rohatgi, N., "Trace Metals
in Wastewater Effluent," Journal of Water Pollution Control
Federation, Vol. 46, No. 12, December, 1974, pp. 2663-2675.
"Chlorinated Ethanes" Final Water Quality Criteria, PB117400, and
Standards (45 FR 79318-79379, Nobember 28, 1980).
"Chloroform" Filial Water Quality Criteria, PB117442, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
663
-------
"Chromium" Final Water Quality Criteria, PB117467, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Collins, D.H. Power Sources 3. New Castel upon Tyne: Oriel
Press, 1971.
The Condensed Chemical Dictionary. Van Nostrand Reinhold Co.,
Ninth Edition, 1977.
"Control technology for the metal finishing industry - sulfide
precipitation." Centec Corporation, Reston, VA., Prepared for
U.S. Environmental Protection Agency, Contract No. 68-03-2672
Work Directive 14, September, 1979.
"Copper" Final Water Quality Criteria, PB 117475, Criteria and
Standards Division Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Curry, Nolan A., "Philogophy and Methodology of Metallic Waste
Treatment," 27th Industrial Waste Conference.
"Cyanide" Final Water Quality Criteria, PB117483, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Dean, J. Lange's Handbook of Chemistry. McGraw Hill, 1973.
Davis, III, James A., and Jacknow, Joel, "Heavy Metals in
Wastewater in Three Urban Areas", Journal of Water Pollution
Control Federation, September, 1975, pp. 2292-2297.
"Development document for interim final and proposed effluent
limitations guidelines and new source performance standards for
the ore mining and dressing point source category." U.S.
Environmental Protection Agency, EPA 440/1-75/061-c, October,
1975.
"Development document for proposed effluent limitations guide-
lines and new source performance standards for the battery
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664
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"Dichloroethylenes" Final Water Quality Criteria, FBI 17525,
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"Everready" Battery Applications and Engineering Data. Union
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665
-------
Hall, Ernst P. and Barnes, Devereaux, "Treatment of
Electroplating Rinse Waters and Effluent Solutions, "presented to
the American Institute of Chemical Engineers, Miami Beach, Fl.,
November 12, 1978.
"Halomethanes" Final Water Quality Criteria, FBI 17624, Criteria
and Standards Division, Office of Water Regulations and Standards
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Handbook of Analytical Chemistry. L. Meites (editor), McGraw
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Hayes, Thomas D. and Theis, Thomas L., "The Distribution of Heavy
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Heise, G.W., and Cahoon, N.C. The Primary Battery. John Wiley &
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"An Investigation of Techniques for Removal of Cyanide from
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"Ionic equilibrium as applied to qualitative analysis." Hogness
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Intersociety of Energy Conversion Engineering Converence,
Proceedings of the 7th Annual Conference, 1972.
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666
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Jenkins, S. H., Keight, D.G. and Humphreys, R.E., "The
Solubilities of Heavy Metal Hydroxides in Water, Sewage and
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"Lead" Final Water Quality Criteria, PB117681, Criteria and
Standards Division, Office of Water Regulations and Standards (45
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Lonouette, Kenneth H., "Heavy Metals Removal," Chemical
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Martin, L. Storage Batteries and Rechargeable Cell Technology
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"Mercury" Final Water Quality Criteria, PB117699, Criteria and
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Mezey, Eugene J. "Characterization of priority pollutants from a
secondary lead-acid battery manufacturing facility." U.S.
Environmental Protection Agency, EPA-600/2-79-039, January 1979.
667
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Mohler, J. B. "The rinsing equation." Metal Finishing, p. 64
(February 1978).
"More power to you." C&D batteries Division, Plymouth Meeting,
PA, no date provided.
Mowat, Anne, "Measurement of Metal Toxicity by Biochemical Oxygen
Demand," Journal of Water Pollution Control Federation, Vol. 48,
No. 5, May, 1976, pp. 853-866.
Mytelka, Alan I., Czachor, Joseph S., Guggino William B. and
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"Naphthalene" Final Water Quality Criteria, FBI 17707, Criteria
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Neufeld, Howard D. and Hermann, Edward R., "Heavy Metal Removal
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Kinetic Model and Equilibrium Relationship for Metal
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"New batteries." Recovery Engineering News - Recycling and
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"Nickel" Final Water Quality Criteria, PB117715, Criteria and
Standards Division, Office of Water Regulations and Standards (45
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Patterson, J. W. Wastewater Treatment Technology. Ann Arbor
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668
-------
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in the Buffalo municipal system." U.S. Environmental Protection
Agency, 1977.
"Pentachlorophenol" Final Water Quality Criteria PB117764,
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"Polynuclear Aromatic Hydrocarbons" Final Water Quality Criteria,
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669
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670
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*•
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671
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7 • :
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672
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SECTION XVI
GLOSSARY
»
Active Material - Electrode material that reacts chemically to
produce electrical energy when a cell discharges. Also, such
material in its original composition, as applied to make an
electrode.
Air Scrubbing - A method of removing air impurities such as dust
or fume by contact with sprayed water or an aqueous chemical
solution.
Alkalinity - (1) The extent to which an aqueous solution contains
more hydroxyl ions than hydrogen ions. (2) The capacity of water
to neutralize acids, a property imparted by the water's content
of carbonates, bicarbonates, hydroxides, and occasionally
borates, silicates and phosphates.
Amalgamation - (1) Alloying a zinc anode with mercury to prevent
internal corrosion and resultant gassing in a cell. (2)
Treatment of wastewater by passing it through a bed of metal
particles to alloy and thereby remove mercury from the water.
Anode - The electrode by which electrons leave a cell. The
negative electrode in a cell during discharge.
Attrition Mill - A ball mill in which pig lead is ground to a
powder and oxidized to make the active material (a mixture of
lead and lead oxide called leady oxide) in lead acid batteries.
Backwashing - The process of cleaning a filter or ion exchange
column by a reverse flow of water.
Baffles - Deflector vanes, guides, grids, gratings, or similar
devices constructed or placed in flowing water or wastewater to
(1) effect a more uniform distribution of velocities or (2)
divert, guide, or agitate the liquids.
Bag House - The large chamber for holding bag filters used to
filter gas streams from a furnace such as in manufacture of lead
oxide.
Ball Mill - A reactor in which pig lead is ground to a powder and
oxidized to make the active material (a mixture of lead and lead
oxide called leady oxide) for lead acid batteries.
673
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Barton Pot - A reactor vessel, used in the Barton process, into
which molten lead is fed and vigorously agitated to form fine
lead droplets in the presence of air. The resulting mixture of
unoxidized lead and lead oxides (leady oxide) comprises an active
material in lead acid batteries.
Batch Treatment - A waste treatment method where wastewater is
collected over a period of time and then treated before
discharge, often in the same vessel in which it is collected.
Battery - A device that transforms chemical energy into
electrical energy. This term usually applies to two or more
cells connected in series, parallel or a cpmbination of both.
Common usage has blurred the distinction between the terms "cell"
and "battery" and frequently the term battery is applied to any
finished entity sold as a single unit, whether it contains one
cell, as do most flashlight batteries, or several cells, as do
automotive batteries.
Bobbin - An assembly of the positive current collector and
cathode material, usually molded into a cylinder.
Buffer - Any of certain combinations of chemicals used to
stabilize the pH values or alkalinities of solutions.
Burn - Connection of terminals, posts, or connectors in a lead
acid battery by welding.
Button Cell - -A tiny, circular battery, any of several types,
made for a watch or for other microelectronic applications.
Can - The outer case of a cylindrical cell.
Carcinogen - A substance that causes cancer.
Casting - The process by which grids for lead acid batteries are
made by pouring molten lead into molds and allowing
solidification. , ,
•> . ' .". .''..'
Cathode - The electrode by which electrons enter a cell. The
positive electrode in a cell during discharge.
Cathodic Polarization - Electrical connection of a nickel
electrode plaque to promote deposition of active nickel material.
Caustic - (1) An alkaline battery electrolyte, sodium or
potassium hydroxide. (2) Sodium hydroxide, used to precipitate
heavy metals from wastewater.
674
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Cell - The basic building block of a battery. It is an
electrochemical device consisting of an anode and a cathode in a
common electrolyte kept apart with a separator. This assembly
may be used in its own container as a single cell battery or be
combined and interconnected with other cells in a container to
form a multicelled battery.
Central Treatment Facility - Treatment plant which co-treats
process wastewaters from more than one manufacturing operation or
co-treats process wastewaters with noncontact cooling water, or
with nonprocess wastewaters (e.g., utility blowdown,
miscellaneous runoff, etc).
Centrifugation - Use of a centrifuge to remove water in the
manufacture of active material or in the treatment of wastewater
sludge.
Charge - The conversion of electrical energy into chemical energy
within a cell-battery. This restoration of active electronic
materials is done by forcing a current through the cell-battery
in the opposite direction to that during discharge. See
"Formation."
Chemical Coagulation - The destablization and initial aggregation
of colloidal and finely divided suspended matter by the action of
a floe-forming chemical.
Chemical Oxygen Demand (COD) - (1) A test based on the fact that
organic compounds, with few exceptions, can be oxidized to carbon
dioxide and water by the action of strong oxidizing agents under
acid conditions. Organic matter is converted to carbon dioxide
and water regardless of the biological assimilability of the
substances. One of the chief limitations is its inability to
differentiate between biologically oxidizable and biologically
inert organic matter. The major advantage of this test is the
short time required for evaluation (2 hrs). (2) The amount of
oxygen required for the chemical oxidization of organics in a
liquid.
Chemical Precipitation - The use of an alkaline chemical to
remove dissolved metals from wastewater.
Chemical Treatment - Treating contaminated water by chemical
means.
Clarifier - A unit which provides settling and removal of solids
from wastewater.
675
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Closed Formation - Formation of lead battery plates done with the
plates already in the battery case.
CMC - Sodium carboxymethyl cellulose; an organic liquid used as a
binder in electrode formulations.
Colloids - A finely divided dispersion of one material called the
"Dispersed phase" (solid) in another material which is called the
"dispersion medium" (liquid).
Compatible Pollutant - An industrial pollutant that is
successfully treated by a secondary municipal treatment system.
Composite Wastewater Sample - A combination of individual samples
of water or wastewater taken at selected intervals and mixed in
proportion to flow or time to minimize the effect of stream
variability.
Concentration, Hydrogen Ion - The weight of hydrogen ions in
grams per liter of solution. Commonly expressed as the pH value
that represents the logarithm of the reciprocal of the hydrogen
ion concentration.
Contamination - A general term signifying the introduction into
water of microorganisms, chemicals, wastes or sewage which
renders the water unfit for its intended use.
Contractor Removal - The disposal of oils, spent solutions,
wastewaters, or sludge by means of an approved scavenger service.
Cooling Tower - A device used to remove heat from cooling water
used in the manufacturing processes before returning the water
for recycle or reuse.
Countercurrent Cascade Rinsing - A method of rinsing or washing
using a segmented tank system in which water flows from one tank
segment to the next counter to the direction of movement of the
material' being washed.
Current Collector - The grid portion of the electrode which
conducts the current to the terminal.
Cyclone Separator - A funnel-shaped device for removing particles
from air or other fluids by centrifugal means.
Decantation - A method for mechanical dewatering of a wet solid
by pouring off the liquid without disturbing the underlying
sediment or precipitate.
676
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Demineralization - The removal from water of mineral contaminants
usually present in ionized form. The methods used include ion-
exchange techniques, flash distillation or reverse osmosis.
Depolarizer - A term often used to denote the cathode active
material.
»
Dewatering - Any process whereby water is removed from sludge.
Discharge - Release of electric power from a battery.
Discharge o_f Pollutant(s) - The addition of any pollutant to
waters of the U.S. from any point source.
Dissolved Oxygen (DO; - The oxygen dissolved in sewage, water, or
other liquid, usually expressed in milligrams per liter.
Dissolved Solids - Theoretically the anhydrous residues of the
dissolved constituents in water. Actually the term is defined by
the method used in determination. In water and wastewater
treatment, the Standard Methods tests are used.
Dry Charge Process - A process for the manufacture of lead acid
storage batteries in which the plates are charged by electrolysis
in sulfuric acid, rinsed, and drained or dried prior to shipment
of the battery. Charging of the plates usually occurs in
separate containers before assembly of the battery but may be
accomplished in the battery case. Batteries produced by the dry-
charge process are shipped without acid electrolyte. Also
referred to as dehydrated plate or dehydrated batteries.
Drying Beds - Areas for dewatering of sludge by evaporation and
seepage.
Effluent - Industrial wastewater discharged to a sanitary sewer,
stream, or other disposal point outside the plant property.
Electrode - The positive (cathode) or negative (anode) element in
a cell or battery, that enables it to provide electric power.
Electrodeposition - Electrochemical deposition of an active
material from solution onto an electrode grid or plaque.
Electroforming - See (1) Electrodeposition, and (2) Formation.
Electroimpregnation - See Cathodic Polarization.
Electrolyte - The liquid or material that permits conduction of
ions between cell electrodes.
677
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Electrolytic Precipitation - Generally refers to making powdered
active material by electrodeposition and physical removal; e.g.,
silver powder from silver bars.
Electroplating - (1) Electrodeposition of a metal or alloy from a
suitable electrolyte solution; the article to be plated is
connected as the ca/thode in the electrolyte solution; direct
current is introduced 'through the anode which consists of the
metal to be deposited. (2) The Electroplating Point Source
Category.
Element - A combination of negative and positive plates and
separators to make a cell in a lead-acid storage battery.
End-of-Pipe Treatment - The reduction or removal of pollutants by
treatment just prior to actual discharge to a point outside an
industrial plant.
Equalization - The collection of waste streams from different
sources, which vary in pH, chemical constituents, and flow rates
in a common container. The effluent stream from this
equalization tank has a fairly constant flow and pH level, and
will contain a homogeneous chemical mixture. This tank helps to
prevent an unnecessary shock to the waste treatment system.
Evaporation Ponds - A pond, usually lined, for disposal of
wastewater by evaporation; effective only in areas of low
rainfall.
Filter, Rapid Sand - A filter for the purification of water where
water which has been previously treated, usually by coagulation
and sedimentation, is passed through a filtering medium
consisting of a layer of sand or prepared anthracite coal or
other suitable material, usually from 24 to 30 inches thick and
resting on a supporting bed of gravel or a porous medium such as
carborundum. The filtrate is removed by a drain system. The
filter is cleaned periodically by reversing the flow of the water
upward through the filtering medium. Sometimes supplemented by
mechanical or air agitation during backwashing to remove
impurities that are lodged in the sand.
Filter, Trickling - A filter consisting of an artificial bed of
coarse material, such as broken stone, clinkers, slats, or
plastic media over which wastewater is distributed and applied in
drops, films, or spray, from troughs, drippers, moving
distributors or fixed nozzles and through which it trickles to
the under-drain, oxidizing organic materials by means of
microorganisms attached to the filter media.
678
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Filter, Vacuum - A filter consisting of a rotating cylindrical
drum mounted on a horizontal axis, covered with a filter cloth
partially submerged in a liquid. A vacuum is maintained under
the cloth for the larger part of a revolution to extract
moisture. Solids collected on the surface of the filter cloth
are continuously scraped off.
Filtrate - Liquid that has passed through a filter.
Filtration - Removal of solid particles from liquid or particles
from air or gas stream through a permeable membrane or deep bed.
The filter types include: gravity, - pressure, microstraining,
ultrafiltration, reverse osmosis (hyperfiltration).
Float Gauge - A device for measuring the elevation of a liquid
surface, the actuating element of which is a buoyant float that
rests on the liquid surface and rises or falls with it. The
elevation of the surface is measured by a chain or tape attached
to the float.
Floe - A very fine, fluffy mass formed by the aggregation of fine
suspended particles.
Flocculator - An apparatus designed for the formation of floe in
water or sewage.
Flocculation - In water and wastewater treatment, the
agglomeration of colloidal and finely divided suspended matter
afcer coagulation by addition of chemicals and gentle stirring by
either mechanical or hydraulic means.
Flock - Natural or synthetic fiber added to lead-acid battery
paste as a stiffening agent.
Flow Proportioned Sample - See "Composite Wastewater Sample."
Formation - An electrochemical process which converts the battery
electrode material into the desired chemical condition. For
example, in a silver-zinc battery the silver applied to the
cathode is converted to silver oxide and the zinc oxide applied
to the anode is converted to elemental zinc. "Formation" is
generally used interchangeably with "charging," although it may
involve a repeated charge-discharge cycle.
Gelled Electrolyte - Electrolyte which may or may not be mixed
with electrode material, that has been gelled with a 'chemical
agent to immobilize it.
GPP - Gallons per day.
679
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Grab Sample - A single sample of wastewater taken without a set
time or at a set flow.
Grease - In wastewater, a group of substances including fats,
waxes, free fatty acids, calcium and magnesium soaps, mineral
oil, and certain other nonfatty materials.
Grease Skimmer - A device for removing grease or scum from the
surface of wastewater in a tank.
Grid - The support for the active materials and a means to
conduct current from the active materials to the cell terminals;
usually a metal screen, expanded metal mesh, or a perforated
metal plate.
Hardness - A characteristic of water, imparted by salts of
calcium, magnesium, and iron such as bicarbonates, carbonates,
sulfates, chlorides, and nitrates that cause curdling of soap,
deposition of scale in boilers, damage in some industrial
processes, and sometimes objectionable taste. It may be
determined by a standard laboratory procedure or computed from
the amounts of calcium and magnesium as well as iron, aluminum,
manganese, barium, strontium, and zinc, and is expressed as
equivalent calcium carbonate.
Heavy Metals - A general name given to the ions of metallic
elements such as copper, zinc, chromium, and nickel. They are
normally removed from wastewater by forming an insoluble
precipitate (usually a metallic hydroxide).
Holding Tank - A tank for accumulating wastewater prior to
treatment.
Hydrazine Treatment - Application of a reducing agent to form a
conductive metal film on a silver oxide cathode.
Hydroquinone - A developing agent used to form a conductive metal
film on a silver oxide cathode.
Impregnation - Method of making an electrode by precipitating
active material on a sintered nickel plaque.
In-Process Control Technology - The regulation and conservation
of chemicals and rinse water throughout the operations as opposed
to end-of-pipe treatment.
Industrial Wastes - The liquid wastes from industrial processes
as distinct from domestic or sanitary wastes.
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Influent - Water or other liquid, either raw or partly treated,
flowing into a treatment step or plant.
Ion Exchange - Wastewater treatment by contact with a resin that
exchanges harmless ions (e.g. sodium) for toxic inorganic ions
(e.g. mercury), which the resin adsorbs.
Jacket - The outer cover of a dry cell battery, usually a paper-
plastic laminate.
Kjeldahl Nitrogen - A method of determining the ammonia and
organically bound nitrogen in the -3 valence state but does not
determine, nitrite, azides, nitro, nitroso, oximes or nitrate
nitrogen.
Lagoon - A man-made pond or lake for holding wastewater for the
removal of suspended solids. Lagoons are also used as retention
ponds after chemical clarification to polish the effluent and to
safeguard against upsets in the clarifier; for stabilization of
organic matter by biological oxidation; for storage or sludge;
and for cooling of water.
Landfill - Land area used for controlled burial of solid wastes,
sludges, ashes, industrial wastes, construction wastes, or
demonition wastes. Solid wastes are garbage, refuse, and other
discarded material including solid, liquid, semisolid, or
contained gaseous material resulting from industrial, commercial,
mining, and agricultural operations, and from community
activities.
Leaching - The solubilizing of pollutants by the action of a
percolating liquid, such as water, seeping through a landfill,
which potentially contaminates ground water.
Leady Oxide - Active material used for manufacture of lead-acid
battery plates consisting of a mixture of lead oxides and finely
divided elemental lead.
Lime - Any of a family of chemicals consisting essentially of
calcium hydroxide made from limestone (calcite) which is composed
almost wholly of calcium carbonates or a mixture of calcium and
magnesium ceirbonates.
Limiting Orifice - A device that limits flow by constriction to a
relatively small area. A constant flow can be obtained over a
wide range of upstream pressures.
Make-Up Water - Net amount of water used by any process or
process step, not including recycled water.
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Mass - The active material used in a pocket plate cell, for
example "nickel mass."
Milligrams Per Liter (tng/1) - This is a weight per volume
concentration designation used in water and waste analysis.
Mixed Media Filtration - A depth filter which uses two or more
filter materials of differing specific gravities selected so as
to produce a filter uniformly graded from coarse to fine.
National Pollutant Discharge Elimination System (NPDES) - This
federal mechanism for regulating point source discharge by means
of permits.
Neutralization - Chemical addition of either acid or base to a
solution to adjust the pH to approximately 7.
Non-Contact Cooling Water - Water used for cooling which does not
come into direct contact with any raw material, intermediate
product, waste product or finished product.
Open Formation - Formation of lead battery plates done with the
plates in open tanks of sulfuric acid. Following formation
plates are placed in the battery cases.
Outfall - The point or location where wastewater discharge from a
sewer, drain, or conduit.
Oxidation - 1. Chemical addition of oxygen atom(s) to a chemical
compound; 2. In general any chemical reaction in which an element
or ion is raised to a more positive valence state; 3. The process
at a battery anode during discharge.
Parshall Flume - A calibrated device developed by Parshall for
measuring the flow of liquid in an open conduit. It consists
essentially of a contracting length, a throat, and an expanding
length.- At the throat is a sill over which the flow passes as
critical depth. The upper and lower heads are each measured at a
definite distance from the sill. The lower head cannot be
measured unless the sill is submerged more than about 67 percent.
Paste - Powdered active material mixed with a liquid to form a
paste to facilitate application to a grid to make an electrode.
Pasting Machine - An automatic machine for applying lead oxide
paste in the manufacture of lead-acid batteries.
pH - The reciprocal of the logarithm of the hydrogen ion
concentration. Th6 concentration is the weight of hydrogen ions,
682
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in grams per liter of solution. Neutral water, for example, has
a pH value of 7. At pH lower than 7, a solution is acidic. At
pH higher than 7, a solution is alkaline.
pH Adjustment - A means of treating wastewater by chemical
addition; usually the addition of lime to precipitate heavy metal
pollutants.
Plaque - A porous body of sintered' metal on a metal grid used as
a current collector and holder of electrode active materials,
especially for nickel-cadmium batteries.
Plate - A positive or negative electrode used in a battery,
generally consisting of active material deposited on or in a
current-collecting support.
Pocket Plate - A type of battery construction where the electrode
is a perforated metal envelope containing the active material.
Point Source - Any discernible, confined and discrete conveyance,
including but not limited to any pipe, ditch, channel, tunnel,
conduit, well, discrete fissure, container, rolling stock,
concentrated animal feeding operation, or 'vessel or other
floating craft, from which pollutants are or may be discharged.
Pollutant Parameters - Those constituents of wastewater
determined to be detrimental to the public health or the
environment and, therefore, requiring control.
Po 1 y e 1 ec t r o.l y tes - Materials used as a coagulant or a coagulant
aid in water and wastewater treatment. They are'synthetic or
natural polymers containing ionic constituents. They may be
cationic, anionic, or nonionic.
Post - A battery terminal, especially on a lead-acid battery.
Precipitation - Process of separation of a dissolved substance
from a solution or suspension by chemical or physical change,
usually as an insoluble solid.
Pressed Powder - A method of making an electrode by pressing
powdered active material into a metal grid.
Pressure Filtration - The process of solid-liquid phase
separation effected by forcing the more permeable liquid phase
through a mesh which is impenetrable to the solid phase.
683
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Pretreatment - Any wastewater treatment process used to partially
reduce pollution load before the wastewater is introduced into a
main sewer system or delivered to a municipal treatment plant.
Primary Battery - A battery which must usually be replaced after
one discharge; i.e., the battery cannot be recharged.
Primary Settling - The first settling unit for the removal of
settleable solids through which wastewater is passed in a
treatment works.
Primary Treatment - A process to remove substantially all
floating and settleable solids in wastewater and partially reduce
the concentration of suspended solids.
Priority Pollutant - Any one of the 129 specific pollutants
established by the EPA from the 65 pollutants and classes of
pollutants as outlined in the Consent Decree of June 8, 1976.
Process Wastewater - Any water which, during manufacturing or
processing, comes into direct contact with or results from the
production or use of any raw materials, intermediate product,
finished product, by product, or waste product.
Raw Water - Plant intake water prior to any treatment or use.
Recycled Water - Process wastewater or treatment facility
effluent which is recirculated to the same process.
Reduction - 1. A chemical process in which the positive valence
of species is decreased. 2. Wastewater treatment to (a) convert
hexavalent chromium to the trivalent form, or (b) reduce and
precipitate mercury ions.
Reserve Cell - A class of cells which are designated as
"reserve", because they are supplied to the user in a non-
activated state. Typical of this class of cell is the carbon-
zinc air reserve cell, which is produced with all the components
in a dry or non-activated state, and is activated with water when
it is ready to be used.
Retention Time - The time allowed for solids to collect in a
settling tank. Theoretically retention time is equal to the
volume of the tank divided by the flow rate. The actual
retention time is determined by the purpose of the tank. Also
the design residence time in a tank or reaction vessel which
allows a chemical reaction to go to completion, such as the
reduction of hexavalent chromium or the destruction of cyanide.
684
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Reused Water - Process wastewater or treatment facility effluent,
which is further used in a different manufacturing process. For
example, the reuse of process wash water as non-contact cooling
water.
Reverse Osmosis (Hyperfiltration) - A treatment or recovery
process in which polluted water is put under a pressure greater
than the osmotic pressure to drive water across the membrane
while leaving behind the dissolved salts as a concentrate,
Reversible Reaction - A chemical reaction capable of proceeding
in either direction depending upon the conditions.
Rinse - Removal of foreign materials from the surface of an
object by flow or impingement of a liquid (usually water) on the
surface. In the battery industry, "rinse" may be used
interchangeably with "wash".
Ruben - Developer of the mercury-zinc battery; also refers to the
mercury-zinc battery.
Sand Filtration - A process of filtering wastewater through sand.
The waste water is trickled over the bed of sand, which retains
suspended solids. The clean water flows out through drains in
the bottom of the bed. The solids accumulating at the surface
must be removed from the bed periodically.
Sanitary Sewer - A sewer that carries liquid and water carried
wastes to a municipal treatment plant.
Sanitary Water - Wastewater from toilets, sinks, and showers.
Scrubber _ General term used in reference to an air pollution
control device that uses a water spray.
Sealed Cell - A battery cell which can operate in a sealed
condition during both charge and discharge.
Secondary Cel1 - An electrochemical cell or battery system that
can be recharged; a storage battery.
Secondary Wastewater Treatment - The treatment of wastewater by
biological methods after primary treatment by sedimentation.
Sedimentation - The gravity induced deposition of suspended
matter carried by water, wastwater, or other liquids, by.gravity.
It is usually- accomplished by reducing the velocity of the
suspended material. Also called settling.
685
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Separator - A porous material, in a battery system, used to keep
plates of opposite polarity separated, yet allowing conduction of
ions through the electrolyte.
Service Water - Raw water which has been treated preparatory to
its use in a process of operation; i.e., make-up water.
Settling Ponds - A large shallow body of water into which
industrial wastewaters are discharged. Suspended solids settle
from the wastewaters due to the long retention time of the water
in the pond.
Settleable Solids (1) That matter in wastewater which will not
stay in suspension during a preselected settling period, such as
one hour, but settles to the bottom. (2) In the Imhoff cone
test, the volume of matter that settles to the bottom of the cone
in one hour.
Sewer - A pipe or conduit, generally closed, but normally not
flowing full or carrying sewage and other waste liquids.
SIC - Standard Industrial Classification - Defines industries in
accordance with the composition and structure of the economy and
covers the entire field of economic activity.
Silver Etch - Application of nitric acid to silver foil to
prepare it as a support for active material.
Sinter - Heating a metal powder such as nickel to an elevated
temperature below its melting point which causes it to
agglomerate and adhere to the supporting grid.
Sintered-plate Electrode - The electrode formed by sintering
metallic powders to form a porous structure, which serves as a
current collector, and on which the active electrode material is
deposited.
Skimming Tank - A tank so designed that floating matter will rise
and remain on the surface of the wastewater until removed, while
the liquid discharges continuously under certain wall or scum
boards.
Sludge - A suspension, slurry, or solids matter produced in a
waste treatment process.
Sludge Conditioning - A process employed to prepare sludge for
final disposal. Can be thickening, digesting, heat treatment
etc.
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Sludge Disposal - The final disposal of solid wastes.
Sludge Thickening - The increase in solids concentration of
sludge in a sedimentation or digestion tank or thickener.
Solvent - A liquid capable of dissolving or dispersing one or
more other substances.
Spills - A chemical or material spill is an unintentional
discharge of more than 10 percent of daily usage of a regularly
used substance. In the case of a rarely used (one per year or
less) chemical or substance, a spill is that amount that would
result in 10% added loading to the normal air, water or solid
waste loadings measured as the closets equivalent pollutant.
Sponge - A highly porous metal powder.
Stabilization Lagoon - A shallow pond for storage of wastewater
before discharge. Such lagoons may serve only to detain and
equalize wastewater composition before regulated discharge to a
stream, but often they are used for biological oxidation.
Stabilization Pond - A type of oxidation pond in which biological
oxidation of organic matter is effected by natural or
artificially accelerated transfer of oxygen to the water from
air. •
Storage Battery - A battery that can store chemical energy with
the potential to change to electricity. This conversion of
chemical energy to electricity can be reversed thus allowing the
battery*to be recharged.
Strap - A metal conductor connecting individual cells to form a
battery.
Sump - A pit or tank which receives and temporarily stores
drainage or wastewater at the lowest point of circulating or
drainage system.
Suspended Solid - (1) Solids that are in suspension in water,
wastewater, or other liquids, and which are largely removable by
laboratory filtering. (2) The quantity of material removed from
wastewater in a laboratory test, as prescribed in "Standard
Methods for the Examination of Water and Wastewater" and referred
to as non-filterable residue.
Surface Waters - Any visible stream or body of water.
687
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Terminal - The part of a battery to which an external circuit is
connected.
Thickener - A device wherein the solids in slurries or
suspensions are increased by gravity settling and mechanical
separation of the phases, or by floatation and mechanical
separation of the phases.
Total Cyanide - The total content of cyanide including simple
and/or complex ions. In analytical terminology, total cyanide is
the sum of cyanide amenable to chlorination and that which is not
amenable to chlorination according to standard analytical
methods.
Total Solids - The total amount of solids in wastewater including
both dissolved and suspended solids.
Toxicity - The ability of a substance to cause injury to an
organism through chemical activity.
Treatment Efficiency - Usually refers to the percentage reduction
of a specific pollutant or group of pollutants by a specific
wastewater treatment step or treatment plant.
Treatment Facility Effluent - Treated process wastewater.
Turbidity - (1) A condition in water or wastewater caused by the
presence of suspended matter, resulting in the scattering and
absorption of light rays. (2)' A measure of fine suspended matter
in liquids. (3) An analytical quantity usually reported in
arbitrary turbidity units determined by measurements'of light
diffraction.
Vacuum Filtration - See Filter, Vacuum.
Vented Cell - A type of battery cell which has a vent that allows
the escape of gas and the addition of water.
Wash - Application of water, an aqueous solution, or an organic
solvent to a battery part to remove contaminating substances.
Water Balance - An accounting of all water entering and leaving a
unit process or operation in either a liquid or vapor form or via
raw material, intermediate product, finished product, by-product,
waste product, or via process leaks, so that the difference in
flow between all entering and leaving streams is zero.
Weir - A device that has a crest and some containment of known
geometric shape, such as a V, trapezoid, or rectangle and is used
688
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to measure flow of liquid. The liquid surface is exposed to the
atmosphere. Flow is related to upstream height or water above
the crest, to position of crest with respect to downstream water
surface, and to geometry of the weir opening.
Wet Charge Process - A process for the manufacture of lead acid
storage batteries in which the plates are formed by electrolysis
in sulfuric acid. The *pLate forming process is usually done with
the plates inside the assembled battery case but may be done with
the plates in open tanks. In the case of large industrial wet
lead acid batteries, problems in formation associated with
inhomogeneities in the large plates are alleviated by open tank
formation. Wet charge process batteries are shipped with acid
electrolyte inside the battery casing.
Wet Shelf Life - The period of time that a secondary battery can
stand in the charged condition before total degradation.
Wet Scrubber - A unit in which dust and fumes are removed from an
air or gas stream to a liquid. Gas-liquid contact is promoted by
jets, sprays, bubble chambers, etc.
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METRIC UNITS
CONVERSION TABLE
VO
o
MULTIPLY (ENGLISH UNITS)
"ENGLISH UNIT ABBREVIATION
acre ac
acre - feet ac ft
British Thermal Unit BTU
British Thermal Unit/
pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet > cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square inch
(gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
by
CONVERSION
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
TO OBTAIN (METRIC UNITS)
ABBREVIATION METRIC UNIT .
ha . hectares
cu m cubic meters
kg cal kilogram - calories
kg cal/kg kilogram calories/
kilogram
cu in/min cubic meters/minute
cu m/min cubic meters/minute
cu m cubic meters
1 ' liters
cu cm „ cubic centimeter
°C degree Centigrade
m meters
1 liters
I/sec liters/second
kw killowatts
cm centimeters
atm atmospheres
kg kilograms
cu m/day cubic meters/day
km , kilometer
atm atmospheres (absolute)
sq m square meters
sq cm square centimeters
kkg metric ton (1000
kilogram)
m meter
*Actual conversion, not a multiplier.
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