United States Effluent Guidelines Division
Environmental Protection WH-552 £PA 440/1 -80/06/-a
Agency Washington, DC 20460 September, 1980
Water and Waste Management
«>EPA Development Draft
Document for
Effluent Limitations
Guidelines and
Standards for the
Battery Manufacturing
Point Source Category
-------
DRAFT
DEVELOPEMENT DOCUMENT
FOR
PROPOSED EFFLUENT LIMITATIONS GUIDELINES
AND
NEW SOURCE PERFORMANCE STANDARDS
FOR THE
BATTERY MANUFACTURING POINT SOURCE CATEGORY
.
\
Douglas M. Costle
Administrator
Steven Schatzow
Deputy Assistant Administrator
for Water Regulations and Standards
Robert B. Schaffer
Director, Effluent Guidelines Division
Ernst P. Hall, P.E.
Chief, Metals & Machinery Branch
Mary L. Belefski
Project Officer, Battery Manufacturing
September 1980
EFFLUENT GUIDELINES DIVISION
OFFICE OF WATER AND WASTE MANAGEMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
-------
In order to comply with requests for
confidentiality, plant identification
numbers have been deleted from the text
and plants are referenced by letters. The
same plant does not necessarily have the
same letter for every reference.
-------
CONTENTS
SECTION TITLE
I- Conclusions
II. Recommendations 3
III. Introduction 5
Legal Authority 5
Guideline Development Summary 7
Industry Description 13
Industry Summary 32
Industry Outlook 44
IV. Industry Subcategorization 71
Subcategorization 71
Final Subcategories And Production
Normalizing Parameters 78
Operations Covered Under Other
Categories 88
V. Water Use and Waste Characterization 93
Data Collection And Analysis 93
Cadmium Subcategory 106
Calcium Subcategory 124
Lead Subcategory 127
Leclanche Subcategory 148
Lithium Subcategory 157
Magnesium Subcategory 161
Zinc Subcategory 166
VI. Selection Of Pollutant Parameters 383
Verification Parameters 383
Regulation Of Specific Pollutants 431
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SECTION TITLE PAGE
VII Control and Treatment Technology 479
End-of-Pipe Treatment Technologies 479
Major Technologies 479
Chemical Precipitation 480
Chemical Reduction of Chromium 489
Cyanide Precipitation 490
Pressure Filtration 495
Settling 497
Skimming 500
Major Technology Effectiveness 504
L & S Performance 504
LS & F Performance 506
Minor Technologies 513
Carbon Adsorption 513
Centrifugation 515
Coalescing 517
Cyanide Oxidation By Chlorine 519
Cyanide Oxidation By Ozone 520
Cyanide Oxidation By Ozone With
UV Radiation 521
Cyanide Oxidation By Hydrogen Peroxide 522
Evaporation 523
Flotation 526
Gravity Sludge Thickening 528
Insoluble Starch Xanthate 529
Ion Exchange 530
Membrane Filtration 533
Peat Adsorption 535
Reverse Osmosis 537
Sludge Bed Drying 540
Ultrafiltration 542
Vacuum Filtration 544
In-Process Pollution Control Techniques 546
VIII. Cost Of Wastewater Control And Treatment 607
Cost Estimation Methodology 607
Cost Estimates For Individual Treatment
Technologies 615
Treatment System Cost Estimates 630
Energy And Non-Water Quality Aspects 641
11
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SECTION TITLE PAGE
IX Best Practicable Control Technology Currently
Available 723
Technical Approach To BPT 723
Cadmium Subcategory 725
Calcium Subcategory 727
Lead Subcategory 728
Leclanche Subcategory 730
Lithium Subcategory 731
Magnesium Subcategory 733
Zinc Subcategory 735
X Best Available Technology Economically Achievable 745
Technical Approach To BAT 745
Cadmium Subcategory 747
Calcium Subcategory 751
Lead Subcategory 753
Lithium Subcategory 758
Magnesium Subcategory 760
Zinc Subcategory 762
XI New Source Performance Standards 785
Technical Approach To BDT 785
Identification Of BDT 786
XII Pretreatment 791
Technical Approach To Pretreatment 791
Identification of Pretreatment Options 792
XIII Best Conventional Pollutant Control Technology 793
XIV Acknowledgements 795
XV Bibliography 797
XVI Glossary 809
ill
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TABLES
Number Title Page
III-l Survey Summary 11
II1-2 Battery General Purposes and Applications 18
III-3 Anode Half-Cell Reactions 21
III-4 Cathode Half-Cell Reactions 21
III-5 Consumption of Toxic Metals in Battery Manufacture 34
II1-6 Raw Materials Used in Lithium Anode Battery
Manufacture 41
IV-1 Subcategory Elements And Production Normalizing
Parameters (PNP) 90
IV-2 Operations AT Battery Plants Included In Other
Industrial Categories 92
V-l Screening Analysis Results - Cadmium Subcategory 228
V-2 ' Screening Analysis Results - Calcium Subcategory 232
V-3 Screening Analysis Results - Lead Subcategory 237
V-4 Screening Analysis Results - Leclanche Subcategory 241
V-5 Screening Analysis Results - Lithium Subcategory 245
V-6 Screening Analysis Results - Magnesium Subcategory 252
V-7 Screening Analysis Results - Zinc Subcategory 257
V-8 Verification Parameters 262
V-9 Cadmium Subcategory Process Elements (Reported
Manufacture) 263
V-10 Cadmium Subcategory Effluent Flow Rates From
Individual Facilities 264
V-ll Normalized Discharge Flows Cadmium Subcategory
Elements 265
V-12 Cadmium Subcategory Effluent Quality (From DCP's) 266
iv
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Number Title Page
V-13 Pollutant Concentrations In Cadmium Pasted And
Pressed Powder Anode Element Waste Streams 267
V-14 Pollutant Mass Loadings In Cadmium Pasted And
Pressed Powder Anode Element Waste Streams 268
V-15 Pollutant Concentrations In The Cadmium Electro-
deposited Anode Element Waste Stream 269
V-16 Pollutant Mass Loadings In The Cadmium Electro-
deposited Anode Element Waste Streams 270
V-17 Pollutant Concentrations And Mass Loadings In
The Cadmium Impregnated Anode Element Waste Streams 271
V-18 Pollutant Concentrations In The Nickel Electro-
deposited Cathode Element Waste Streams 272
V-19 Pollutant Mass Loadings In The Nickel Electro-
deposited Cathode Element Waste Streams 273
V-20 Pollutant Concentrations In The Nickel Impregnated
Cathode Element Waste Streams 274
V-21 Pollutant Mass Loadings In The Nickel Impregnated
Cathode Element Waste Streams 275
V-22 Statistical Analysis (mg/1) Of The Nickel
Impregnated Cathode Element Waste Streams 276
V-23 Statistical Analysis (mg/kg) Of The Nickel
Impregnated Cathode Element Waste Streams 277
V-24 Pollutant Concentrations In The Floor And Equipment
Wash Element Waste Streams 278
V-25 Pollutant Mass Loadings In The Floor And Equipment
Wash Element Waste Streams 279
V-26 Pollutant Concentrations In Employee Wash
Element Waste Streams 280
V-27 Pollutant Mass Loadings In Employee Wash
Element Waste Streams 281
V-28 Mean Concentrations and Pollutant Mass Loadings
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TABLES
Number Title Page
In The Cadmium Element Waste Streams 282
V-29 Cadmium Subcategory - Statistical Analysis
Of Total Raw Waste Concentrations (mg/1) 283
V-30 Effluent Characteristics From Calcium Subcategory
Elements - DCP Data 284
V-31 Normalized Discharge Flows Lead Subcategory
Elements 285
V-32 Observed Discharge Flow Rates For Each
Plant In Lead Subcategory 286
V-33 Effluent Characteristics Reported By Plants
Practicing pH Adjustment And Settling Technology 289
V-34 Effluent Quality Data From Plants Practicing
pH Adjustment And Filtration 290
V-35 Effluent Quality Data From Plants Practicing
pH Adjustment Only 291
V-36 Total Raw Waste For Visits 292
V-37 Lead Subcategory Total Raw Waste Loading 294
V-38 Statistical Summary Of The Lead Subcategory
Raw WAste (mg/1) 296
V-39 Statistical Analysis Of The Lead Subcategory
Total Raw Waste Loadings (mg/kg) 297
V-40 Lead Subcategory Characteristics Of Individual
Process Wastes 298
V-41 Pasting Waste Characteristics (mg/1) 299
V-42 Pasting Waste Loadings (mg/kg) 300
V-43 Closed Formation PollutantICharacteristics of Both
Wet and Damp Batteries 301
V-44 Closed Formation Waste Loadings of Both
Wet and Damp Batteries 302
VI
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TABLES
Number Title Page
V-45 Open Formation Dehydrated Battery Waste
Characteristics 303
V-46 Open Formation Dehydrated Battery Waste Loadings 304
V-47 Battery Wash Wastewater Characteristics 305
V-48 Battery Wash Wastewater Loadings 306
V-49 Battery Repair And Floor Wash Waste
Characteristics 307
V-50 Battery Repair And Floor Wash Waste Loadings 308
V-51 Effluent From Sampled Plants 309
V-52 Leclanche Subcategory Elements (Reported
Manufacture) 311
V-53 Normalized Discharge Flows Leclanche Subcategory
Elements 312
V-54 Leclanche Subcategory Effluent Quality (from DCP's) 313
V-55 Pollutant Concentrations Of The Cooked Paste
Separator Element Waste Streams 314
V-56 Pollutant Mass Loading Of The Cooked Paste
Separator Element Waste Streams 315
V-57 Pollutant Concentrations Of The Paper Separator
(With Mercury) Element Waste Streams 316
V-58 Pollutant Mass Loadings Of The Paper Separator
(With Mercury) Element Waste Streams 317
V-59 Flow Rates (I/kg) Of Ancillary Operation
Waste Streams 318
V-60 Pollutant Concentrations Of The Equipment
And Area And Cleanup Element Waste Stream 319
V-61 Pollutant Mass Loadings Of The Equipment
And Area Cleanup Element Waste Streams 320
V-62 Statistical Analysis (mg/1) Of The Equipment
VII
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Number
And Area Cleanup Element Waste Streams 321
V-63 Statistical Analysis (mg/kg) Of The Equipment
And Area Cleanup Element Waste Streams 322
V-64 Statistical Analysis Of The Leclanche Subcategory
Raw Waste Concentrations 323
V-65 Normalized Discharge Flows Lithium Subcategory
Elements 324
V-66 Normalized Discharge Flows Magnesium Subcategory
Elements 325
V-67 Plant Discharge Flows Magnesium Subcategory
Elements - DCP Data 326
V-68 Zinc Subcategory Process Elements (Reported
Manufacture) 327
V-69 Observed Flow Rates For Each Plant In Zinc
Subcategory 329
V-70 Normalized Discharge Flows Zinc Subcategory
Elements 330
V-71 Treatment Practices And Effluent Quality At
Zinc Subcategory Plants Effluent Analysis 331
V-72 Pollutant Concentrations In The Zinc Powder
Wet Amalgamated Anode Element Waste Streams 332
V-73 Pollutant Mass Loadings In The Zinc Powder
Wet Amalgamated Anode Element Waste Streams 333
V-74 Statistical Analysis (mg/1) Of The Zinc Powder
Wet Amalgamated Anode Element Waste Streams 334
V-75 Statistical Analysis (mg/kg) Of The Zinc Powder
Wet Amalgamated Anode Element Waste Streams 335
V-76 Pollutant Concentrations In The Zinc Powder
Gelled Amalgammed Anode Element Waste Streams 336
V-77 Pollutant Mass Loading In The Zinc Powder
Gelled Amalgam Anode Element Waste Stream 337
viii
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TABLES
Number Title Page
V-78 Statistical Analysis (mg/1) Of The Zinc Powder
Gelled Amalgam Anode Element Waste Streams 338
V-79 Statistical Analysis (mg/kg) Of The Zinc Powder
Gelled Amalgam Anode Element Waste Streams 339
V-80 Pollutant Concentrations In The Zinc Oxide
Powder-Pasted Or Pressed, Reduced Anode Element
Waste Streams 340
V-81 Pollutant Mass Loadings In The Zinc Oxide Powder
Pasted and Pressed, 'Reduced Anode 341
V-82 Statistical Analysis (mg/1) Of The Zinc Oxide
Powder-Pasted Or Pressed, Reduced Anode Element
Waste Streams 342
V-83 Statistical Analysis (mg/kg) Of The Zinc Oxide
Powder-Pasted Or Pressed, Reduced Anode Element
Waste Streams 343
V-84 Pollutant Concentrations In The Zinc Electro-
deposited Anode Element Waste Streams 344
V-85 Pollutant Mass Loadings In The Zinc Electro-
deposited Anode Element Waste Streams 345
V-86 Normalized Flows Of Post-Formation Rinse
Waste Streams 346
V-87 Pollutant Concentration In The Silver Powder
Pressed And Electrolytically Oxidized Element
Waste Streams 347
V-88 Pollutant Mass Loadings In The Silver Powder
Pressed and Electrolytically Oxidized Cathode
Element Waste Streams 348
V-89 Statistical Analysis (mg/1) Of The Silver Powder
Pressed And Electrolytically Oxidized Cathode
Element Waste Streams 349
V-90 Statistical Analysis (mg/kg) Of The Silver
Powder Pressed And Electrolytically Oxidized
Cathode Element Waste Streams 350
IX
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TABLES
Number Title Page
V-91 Pollutant Concentrations In The Silver Oxide (Ag20)
Powder-Thermally Reduced And Sintered, Electro-
lytically Formed 351
V-92 Pollutant Mass Loadings In The Silver Oxide (Ag20)
Powder-Thermally Reduced And Sintered, Electro-
lytically Formed Cathode Element Waste Streams
(Plant B) 352
V-93 Pollutant Concentrations In The Silver Peroxide
(AgO) Powder Cathode Element Waste Streams 353
V-94 Pollutant Mass Loadings In The Silver Peroxide (AgO)
Powder Cathode Element Waste Streams 354
V-95 Statistical Analysis (mg/1) Of The Silver Peroxide
(AgO) Powder Cathode Element Waste Streams 355
V-96 Statistical Analysis (mg/kg) Of The Silver Peroxide
(AgO) Powder Cathode Element Waste Streams 356
V-97 Production Normalized Discharges From Cell Wash
Element 357
V-98 Pollutant Concentrations In The Cell Wash
Element (mg/1) 358
V-99 Pollutant Mass Loadings In The Cell Wash
Element (mg/1) 359
V-100 Statistical Analysis (mg/1) Of The Cell Wash
Element Waste Streams 360
V-101 Statistical Analysis (mg/kg) Of The Cell Wash
Element Waste Streams 361
V-102 Pollutant Concentrations In The Electrolyte
Preparation Element Waste Streams 362
V-103 Pollutant Mass Loadings In The Electrolyte
Preparation Element Waste Streams 363
V-104 Pollutant Concentrations In The Silver Etch
Element Waste Stream 364
V-105 Pollutant Mass Loadings In The Silver Etch
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TABLES
Number Title Page
Element Waste Stream 365
V-106 Pollutant Concentrations Of The Laundry Wash
And Employee Shower Waste Streams 366
V-107 Pollutant Concentrations In The Mandatory
Employee Wash Waste Stream (Plant A) 367
V-108 Pollutant Mass Loadings In The Mandatory
Employee Wash Waste Streams (Plant A) 368
V-109 Pollutant Concentrations Cf The Reject Cell
Handling Waste Streams (Plant A) 369
V-110 Pollutant Concentrations In The Reject Cell
Handling Waste Streams (Plant B) 370
V-lll Pollutant Mass Loadings In The Reject Cell
Handling Waste Streams 371
V-112 Pollutant Concentrations In The Floor Wash
Waste Stream (Plant A) 372
V-113 Pollutant Mass Loadings In The Floor Wash
Element Waste Stream 373
V-114 Pollutant Concentrations In The Equipment
Wash Element Waste Streams 374
V-115 Pollutant Mass Loadings In The Equipment
Wash Element Waste Streams 375
V-116 Statistical Analysis (mg/1) Of The Equipment
Wash Element Waste Streams 376
V-117 Statistical Analysis (mg/kg) Of The Equipment
Wash Waste Streams 377
V-118 Pollutant Concentrations In The Silver Powder
Production Element Waste Streams 378
V-119 Pollutant Mass Loadings In The Silver Powder
Production Waste Streams 379
V-120 Pollutant Concentrations In The Waste Streams
From Silver Peroxide Production Element 380
XI
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TABLES
Number Title Page
V-121 Pollutant Mass Loadings In The Waste Streams
From Silver Peroxide Production Element 381
VI-1 Priority Pollutant Disposition Cadmium Subcategory 449
VI-2 Priority Pollutant Disposition Calcium Subcategory 453
VI-3 Priority Pollutant Disposition Lead Subcategory 457
VI-4 Priority Pollutant Disposition Leclanche Subcategory 461
VI-5 Priority Pollutant Disposition Lithium Subcategory 465
VI-6 Priority Pollutant Disposition Magnesium Subcategory 469
VI-7 Priority Pollutant Disposition Zinc Subcategory 473
VI-8 Other Pollutants Considered For Regulation 477
VII-l pH Control Effect On Metals Removal 482
VII-2 Effectiveness Of NaOH For Metals Removal 482
VII-3 Effectiveness of Lime And NaOH For Metals Removal 484
VII-4 Theoretical Solubilities of Hydroxides and Sulfide
of Selected Metals In Pure Water 485
VII-5 Sampling Data From Sulfide Precipitation-Sedimentation
Systems 485
VII-6 Sulfide Precipitation-Sedmentation Performance 48^
VII-7 Concentration of Total Cyanide 491
VII-8 Multimedia Filter Performance 4^4
VII-9 Performance of Sampled Settling Systems 4^
VII-10 Skimming Performance ^2
VII-11 Trace Organic Removal By Skimming 503
VII-12 Hydroxide Precipitation - Settling (L&S) Performance 505
xii
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TABLES
Number Title P^S6.
VII-13 Hydroxide Precipitation - Settling (L&S) Performance
Additional Parameters
VII-14 Precipitation - Settling - Filtration (LS&F) Performance
Plant A 507
VII-15 Precipitation - Settling - Filtration (LS&F) Performance
Plant B 508
VII-16 Summary of Treatment Effectiveness
VII-17 Activated Carbon Performance 514
VII-18 Treatability Rating of Priority Pollutants Utilizing.
Carbon Adsorption
602
VII-19 Classes of Organic Compounds Absorbed On Carbon
Vll-20 Ion Exchange Performance 532
VII-21 Membrane Filtration System Effluent 534
VII-22 Peat Adsorption Performance 536
VII-23 Ultrafiltration Performance 543
VII-24 Process Control Technologies In Use At Battery Manufacturing
Plants 603
VIII-1 Cost Program Pollutant Parameters 677
VII1-2 Treatment Technology Subroutines 678
VII1-3 Waste Water Sampling Frequency 679
VIII-4 Index To Technology Cost Tables 680
VIII-5 Lime Additions For Lime Precipitation 681
VIII-6 Reagent Additions For Sulfide Precipitation 682
VIII-7 Neutralization Chemicals Required 683
VII1-8 Water Treatment Component Costs - Hydroxide
Precipitation And Settling 684
VII1-9 Water Treatment Component Costs - Sulfide
Precipitation And Settling - Batch 685
VIII-10 Water Treatment Component Costs - Sulfide
xiii
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Number
TABLES
Title
VIII-11
VIII-12
VIII-13
VIII-14
VIII-15
VIII-16
VIII-17
VIII-18
VIII-19
VIII-20
VIII-21
VIII-22
VIII-23
VIII-24
VIII-25
VIII-26
VIII-27
Precipitation And Settling - Continuous 686
Water Treatment Component Costs - Multimedia
Filtration 687
Water Treatment Component Costs - Membrane
Filtration 688
Water Treatment Component Costs - Reverse Osmosis 689
Water Treatment Component Costs - Vacuum Filtration 690
Water Treatment Component Costs - Holding And
Settling Tanks 691
Water Treatment Component Costs - pH Adjustment 692
Water Treatment Component Costs - Aeration 693
Water Treatment Component Costs - Carbon
Adsorption 694
Water Treatment Component Costs - Chrome
Reduction 695
Water Effluent Treatment Costs Cadmium Subcate- 696
gory - BPT
Water Effluent Treatment Costs Calcium Subcate- 697
gory - BPT
Water Effluent Treatment Costs Lead Subcate- 698
gory - BPT
Water Effluent Treatment Costs Leclanche Subcate-
gory - BPT 699
Water Effluent Treatment Costs Lithium Subcate- 700
gory - BPT
Water Effluent Treatment Costs Magnesium Subcate-
gory - BPT 701
Water Effluent Treatment Costs Zinc Subcategory - BPT 702
Water Effluent Treatment Costs Cadmium Subcategory -
xiv
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TABLES
Number Title Page
BAT Option 1 703
VIII-28 Water Effluent Treatment Costs Cadmium Subcategory -
BAT Option 2 704
VIII-29 Water Effluent Treatment Costs Cadmium Subcategory -
BAT Option 3 705
VIII-30 Water Effluent TReatment Costs Calcium Subcategory -
BAT Option 1 706
VIII-31 Water Effluent Treatment Costs Calcium Subcategory -
BAT Option 2 707
VI11-32 Water Effluent Treatment Costs Lead Subcategory -
BAT Option 1 708
VII1-33 Water Effluent Treatment Costs Lead Subcategory -
BAT Option 2 709
VII1-34 Water Effluent Treatment Costs Lead Subcategory -
BAT Option 3 710
VII1-35 Water Effluent Treatment Costs Lead Subcategory -
BAT Option 4 711
VIII-36 Water Effluent Treatment Costs Lithium Subcategory -
BAT Option 1 712
VIII-37 Water Effluent Treatment Costs Lithium Subcategory -
BAT Option 2 713
VIII-38 Water Effluent Treatment Costs Magnesium Subcategory -
BAT Option 1 714
VII1-39 Water Effluent Treatment Costs Magnesium Subcategory -
BAT Option 2 715
VIII-40 Water Effluent Treatment Costs Magnesium Subcategory -
BAT Option 3 716
VII1-41 Water Effluent Treatment Costs Zinc Subcategory -
BAT Option 1 717
VI11-42 Water Effluent Treatment Costs Zinc Subcategory -
BAT Option 2 718
xv
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TABLES
Number Title
VII1-43 Water Effluent Treatment Costs Zinc Subcategory -
BAT Option 3 719
VI11-44 Nonwater Quality Aspects Of Waste Water Treatment 720
VII1-45 Nonwater Quality Aspects Of Sludge And Solids
Handling 721
xvi
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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 46
HI-2 Performance Capability of Various Battery Systems 47
II1-3 Cutaway View of An Impregnated Sintered Plate
Nickel-Cadmium Cell 48
HI-4 Cutaway View of A Cylindrical Nickel-Cadmium
Battery 49
II1-5 Cutaway View of Lead Acid Storage Battery 50
II1-6 Cutaway View of A Leclanche Cell 51
II1-7 Exploded View of A Flat Leclanche Battery Used
In Film Pack 52
III-8 Cutaway View of Two Solid Electrolyte Lithium
Cell Configurations 53
II1-9 Cutaway View of A Reserve Type Battery 54
111-10 Cutaway View of A Carbon-Zinc-Air Cell 55
III-ll Cutaway View of An Alkaline-Manganese Battery 56
II1-12 Cutaway View of A Mercury (Ruben) Cell 57
111-13 Major Production Operations in Nickel-Cadmium
Battery Manufacture 58
111-14 Simplified Diagram of Major Production Operations
In Lead Acid Battery Manufacture 59
II1-15 Major Production Operations In Leclanche Dry
Battery Manufacture 60
HI-16 Major Production Operations in Lithium-Iodine
Battery Manufacture 61
111-17 Major Production Operations In Ammonia-Activated
Magnesium Reserve Cell Manufacture 62
xvii
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FIGURES
Number Title Page
111-18 Major Production Operations In Water-Activated
Carbon-Zinc-Air Cell Manufacture 63
111-19 Major Production Operations In Alkaline-Manganese
Dioxide Battery Manufacture 64
111-20 Simplified Diagram of Major Operations In Mercury
(Ruben) Battery Manufacture 65
111-21 Value of Battery Product Shipments 1963-1977 66
II1-22 Battery Manufacturing Category Summary 67
II1-23 Distribution of Lead Subcategory Production Rates 68
111-24 Distribution of Employment At Lead Subcategory
Manufacturing Facilities 69
IV-1 Summary Of Category Analysis 89
V-l Generalized Cadmium Subcategory Manufacturing Process 192
V-2 Cadmium Subcategory Analysis 193
V-3 Production Of Cadmium Electrodeposited Anodes 195
V-4 Production Of Cadmium Impregnated Anodes 196
V-5 Production Of Nickel Electrodeposited Cathodes 197
V-6 Production Of Nickel Impregnated Cathodes 198
V-7 Generalized Calcium Subcategory Manufacturing Process 199
V-8 Calcium Subcategory Analysis 200
V-9 Lead Subcategory Generalized Manufacturing Processes 201
V-10 Lead Subcategory Analysis 202
V-ll Production Of Closed Formation Wet Batteries 203
V-12 Production Of Damp Batteries 204
V-13 Production Of Dehydrated Batteries 205
xviii
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FIGURES
Number Title Page
V-14 Production Of Batteries From Green (Unformed) Plates 206
V-15 Production Of Batteries From Purchased Formed
Plates 207
V-16 Percent Production Normalized Discharge From
Lead Subcategory Process Operations 208
V-17 Production Normalized Discharge From Double And
Single Fill Formation 209
V-18 Generalized Schematic For Leclanche Cell
Manufacture 210
V-19 Leclanche Subcategory Analysis 211
V-20 Generalized Lithium Subcategory Manufacturing Process 212
V-21 Lithium Subcategory Analysis 213
V-22 Generalized Magnesium Subcategory Manufacturing
Process 214
V-23 Magnesium Subcategory Analysis 215
V-24 Generalized Zinc Subcategory Manufacturing
Processes 216
V-25 Zinc Subcategory Analysis 217
V-26 Production Of Zinc Powder-Wet Amalgamated
Anodes 219
V-27 Production Of Gellied Amalgam Anodes 220
V-28 Production Of Pressed Zinc Oxide Electrolytically
Reduced Anodes 221
V-29 Production Of Pasted Zinc Oxide Electrolytically
Reduced Anodes 222
V-30 Production Of Electrodeposited Zinc Anodes 223
V-31 Production -Of Silver Powder Pressed Electrolytically
Oxided Cathodes 224
xix
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FIGURES
Number Title Page
V-32 Production Of Silver Oxide (Ag20) Powder Thermally
Reduced Or Sintered, Electrolytically Formed
Cathodes 225
V-33 Chemical Treatment Of Silver Peroxide Cathode
Pellets 226
V-34 Production Of Pasted Silver Peroxide Cathodes 227
VII-1 Comparative Solubilities Of Metal Hydroxides And
Sulfide As A Function Of pH 571
VII-2 Effluent Zinc Concentrations vs. Minimum
Effluent pH 572
VII-3 Hydroxide Precipitation Sedimentation Effectiveness
Cadmium 573
VI1-4 Hydroxide Precipitation Sedimentation Effectiveness
Chromium 574
VI1-5 Hydroxide Precipitation Sedimentation Effectiveness
Copper 575
VI1-6 Hydroxide Precipitation Sedimentation Effectiveness
Iron " 576
VII-7 Hydroxide Precipitation Sedimentation Effectiveness
Lead 577
VI1-8 Hydroxide Precipitation Sedimentation Effectiveness
Manganese 578
VII-9 Hydroxide Precipitation Sedimentation Effectiveness
Nickel • 579
VII-10 Hydroxide Precipitation Sedimentation Effectiveness
Phosphorus 580
VII-11 Hydroxide Precipitation Sedimentation Effectiveness
Zinc 581
VII-12 Lead Solubility In Three Alkalies 582
VI1-13 Representative Types Of Sedimentation 583
xx
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FIGURES
Number Title Page
VII-14 Granular Bed Filtration 584
VII-15 Pressure Filtration 585
VII-16 Vacuum Filtration 586
VII-17 Centrifugation 587
VII-18 Gravity Thickening 588
VII-19 Sludge Drying Bed 589
VI1-20 Types Of Evaporation Equipment 590
VII-21 Ion Exchange With Regeneration 591
VI1-22 Simplified Reverse Osmosis Schematic 592
VI1-23 Reverse Osmosis Membrane Configurations 593
VII-24 Dissolved Air Flotation 594
VII-25 Simplified Ultrafiltration Flow Schematic 595
VI1-26 Activated Carbon Adsorption Column 596
VII-27 Treatment Of Cyanide Waste By Alkaline
Chlorination 597
VI1-28 Typical Ozone Plant For Waste Treatment 598
VII-29 UV/Ozonation 599
VII-30 Chromium Reduction 600
VIII-1 Simplified Logic Diagram System Cost Estimation
Program 643
VI11-2 Simple Waste Treatment System 644
VIII-3 Predicted Lime Precipitation/Clarification
Costs Continuous 645
VIII-4 Predicted Costs For Precipitation-Clarification
Bath 646
VIII-5 Chemical Precipitation-Clarification Costs 647
xxi
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FIGURES
Number Title Page
VIII-6 Predicted Costs Of Multimedia Filtration 648
VIII-7 Membrane Filtration Costs 649
VII1-8 Reverse Osmosis Investment Costs 650
VII1-9 Reverse Osmosis Labor Requirements 651
VI11-10 Reverse Osmosis Material Costs 652
VI11-11 Reverse Osmosis Powder Requirements 653
VIII-12 Vacuum Filtration Investment Costs 654
VI11-13 Vacuum Filtration Labor Requirements 655
VIII-14 Vacuum Filtration Material Costs 656
VIII-15 Vacuum Filtration Electrical Costs 657
VII1-16 Holding Tank Investment Costs 658
VIII-17 Holding Tank Electrical Costs 659
VII1-18 Holding Tank Labor Requirements 660
VIII-19 Neutralization Investment Costs 661
VII1-20 Neutralization Labor Requirements 662
VII1-21 Carbon Adsorption Costs 663
VII1-22 Chemical Reduction Of Chromium Investment Costs 664
VII1-23 Annual Labor For Chemical Reduction Of Chromium 665
VII1-24 Lead Subcategory-Dehydrated Battery In-Process
Control Costs 666
VII1-25 Labor For Countercurrent Rinses Dehydrated Batteries 667
VII1-26 In-Process Piping And Segregation Costs For The
Lead Subcategory 668
VII1-27 Holding Tank Costs For Battery Wash Water Recycle -
Lead Subcategory 669
xxn
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FIGURES
Number Title Page
VIII-28 In-Process Costing For Slow Charging Batteries
Lead Subcategory 670
VI11-29 In-Process Investment Costs - Cadmium Subcategory 671
VI11-30 In-Process Annual Costs - Cadmium Subcategory 672
VIII-31 In-Process Investment Costs - Lead Subcategory 673
VI11-32 In-Process Annual Costs - Lead Subcategory 674
VI11-33 In-Process Investment Costs - Zinc Subcategory 675
VI11-34 In-Process Annual Costs - Zinc Subcategory 676
IX-1 Cadmium Subcategory BPT Treatment 738
IX-2 Calcium Subcategory BPT Treatment 739
IX-3 Lead Subcategory BPT Treatment 740
IX-4 Lithium Subcategory BPT Treatment 741
IX-5 Magnesium Subcategory BPT Treatment 742
IX-6 Zinc Subcategory BPT Treatment 743
X-l Cadmium Subcategory BAT Option 1 Treatment 766
X-2 Cadmium Subcategory BAT Option 2 Treatment 767
X-3 Cadmium Subcategory BAT Option 3 Treatment 768
X-4 Cadmium Subcategory BAT Option 4 Treatment 769
X-5 Calcium Subcategory BAT Option 1 Treatment 770
X-6 Calcium Subcategory BAT Option 2 Treatment 771
X-7 Lead Subcategory BAT Option 1 Treatment 772
X-8 Lead Subcategory BAT Option 2 Treatment 773
X-9 Lead Subcategory BAT Option 3 Treatment 774
X-10 Lead Subcategory BAT Option 4 Treatment 775
xxiii
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FIGURES
Number Title F-3^6-
X-ll Lithium Subcategory BAT Option 1 Treatment 776
X-12 Lithium Subcategory BAT Option 2 Treatment 777
X-13 Lithium Subcategory BAT Option 3 Treatment 778
X-14 Magnesium Subcategory BAT Option 1 Treatment 779
X-15 Magnesium Subcategory BAT Option 2 Treatment 780
X-16 Magnesium Subcategory BAT Option 3 Treatment 781
X-17 Zinc Subcategory BAT Option 1 Treatment 782
X-18 Zinc Subcategory BAT Option 2 Treatment 783
X-19 Zinc Subcategory BAT Option 3 Treatment 784
XI-1 Lead Subcategory NSPS Treatment 788
XI-2 Zinc Subcategory NSPS Treatment 789
XXIV
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SECTION I
CONCLUSIONS
This is a draft development document and is being circulated for
review of its technical merit. This draft document is subject to
corrections and revisions as appropriate prior to its issuance at the
time of proposed rulemaking.
> *
Treatment technologies for best practicable control technology
currently available (BPT) and treatment options for best available
technology economically achievable (BAT) for the control of toxic
pollutants have been developed and are presented herein. However, no
regulatory numbers have been attached. Before proposal of effluent
limitations and standards, the Agency will choose among and between
BAT options and will set regulatory numbers based on the final
treatment technologies selected.
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SECTION II
RECOMMENDATIONS
This section will be completed after the Environmental Protection
Agency has made a final selection of treatment options and effluent
levels preparatory to proposing a regulation.
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SECTION III
INTRODUCTION
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 March 9, 1979. 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
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
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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 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 glasses of pollutants which Congress declared "toxic"
under Section \07(a) of the Act. Likewise, EPA's programs for new
source performance^ standards and pretreatment standards are now aimed
principally at to\ic 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.
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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). 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 searches, 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 base and the wastewater
generation and discharge varied widely, the establishment of
subcategories was determined to be necessary. The initial
subcategorization of the category was made by using recognized battery
type as the subcategory description:
Lead Acid
Nickel-Cadmium (Wet
Nickel-Cadmium (Dry
Carbon-Zinc (Paper)
Carbon-Zinc (Paste)
Mercury (Ruben)
Alkaline-Manganese
Magnes i urn-Carbon
Process)
Process)
Carbon-Zinc (Air)
Silver Oxide-Zinc
Magnesium Cell
Nickel-Zinc
Lithium Cell
Mercury (Weston)
Lead Acid Reserve
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.
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In addition to existing and plant supplied information (via dcp), data
were obtained through a sampling program carried out 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 utilized 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 upon
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 involving 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 subcategorization discussion, but are not otherwise
considered in this document. 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 this document.
An analysis of production methods, battery structure and electrolytic
couple variations for each battery type revealed that there are
theoretically about 600 distinct variations that could require further
subgrouping. Based upon dcp responses and actual plant visits, over
200 distinct variations have been positively identified. Because of
the large number of potential subgroupings 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:
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Anode Material Designation For This Document
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
As is 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 Section 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
technology such as the 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 based on
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. Where appropriate, the
data were also used to identify the best conventional pollutant
control technology (BCT), although the presence of toxic metals in
most waste streams may limit applicability of these techniques. 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
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achieved, the age of equipment and facilities 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 the battery manufacturing category were gathered from
literature studies, previous industry studies by the Agency, a plant
survey and evaluation, 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 XIV. The material research
covered battery chemistry, the manufacturing 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.
Plant Survey and Evaluation - The 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's 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 were in other business areas.
Some plants responded with 1977 or 1978 data, and some provided 1976
data although production has subsequently ceased. Table III-l
summarizes the survey responses received in terms of number of plants
which 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
10
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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 plant owned or operated by the
company. Also, some plants manufacture batteries in more than one
subcategory, and currently four plants are active in three
subcategories and nine plants are active in two subcategories. Due to
changes in ownership and changes in production lines, the number of
companies and also the number of plant sites active in the category
often vary. The result is that about 230 plant sites are currently
included in this category. All information received was reviewed and
evaluated, and will be discussed as appropriate in subsequent
sections.
TABLE III-l
SURVEY SUMMARY
SUBCATEGORY
Cadmium
Calcium
Lead
Leclanche
Lithium
Magnesium
Nuclear
Zinc
Totals
NUMBER OF PLANTS
(Information Received)
NUMBER OF PLANTS
(Currently Active)
253
247
Total Number of Plant Sites in Category - 230.
*Includes plate manufacturers and assemblers.
The second phase of the data collection effort included the visitation
of selected plants, for screening and verification sampling of
wastewaters from battery manufacturing operations. The dcp's served
as a primary source in the selection of plants for visitation and
sampling. Specific criteria used to choose visitation sites included:
1. Distributing visits according to the type of battery manufactured.
2. Distributing visits among various manufacturers of each battery
type.
3. Selecting plants whose production processes were representative of
the processes performed at many plants for each subcategory.
Consideration was also given to the understanding of unique
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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.
Forty plants were visited and a wastewater sampling program was
conducted at nineteen 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 the com-
pletion 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.
7. BCT practices at 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 as well as the overall sampling program
results are described in Section V of this document.
Waste Treatment Equipment Manufacturers - Various manufacturers of
waste treatment equipment were contacted by phone or visited to de-
termine cost and performance data on specific technologies. Infor-
mation collected was based both on manufacturer's research as well as
on in-situ operation at plants that were often not battery manu-
facturers but had similar wastewater characteristics (primarily toxic
metal wastes).
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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 as well as the literature provided the basis for the initial
battery subcategorization discussed in Section IV. This sub-
categorization 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 as to be 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, respectively) for the selection of applicable treatment systems
and the presentation of achievable effluent levels and actual effluent
levels obtained for each battery subcatgegory.
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 radio-
active decay source when 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 followed by 12
years the discovery of the galvanic cell by Galvani; and by 2000 years
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
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experiments, Davy, and then Faraday, used galvanic cells to carry out
electrolysis studies. In 1836 Daniell invented the cell bearing 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 1880's 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 dioxide in the air with the
caustic soda electrolyte. Batteries with capacities to 1000 ampere
hours were available.
A storage battery of great commercial importance during the first half
of this century was the Edison cell. Although the system is not manu-
factured 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 strip. 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, of which tens of thousands are in use. Huge development
14
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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 46), 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, as well as 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 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 this document the marketed end product
is usually referred to as a battery. Manufacturing flow charts and
construction diagrams reveal the actual assembly details.
In this document, the cerms "bactery1 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 in
which 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, some-
15
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times 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
current collector, 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
anode system.
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.
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, respectively, 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-lead 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 47) illustrates how these measures of
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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.
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 usefully be
considered, however, in groups for which the general purpose and
primary performance requirements are similar. Such groups are shown
in Table III-2.
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Table III-2
Purpose
1. Portable electric power
2. Electric power storage
3. Standby or emergency
electrical power
4. Remote location electrical power
5. Voltage leveling
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 PBX's
regulated power supplies
The requirements for a flashlight battery are: low cost, long shelf
life, intermittent use, 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. Instantaneous
response is not a requirement although a short time for activation is
expected.
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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 overall cost of
launching a satellite or travel to a remote location far exceeds 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 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 are 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 with 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 become secondary considerations also, in both of
these applications.
Battery Function and Manufacture
The extremely varied requirements outlined have led to 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 electrochemistry of batteries, battery construction and
manufacturing are presented to help orient the reader.
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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, the current is measured in
amperes. The discrete charges carrying current in the external
circuit, or load, are electrons, which bear a 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 non-electrochemical 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 which has 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 discus-
sed. 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 II1-4 show the reactions as they are used in practical cells for
delivery of power. In those cells which are rechargeable, charging
reverses the direction of the reaction as written in the tables.
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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)
+ 2e (acidic)
e (molten salt, organic, nonaqueous inorganic)
Mgf=5: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 + 2H20^=^ 2Ag + 40H- (alkaline)
2e + Ag2O + 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,e (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 + H^Of^-MnOOH + OH~ (alkaline)
e + MnOOH + H2O^Mn(OH)2 + OH- (alkaline)
Be + m-C6H4(N02)2 + 6NH4+ + Mg+2:^m-bis-C6H4(NHOH)2
+ 6NH3 + Mg(OH)2 (ammonia)
2e + PbCl2-£=^Pb + 2C1- (sea water)
e + CuClf^.Cu + Cl- (sea water)
e + AgClf^Ag + Cl~ (sea water)
4e + 02 + 2H20± 4OH- (alkaline)
21
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Most presently produced battery systems are based on aqueous
electrolytes. However, lithium and thermal batteries, and at least
one magnesium cell have non-aqueous 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
pyrotecnic 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, providing 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+*£—Mn203 + H20 + Zn(NH3)2Clz (acid)
cell: Zn + 2Mn02 + 2NH4Cl^Mn203 + H20 + Zn(NH3)2Cl2
Alkaline Manganese;
anode: Zn + 2OH~^Zn(OH)2 + 2e (alkaline)
cathode: e + MnO2 + H20^;MnOOH + OH~ (alkaline)
e + MnOOH- + H20^;Mn(OH)2 + OH- (alkaline)
cell: Zn + Mn02 + 2H2O^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
prevention of 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 lead 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 compatability of separators and electrolytes is
an important factor in battery design.
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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 cell failure.
As an example, corrosion of the zinc anode in Leclanche cells may
result in perforation of the anode and leakage of 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 twenty-five 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 bat-
teries, 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 manufactured 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 must be accommodated by design and
23
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materials. Pressure changes normally occur during discharge-charge
cycling and must be accomodated 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 the 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 function 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 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
24
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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 which 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 is 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 + SO^F^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 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
25
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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
electrodes. 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, 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
26
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operations are illustrated by reference to particular battery types.
Ten battery types were chosen to illustrate a range of materials,
applications, and sizes. Figures III-3 through 111-12 (Pages 48-57)
are drawings or cutaway views of these ten batteries. Figures 111-13
through 111-20 (Pages 58-65) 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, then
the paste is applied to a support structure and dried.
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 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
27
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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. 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, are considered as 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 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. Fre-
quently, electrodes are formed in the cell or battery after final
assembly. However the electrodes are arranged physically, 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.
28
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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.
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 produced 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 (24-30 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 are considered part of battery
manufacturing usually as an ancillary operation.
29
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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 (m-
DNB), 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 cathode struc-
ture 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
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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) are considered as 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 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 Leclanche 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
sealed in place, electrolyte is applied to it before the next
electrode is sealed in place. When the battery is completed the
entire assembly is sandwiched between two thin steel sheets. Assembly
is completely automated. The resulting six-volt battery is about
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three inches by four inches by three-sixteenths of an inch thick and
has high specific power and power density, but short life.
A contrasting battery is the carbon-zinc (air) cell. The cast amalga-
mated zinc anodes positioned on each side of a porous carbon air elec-
trode are attached to the cover of the cell. Dry potassium hydroxide
and lime are placedin the bottom of the cell case, the cover is put in
place and sealed, and a bag of dessicant is placed in the filler open-
ing. 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 a battery
type as are the anode and cathode fabrication operations.
INDUSTRY SUMMARY
The battery manufacturing industry in the United States includes 230
active facilities operated by 132 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 thirty-three
thousand workers. As Figure II1-21 (Page 66) shows7 both the value of
industry products, and the number of employees 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 decline and phasing 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
facilities are fairly new with over half reported to have been built
in the past twenty years. Most have been modified even more recently.
Plants commonly manufacture a variety of cells and batteries differing
in size, shape, and performance characteristics. Further, a
signficant 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
facilities currently produce cells or batteries using two or more
different anode materials and therefore are considered in two or more
subcategories. Some battery manufacturing facilities purchase
finished cell components and assemble the final battery products
without performing some of the whole range of manufacturing process
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steps on-site. Other facilities 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 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 cathode and anode in the familiar lead-acid storage
battery. Mercuric oxide 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. 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. Figure 111-22 (Page 67) and
subsequent discussion summarizes separately the characteristics of
plants manufacturing batteries in each of the groups based on anode
and electrolyte.
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Table III-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's. Numbers shown are sums of
provided data. Because response to raw materials question is
incomplete, actual consumption will be higher by 10-20 percent.
Cadmium Subcategory
Cadmium anode cells presently manufactured are based on nickel-
cadmium, silver-cadmium and mercury-cadmium couples. Nickel-cadmium
batteries are among the most widely used rechargeable cells finding
applications in calculators, radios and numerous other portable
electronic devices in addition to a variety of industrial
applications. Total annual shipments of nickel-cadmium batteries were
valued at over one-hundred million dollars in 1977. Silver-cadmium
battery manufacture is limited in terms of product weight amounting to
less than one percent of the amount of nickel-cadmium batteries
manufactured. Small quantities of mercury-cadmium batteries are
manufactured for military and industrial applications. Presently ten
plants are manufacturing batteries in the cadmium subcategory. Total
annual production is estimated to be 5200 metric tons (5750 tons) of
batteries with three plants producing over 453.5 metric tons (500
tons) of batteries, and one producing less than .907 metric tons (1
ton) of batteries. Plants vary in size and in number of employees.
Total subcategory employment is estimated to be 2500.
Process wastewater flows from this subcategory are variable and total
114,000 1/hr (30,100 gal/hr). Most plants have flows of
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are also major sources of process wastewater. Additional points of
process water use and discharge include wet scrubbers, electrolyte
preparation, cell wash, floor wash, and employee showers and hand wash
intended to remove process chemicals. The most significant pollutants
carried by these waste streams are the toxic metals, cadmium, nickel,
and silver. The waste streams are predominantly alkaline and
frequently contain high levels of suspended solids including metal
hydroxide precipitates.
Treatment commonly used included settling or filtration for the
removal of solids at all facilities which indicated process wastewater
discharge; three plants also indicated the use of coagulants, six pH
adjustment, and one chemical precipitation. Two plants indicated the
use of material recovery, five plants have sludges contractor hauled,
and one plant has sludge landfilled. On-site observation at several
plants indicate that the treatment provided is often rudimentary and
of limited effectiveness. Battery process wastewater discharges from
two cadmium anode battery manufacturing plant flows directly to
surface waters, four facilities discharge to municipal sewers, one
discharges to both sewers and surface waters, and one plant has zero
discharge to navigable waters of the United States. Two facilities
have zero battery manufacturing process wastewater discharge.
Wastewater treatment provided was not related to the discharge
destination.
Cadmium anode batteries are produced in a broad range of sizes and
configurations corresponding to varied applications. They range from
small cylindrical cells with capacities of less than one ampere-hour
to large rectangular batteries for industrial applications with
capacities in excess of 100 ampere-hours. In general, batteries
manufactured in the smaller cell sizes are sealed while the larger
units are of "open" or vented construction.
Manufacturing processes vary in accordance with these product
variations and among different facilities producing similar products.
Raw materials vary accordingly. All manufacturers use cadmium or
cadmium salts (generally nitrate or oxide) to produce cell anodes, and
nickel, silver, mercury or their salts to produce cell cathodes. The
specific materials chosen depend on details of the process as
' discussed in Section V. Generally supporting materials are also used
in manufacturing the electrodes to provide mechanical strength and
conductivity. Raw materials for the electrode support structures
commonly include nickel powder and nickel or nickel plated steel
screen. Additional raw materials include nylon, polypropylene and
other materials used in cell separators, sodium and potassium
hydroxide used as process chemicals and in the cell electrolyte,
cobalt salts added to some electrodes, and a variety of cell case,
seal, cover and connector materials.
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Calcium Subcateqory
All calcium anode batteries presently produced are thermal batteries
for military and atomic applications. Three plants presently
manufacture these batteries to comply with a variety of military
specifications, and total production volume is limited. The total
production of thermal batteries by these facilities was not determined
since one plant which produced no process wastewater reported that
thermal cell production data were not available. The other two
facilities, however, showed total thermal battery production amounting
to less than 23 metric tons (25 tons). Total employment for the three
facilities manufacturing in the calcium subcategory is estimated to be
240.
Process water use and discharge in this subcategory are limited.
Wastewater discharge is reported from only one process operation which
is involved in producing the reactive material used to heat the cell
for activation. The cell anode, cathode, and electrolyte are all
handled in dry processes from which no wastewater discharges are
reported. The reported volume of process wastewater discharge from
calcium anode cell manufacture varies between 0 and 37.9 1/hr. (10
gal/hr). In terms of the weight of thermal batteries produced the
flow varies from 0 to 2.5 I/kg (0.67 gal/lb). The most significant
pollutant found in these waste streams is hexavalent chromium which is
present primarily in the form of barium chromate. Another pollutant
found in these wastewaters is asbestos. Wastewater treatment
presently provided is limited to settling for removal of suspended
solids (including BaCr04). One plant reports that sludge wastes are
contractor hauled.
Lead Subcateqory
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 184 battery manufacturing facilities of which
some 144 manufacture electrodes from basic raw materials, and almost
40 purchase electrodes prepared off-site and assemble them into bat-
teries (and are therefore termed assemblers). Most facilities 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 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 subcategory, consumed over
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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 of employees reported by plants in the lead
subcategory ranged from 1 to 643 with total employment estimated to be
18745. Most of the plants employing fewer than 10 employees were
found to be battery assemblers who purchased charged or uncharged
plates produced in other facilities. 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 68 and 69).
With the exception of lead-acid reserve batteries which are man-
ufactured 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; over 18 percent of all lead acid batteries produced.
Twenty-seven plants reported producing damp batteries which is 9.3
percent of the battery manufacture total, or 121,000 metric tons
(136,000 tons). Contacts with battery manufacturers have indicated a
substantial reduction in dehydrated battery manufacture since that
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time due 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, and 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 and employee showers and hand washes used to
remove process materials.
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 5,800 1/hr (1,532 gal/hr) and a median discharge rate of 3,500
1/hr (925 gal/hr). When normalized on the basis of the total amount
of lead used in battery manufacture, these discharge flows vary
between 0 and 52.3 I/kg (6.37 gal/lb) with an average of 4.816 I/kg
(0.577 gal/lb). Over 60 percent of lead subcategory plants discharge
wastewater to POTW. The wastewater from these facilities 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 provide settling to remove particulates and
precipitated lead. In-process treatment and reuse of specific waste
streams is also common.
Leclanche Subcategory
Plants included in this subcategory manufacture the conventional
carbon-zinc Leclanche cell and some silver chloride-zinc and carbon-
zinc air cells as well. All of the battery types included have in
common the use of an acidic (chloride) electrolyte and use of a zinc
anode. Among carbon-zinc air batteries, only "dry" cells which use
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ammonium chloride in the electrolyte are included in this subcategory.
Carbon-zinc air depolarized batteries which use alkaline electrolytes
are included in the zinc subcategory. The Leclanche subcategory also
includes the production of pasted paper separator material containing
mercury for use in battery manufacture.
Plants in this subcategory produce a total of over 108,000 metric tons
(111,000 tons) of batteries and employ approximately 4,200 persons.
Individual plant production ranges from approximately 1.4 metric tons
(1.5 tons) to 24,000 metric tons (26,000 tons). In 1977, the total
value of product shipments in this subcategory was over 261 million
dollars.
A wide variety of cell and battery configurations and sizes are
produced in this subcategory including cylindrical cells in sizes from
AAA to No. 6, flat cells which are stacked to produce rectangular nine
volt transistor batteries, various rectangular lantern batteries, and
flat sheet batteries for photographic applications. Only the flat
photographic cells are somewhat different in raw material use and
production techniques. For specific cell configurations, however,
significant differences in manufacturing processes and process
wastewater generation are associated with differences in the cell
separator chosen (i.e. cooked paste, uncooked paste, pasted paper).
Major raw materials used in the manufacture of batteries in this
subcategory include zinc, mercury, carbon, manganese dioxide, ammonium
chloride, zinc chloride, silver chloride, paper, starch, flour, and
pitch or similar materials for sealing cells. Plastics are also used
in producing flat cells for photographic use. The zinc is most often
obtained as sheet zinc pre-formed into cans which serve as both cell
anode and container although some facilities form and clean the cans
on site. For one type of battery, zinc powder is used. The mercury,
used to amalgamate the zinc and reduce internal corrosion in the
battery, is generally added with the cell electrolyte or separator.
It amounts to approximately 1.7 percent by weight of the zinc
contained in these cells.
Process water use in this subcategory is limited, and process
wastewater production results primarily from cleaning production
equipment used in handling cathode and electrolyte materials. Process
wastewater is also reported from the production and setting of cooked
paste cell separators and from the manufacture of pasted paper
separator material.
Estimated total process wastewater flow rates reported by plants in
this subcategory range from 0 to 2,158 1/hr (570 gal/hr) with an
average of 208 1/hr (55 gal/hr). Eleven facilities reported zero
discharge of process wastewater. The maximum reported volume of
process wastewater per unit of production (weight of cells produced)
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in this subcategory is 6.4 I/kg (0.76 gal/lb) and the average value is
0.45 I/kg (0.054 gal/lb). All plants reporting process wastewater
discharge in this subcategory discharge to municipal treatment
systems, except for one plant which discharged 1 gal/day to a dry
well. Significant flow rate variations among plants in this
subcategory are attributable to manufacturing process differences, to
variations in equipment clean-up procedures employed, and the degree
of water conservation practiced at each plant.
The most significant pollutants in waste streams from plants in this
subcategory are mercury and zinc, ammonium chloride, particulate
manganese dioxide and carbon, and starch and flour (used in separator
manufacture). Treatment technologies applied are variable but
generally include provisions for suspended solids removal. Four
plants report the use of filtration and four the use of settling
tanks. Treatment by adsorption is reported by one facility, and two
report pH adjustment. Some facilities discharge without treatment,
and the use of contractor hauling for disposal of some waste streams
is common.
Lithium Subcateqory
This subcategory encompasses the manufacture of batteries which employ
lithium as the reactive anode material. At present, the batteries
included in this subcategory are generally high-cost, special purpose
products manufactured in limited volumes. These include batteries for
heart pacemakers, lanterns, watches, and special military
applications. A variety of cell cathode materials are presently used
with lithium anodes including iodine, sulfur dioxide, thionyl chloride
and iron disulfide. Electrolytes in these cells are generally not
aqueous and may be either solid or liquid organic materials or ionic
salts (used in thermally activated cells).
Because the commercial manufacture of lithium anode batteries is
relatively new and rapidly changing, 1976 production figures were not
available in all cases. Three of seven plants reporting lithium anode
battery manufacture, reported production for 1977, 1978 and 1979
because the facilities had commenced operation after 1976. Based on
1976 figures where available and data for other years where necessary,
total annual production of lithium anode cells is estimated to be over
22.2 metric tons (24.5 tons). Individual plant production ranges from
less than 50 kg (100 Ibs) to 14 metric tons (15.5 tons). Total
employment for this subcategory is estimated to be 400.
Because of lithium's high reactivity with water, anode processing and
most cell assembly operations are performed without the use of process
water. In fact they are usually accomplished in areas of controlled
low humidity. Process water is used, however, in producing some cell
cathodes, either in washing reactive materials or for air pollution
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control and area clean-up. One plant also reports process water use
in manufacturing reactive materials for activating thermal batteries
as discussed in conjunction with calcium anode batteries. Three of
seven plants manufacturing lithium anode batteries reported process
wastewater discharges which ranged from 3.9 1/hr (1.0 gal/hr) to 150
1/hr (39 gal/hr). The maximum reported flow rate includes 60 1/hr (16
gal/hr) resulting from the manufacture of heating elements.
Wastewater streams from plants in this subcategory may be expected to
vary considerably in their chemical composition due to the widely
varying raw materials and processes used. Raw materials reported to
be used in lithium anode battery manufacture are shown in Table II1-6.
TABLE II1-6
RAW MATERIALS USED IN LITHIUM ANODE BATTERY
MANUFACTURE
Acetonitrile Lithium Perchlorate
Aluminum Methyl Acetate
Aluminum Chloride Methyl Formate
Barium Chromate Nickel
Carbon Oil
Dioxolane Paper
Glass Fiber Poly-2-Vinyl Pyridine
Hydrochloric Acid Potassium Chloride
Iodine Potassium Perchlorate
Iron Steel
Iron Disulfide Sulfur
Isopropyl Alcohol Sulfur Dioxide
Lead Teflon
Lead Iodide Tetraphenyl Boron
Lithium Thionyl Chloride
Lithium Bromide Titanium Disulfide
Lithium Chloride Vanadium Pentoxide
Lithium Fluoborate Zirconium
Pollutants reported to be present include lead, chromium and cadmium.
In addition, asbestos, iron, lithium, sodium sulfite and suspended
solids may be anticipated in waste streams from specific operations.
Cadmium results from electroplating cell uses and is therefore not
attributable to operations included for regulation under this subcate-
gory. Chromium and asbestos originate in the manufacture of thermal
activators for high temperature military batteries as discussed for
calcium anode cells. Wastewater treatment and control practices at
these plants are limited to settling and pH adjustment.
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Magnesium Subcateqory
The magnesium subcategory encompasses the manufacture of magnesium-
carbon batteries, magnesium-vanadium pentoxide thermal cells, ammonia
activated magnesium anode cells, and several different types of
magnesium reserve cells using metal chloride cathodes. These cell
types are manufactured at eight plants with total annual production
amounting to 1220 metric tons (1340 tons). Annual production at
individual plants range from 0.4 metric tons (0.5 tons) to 570 metric
tons (630 tons) of magnesium anode batteries. Over 85 percent of all
magnesium anode batteries produced are magnesium carbon cells. Total
employment for this subcategory is estimated to be 350.
A wide variety of raw materials are used in the manufacture of
magnesium anode batteries due to the diversity of cell types
manufactured. While the anode is magnesium in every case, principal
raw materials used in cathode manufacture include manganese dioxide,
barium chromate, lithium chromate, magnesium hydroxide and carbon for
magnesium-carbon batteries; vanadium pentoxide for thermal batteries;
copper chloride, lead chloride, silver, or silver chloride for
magnesium reserve cells, and m-dinitrobenzene for ammonia activated
cells. Electrolyte raw materials for these cells include magnesium
perchlorate, magnesium bromide and ammonia. Separators are most often
reported to be cotton or paper.
As for raw materials, product and process differences among plants in
this subcategory result in significant variability in wastewater flow
rates and characteristics. The production of process wastewater is
reported by four of the eight plants active in this subcategory.
Processes reported to yield process wastewater include alkaline and
acid cleaning and chromating of magnesium anodes (which is not
considered as battery process wastewater), chemical reduction and
electrolytic oxidation processes in the production of silver chloride
cathodes, fume scrubbers, battery testing, separator processing, and
activator manufacture for thermal batteries. Process wastewater from
only one of these sources was reported by two plants. All other waste
streams were indicated by only one manufacturer of magnesium anode
batteries. This diversity among plants in sources of wastewater is
reflected in discharge flow rates which range from 0 to 5200 1/hr
(1370 gal/hr) or when normalized based on the weight of cells
produced, from 0 to 1,160 I/kg (139 gal/lb). The average discharge
flow rate from plants in this subcategory is 670 1/hr (180 gal/hr)
equivalent to 8.8 I/kg (1.05 gal/lb) of magnesium anode batteries
produced.
Significant pollutants in wastewater streams resulting from magnesium
anode battery manufacture include hexavalent chromium, silver, lead,
fluorides, oil and grease, ammonia and suspended solids. Treatment
practices presently applied to these wastes include chemical chromium
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reduction, pH adjustment, filtration, and settling. Three plants
utilize pH adjustment of these wastes and two provide solids removal
in settling tanks. Filtration and chromium reduction are each
practiced by only one plant.
Zinc Subcateqory
Zinc anode alkaline electrolyte batteries are presently manufactured
using six different cathode reactants: manganese dioxide, mercuric
oxide, nickel hydroxide, monovalent and divalent oxides of silver, and
atmospheric oxygen. A wide range of cell size, electrical capacities
and configurations are manufactured, and both primary and secondary
(rechargeable) batteries are produced within this subcategory. The
manufacture of zinc-anode alkaline electrolyte batteries is increasing
as new battery designs and applications are developed. These products
presently find use in widely varying applications including toys and
calculators, flashlights, satellites and railroad signals. In the
future, zinc -anode batteries may provide motive power for automobiles.
In 1976, seventeen plants produced approximately 23,000 metric tons
(25,000 tons) of batteries in this subcategory. Individual plant
production of zinc anode alkaline electrolyte batteries ranged from
0.36 metric tons (0.40 tons) to 7,000 metric tons (7,700 tons).
Of the sixteen plants currently producing batteries, five manufacture
more than one type of battery within this subcategory. Employment for
this subcategory is estimated to be 4680.
Raw materials used in producing these batteries include zinc, zinc
oxide, mercury, manganese dioxide, carbon, silver, silver oxide,
silver peroxide, mercuric oxide, nickel and nickel compounds, cadmium
oxide, potassium hydroxide, sodium hydroxide, steel and paper. Zinc
is obtained either as a powder or as cast electrodes depending on the
type of cell being produced. Process raw materials at specific plants
vary significantly depending on both the products produced and the
production processes employed. Zinc and zinc oxide are both used to
produce zinc anodes. Mercury is used both to produce mercuric oxide
cell cathode material and to amalgamate zinc anodes to limit cell
corrosion and self discharge. Manganese dioxide is blended with
carbon to form cathodes for alkaline manganese cells and is also
included in cathode mixes for some mercury and silver oxide batteries.
Silver is used in the form of wire screen as a support grid for cell
electrodes, and in the form of powder for the production of silver
oxide cathode materials. Silver oxide is used in the
production of both silver oxide and silver peroxide cell cathodes,
and silver peroxide is also obtained directly for use in silver
oxide cell cathodes. Nickel and nickel compounds are used in
producing cathodes for nickel-zinc batteries identical to those used
in some nickel-cadmium batteries. Potassium and sodium hydroxide are
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used in cell electrolytes which may also include zinc oxide and
mercuric oxide, and also as reagents in various process steps. Steel
is used in cell cases, and paper and plastics in cell separators and
insulating components.
Process water use and wastewater generation is highly variable among
the products and manufacturing processes included in this subcategory.
In general terms, major points of water use and discharge include zinc
anode amalgamation, electrodeposition of electrode reactive materials,
oxidation and reduction of electrode materials, nickel cathode
impregnation and formation, cell wash, equipment cleaning, sinks and
showers, and floor wash. Only some of these uses and discharge
sources are encountered at each plant, and their relative significance
varies.
The total volume of process wastewater produced varies from 4 1/hr (1
gal/hr) to 26,000 1/hr (7,000 gal/hr) and averages 4,300 1/hr (1,100
gal/hr). In terms of the weight of cells produced, this corresponds
to a maximum flow of 400 I/kg (48 gal/lb) and an average flow per unit
of product of 3.8 I/kg (0.46 gal/lb).
The pollutants found in waste streams from plants producing batteries
in this subcategory are primarily metals. Zinc and mercury are
encountered in most wastewater streams. Silver, mercury, and nickel
are found in waste streams resulting from the manufacture of specific
cell types, and hexavalent chromium is found in some waste streams as
a result of the use of chromates in cell wash operations. Wastewater
discharges in this subcategory are predominantly alkaline, and may
contain significant concentrations of suspended solids. Oil and
grease and organic pollutants are also encountered. Wastewater
treatment provided is also variable, but commonly includes solids
removal by settling or filtration (eleven plants). Sulfide
precipitation is practiced at two sites, oil skimming at one, and ion
exchange at one facility. Several plants employ amalgamation with
zinc for the removal of mercury from process waste streams from this
subcategory. Most treatment is provided as pretreatment for discharge
to POTW since twelve plants discharge to municipal sewers.
INDUSTRY OUTLOOK
The pattern of strong growth and rapid change which has characterized
the battery industry during the past decade may be expected to
continue in the future. A number of technological changes which have
occured 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
44
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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 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 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 is 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 is 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 rapid growth within 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 to another is more likely than plant
closings where demand for specific battery types is not strong.
45
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* MOLTtN SALT *r CCIUMIC
O MUCOUS
• ORGANIC
• MOLTEN MLT •>« MUCOUS
tO 40 «0 K) OO
EQUIVALENT WEIOKT.
COO 300 400
FIGURE III-l
THEORETICAL SPECIFIC ENERGY AS A .FUNCTION
OF EQUIVALENT WEIGHT AND CELL VOLTAGE
FOR VARIOUS ELECTROLYTIC COUPLES
46
-------
K>00
SPECIFIC ENERGY, W-hr/Kg
10 100 1000
- 1000
i—m
COMBUSTION
ENGINES I
HEAVY
DUTY
LECLANCHE
ORGANIC
ELECTROLYTE
CELLS ~
LOW-DRAIN
_ LECLANCHE
ft
I it'
O.I
- 0.4
• - - I I .,J—* ___'. '.'*•--*•• M_* J ' ' F I... ' *
2 4 6 10 20 4060 100 200 400 IOOO
SPEQRC ENERGY WATT HOURS/UB
FIGURE III-2
PERFORMANCE CAPABILITY OF VARIOUS BATTERY SYSTEMS
47
-------
Ttrminol
Baffle
Negative Plate —
Stparator --
Poiitivt Platt -
Cell Jar
Vent
Terminal Comb
Plate Tabs 6 — 9
Inches
r-Electrolyte
Plate Pack
FIGURE III-3
CUTAWAY VIEW OF AN IMPREGNATED SINTERED
PLATE NICKEL-CADMIUM CELL
(Similar In Physical Structure To Some
Silver Oxide-Zinc And Nickel-Zinc Cells)
48
-------
Nickel-pined
tteei cover
Polyethylene
insulator ~
Nickel-pi»te<1
ste*i case
Separator
Nickel negative
contact lug
FIGURE III-4
CUTAWAY VIEW OF A CYLINDRICAL
NICKEL-CADMIUM BATTERY
(Similar In Physical Structure To
Cylindrical Lead Acid Batteries)
49
-------
Inter-eel)
Connector
Cover
Positive
Strep
Positive
Plate
Container
Vent Plug
POM
FIGURE 3-5
CUTAWAY VIEW OF LEAD ACID STORAGE BATTERY
(Without electrolyte)
50
-------
MITAl CAP
IXPANSION SPAM
XINC CAN
(4NODC)
1IPARATOR
MIIAL IOTTOM
•OffOM INSUIATOI
MITAl COVIR
INSULATING WASHIR
tUR HAL
CARION ItlCTROOl
MAN6ANCCC
1-9
Inches
M»*
COMP1ITI Clll
FIGURE III-6
CUTAWAY VIEW OF A LECLANCHE CELL
(Similar In Physical Structure To Carbon-Zir.c-Air
And Silver Chloride-Zinc Dry Cells)
51
-------
Negative End (-)
Manganese
Dioxide
Zinc
Connector
(Conductive sheet)
Thickness, 1/4 Inch
Steel Covered With Conductive
Plastic Bearing A Patch
Of Zinc On The Underside
(Steel wraps around
steel at other end)
Duplexes
(Conductive Plastic-
Upper Side Manganese
Dioxide, Lower Side Zinc)
Separator Containing
Electrolyte
Adhesive Around Edge
Of Separator
Manganese Dioxide On
Conductive Plastic On Steel
Positive End ( + )
Completed Battery
Assembled On Card
With Contact Holes
FIGURE III-7
EXPLODED VIEW OF A FLAT LECLANCHE
BATTERY USED IN FILM PACK
52
-------
*
• t
l(
r;
fi
a
ri
i!
J
i
Ji
POLYESTER
JACKET
CATHODE CURRENT
COLLECTOR
ANODE CURRENT
COLLECTOR
DEPOLARIZER
LITHIUM ANODE
FLUOROCARBON
PLASTIC JACKET
PLASTIC LA YCRS SEPARA TE
DEPOLARIZER FROM CASE
LITHIUM ENVELOPE A\D
FLUOROCARBO\ PLASTIC IACKET
SEPARA TE DEPOLARIZER FROM CASE
FIGURE III-8
CUTAWAY VIEW OF TWO SOLID ELECTROLYTE
LITHIUM CELL CONFIGURATIONS
53
-------
TOP CAP
DRIVE DISK
ACTIVATOR
CUP
OUTER
CASE
BATTERY
ASSEMBLAGE
B-C SECTION
TERMINAL PLATE
CAS GENERATOR
LANCE
fLEC.TROl.YTl
RESERVOIR
BULKHEAD
3
Inches
QUAD RING
A SECTION
Example Shown For Liquid-Ammonia-Activated Magnesium Reserve Battery:
Cathode
Anode
Electrolyte
- carbon depolarized meta-dinitrobenzene
- magnesium
- dry ammonium thiocyanate activated by liquid ammonia
FIGURE III-9
CUTAWAY VIEW OF A RESERVE TYPE BATTERY
("A" SECTION AND "B-C" SECTION CONTAIN ANODE AND CATHODE)
54
-------
Filler
Tube Cap
Filler Tube
For Water
Cast Caustic
Sticks
Cylindrical
Zinc Anode
Carbon Cathode
Mixture Of
Pelleted Lime
And Granular
Caustic Soda
FIGURE 111-10
CUTAWAY VIEW OF A CARBON-ZINC-AIR CELL
55
-------
1/4-3
Inches
COVER {+)
CAN
CATHODE
ANODE AND ELECTROLYTE
H-JS$L-- SEPARATOR (INSIDE)
METAL JACKET
INSULATING TUBE
CURRENT? COLLECTOR
SEAL
- INSULATOR
SSSa-jT^
IT Y\J- INNER METAL BOTTOM
1 \\- PRESSURE SPRING
1 C
CUTER METAL BOTTOM (-)
i RIVET
FIGURE III-ll
CUTAWAY VIEW OF AN ALKALINE-MANGANESE BATTERY
(Similar In Physical Structure To
Cylindrical Mercury-Zinc Batteries)
56
-------
Cell Con
1/8-1/2 Inches
Scpecaler
Gatio
4nod.
Calfcod.
FIGURE 111-12
CUTAWAY VIEW OF A MERCURY (RUBEN) CELL
(Similar In Physical Structure
To Alkaline-Manganese And
Silver Oxide-Zinc Button Cells)
57
-------
POSITIVE PLATE PROCESS
NICKEL
POWDER
NICKEL
STRIP
SINTERED
STR IP
RAW .
MATER IALS '
IMPREGNATION
BRUSH
FORMATION
SEPARATOR .
POTASSIUM HYDROXIDE
SODIUM HYDROXIDE
WATER ~~
METAL
SCREEN
RAW
IALS
ASSEMBLY
ELECTROLYTE
ADDITION
NEGATIVE
PLATE
PROCESS
NICKEL PLATED
STEEL CASE
TEST
PRODUCT
FIGURE 111-13
MAJOR PRODUCTION OPERATIONS IN
NICKEL-CADMIUM BATTERY MANUFACTURE
58
-------
LEAD-
LEAD OXIDE
SULFUR 1C
ACID
LKADV OXIDE
PRODUCTION
PIG LEAD
PASTING
MACHINE
WITH DRYER
SEPARATORS-
BATTERY CASE
flk COVER
STORAGE
OR CURE
OF PLATES
STACKER
WELD
ASSEMBLED
ELEMENTS
ASSEMBLY
BURN
POST
ACID
FILL
PRODUCT
FIGURE 111-14
SIMPLIFIED DIAGRAM OF MAJOR PRODUCTION OPERATIONS IN
LEAD ACID BATTERY MANUFACTURE
59
-------
~1
WATtR, STARCH.
| ZINC CHLORIDE. _
MERCU«OUf. CHLORIDE,
I AMMONIUM CHLORIDE
t_ _ _ __ _ _ —
PASTr
MAKE-UP
ADD IT ION
OF PASTE
ZINC CANE
DEPOLARIZE R •
(MANGANESE DIOXIDE
4 CARBON BLACKl
ELECTROLYTE
(AMMONIUM CHLORIDE »
ZINC CHLORIDE + W.ATER)
. CAR BON ROD
PAM* UNtO
— Z INC CANS
SUF PORT
WASHER ADDED
PASTE
SETT ING
_ -i- jH- J
CELL
SEALED
CR IMP
TEST AND
F INISH
AGE AND
TEST
ALTERNATE PRODUCTION STEPS
PRODUCT
FIGURE 3-15
MAJOR PRODUCTION OPERATIONS IN LECLANCHE
DRY BATTERY MANUFACTURE
60
-------
IODINE•
POLY—2— VINYL-PYR ID INE-
MIX
ELECTROLYTE
LITHIUM '
DECREASE
ANODE
CELL CASE,
CONTACTS,
SEALS
ASSEMBLE
TEST
I
PRODUCT
FIGURE III-]6
MAJOR PRODUCTION OPERATIONS IN
LITHIUM-IODINE BATTERY MANUFACTURE
61
-------
CARBON -
DEIONIZED-
WATER
SLURRY
PREPARATION
MAGNESIUM
STRIP
DRY
PUNCH
PUNCH
CATHODE
ANODE
ASSEMBLY
— AMMONIA
AMMONIUM-
THIOCYANATE
PRODUCT
FIGURE 111-17
MAJOR PRODUCTION OPERATIONS IN AMMONIA -
ACTIVATED MAGNESIUM RESERVt CELL MANUFACTURE
62
-------
CONTAINER
LIME.
DRY ELECTROLYTE
PLACED IN
CONTAINER
MANGANE-SE
DIOXIDE *~
GRAPHITE
CHARCOAL
POWDER '
POROUS ACTIVATED
CARBON
ELECTRODE
ELECTRODE
INSERTED
ZINC.
MERCURY.
AMALGAMATED
ZINC ELECTRODE
INSERTED
ZINC
ELECTRODE
SEALED
TEST AND
PACK
PRODUCT
FIGURE Ill-IE
MAJOR PRODUCTION OPERATIONS IN WATER ACTIVATED
CARBON-ZINC-AIR CELL MANUFACTURE
63
-------
BINDER
CARBON Ik
MANGANESE
DIOXIDE:
i
FORMED INTO
CATHODE
POTASSIUM HYDROXIDE,
WATER fll BINDER
CONTAINER
PRODUCED
1
CATHODE
INSERTED
SEPARATOR
INSERTED
ELECTROLYTE
ZINC &
MERCURY
ANODE
ANODE
INSERTED
CURRENT
COLLECTOR
RIVET AND
SEAL INSERTED
CRIMP
PRODUCT-
TEST AND
PACK
COVERS
ATTACHED
PRESSURE
SPRING'
INSERTED
JACKET AND
PAPER
INSULATOR
ATTACHED
PRE
-TEST
CELL
WASH
FIGURE 111-19
MAJOR PRODUCTION OPERATIONS IN ALKALINE
MANGANESE DIOXIDE BATTERY MANUFACTURE
-------
CASE WELDED
MERCURIC
OXIDE
GRAPHITE
MANGANESE
DIOXIDE
CATHODE
CATHODE
PRESSED
INTO CASE
INSULATORS
ADDED
SODIUM
HYDROXIDE-
WATER .
ELECTROLYTE
PREPARED
ELECTROLYTE
ADDED
ZINC
MERCURY-
AMALGAM
ZINC ANODE
ANODE ADDED
TEST
TOP AND
GASKET ADDED
CELL CRIMPED
AND WASHED
STORAGE
TEST AND
PACK
PRODUCT
FIGURE 111-20
SIMPLIFIED DIAGRAM OF MAJOR OPERATIONS
IN MERCURY (RUBEN) BATTERY MANUFACTURE
65
-------
CM
FIGURE 111-21
FROM U.S. OEPT. OF COMMERCE DATA
1977 CENSUS OF MANUFACTURERS
VALUE OF BATTERY PRODUCT SHIPMENTS 1963-1977
-------
FIGURE II1-22
BATTERY MANUFACTURING CATEGORY SUMMARY
Subcategory
Cadmium
Calcium
Lead
Leclanche
Lithium
Magneslun
Batteries Number of
Manufactured Plants
Nickel-Cadmium
Silver Oxide-Zinc
Mercury Cadmium
Thermal
Lead Acid
Lead Acid
Reserve
Carbon Zinc
Carbon Zinc,
Air Depolarized
Silver Chloride-Zinc
Lithium
Thermal
Magnesium Carbon
10
3
184
19
7
8
Estimated
Total Annual Production
metric tons (tons)
5,250
<23
1.300,000
108,000
<23
1,220
(5,790)
«25)
(1,430,000)
(119.000)
«25)
(1,340)
Estimated
Total Number
of Employees
2.500
240
18.745
4,200
400
350
Dischargers
Direct POTW Both Zero Unknown
2 4
2
15 99
0 7
1 4
1 3
1
0
0
0
0
3
1
50 20
12
2
4
Zinc
Magnesium Reserve
Thermal
Alkaline Manganese
Silver Oxide-Zinc
Mercury Zinc
Carbon Zinc-Air
Depolarized
Nickel Zinc
16
23,000 (25,000)
4.680
2 12 02
Estimated Total Process
Process Mastewater Flow
1/yr ( gal/yr )
6.9xl08 (l.BxlO8)
1.3xl05 (3.4xl04)
7.2xl09 (I.9xl09)
l.SxlO7 (3.9xl06)
4.9xl05 (l.3x!05)
l.ZxlO7 (3.2xl06)
6.U107 (I.6xl06)
-------
Ol
00
n
h
z
<
j
k
o
u
CD
S
D
Z
20
10
5Z
PRODUCTION (METRIC TONS X 10S)
FIGURE 111-23
DISTRIBUTION OF LEAD SUBCATEGORY
PRODUCTION RATES
-------
CTv
n
f-
z
0
u
o
2
3
Z
too
200
300
400
500
600
700
NUMBER OF EMPLOYEES
FIGURE 111-24
DISTRIBUTION OF EMPLOYMENT AT LEAD
SUBCATEGORY MANUFACTURING FACILITIES
-------
SECTION IV
INDUSTRY SUBCATEGORIZATION
Subcategorization should take into account pertinent industry
characteristics, manufacturing process variations, water use,
wastewater characteristics, and other factors which do or could compel
a specific grouping of segments of industry 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 which 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 components and raw
materials produced on-site at some facilities or purchased at others.
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 characteristics is discussed in the ensuing paragraphs
after which the process leading to selection of the anode
subcategorization is described.
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
11. Number of Employees
12. Total Energy Requirements (Manufacturing Process
and Waste Treatment and Control)
71
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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 subcategorization.
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 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 in a single facility 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 an
intractable number of subcategories, battery type was not found to be
an acceptable 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 wastewater sources 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 combinations. 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 which result in
significant differences in waste water generation are reflected in the
manufacturing process elements for which specific discharge allowances
were developed within each subcategory.
Water Use - Water usage alone is not a comprehensive enough factor
upon which to subcategorize. While water use is a key element in the
limitations established, it does not inherently relate to the source
or the type and quantity of the waste. Water usage must be related to
the manufacturing process utilizing the water since it effects the
water usage and cannot be used alone as an effective categorization
base.
72
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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. It does not affect the raw wastewater
characteristics. Likewise, the effluent discharge destination does
not affect the raw wastewater characteristics or treatability.
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 waste characteristics as well as wastewater characteristics are
a function of the specific battery type and manufacturing process.
Furthermore, solid waste disposal techniques may be identical for a
wide variety of solid wastes and 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 of a
plant per unit of production are essentially the same for plants of
all sizes that have similar processing sequences. However, the size
of a facility determines the production capacity of a plant. 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 since the wastewater characteristics of
plants are also dependent on the type of processes performed as
determined by the battery type manufactured.
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 grouping battery manufacturing into
subcategories because it does not take into consideration the
significant parameters which affect the raw wastewater
characteristics. In addition, a categorization based on age would
have to distinguish between old plants with old equipment, old plants
with new equipment, new plants with old equipment, and every possible
combination thereof. Since plants in this industry modernize and
replace equipment relatively frequently, changes of subcategory would
often result from this approach to make subcategorization infeasible.
Number of Employees - The number of employees in a plant does not
directly provide a basis for subcategorization since the number of
employees does not reflect either production processes used or the
73
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production or water usage rate at any plant. Plants producing most
battery types varied over a wide range in terms of number of
production employees. The volume and characteristics of process
wastewater was not found to 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 obtian reliable energy
estimates specifically for production and waste treatment. When
available, estimates are likely to include other energy requirements
such as lighting, process, air conditioning, and heating or cooling
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 prime cause of wastewater
generation in the battery manufacturing category, and therefore, not
acceptable as an overall categorization factor.
Unique Plant Characteristics - Unique plant 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 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. It 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
facilities which have access to plentiful water supplies and
constitute a basis for effluent control rather than for
subcategorization. Waste treatment procedures can be utilized in any
geographical location.
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.
74
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Subcateqorization Development
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. It 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 facilities. 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's
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. The initial battery types
considered and additional battery types identified have been presented
in Section III.
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 two hundred. It was also found that 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
facilities 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 facilities 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
75
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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 facilities 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.
Subcategorization of the battery category was re-evaluated and
redefined in the 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 managable
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 facilities
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
76
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producing zinc anode cells with alkaline electrolytes and Leclanche
cells necessitated further subcategorization based on cell
electrolyte. Subcategorization on these bases yielded eight
subcategories: cadmium, calcium, lead, Leclanche, lithium, magnesium,
nuclear, and zinc.
These subcategories preserve most recognized battery types within a
single subcategory and greatly reduce the extent of 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 by this approach to
subcategorization 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 sub-
categorization. In most cases where process operations are common to
multiple battery types, they 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
facilities show similarity.
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, ancillary) there
are numerous manufacturing processes or production functions. These
processes or functions generate or 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
89). 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, which will be 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
77
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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.
Elements are combined or can be combined in various ways at specific
facilities. At the element level, flows and pollutant characteristics
can be related to production. Wastewater treatment however can be
related to the specific subcategory which is considered the level of
regulation. The detailed information which led to the adoption of the
above subcategorization approach is presented in the discussion of
process wastewater sources and characteristics in Section V of this
document.
FINAL SUBCATEGORIES AND PRODUCTION NORMALIZING PARAMETERS
The final approach to subcategorization based on anode reactant
material and electrolyte composition yielded eight subcategories:
Cadmium . Lithium
Calcium . Magnesium
Lead . Nuclear
Leclanche . Zinc
Specific elements within each subcategory and corresponding production
normalizing parameters are summarized in Table IV-1 (Pages 90-91.).
Selection of each production normalizing parameter is discussed within
each subcategory discussion.
Cadmium Subcategory
This subcategory encompasses the manufacture of all batteries in which
cadmium is the reactive anode material. Cadmium anodes for these
cells are manufactured by three distinct processes and combined with
either nickel, silver, or mercury cathodes. Nickel cathodes are
produced by three different techniques, and silver and mercury
cathodes by one each. In addition, eight ancillary process operations
producing wastewater discharges were identified at plants in this
subcategory. These process variations are all studied as individual
elements for discharge limitations under this subcategory.
Consideration of the characteristics of each of the process elements
discussed above results in the selection of production normalizing
parameters. It was necessary to select specific production
normalizing parameters for each process element because production
activity areas in different elements was not found to be reliably
related on a day-to-day basis at some facilities. The selected
78
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parameters, cadmium in the anode, active metal in the cathode, and
total cell weight for ancillary operations (except for chemical powder
production which is weight of metal in the powder produced or weight
of metal used) correspond with the available production data and water
use in the process operations addressed.
Use of active metal (cadmium, nickel, mercury or silver) as the
production normalizing parameter for anode and cathode production
operations reflects the fact that water use and discharge in these
operations can be associated almost exclusively with the deposition,
cleaning and formation (charging) of the active material. Similarly,
the weight of metal in the chemical powder used or produced (cadmium,
nickel, and silver) is the logical production normalizing parameter in
considering discharges from chemical powder production. Other
ancillary operations generally produce smaller volumes of process
wastewater which are related to the total cell assembly or the overall
level of production activity. The total weight of cadmium anode
batteries produced was found to be the best production normalizing
parameter for these discharges which could be readily derived from
data available from most plants. The use of water in washing cells
should correlate most closely with the cell surface area. Surface
area data were not available, however, and total product weight was
the best available approximation to it.
Alternatives to the production normalizing parameters discussed above
were evaluated and include:
1. the use of battery weight for all operations
2. electrode surface area
3. total electrode weight
4. battery electrical capacity
5. number of employees
Total battery weight was found to be readily available from most
manufacturers, and was initially considered a logical choice for the
production normalizing parameter for these plants. This parameter
would have allowed the use of a single parameter for all waste sources
in a plant, potentially simplifying the application and enforcement of
effluent limitations. Following plant visits, it became evident,
however, that production patterns at some facilities would render this
production normalizing parameters inapplicable, and that production
variations resulted in significant variability between production
activity in the major wastewater producing operations and the weight
of batteries ultimately shipped. Some plants were identified which
produced cell electrodes but did not produce finished batteries, and
79
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i
others indicated the production of finished batteries from electrodes
processed at other locations. For such facilities the battery weight
production normalizing parameter is clearly inapplicable to the
determination of wastewater discharges from electrode manufacturing
operations. Batteries are produced in this subcategory for a wide
range of applications and in many different configurations. As a
result, the ratio of battery weight to the weight of reactive
materials contained by the battery varies significantly. Since the
most significant water use and discharge is associated with the
reactive materials, the use of battery weight as a production
normalizing parameter for all operations would result in non-uniform
application of effluent limitations and standards to plants in this
subcategory.
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 these operations. Significant difficulty is encountered in
defining the surface area, however, and data were not 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 areas were not chosen as the
production normalizing parameters for these operations.
Total electrode weights were found to be less desirable than active
material weights because the use of process water is involved pri-
marily with the active materials. Since most electrodes produced in
this subcategory include non-reactive support and current collecting
structures which account for varying fractions of the total electrode
weight, the relationship between electrode weight and wastewater
volume is less consistent than that between wastewater and the weight
of reactive materials in the electrode.
Battery electrical capacity should, in concept, correspond well with
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 materials is the major source
of process wastewater for most cell types. It was not, however,
considered a viable production normalizing parameter for use in this
study because electrical capacity data were not obtained.
Because 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. While the number of employees would be a suitable basis
80
-------
for limiting discharges from employee showers and hand washes, battery
weight was chosen instead to achieve uniformity with other ancillary
wastewater sources and minimize the number of production normalizing
parameters to be applied.
Calcium Subcateqory
Batteries included in this subcategory use calcium as the reactive
anode material. At present, only thermal batteries, in which a fused
mixture of potassium chloride and lithium chloride serves as the
electrolyte and calcium chromate as the cathode depolarizer, are
produced in this subcategory. While many different configurations of
these batteries are manufactured, most production can be accomplished
without the use of process water. Significant elements in this
subcategory include anode manufacture (vapor-deposited or fabricated
calcium), cathode production (calcium chromate), and one ancillary
element for the manufacture of reactive material used to heat the cell
to its operating temperature upon activation (heating component
production).
The production normalizing parameter selected for the thermal cell
activator is the combined weight of reactive materials used in
production of the heating component (usually barium chromate and
zirconium). The selection of a production normalizing parameter
specific to heating component production is necessary because the
amount of activator material contained in thermal cells-is highly
variable; hence total battery production weight is not meaningfully
related to wastewater generation and discharge. The production
normalizing parameter selected for the anode manufacture is weight of
calcium used, and for the cathode is weight of reactive cathode
material in the cells.
Lead Subcategory
Two basic electrochemical systems are included in this subcategory:
lead acid reserve or lead; and lead-acid storage or lead-lead
peroxide. As discussed in Section V for the manufacture of lead acid
reserve cells, lead electroplated on a steel carrier is produced,
which is not considered part of battery manufacturing. Lead acid
storage batteries all 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
81
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Leady Oxide Production
Purchased oxide
On site production
Ball Mill process
Barton process
Plate Grids
Antimonial alloy (cast)
Pure lead (cast, punched, or rolled)
Calcium alloy (cast, punched, or rolled)
Plate Curing
With steam
Without steam
Plate Formation (Charging)
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
Electrolyte
Immobilized
Liquid
Case
Sealed
Vented
Battery Wash
None
With water only
With detergent
82
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Configuration
Cylindrical
Rectangular
Separators
Rubber
Paper-Phenolic
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. 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 batteries produced was chosen as the
production normalizing parameter for all process elements for which
discharge allowances are provided in this subcategory. As discussed
for the cadmium subcategory, total battery weight, electrode surface
area, total electrode weights, battery electrical capacity, 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 reproducible basis for effluent
limitations and standards. Factors which led to the rejection of
electrode surface area, battery electrical capacity, and number of
employees as production normalizing parameters for the lead
subcategory are the same as those discussed for the cadmium
subcategory.
Leclanche Subcategory
The Leclanche dry cell uses an amalgamated zinc anode, a carbon
cathode with manganese dioxide depolarizer, and ammonium chloride and
zinc chloride electrolyte. Batteries manufactured in this subcategory
use zinc anodes and acid chloride electrolytes. Most also use
83
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manganese dioxide as the cell depolarizer although cells using
atmospheric oxygen and silver chloride depolarizers are also included
in this subcategory. All of these cells are produced in manufacturing
processes in which water use is limited, and the volume of process
wastewater produced is small.
Significant product and process variations within the subcategory
include:
Anode Structure
Sheet Zinc - stamped
Sheet zinc formed as cell container
Sheet Zinc - Fabricated
Powdered zinc deposited on substrate
Cathode Material
Manganese-dioxide and carbon
Silver chloride
Cell Separator
Paste
Cooked
Uncooked
Pasted Paper
With Mercury
Without Mercury
Amalgamation
Mercury in electrolyte
Mercury in separator
The most significant elements in this subcategory include the
separator processes. Pasted paper can be manufactured at the battery
facility or purchased. Paper which contains mercury in the paste is
included under battery manufacturing. The production normalizing
parameter for this operation is the weight of dry paste material,
which can easily be related to this process. For cooked paste and
uncooked paste separators, the weight of cells produced is the
selected production normalizing parameter which can be related to
these processes. Cell weight was supplied by most plants. Weight
of cells produced can also be related to all other process operations
in this subcategory such as zinc powder production, cathode
production, and equipment and area cleanup operations. The
production of stamped, drawn or fabricated zinc anodes is not
considered under battery manufacturing.
Alternative production normalizing parameters including electrode
surface area, separator paper consumption and electrode raw materials
were also considered. Electrode surface areas could be readily
84
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determined for those anodes prepared from sheet zinc, but do not
correspond to the production activities which might result in battery
manufacturing process wastewater. As discussed for other
subcategories, surface areas are not readily determined for cell
cathodes and for anodes prepared using powdered zinc. In addition,
there is little evident relationship between process water use and
electrode surface area in this subcategory. The consumption of
separator paper is a conceivable basis for the limitation of dis-
charges from pasted paper separator production, or from the manu-
facture of cells containing pasted paper separators. It is subject to
variability, however, due to the varying amounts of paste applied, and
also does not apply to batteries manufactured with other separators.
Electrode materials are frequently used as structural parts of
Leclanche cells and the weight of zinc used is not necessarily
stoichiometrically related to the other battery reactants or to water
use in process steps.
Lithium Subcategory
This subcategory encompasses the manufacture of several battery types
in which lithium is the anode reactant. Depolarizers used in these
batteries include iodine, lead iodide, sulfur dioxide, thionyl
chloride, iron disulfide, titanium disulfide, and lithium perchlorate.
Electrolytes used within this subcategory include liquid organic
compounds such as acetonitrile and methyl formate, solid organic
compounds such as poly-2-vinyl pyridine, solid inorganic salts, and
fused inorganic salts (in thermal batteries). None of the cells
reported to be in current manufacture uses an aqueous electrolyte.
Thermal batteries produced with lithium anodes include heat generation
component production which was discussed under the calcium
subcategory.
Anode production for this subcategory includes formed and stamped
lithium metal. This operation is considered unique to battery
manufacturing. Process wastewater might result from air scrubbers and
therefore the weight of lithium is selected as the production
normalizing parameter. For those processes associated with cathode
production operations (including addition of the depolarizer to the
cell electrolyte), the weight of cathode reactant in the cells has
been chosen as the production normalizing parameter. This information
was available from plants manufacturing these batteries, and is
directly related to the production activities for which limitations
and standards can be developed. For ancillary operations, two
distinct production normalizing parameters are chosen. As discussed
for calcium anode battery manufacture, the production normalizing
parameter for discharges from heating component manufacture is the
total weight of heating component reactive materials. For all other
ancillary operations, the production normalizing parameter is the
weight of cells produced. These operations are either directly
85
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involved with the complete cell assembly (testing and cell wash) or
with a process by product (lithium scrap disposal). For those
operations related to the total cell assembly, the total weight of
batteries produced is a sound basis for predicting water use and
discharge.
Magnesium Subcategory
This subcategory, addressing cells with magnesium anodes, include
magnesium-carbon batteries in which the depolarizer is manganese
dioxide, magnesium anode thermal batteries in which the depolarizer is
vanadium pentoxide, magnesium reserve cells using copper chloride,
silver chloride, or lead chloride depolarizers, and ammonia activated
cells in which meta-dinitrobenzene serves as the depolarizer. Cell
electrolytes include aqueous solutions of magnesium perchlorate, or
magnesium bromide, sea water (added to reserve cells at the time of
activation), fused mixtures of potassium chloride and lithium
chloride, and ammonium thiocyanate (dissolved in ammonia to activate
ammonia activated cells). Magnesium anodes for many of these cells
are protected from corrosion during storage by chromate coatings which
may be on the magnesium when it is obtained by the battery plant or
may be applied at the battery manufacturing site.
Production normalizing parameters were selected on the same general
basis as discussed for other subcategories. Magnesium anode
production which includes sheet magnesium that is stamped, formed or
fabricated and magnesium powder related processes are not included
under battery manufacturing. Depolarizer weight is the production
normalizing parameter for depolarizer production. Heating component
production is limited on the basis of the weight of reactants as
discussed previously for the calcium anode subcategory, and the weight
of batteries produced is selected as the production normalizing
parameter for cell testing and cell separator processing operations,
floor area maintenance, and assembly area air scrubbers.
Nuclear Subcategory
Commercial nuclear batteries were produced primarily for use in heart
pacemakers. Production of these batteries has ceased with the
increase in production of lithium batteries. Although wastewater was
generated by the manufacture of nuclear batteries, the subcategory
will not be further defined, and production normalizing parameters
will not be examined until production again resumes.
Zinc Subcategory
Batteries produced in this subcategory have an amalgamated zinc anode
and a sodium or potassium hydroxide electrolyte. Cells using ten
different depolarizer combinations are presently produced within the
86
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subcategory in a wide variety of cell configurations and sizes. Zinc
anodes for these cells are produced in seven distinct processes, but
anodes produced by each process are typically combined with several
different types of cathodes, and anodes produced by two or more
different processes are commonly used with a given depolarizer.
The weight of reactive material contained in the electrode was found
to be the best production normalizing parameter for anode and cathode
manufacturing processes. For most ancillary operations, which are
usually associated with cell assemblies or with general plant pro-
duction activity, the production normalizing parameter is the total
weight of batteries produced. For one ancillary operation, the et-
ching of silver foil used as a substrate for zinc anodes, the weight
of silver foil used for etching is chosen as the production
normalizing parameter. The use of this parameter rather than total
battery weight is necessary because not all batteries at any given
plant are produced using etched foil. The volume of wastewater from
this operation will therefore not be directly related to the total
product weight. For silver powder production, the weight of silver
powder produced is used as the production normalizing parameter, and
for silver peroxide powder production, the weight of silver powder
used is the production normalizing parameter.
Alternatives to the selected production normalizing parameters which
were considered include the use of total battery weight for all
operations, electrode surface area, total electrode weight, battery
electrical capacity, and the number of production employees. These
were evaluated and rejected in favor of the selected parameters on the
basis of factors very similar to those discussed for the cadmium anode
subcategory. Electrode manufacturing processes are common to multiple
battery types at several plants in this subcategory, with the fraction
of total cell weight comprising active material in each electrode
unique to each cell type. Further, electrode production (or active
material processing) may not be scheduled concurrently with cell
assembly for all products, and may be performed at one facility for
cells assembled at another site. As a result, it is necessary that
discharges from electrode production be limited on the basis of a
parameter unique to the electrode itself, and total product weight is
not a useful discharge limiting factor for these operations.
Electrode surface area was not chosen as the production normalizing
parameter because, as discussed previously, it is not available and
not readily determined. Because some electrodes include non-reactive
materials for support and current collection and others (with the same
reactants) do not, total electrode weights do not correspond as well
to water used in processing active materials as do the weights of
active materials themselves. As discussed previously, total
electrical capacity has potential as a production normalizing
parameter but supporting data is not presently available. The number
87
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of employees does not correlate well with process water use and
discharge.
OPERATIONS COVERED UNDER OTHER CATEGORIES
Many 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 have been
identified in Table IV-2 (Page 9.2) and are discussed with reference to
the lead subcategory and in general for the other subcategories.
Specific operations are discussed in Section V.
Lead Subcategory
Plants producing batteries within the lead subcategory practice a
number of processes included in other industrial categories. Most
facilities 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. Some lead anode battery plants also produce rubber or
plastic battery cases on-site.
The production of lead oxide at battery plants is a unique operation
yielding a "leady oxide" distinct from lead oxide produced under
inorganic chemical production. It is included under the battery
manufacturing category for effluent limitations.
Other Subcategories
Battery manufacturing plants in other subcategories have been observed
to employ a number of manufacturing processes including: metal forming
and shaping, metallurgical plant operations, metal plating, paper
pasting processes (without mercury) and inorganic chemicals
preparation.
These manufacturing operations are not considered as battery
manufacturing operations. Metal forming and shaping operations
including deburring and cleaning are involved in the production of
anodes (which may also serve as the cell container), and various cell
contacts, covers and jackets. Several battery plants report the
preparation of metal alloys or the operation of secondary metals
recovery operations. A number of battery manufacturing processes
involve plating or chromating metals on battery parts or assembled
battery cases. Some facilities paste paper with flour and starch
without using mercury. Inorganic chemicals not specific to battery
manufacturing are often purchased, but may be produced on-site. None
of these operations are addressed in the development of battery
manufacturing effluent limitations and standards.
88
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FIGURE IV-1
SUMMARY OF CATEGORY ANALYSIS
CO
SUBCATEGORY
t t f
L
1
1 ,
I
L
1 | L
Anode Manufacture. 1
Element
4
mm
4
m*
4
•••
k
i
MMMHI
1
|
Element
1
^"2
ft mm
L A
mm
\
\
\
mm
1 I
Cathode Manufacture
Element
4
••»
k 4
<••••
Individual Process
k.
4HM
mmn
Element
. — —
• mm
Element
4
mm
k 4
» m
i 4
mmm
k
i
i
i
i
i
i
1
Ancillary Operations
Element
4
JL.
k
mm- ••
mmmm m
1
1
Element .
1
4
mmmm*
^ A
mm
' 1
1
J
Wastewater Streams ( Subelements )
Regulation
Manufacturing Process
Operations-
Determination of
Flows and Pollutant
Characteristics
Generation of
Wastewater
Pollutants
-------
TABLE W-l
SUBCATEQORY ELEMENTS AND PRODUCTION NORMALIZING PARAMETERS (PNP)
SUBCATEGOKY ELEMENT
Cadmium Anodes
Cathodes
Ancillary
VD
o
Calcium Anodes
Cathodes
Ancillary
Pasted And Pressed Powder
Electrodeposiled
Impregnated
Silver Powder Pressed
Mercuric Oxide Powder
Pressed
Nickel Pasted and Pressed
Powder
Nickel Eleclrodeposited
Nickel Impregnated
Cell Wash
Electrolyte Preparation
Floor and Equipment Wash
Employee Wash
Cadmium Powder Production
Cadmium Hydroxide Production
Nickel Hydroxide Production
Silver Powder Production
Vapor Deposited
Fabricated
Calcium Chromate
Tungstic Oxide
Potassium Dichromate
Heat Generation Component
Production
PNP
Weight of Cadmium
in Anode
Weight of Silver
in Cathode
Weight or Mercury
in Cathode
Weight of Applied
Nickel
Weight of Cell
Produced
Weight of Cadmium
Used
Weight of Nickel
Used
Weight of Silver
Used
Weight of Calcium
Used
Weight of Reactive
Material
Total Weight of
Reactive Materials
8UBCATEOORY
Lead Anodes
and
Cathodes
Ancillary
Leclunche Anodes
Cathodes
Ancillary
ELEMENT
Electroplated Lead
Leady Oxide Production
Paste Preparation and
Application
Curing
Closed Formation
(In Case)
Single Fill
Double Fill
Pill and Dump
Open Formation (Out of
Case)
Dehydrated
Wet
Battery Wash
Floor Wash
Sinks and Shower
Battery Repair
Zinc Powder
Sheet zinc
stamped
drawn
fabricated
Managanese Dioxide-
electrolyte with
mercury
Manganese Dioxide-
electrolyte without
mercury
Manganese Dioxide-
gelled electrolyte
with mercury
Pasted Manganese Dioxide
Carbon
Silver Chloride
Separator
Cooked Paste
Separator
Uncooked Paste
Separator
Pasted Paper with mercury
Separator
Pasted Paper w/o mercury
Equipment and
Area Cleanup
PNP
NA
Total Weight of Lead
Used
Weight of Cells
Produced
NA
Weight of Cells
Produced
Weight of Cells
Produced
Weight of Dry
Pasted Material
NA
Weight of Cells.
Produced
-------
TABLE IV-1
SUBCATECOHY ELEMENTS AND PRODUCTION NORMALIZING PARAMETERS (PNP)
SUBCATEGORV ELEMENT
Lithium Anodes
Cathodes
Ancillary
Magnesium Anodes
vo
i— >
Cathodes
Ancillary
•ormed It Stamped
Sulfur Dioxide
odine
ron Disulfide
.nhium Perchlorale
'itanium Disulfide
'tiionyl Chloride
-ead Iodide
Heat Generation Component
Production
,ithium Scrap Disposal
'esting
Sheet Magnesium
stamped
formed
fabricated
Magnesium Powder
Silver Chloride-
Surface Reduced
Silver Chloride-
Electrolytic
Copper Chloride
Lead Chloride
Vanadium Pentoxide
Carbon
M-Dmitrobenzene
Heat Generation Component
Production
Testing
Separator Processing
Fluor Wash
Scrubbers
PNP iSUBCATEGORY ELEMENT
Weight of Lithium
Weight of Reactive
Material
Weight of Reactive
Materials
Weight of Cells
Produced
NA
Weight of Magnesium
Used
Weight of Depolarizei
Material
Weight of Reactive
Materials
Weight of Cells
Produced
NA- Not Applicable to Battery Manufacturing Category
Line Anodes
Cathodes
Ancillary
Cast or Fabricated
Wet Amalgamated Powder
Gell Amalgam
Dry Amalgamated Powder
Pasted and Pressed Zinc
Oxide Powder
Pasted and Pressed ZincO*«le
Powder, Reduced
Elect rode posited
Porous Carbon
Manganese Dioxide
Carbon
Mercuric Oxide (and
Manganese Dioxide-
Carbon)
Mercuric Oxide-
Cadmium Oxide
Silver Powder Pressed
Silver Powder Pressed
and Elecirolytically
Oxidized
Silver Oxide
Powder Thermally
Reduced or Sintered,
Electrolytically
Formed
Silver Oxide Powder
Silver Peroxide Powder
Nickel Impregnated and
Formed
Cell Wash
Electrolyte Preparation
Mandatory Employee
Wash
Reject Cell Handling
Floor Wash
Equipment Wash
Silver Etch
Silver Peroxide
Production
Silver Powder
Production
PNP
Weight ol Zinc
Used
Weight of Deposited
Zinc
Weight of Carbon
Weight of Manganese
Dioxide
Weight of Mercury
Weight of Mercury
and Cadmium
Weight of Applied
Silver
Weight of Applied
Nickel
Weight of Cells
Produced
Weight of Silver
Used
Weight of Silver
Powder Produced
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TABLE IV-2
OPERATIONS AT BATTERY PLANTS INCLUDED
IN OTHER INDUSTRIAL CATEGORIES
( PARTIAL LISTING)
Lead Alloy Grid Casting and Forming
Plastic and Rubber Battery Case Manufacture
Forming Cell Containers and Components ( Including Zinc and
Magnesium Can Anodes)
Cleaning and Deburring Formed Cell Components
Retorting, Smelting and Alloying Metals
Metal Plating ( Includes Chromating of Zinc and Magnesium Cans )
Inorganic Chemical Production ( Not Specific to Battery Manufacturing )
Pasted Paper Manufacture ( Without Mercury )
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SECTION V
WATER USE AND WASTEWATER CHARACTERIZATION
This section describes the collection, analysis, and characterization
of data which form the basis for effluent limitations and standards
for the battery manufacturing category, and presents the results of
these efforts. Data were collected from a variety of published
sources, from previous studies of battery manufacturing, through data
requests mailed to all known battery manufacturers, and through on-
site data collection and sampling at selected facilities. Data
analysis began with an investigation of the total category, the
manufacturing processes practiced, the raw materials used, the process
water used and the wastewater generated. This led to the
subcategorization and production normalizing parameters selected and
discussed in detail in Section IV. Further analysis included
wastewater sample collection and characterization of the wastewater
streams within each subcategory. Specific discussions of data
analysis and presentation of results for each subcategory follows a
general description of data collection and analysis approach.
DATA COLLECTION AND ANALYSIS
The sources of data used in this study have been discussed in Section
III. Published literature and previous studies of battery
manufacturing provided a basis for initial data collection efforts and
general background for the evaluation of data from specific plants.
Data collection portfolios (dcp's) sent to all battery manufacturing
companies provided the most complete and detailed description of the
category which could be obtained. They were used to develop category
and subcategory data summaries and were the primary basis for the
selection of plants for on-site sampling and data collection. Data
from plant visits provided characterization of raw and treated
wastewater streams within the category and allowed in-depth evaluation
of the impact of product and process variations on wastewater
characteristics and treatability.
Data analysis proceeded concurrently with data collection and provided
guidance for the data collection effort. Initially, a review and
analysis of the available information from published sources and
previous studies was used as the basis for developing the dcp used to
obtain information about battery manufacturing facilities, and as a
preliminary data base structure within which analysis of the completed
dcp's could proceed. This included the definition of preliminary
subcategories within the battery manufacturing category which were
expected to differ significantly in manufacturing processes and
wastewater discharge characteristics, and which consequently should be
represented in on-site data collection and wastewater sampling.
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Specific sites for sampling were selected on the basis of data
obtained in completed dcp's. During one sampling visit for each
subcategory screening samples were obtained which were analyzed for
all priority pollutants and other selected parameters. The results of
these screening analyses together with data obtained in completed
dcp's were evaluated to select significant pollutant parameters for
each subcategory whose presence and concentrations were verified by
analysis in all subsequent wastewater samples.
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, and effluent quality from battery
manufacturers. The dcp was comprised of two segments, the first of
which requested information about manufacturing processes, water use,
wastewater discharge, and waste treatment practices in addition to
analysis results characterizing process wastewater. The second
segment of the dcp requested information specifically pertaining to
the presence of priority pollutants in process wastewater from the
facility. Because many battery manufacturing plants, particularly
lead acid battery manufacturers operate on-site casting facilities, a
dcp addressing casting operations was included with the battery
manufacturing dcp. Process wastewater discharges from casting are not
regulated as part of the battery manufacturing category.
Developed during 1977, the dcp requested data for the year 1976 which
was the last full year for which production information was expected
to be available. Mailing of the dcp, however, was in 1978.
Consequently, a few plants provided information for the years 1977 and
1978 rather than 1976 as requested in the dcp. All of the data
received were used in characterizing the industry.
The dcp's were mailed to all known companies manufacturing batteries
as determined from SIC code listings compiled by Dun and Bradstreet
Inc., membership in battery industry trade associations, listings in
the Thomas Register, and lists of battery manufacturers compiled
during previous EPA studies. These lists, which sometimes included
battery distributors and wholesalers as well as manufacturers, and
also included both corporate headquarters and individual plant
locations, were screened to identify corporate headquarters for
companies which manufacture batteries and to eliminate distributors
and wholesalers. Dcp's were mailed to each corporate headquarters,
and a separate response was requested for each battery manufacturing
plant operated by the corporation. As a result of dcp distribution
and follow-up, responses were received confirming battery manufacture
by 133 companies operating 235 manufacturing facilities, of which
currently there are about 132 companies operating about 230
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facilities. Due to the dynamic nature of battery manufacturing, these
numbers may vary from month to month.
Specific information requested in the dcp's was determined on the
basis of an analysis of data available from published sources and
previous EPA studies of the battery manufacturing category, and
consideration of data requirements for the promulgation of effluent
limitations and standards. Basic data required to identify the
facility and facilitate follow-up contacts included the name and
address of the plant and corporate headquarters, and the names and
telephone numbers of contacts for further information. Description of
wastewater treatment practices and data on water use and wastewater
discharge as well as wastewater characteristics fundamental to the
development of effluent limitations were requested. Since the
evaluation of these data is enhanced by a knowledge of water source,
discharge destination, and the type of discharge regulations to which
the plant is subject, the dcp's included requests for this information
as well. In recognition of the fact that analysis for many of the
priority pollutants had not been performed at most facilities, the dcp
included the request for an indication for each priority pollutant of
whether it was known or believed to be present in or absent from
process wastewater from the facility.
The analysis of information prior to development of the dcp indicated
that wastewater volumes and characteristics varied significantly among
different battery types as defined by chemical reactants and
electrolyte employed, and that the raw materials used in battery
manufacture constituted potential sources of significant pollutants.
In addition, it was ascertained that batteries of a given type are
commonly produced in a variety of sizes, shapes, and electrical
capacities. The available data also indicated the possibility of
significant process variations differing in wastewater discharge
character ist i cs.
As a result of these considerations, the dcp was developed to obtain
identification of the specific battery types manufactured and the raw
materials used for each type. Production volume was requested in
terms of the total weight of each battery type produced since this was
exp'ected to be more meaningful in terms of wastewater discharge than
the number of units manufactured. Production information was
requested both in terms of total annual production and in terms of
production rate (Ibs/hr) to provide correspondence with wastewater
flow rates which were obtained in gallons per hour. A complete
description of the manufacturing process for each battery type
including designation of points of water use and discharge and of raw
material usage as well as specification of water flow rates was also
requested. Finally, chemical characteristics of each process
wastewater stream were requested.
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Of the 235 confirmed battery manufacturing facilities, all but ten
returned either a completed dcp or a letter providing available in-
formation submitted in lieu of the dcp. This level of response was
achieved through follow-up telephone and written contacts alter
mailing of the original data requests. Follow-up contacts indicated
that most plants which did not provide a written response were very
small and together comprised a negligible fraction of the industry.
The quality of the responses obtained varied significantly, however.
While most facilities were able to provide most of the information
requested in the dcp, a few (generally small) plants indicated that
the available information was limited to the plant name and location,
product, and number of employees. These facilities usually reported
that they discharged no process wastewater. There was also
considerable variability in the process descriptions provided.
Information was asked for descriptions of all process operations
including those that generated process wastewater. Over 50 percent of
the lead subcategory plants and approximately 40 percent of the other
plants submitting dcp's did not supply discharge flows for some
specific process operations, indicating that process wastewater was
not generated for these specific processes. In some additional dcp s
specific process flow rates were found to conflict with water use and
discharge rates reported elsewhere in the dcp. Nonetheless,
sufficient specific process flow information was provided in the dcp s
to provide flow rate characterization of most process elements for
each 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 facilities. Raw waste chemical
analysis were almost universally absent from the dcp s and had to be
developed almost entirely from sampling at visited plants and from
data developed in previous EPA studies.
When received, each dcp was reviewed to determine plant products,
manufacturing processes, wastewater treatment and control practices,
and effluent quality (if available). This review provided the basis
for selection of sites for plant visits for on-site data collection
and sampling. Subsequently, selected data contained in each portfolio
was entered into a computer data base which was used to rapidly
identify plants with specific characteristics (e.g. specific products,
process operations, or waste treatment processes), and to retrieve
basic data for these facilities. Review of the complete dcp data base
together with data collected on-site at specific plants formed the
basis for definition of the final industry subcategorization as
described in Section IV. The dcp data base was then used to define
production normalized process wastewater flows for each distinct
process operation or function within each subcategory. It also was
the primary source for the identification of wastewater treatment
technologies and in-process control techniques presently employed
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within each subcategory and provided information about the
effectiveness of many of these.
Plant Visits and Sampling
A total of 40 battery manufacturing facilities were visited as part of
the data collection effort. At all of the visited plants information
was obtained about the manufacturing process, raw materials, process
wastewater sources (if any), and wastewater treatment and control
practices. At nineteen plants, wastewater samples were also
collected.
Because of the large number of pollutants to be investigated, a two
stage approach to sampling was used to ensure the most effective use
of program resources. Initially, influent water, raw wastewater, and
treated effluent samples obtained from a single plant in each
subcategory were analyzed for all of the pollutants under
consideration. Results of this screening analysis were used to select
a smaller list of parameters found to be potentially significant for
the subcategory. The significance of the parameters was verified by
analysis in all remaining wastewater samples from plants in the
subcategory. This screening-verification approach allowed both
investigation of a large number of pollutants and in-depth
characterization of individual process wastetwater streams without
incurring prohibitive costs.
Sampling and Analysis Procedures
Sites for visits to battery manufacturing facilities were initially
selected based on a review of the dcp's. Somewhat different criteria
were applied to the selection of sites for screening and verification
sampling. For screening the most important basis for selection was
that process wastewater generation at the plant be representative of
the subcategory, ie. that manufacturing processes, raw materials, and
products be similar to those at other sites. For screening, sampling
was done on the basis of the battery type subcategorization.
Preference was given to plants with multiple products or processes.
For verification sampling, wastewater control and treatment practices
assumed major importance with emphasis on the selection of plants
which demonstrated effective pollutant reductions as determined by
effluent volume or quality. For some subcategories, however, the
number of plants was sufficiently small that production in the sub-
category and generation of wastewater became sufficient grounds for
selection regardless of wastewater treatment and control practices.
Each site selected as a potential sampling site was initially con-
tacted 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 specific process
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wastewater samples to be obtained to characterize process raw waste
streams and wastewater treatment performance and also data required in
addition to that provided in the dcp. The plant was then visited for
one day to determine specific sampling locations and collect
additional information. In some cases, it was determined during this
preliminary visit that existing wastewater plumbing at the plant would
not permit meaningful characterization of battery manufacturing
process wastewater, and plans for sampling the site were discontinued.
Where sampling was performed, a detailed sampling plan identifying
sampling locations, flow measurement techniques, sampling schedules
(where flows were not continuous), and background data to be developed
during sampling was developed on the basis of the preliminary plant
visit.
Wastewater samples collected at most sites were selected to provide a
characterization of process wastewater from each distinct process
operation, of the total process waste stream, and of the effluent from
wastewater treatment. Multiple wastewater streams from a single
process operation or unit, for example individual stages of a series
rinse, were generally flow proportionally composited and were not
sampled separately. In some cases, wastewater flow patterns at
specific plants did not allow separate sampling of some process waste
streams, and only samples combining wastes from two or more process
operations could be obtained. Where possible, chemical characteris-
tics 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 obtained prior to any treatment, settling in sumps,
dilution, or mixing which would change their characteristics. Where
this was not possible, sampling conditions were carefully noted in the
documentation of the sampling visit and considered in evaluation of
the sampling results.
In all 257 raw waste samples were obtained characterizing 75 distinct
wastewater sources associated with 37 different battery manufacturing
process operations. In addition, 22 samples were obtained from plant
water supplies. Samples were also obtained for analysis which
characterized either wastewater streams from sources other than
battery manufacturing which were combined for treatment with battery
manufacturing wastes, or wastewater at intermediate points in
treatment systems incorporating several operations.
Screening samples were obtained to characterize the total process
wastewater before and after treatment. As a result, only the combined
raw waste stream and total process effluent were sampled for
screening. At plants where a single combined raw waste stream or
treated effluent did not exist, samples from discrete waste sources
were flow proportionally composited to represent the total waste
streams for screening.
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Samples were collected at each site on three successive days. Except
where production or wastewater discharge patterns precluded it, 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 once each
hour. For batch operations composites were prepared by compositing
grab samples from each batch. Wastewater flow rates, pH, and
temperature were measured at each sampling point on an hourly basis or
for batch operations, when each sample was taken. At the end of each
sampling day, aliquots of each composite sample were taken for
analysis for organic priority pollutants, metals, and for TSS,
cyanide, ammonia and oil and grease. Grab samples were taken for
analysis for volatile organic compounds and for total phenols because
these parameters would not remain stable during compositing.
Composite samples were kept on ice during compositing, shipment, and
holding until analyzed. Analysis for metals was by plasma arc
spectrograph for screening and by atomic absorption for verification
analysis. Analysis for organic priority pollutants was performed by
gas chromatograph-mass spectrometer for screening and some
verification analysis, and by gas chromatograph alone for others.
Both sampling and sample analysis were performed in conformance with a
protocol developed by the EPA.
Screening Analysis Results
The results of screening analysis for each subcategory are presented
in Tables V-l through V-7 (Pages 228 - 261) which also show the extent
to which each pollutant was reported in dcp's to be known or believed
present in process wastewater from plants in the subcategory. In the
tables ND indicates that the pollutant was not detected, and for
organic pollutants, * and ** indicate detection at levels below
quantifiable limits. For most organics, * is used to indicate equal
to or less than 0.01 mg/1. For pesticides (pollutants 89-105), **
indicates detection equal to or less than a 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. NA
indicates that analysis for the specific pollutant was not performed.
For certain pollutant parameter pairs, concentrations cannot be
separated by the type of analysis used. Therefore pollutants numbered
72 and 76 will have the same concentration reported as well as 78 and
81, and 74 and 75. Dioxin, alkyl epoxides, and xylenes, were not
analyzed in any samples because established analytical procedures or
standards were not available. Analytical procedures were developed
for asbestos sampling after screening had already occurred. The
sampling results reported for this pollutant are not necessarily from
the same plant which was used for screening. For selected plants
asbestos self-sampling kits along with established protocol were sent
for influent, raw wastewater and effluent samples for each
subcategory. No analyses for non-volatile organic pollutants were
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performed on one of the zinc subcategory screening samples due to loss
of the sample in shipment. Two sets of screening data are presented
for the zinc subcategory. Two plants in this subcategory were
screened because screening was initially performed on the basis of the
preliminary product type subcategories. This fact also resulted in
some instances where not all samples in a given subcategory were
analyzed for the same set of verification parameters as will be
discussed later.
Selection Of_ Verification Parameters
Verification parameters for each subcategory were selected based on
screening analysis results, occurrence of the pollutants in process
waste streams as reported in dcp's, and a technical evaluation of
manufacturing processes and raw materials used within each
subcategory. Criteria for selection included:
1. Occurrence of the pollutant in process wastewater from the
subcategory may be anticipated based on its presence in, or
use, as a raw material or process chemical. Also the
pollutant was indicated in dcp priority pollutant segments as
being known or believed to be present in process wastewaters.
2. The pollutant was found to be present in 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 observed concentrations are environmentally significant.
This included an analysis of the proposed ambient water
quality criteria concentrations presently available. Also
included was an evaluation of concentrations detected in
blank, 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 for each subcategory is presented in the following
paragraphs.
Cadmium Subcategory. Based on screening analysis and evaluation of
this subcategory, sixteen pollutant parameters were selected for
further analysis. The sixteen are:
44 methylene chloride 126 silver (for silver cathodes only)
87 trichloroethylene 128 zinc
118 cadmium ammonia
119 chromium cobalt
121 cyanide phenols (4AAP)
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122 lead oil and grease
123 mercury TSS
124 nickel pH
The organic pollutants benzene, dichlorobromomethane and bis(2-
ethylhexyl)phthalate were all detected in screening samples at con-
centrations below the quantifiable limit and were not selected for
verification because there was no clear relationship between these
pollutants and manufacturing processes in this subcategory.
Chloroform was also detected in screening but was attributable to
influent water and was therefore not selected for verification
sampling. Toluene was observed at concentrations as high as 0.025
mg/1 but was not chosen for verification because this pollutant is not
expected to be related to any manufacturing process. All other
organic priority pollutants detected in screening anaylsis for this
subcategory were included in verification analysis.
Of the metal priority pollutants, beryllium was reported at its
quantifiable limit of detection in all samples, is not known to be
used as a raw material and is therefore not selected. Copper is not
known to be related to any manufacturing process in this subcategory,
was detected at a concentration above its limit of detection in only
the influent sample, and is therefore not selected. Although silver
was not detected in screening, it is selected as a verification
parameter for process wastewaters associated with silver cathode
production. All other metal priority pollutants detected in screening
analysis for this subcategory were selected for verification. Cyanide
was also selected to be analyzed.
A number of nonconventional pollutants were also detected in screening
analyses of cadmium subcategory process wastewater. Of these,
fluoride, iron, magnesium, manganese, phosphorous, sodium, and tin
were detected, but not selected for verification
analyses. Ammonia and total phenols were detected in screening and
were selected as verification parameters. Cobalt was also selected
for verification analysis although it was not detected in screening
because it is known to be used as a process raw material at some sites
in the subcategory and was expected to occur as a wastewater pollutant
at those sites. In addition, the conventional pollutants, TSS, oil
and grease, and pH were included for verification analysis.
Calcium Subcategory. Screening results are presented for this
subcategory, however, verification parameters have not been selected.
Lead Subcategory. Based on screening analysis and evaluation of this
subcategory analysis and evaluation of this subcategory twenty-eight
pollutant parameters were selected for further analysis. The
twenty-eight are:
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11 1,1,1-trichloroethane 118 cadmium
23 chloroform 119 chromium
44 methylene chloride 120 copper
55 naphthalene 122 lead
65 phenol 123 mercury
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 iron
78 anthracene phenols (4AAP)
81 phenanthrene strontium
84 pyrene oil and grease
114 antimony TSS
115 arsenic pH
Eighteen organic priority pollutants were detected in screening at
concentrations below the quantification level. These pollutants,
acenaphthene, benzene, 2,4,6-trichlorophenol, 2-chlorophenol, 1-3
dichlorobenzene, 2,4-dichlorophenol, ethylbenzene, fluoranthene,
dichlorobromomethane, chlorodibromomethane, 1,2benzanthracene,
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 present in process
wastewater by at least one plant in the subcategory but were not
detected in screening analysis. On the basis of these negative
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 present in one dcp, and 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
although they were detected only at trace concentrations, because they
were reported to be present in process wastewater in dcp's 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 although they
also were detected only in trace concentrations. 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 only
at the limit of detection, is not known to be related to battery
manufacture, and is therefore not selected. Antimony, although
reported at the limit of detection was selected because of dcp
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responses. All metal pollutant parameters detected in screening 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 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.
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.
Leclanche Subcateqorv. Based on screening analysis and evaluation of
this subcategory sixteen pollutant parameters were selected for
further analysis. The sixteen are:
70 diethyl phthalate
114 antimony
115 arsenic
118 cadmium
119 chromium
120 copper
122 lead
123 mercury
124 nickel
125 selenium
128 zinc
manganese
phenols (4AAP)
oil and grease
TSS
PH
Eleven organic priority pollutants were detected at concentrations
less than the quantification levels in screening samples for this
subcategory. Eight of these pollutants, 1,1,2,2-tetrachloroethane,
dichlorobromomethane, chlorodibromomethane, phenol, bis(2-
ethylhexyDphthalate, di-n-butyl phthalate, butyl benzyl phthalate,
and dimethyl phthalate, were neither reported to be present in process
wastewater by plants in this subcategory nor known to be used in the
manufacturing process. The remaining three pollutants, methylene
chloride, tetrachloroethylene, and toluene, were reported as known or
believed to be present in process wastewater in the priority pollutant
section of at least one dcp. Methylene chloride was reported as known
to be present and as used in the manufacturing process by one plant.
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This facility also reported, however, that use of this material had
been discontinued. Tetrachloroethylene and toluene were reported to
be believed to be present in process wastewater by one and two plants,
respectively. Their presence cannot be traced to any use in battery
manufacturing processes, however, and is believed to derive from on-
site plastics processing and vapor degreesing operations which are not
regulated as part of the battery manufacturing category. On the basis
of these considerations, none of these eleven pollutants were included
in verification analyses. Chloroform was detected in screening at
concentrations as high as 0.043 mg/1 but was not selected for veri-
fication because this concentration was in the influent sample.
Diethyl phthalate was the only organic priority pollutants detected in
screening which was selected for verification analysis.
For metal priority pollutants beryllium and silver were not selected
because they were reported at the limits of detection and were not
known to be a part of any manufacturing process in this subcategory.
Arsenic was selected as a verification parameter although it was not
found in screening samples. Arsenic was reported to be believed
present in process wastewater by three plants in this subcategory.
Further, it is highly toxic and known to be a potential contaminant of
zinc which is a major raw material. Selenium was reported to be
present in process wastewater by one manufacturer and was reported in
screening in the influent sample at the limit of detection. It was
therefore included in verification analyses. All-other metal priority
pollutants were detected in screening and selected for verification.
A number of nonconventional pollutants were detected in screening but
not selected as verification parameters. Manganese and total phenols
were measured at significant levels in screening and were consequently
included in verification analyses. In addition, the conventional
pollutants oil and grease, TSS, and pH were selected for verification
analysis.
Lithium Subcateqory. Screening results are presented for this
subcategory, however, verification parameters have not been selected.
Magnesium Subcategory. Screening results are presented for this
subcategory, however, verification parameters have not been selected.
Zinc Subcategory. Based on screening analysis and evaluation of this
subcategory thirty-three pollutant parameters were selected for
further analysis. The thirty-three are:
11 1,1,1-trichloroethane 120 copper
13 1,1-dichloroethane* 121 cyanide
29 1,1-dichloroethylene* 122 lead
30 1,2-trans-dichloroethylene* 123 mercury
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38 ethylbenzene* 124 nickel
44 methylene chloride 125 selenium*
55 naphthalene* . 126 silver
64 pentachlorophenol* 128 zinc
66 bis(2-ethylhexyl)phthalate* aluminum
70 diethyl phthalate* ammonia*
85 tetrachloroethylene* iron
86 toluene* manganese
87 trichloroethylene phenols (total)
114 antimony oil and grease
115 arsenic TSS
118 cadmium pH
119 chromium
*These parameters were verification parameters for only some battery
types within the subcategory.
Screening for this subcategory was performed at two sites producing
different battery types, all of which are within the zinc subcategory.
Twenty-two organic priority pollutants, ten priority pollutant metals,
cyanide, and twenty other pollutants were detected in screening
samples from one or both of these facilities. Because screening and
verification parameter selection were initially performed on the basis
of battery types, two different lists of verification parameters were
defined for plants in the zinc subcategory. A number of priority
pollutants, mostly organics, were consequently analyzed in only some
of the zinc subcategory wastewater samples. These parameters are
marked with a * in the listing of verification parameters selected.
Eight of the organic priority pollutants, benzene, 1,1,2-
trichloroethane, 2,4,6-trichlorophenol, 2-chlorophenol, butyl benzyl
phthalate, di-n-butyl phthalate, anthracene, and phenanthrene, were
detected at concentrations below the quantifiable level. None of
these pollutants was reported to be present in process wastewater by
plants in the subcategory, and none was selected for verification.
All other organic priority pollutants observed in screening samples
were included in verification analysis.
All of the metal priority pollutants detected in screening were
selected for verification with the exception of beryllium which was
reported at its quantifiable limit. In addition, arsenic which was
not detected in screening analysis was selected as a verification
parameter because it is a highly toxic potential contaminant of zinc
which was reported to be present in process wastewater by one
manufacturer in the subcategory. Cyanide was also detected at less
than 0.01 mg/1 but was selected as a verification parameter on the
basis of its toxicity and potential use in cell cleaning formulations.
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Many nonconventional pollutants were also detected in screening. They
were not included in verification analyses. Aluminum, ammonia, iron,
manganese, and total phenols were measured at appreciable levels in
screening samples and were included in verification analyses. Ammonia,
however, was analyzed and selected as a verification parameter based on
screening at one plant only and was consequently analyzed in only some
verification samples. In addition, the conventional pollutants, oil and
grease, T$S and pH were selected as verification parameters.
Summary of Verification Parameters. Table V-8 (Page 262) presents a
summary of the verification parameters selected for each subcategory
of the battery manufacturing category. Under the discussions and
analysis for each subcategory, verification parameter analytical
results are discussed and tabulated. *'s in the tables are used for
quantifiable limits of the organic pollutants (0.01 mg/1). For
chemical analysis, the *'s are calculated as positive values which
cannot be quantified, but for statistical analysis are counted as
zeroes.
CADMIUM SUBCATEGORY
This subcategory encompasses the manufacture of all batteries
employing a cadmium anode. Presently there are ten active plants in
the subcategory, nine of which manufacture cells based on the nickel-
cadmium electrolytic couple. One of these plants also produces
silver-cadmium batteries. The remaining facility manufactures
mercury-cadmium cells although production at that facility is reported
to be sporadic and quite small in volume. Manufacturing processes in
the subcategory vary widely and result in corresponding variations in
process water use and wastewater discharge. A total of sixteen
distinct manufacturing process operations or functions were identified
which are combined in various ways by manufacturers in this
subcategory and which provide a rational basis for effluent
limitations. After a discussion of manufacturing processes employed
in the subcategory and a summary of the available data characterizing
cadmium subcategory facilities, each of these sixteen process elements
is discussed in detail to establish wastewater sources, flow rates,
and chemical characteristics.
Manufacturing Process
As shown in the generalized process flow diagram of Figure V-l, (Page
192), the manufacture of batteries in this subcategory comprises
basically the preparation and formation of the anode and cathode,
assembly of these components into cells and batteries, and ancillary
operations performed in support of these basic manufacturing steps.
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Three distinct process elements for the production of anodes, five for
the manufacture of cathodes, and eight different ancillary operations
are observed in present practice within the subcategory. They are
combined in a variety of ways in existing plants to produce batteries
exhibiting a range of physical and electrical characteristics.
Additional combinations are possible in future manufacturing.
The observed variations in anode and cathode manufacture, and the
combinations of these processes at existing plants are shown in Table
V-9 (Page 2«3). This table also presents the ancillary operations
which have been observed to involve water use and wastewater discharge
and the extent of practice of each of these operations. The x's
presented in the table under each anode type and after each cathode
type and ancillary operation are identification of reported
manufacture of the designated operations. Data from these operations
are used in detailed discussions of each of these process elements.
The process operations and functions shown in Table V-9 formed the
framework for analysis of wastewater generation and control in this
subcategory. Several of them involve two or more distinct process
wastewater sources which must be considered in evaluating wastewater
characteristics. The relationship between the process elements and
discrete waste sources observed at battery manufacturing facilities is
illustrated in Figure V-2 (Page 193).
Anode Manufacture - Except for one plant which obtains electrodes
produced at another facility, all manufacturers use cadmium or cadmium
salts to produce anodes. Three general methods for producing these
anodes are currently used which may be differentiated on the basis of
the technique used to apply the active cadmium to the supporting
structure. In the manufacture of pasted and pressed powder anodes,
physical application of solids is employed. Electrodeposited anodes
are produced by means of electrochemical deposition of cadmium salts
from solution. Impregnated anodes are manufactured by impregnation of
cadmium solutions into porous structures and subsequent precipitation
of cadmium hydroxide in place.
Cadmium powder anodes encompass anodes in which a cadmium hydroxide
mixture is applied to the perforated surface of a supporting grid
(usually nickel plated steel) in either a powdered form or compressed
powder form. Other anodes included in this grouping are those in
which cadmium oxide is blended with appropriate additives prior to
either pressing to form a button or pellet or pasting on a supporting
grid. The charged state for these anodes is achieved in present
practice by formation after cell assembly. The only process
wastewater source presently reported from the manufacture of this type
of anode is the clean-up of anode production equipment and floor
areas.
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One facility reports the manufacture of cadmium hydroxide on-site for
use in battery manufacture. Since the grade of cadmium hydroxide
produced is unique to battery manufacture, this process is included as
an ancillary operation for regulation under this subcategory. Another
plant produces cadmium powder which is then blended and used for the
manufacture of pasted cadmium anodes. Production of the cadmium
powder is considered a separate ancillary operation.
Formation of these anodes outside the battery case, while not
presently practiced in the United States, is anticipated in the near
future by one manufacturer. This process variation may introduce an
additional wastewater source from rinsing the formed anodes prior to
battery assembly.
Electrodeposited anodes are produced by electrochemically
precipitating cadmium hydroxide from nitrate solution onto the support
material. When the appropriate weight of cadmium hydroxide has been
deposited, the deposited material is subjected to a charge and
discharge cycle while submerged in caustic solution and subsequently
rinsed. After drying, the formed material is cut to size for assembly
into cells.
The cadmium nitrate solutions used in electrodeposition may be
partially supplied by redissolution of excess cadmium hydroxide washed
off anodes during processing and recovered from the process rinse
water. Dissolution of this material in nitric acid generates acid
fumes which must be controlled with a scrubber.
Process wastewater sources involved in the manufacture of
electrodeposited anodes include: (1) Rinsing active material
deposited on the grid; (2) rinsing electrode material following each
phase of formation; (3) spent caustic used in formation; and (4) wet
scrubbers.
A third method of cadmium anode manufacture involves submerging porous
sintered nickel stock in an aqueous solution of cadmium salts and
precipitation of cadmium hydroxide on the sintered material by
chemical, electrochemical, or thermal processing. Generally the
impregnated material is immersed in a caustic bath to precipitate
cadmium as the hydroxide followed by a rinsing stage. The entire
impregnation cycle is repeated several times to achieve the desired
active material (cadmium) weight gain. After cleaning the anode
material by brushing or washing to remove excess deposited material,
the anode material is submerged in a caustic solution and an electric
current is applied to repeatedly charge and discharge the anode
material. Formation is generally followed by rinsing.
Process wastewater from the manufacture of cadmium impregnated anodes
results from: (1) cleaning equipment used to prepare porous sintered
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stock; "(2) rinsing deposited active material on the sintered support
material; (3) removing excess deposited materials prior to formation
(which can be preceded by soaking the impregnated stock); (4) rinsing
the anode material after formation; and (5) spent caustic used in both
the impregnation caustic immersion phase and formation process.
Cathode Production - Three of the five cathode manufacturing process
elements involve processes for producing nickel cathodes. The other
two processes deal with producing silver cathodes and mercury
cathodes.
The production of silver cathodes begins with preparing a silver
powder which is sintered. The metallic silver cathode which results
is assembled with an unformed cadmium anode. The resulting batteries
are shipped in the unformed state. The only source of wastewater
discharge associated with this cathode type results from the silver
powder production operation which is addressed as a separate ancillary
operation. The production of mercury cathodes proceeds by physical
compaction of mercuric oxide and generates no process wastewater.
One of the three nickel cathode manufacturing variations {pasted and
pressed powder cathodes) includes cathodes produced by physically
blending the active materials as solids and molding them into pellets
or applying them to supporting grids. This includes cathodes in which
nickel hydroxide is blended and subsequently applied to the perforated
areas of the grid. In present practice, these cathodes which are
produced in the unformed (divalent) state are assembled into batteries
with unformed anodes, and the complete battery is subsequently
charged.
No wastewater discharge is presently reported from manufacturing
cathodes in this group except for effluent from the production of
nickel hydroxide by chemical precipitation at one facility. This
precipitation process is addressed as a separate ancillary operation
in this subcategory.
The other two nickel cathode process variations involve the
precipitation of active material from solution onto a conducting
support grid. One of these variations is the production of nickel
cathodes by electrodeposition. In this process sintered nickel
support material is immersed in a nickel nitrate solution and upon
applying an electrical current, nickel hydroxide precipitates on the
sintered material. The process material is removed from
the nitrate solution when the active material weight gain meets
specifications. Afterwards the cathode material is subjected to an
electrochemical formation process to achieve the charged state of the
active material. The two sources of wastewater discharge from the
electrodeposition process are from: (1) removing spent caustic used in
the formation process; and (2) rinsing the formed cathode material.
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The remaining method of nickel cathode manufacture involves the
impregnation of sintered stock prepared from powdered nickel with
nickel nitrate solution. Afterwards, the process material is removed
from the aqueous solution of nickel salts and immersed in caustic
solution to precipitate nickel hydroxide in the pores. This is
followed by rinsing. The entire impregnation process is repeated
several times to achieve the required active material weight gain.
After completion of impregnation, excess deposited material is removed
by brushing or washing prior to formation.
Formation of impregnated stock is presently accomplished by two
different techniques. The most common practice is to sequentially
oxidize and reduce the nickel hydroxide by electrolysis in a caustic
solution. An alternative technique achieves oxidation and reduction
chemically. In either formation technique, post-formation rinses are
used to remove impurities liberated from the formed material as well
as residual formation solutions. Formation produces changes in the
physical structure of active material within the electrode and also
serves to remove impurities in addition to changing the electrode's
state of charge.
Process wastewater sources observed in the manufacture of impregnated
nickel cathodes include: (1) cleaning equipment used to prepare the
porous sintered stock which is impregnated; (2) rinsing impregnated
stock; (3) washing excess deposited material off impregnated stock
(which can be preceded by "soaking the impregnated stock); (4) spent
formation and impregnation solutions; (5) post-formation rinses; (6)
cleaning impregnation equipment; and (7) wet scrubbers.
Nickel hydroxide washed off the impregnated stock in process rinses
and in post-impregnation cleaning may be recovered and redissolved in
nitric acid to produce some of the nickel nitrate solution used in
impregnation. This process may yield additional wastewater streams.
These waste streams, where generated, are also considered to be
directly attributable to the production of impregnated nickel
cathodes.
Assembly - The assembly of cells in this subcategory is accomplished
without the generation of process wastewater. Specific assembly
techniques differ for different cell types manufactured in this
subcategory. For example, anodes and cathodes for large rectangular
cells are interleaved with separators which may be plastic or hard
rubber rods, while for sealed cylindrical cells, the anodes and
cathodes are spirally wound with flexible sheet separators. Assembly
of all cells, however, involves the assembly of one or more anodes
with cathodes and separators to produce an active cell element. One
or more of these elements is then inserted in a battery case,
electrical connections made, (as required), and electrolyte added,
after which the case is covered and (if appropriate) sealed.
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Separators are a key component in these cells, particularly in
sintered electrode cells (electrodeposited or impregnated) which are
designed to operate at high current drains per unit of electrode
surface area. In these cells, minimum separator thickness is desired
to minimize internal resistance of the cells and maximize gas
diffusion and recombination in sealed cells. The resistance of the
separator material to chemical attack and perforation limits the cell
performance which can be achieved. Separators in open pressed powder
(pocket plate) cells are frequently narrow plastic or hard rubber rods
or may be corrugated, perforated plastic sheets. In cells using
sintered electrodes, a variety of separator materials are used
including woven or non-woven synthetic fabrics, sheet resin, and
cellophane. A three layer separator comprising a layer of cellophane
between two nylon layers is frequently used. In sealed cells,
separators are often made of felted nylon. Separator configurations
in use include flat sheets between cathode and anode and a variety of
wrapped or folded configurations.
The electrolyte used in these cells is usually potassium hydroxide in
solutions ranging between 20 and 30 percent in concentration. Lithium
hydroxide is often added to the electrolyte to improve cell per-
formance. Cell cases may be either steel or plastic. Cases or covers
used in manufacturing batteries in this subcategory include some
provision for venting gases generated in cell charging or on
overcharge. Open or vented cells normally generate some hydrogen and
have vents which function during normal operation. In sealed cells,
design factors minimize gas generation and provide for recombination
before pressures rise excessively. Vents in these cells are normally
sealed and function only when abnormal conditions cause pressures to
rise above normal limits.
Ancillary Operations - A number of process operations or supporting
functions in addition to the basic electrode manufacture and assembly
steps described above are required for the production of cadmium
subcategory batteries. These ancillary operations include: (1)
washing assembled cells; (2) preparing electrolyte solutions; (3)
cleaning process floor -areas; (4) employee hand washing to remove
process chemicals; (5) the production of cadmium powder; (6) the
production of silver powder; (7) the production of nickel hydroxide;
and (8) the production of cadmium hydroxide.
In the course of manufacture and assembly, the cases of batteries are
likely to become contaminated with spilled electrolyte and other
process materials. Since these contaminants may interfere with
electrical contact with the batteries, accelerate contact corrosion,
or even damage devices in which the batteries are used, washing some
batteries prior to shipment is required. Washing batteries produces a
process wastewater stream.
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Electrolyte is prepared for use in batteries by solution of potassium
hydroxide in the correct volume of water. Process wastewater
associated with this operation results from spillage and from washing
reagent preparation equipment at some facilities.
Process floor areas typically require periodic cleaning to maintain
plant safety and hygiene. This is normally accomplished at least in
part by washing, resulting in the production of wastewater
contaminated with a variety of process materials. The amount of water
reported to be used in and discharged from this operation is highly
variable depending on the washing procedures used.
Because nickel and cadmium are both toxic metals, the safety and
health of production workers at plants in this subcategory requires
that process materials be washed from their hands prior to eating or
leaving the work place. Water used in this washing may become
contaminated with nickel, cadmium, and other process chemicals and is
considered process wastewater.
A special grade of cadmium powder may be produced on-site for use in
anode production. The powder is produced by chemical precipitation of
cadmium. The precipitated cadmium metal is subsequently washed with
water prior to being used in anodes.
Silver powder for use in cathode manufacture is produced on-site at
battery manufacturing facilities by electrolytic deposition. This
powder, which has physical properties required for batteries, is
unique to battery manufacturing. This silver powder is also used in
producing cathodes for zinc subcategory cells, and this ancillary
operation is therefore discussed and included in the zinc subcategory.
Nickel and cadmium hydroxides for use in the manufacture of pasted or
pressed powder electrodes may be produced on-site at battery
manufacturing plants. When this occurs, unique grades of these
materials containing additives to enhance battery performance are
produced.
Nickel hydroxide is produced from nickel powder by dissolution and
chemical precipitation. Rinsing the precipitated material generates
process wastewater. The nickel hydroxide product contains specific
additives to enhance battery performance characteristics.
Cadmium hydroxide is produced at battery plants from cadmium metal by
oxidation and hydration. The product contains iron oxide and graphite
as well as cadmium hydroxide. Wastewater from this process results
only from pump seals and is limited in volume.
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Subcategory Data Summary
The manufacture of three battery types, mercury-cadmium, silver-
cadmium, and nickel-cadmium batteries, is included in this sub-
category. Nickel-cadmium batteries, however, account for over 99
percent of the total mass of cadmium anode batteries produced. Manu-
facturing plants in the subcategory vary significantly in production
volume and in raw materials, production technology, wastewater
generation, and in wastewater treatment practices and effluent
quality.
Production - Annual production reported in the subcategory totaled
4800 metric tons of batteries in 1976. Using the latest available
data(1976-1979), estimated annual production broken down among battery
types is shown below:
Battery Type Estimated Annual Production
metric tons(kkg) tons
nickel-cadmium 5242 5780
silver-cadmium 8.6 9.5
mercury-cadmium 0.045 0.05
Total 5251 5790
Production of nickel-cadmium batteries may be further divided among
cells of the pasted or pressed powder varieties and cells containing
sintered plates with impregnated or electrodeposited active material.
Of the total nickel cadmium batteries reported in 1976, 18 percent or
890 metric tons (980 tons) contained pasted or pressed powder
electrodes. The remainder of the nickel cadmium batteries produced
contained sintered electrodes. Production ranges from less than 10
to greater than 1000 kkg of batteries annually.
Plants producing batteries in this subcategory are frequently active
in other battery manufacturing subcategories as well. Six of the ten
present producers of cadmium subcategory batteries also manufacture
products in at least one other subcategory at the same location.
Other subcategories reported at these sites include the lead,
Leclanche lithium, magnesium, and zinc subcategories. Process
operations are common to multiple subcategories at only one of these
plants, however. Production in other subcategories produces process
wastewater at only two other cadmium subcategory plants, and waste
streams are combined for treatment and discharge at only one of these.
Consequently multi-subcategory production has little if any impact on
cadmium subcategory wastewater treatment and effluent quality.
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Geographically, plants in the cadmium anode subcategory are dispersed
throughout the United States. There are two active facilities in each
of EPA Regions I, IV, and V and one each in regions II, VI, VIII, and
IX. These plants do not vary greatly in age with the oldest
manufacturing facilities reported to be only 15 years old.
Raw Materials - Although there were some variations in raw materials
with manufacturing process and product variations, many of the raw
materials used in producing cadmium anode batteries were common to all
or most facilities. For example, cadmium or its salts are used by all
plants, and nickel was reported as a raw material by eleven of
thirteen plants supplying data in the subcategory. Of the remaining
two facilities, one produced only mercury-cadmium batteries and the
other produced nickel-cadmium batteries, but obtained processed
electrode material from another site. Cadmium and cadmium oxide are
used in the preparation of pasted and pressed powder anodes and may
also be used in producing solutions for impregnation and
electrodeposition. Cadmium oxide may also be added to nickel cathodes
as an antipolar mass in some sealed cells. Cadmium nitrate is used as
an aqueous solution in impregnation operations as is nickel nitrate.
Nickel hydroxide is used in producing pasted and pressed powder
cathodes. Nickel is used in the form of wire as a support and current
collector for electrodes and as a powder for the production of
sintered stock into which active material may be introduced by
impregnation or electrodeposition.
Other raw materials which are frequently reported include nylon,
potassium hydroxide, lithium hydroxide, steel, polypropylene, nitric
acid, silver nitrate, silver, mercuric oxide, cobalt nitrate and
sulfate, sodium hypochlorite, methanol, polyethylene, and neoprene.
Nylon is a popular separator material and may also find applications
in a variety of cell components such as vent covers. Potassium
hydroxide and lithium hydroxide are used as the electrolyte in almost
all cells produced in this subcategory although sodium hydroxide is
used in electrolytic process operations (e.g. formation) and may be
used as the electrolyte in a few cells. Steel is widely used in cell
cases and may also be used with a nickel plating as the support grid
in some battery types. Polypropylene, polyethylene, and neoprene may
all be used in separator manufacture or in cell cases or cell case
components. Nitric acid is used in preparing the metal nitrate
solutions used in impregnation, and cobalt nitrate or sulfate is
introduced into some nickel electrodes to yield desireable voltage
characteristics. Silver and silver nitrate are used in producing
silver oxide cathodes for silver-cadmium batteries, and mercuric oxide
is used in producing cathodes for mercury-cadmium batteries.
Water Use and Wastewater Discharge - Water use and wastewater
discharge are observed to vary widely among cadmium subcategory plants
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with process wastewater flow rates ranging from 0 to >450,ooo I/day.
Individual plant effluent flow rates are shown in Table V-10 (Page
264). Most of the observed wastewater flow variation may be
understood on the basis of manufacturing process variations. The
water use and wastewater discharge from specific process functions
varies from zero for the manufacture of pressed powder nickel cathodes
to 1640 liters per kg of impregnated nickel (200 gal/lb) for sintered
impregnated electrodes. Plants with different process sequences
correspondingly produce different volumes of process wastewater. In
some cases, however, large differences in process water use and
discharge are observed among different plants using the same process
operations. As discussed later in this section, on-site observations
and data collection at a number of plants in the subcategory revealed
differences in plant operating practices which result in the observed
flow variations. In general, these differences are observed to result
primarily from differing degrees of awareness of water conservation.
Mean and -median normalized discharge flows from both dcp and visit
data for each of the wastewater producing process elements included in
this subcategory are shown in Table V-ll (Page 265). This table also
presents the production normalizing parameters upon which the reported
flows are based which were discussed in Section IV.
Wastewater Treatment Practices and Effluent Quality - Among plants in
this subcategory which presently report wastewater discharges, all but
one reported treatment of wastewater for removal of suspended solids
by settling or filtration. Four out of seven facilities also report
pH adjustment of the waste prior to discharge. On-site observations,
however, showed that the quality of treatment provided was variable
and that some systems were of marginal design with limited retention
times in setttling devices and little or no control over surge flows.
The effects of these conditions are evident in the effluent monitoring
data provided in dcp's as summarized in Table V-12 (Page 266). One
plant employs ion exchange to recover nickel and cobalt from process
wastewater prior to discharge. Other waste streams at this site are
treated by pH adjustment, sedimentation and filtration.
Specific Process Water Uses and Wastewater Characteristics
Anode Operations
Cadmium Pasted and Pressed Powder Anodes - Preparation of these anodes
involves blending solid constituents and physically applying them to
support structures. In some cases a limited quantity of water may be
added to the solid constituents to form a paste prior to application.
Preparation of the solid active materials is not included in this
process group although it is performed on-site at a few facilities.
Specific materials and techniques differ somewhat among plants and
product types.
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In the manufacture of pocket plate anodes, the current collector-
support structure is a perforated metal sheet upon which a mixture of
cadmium oxide, hydroxide, and binders is pressed. Alternatively, the
active material may be pressed into pellets prior to application to
the electrode support. Two facilities report the preparation of
anodes by the application of a pas£e containing powdered cadmium as
well as cadmium oxides and hydroxides to a supporting grid. In the
manufacture of nickel-cadmium batteries, the supporting grid is
usually nickel-plated steel. The use of a silver grid and a blended
powder containing silver as well as cadmium oxide is reported- in the
production of anodes for silver-cadmium batteries. Six plants
reported production of pasted or pressed powder cadmium anodes. Two
of these facilities were visited for wastewater sampling and on-site
data collection. One additional plant presently produces active
material for use in pocket plate anodes and assembles batteries. One
plant has discontinued production in the cadmium subcategory since
submission of the dcp.
Limited use and discharge of process water is inherent in the
production process involved in producing these anode types. The only
wastewater discharge from anode production in this group is process
area maintenance. Two plants (A and B) use water to clean floors and
equipment. The resultant wastewater was sampled at plant A. The
analysis results are presented in Table V-13 (Page 267). The
normalized flow from this source ranges from 1.5 to 2.7 I/kg of
cadmium applied in anode manufacture (1.9 I/kg mean and 1.8 I/kg
median). Cadmium, nickel, TSS, and oil and grease are the significant
pollutants found in this waste stream. Cadmium, nickel, and TSS
apparently result from spillage of process chemicals which are handled
in bulk in the anode preparation area. The equipment used in handling
both the bulk chemicals and processed materials is also washed
contributing to the oil and grease wastewater levels. Table V-14
(Page 268) shows the pollutant mass loadings in the clean-up waste
stream on three successive days.
Formation of anodes in this group does not presently produce a process
wastewater discharge at any plant in the U.S. Two plants did not report
a formation step in the production of pasted cadmium anodes. One plant
assembles cadmium oxide pressed powder anodes with silver pressed powder
cathodes, and the product is shipped to the customer. Formation is
conducted within the battery case prior to use. Other facilities report
formation of these anodes in assembled batteries without the generation
of process wastewater.
Cadmium Electrodepos i ted Anode - The electrodeposition process
involves the precipitation of cadmium hydroxide from nitrate solution
onto a support material by application of an electric current. It is
followed by an electrolytic discharging charging cycle called
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formation. Rinsing follows both electrodeposition and formation
processes. Figure V-3 (Page 195) is a flow diagram for the production
of anodes by the cadmium electrodeposition process.
The wastewater resulting from cadmium electrodeposition was sampled at
one facility allowing pollutant characterization and confirmation of the
information provided in dcp's. Three sources of wastewater discharge are
associated with cadmium electrodeposition: (1) electrodeposition
rinses, (2) scrubber bleed-off, and (3) caustic removal. The first two
wastewater discharges cited above were sampled separately, and waste-
water flow rates were measured for each source. Formation caustic was
contractor removed and was not characterized by sampling.
Characteristics of the total electrodeposition process wastewater
discharge were determined by combining analysis results of the waste
streams discussed above. Tables V-15 and V-16 (Pages 269 and 270)
show the pollutant concentrations and mass loadings in units of mg/1
and mg/kg, respectively, for the entire process sequence on a daily
basis.
Cadmium Impregnated Anode - The impregnation process involves sub-
merging porous sintered material in an aqueous solution of cadmium
salts and the subsequent precipitation of cadmium hydroxide on the
sintered material by immersion in a caustic bath. The impregnated
stock is later rinsed to remove residual caustic. The-impregnation
cycle is repeated several times to achieve the appropriate weight gain
of active material. After completing impregnation, excess material is
brushed or scrubbed off the grid surface, and the remaining processed
material is ready for formation. The final preparation of the anode
material is conducted during electrochemical formation in which
cadmium is reduced to the charged (metallic) state, residual nitrates
are eliminated, and any remaining poorly-adherent particles are
removed from the anode material. A rinse follows the formation
process to clean the anode material of residual formation caustic.
Figure V-4 (Page 196) is a flow diagram of the entire process sequence
for production of impregnated anodes.
Five plants in the data collection survey reported using the cadmium
impregnation process. One plant has subsequently discontinued cadmium
anode manufacture. Wastewater resulting from the manufacture of im-
pregnated cadmium anodes was characterized by sampling at one
facility. Raw materials used in the manufacture of impregnated
cadmium anodes include cadmium nitrate, sodium hydroxide, potassium
hydroxide, nickel powder, alcohol, and nickel-plated steel.
The manufacture of these anodes generally starts with the preparation
of sintered nickel stock. This is accomplished by applying nickel
powder, either dry or as a paste containing alcohol and binders, to a
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nickel or nickel plated steel screen and sintering the product in a
furnace. Small quantities of wastewater may result from washing
utensils used in preparing and applying the nickel paste or powder.
The sintered stock is then placed in tanks for impregnation. An
electric potential may be applied to the sintered stock during
impregnation to enhance cadmium deposition and reduce residual nitrate
levels. The entire impregnation cycle is repeated several times
before the anode material is taken out of the tank. At some plants it
may then be soaked in water to prevent drying of the active material.
The anode stock remains soaking until cleaned to remove excess cadmium
hydroxide from the grid surface. Afterwards the material may be
returned to soak until formation. In formation the anode material is
submerged in potassium hydroxide and undergoes electrochemical
charge-discharge cycles. At the conclusion of this process, the
charged material is rinsed in softened water and later air dried and
cut to an appropriate size for battery assembly.
There are seven points of discharge in this process sequence including
(1) sintered stock preparation clean-up; (2) cadmium impregnation
rinses; (3) impregnation caustic removal; (4) electrode cleaning water
discharge; (5) soak water discharge; (6) formation caustic removal;
and (7) post-formation rinse.
Two sample days' analysis results are presented to characterize the
raw waste from the cadmium impregnation process. The first day's
sampling results are excluded from use in the characterization since
the impregnation process did not operate on that day. All waste
streams were sampled except sintered stock preparation cleanup and the
formation caustic dump on the third day. The spent formation caustic
waste stream is not included in the combined stream analysis for that
day; however, the spent caustic would not contribute significantly to
the pollutant concentrations since the flow is 0.5 percent of the
total flow. Wastes from anode cleaning, which are included in the
analyses shown, are not observed at all sites producing impregnated
cadmium anodes. Table V-27 (Page 281) shows the raw waste composition
of the combined streams in units of mg/1 on a daily basis. The daily
pollutant mass loadings in units of milligrams per kilogram of applied
cadmium are also presented in Table V-17. In evaluating these data,
it should be noted that the wastewater characteristics for the
impregnation rinse on day 3 are not considered representative of the
normal process discharge. The data for day 2 are considered to
provide the best available characterization of the total raw waste
from this process operation.
Cathode Operations
Silver Powder Pressed Cathode - This process operation addresses the
production of cathodes by the application of silver to conductive
supporting grids. The cathode material in the silver state is
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assembled with cadmium oxide anode material, and the final product is
shipped unformed to the customer. The battery is charged prior to
use.
No process wastewater is generated in this process. Wastewater does
result from the production of silver powder for use in these
electrodes. This discharge source is addressed as a separate
ancillary operation which is common to both the cadmium and zinc
subcategories.
Mercuric Oxide Cathodes - The manufacture of mercuric oxide cathodes
for use in cadmium subcategory batteries proceeds by physical
compaction of the powdered material. No process wastewater discharge
from this operation is reported.
Nickel Pressed Powder Cathodes - The manufacture of pressed powder
cathodes including cathodes commonly described as "pocket plates" in
the literature is accomplished by blending solid powdered material and
physically applying the resultant mixture to a conductive supporting
grid. Subsequently, the electrode may be formed by cycling it through
several charge-discharge sequences to develop maximum electrical
capacity. The materials blended for application to pocket plate grids
generally include nickel hydroxide which is the primary active
material in the cathode, cobalt hydroxide added to modify the
battery's voltage characteristics and increase electrical capacity,
graphite which provides conductivity from the grid through the bulk of
the active material, and binders added to provide mechanical strength.
One plant presently produces nickel cathodes in a process similar to
that described above. Electrode formation prior to assembly into
batteries is not reported by that facility, and no battery
manufacturing process wastewater is produced. One other plant
presently produces active material for use in pressed powder cathode
manufacture and assembles batteries.
No present manufacturer of these electrode types produces process
wastewater in their manufacture.
Nickel Electrodeposited Cathode - The electrodeposition process
involves nickel hydroxide precipitation from nitrate solution by
electrolysis with a subsequent discharging charging cycle in caustic
solution. After electrochemical formation is completed, the cathode
material is rinsed to remove residual caustic. Figure V-5 (Page 197)
is a schematic diagram of the nickel electrodeposition process.
Sintered nickel grids prepared by either the slurry or dry methods are
used as the substrate upon which nickel hydroxide is electrodeposited.
Nickel powder in either a slurry or dry form is layered on nickel-
plated steel which passes through a furnace for sintering. No water
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is discharged from the sintering operation. Afterwards, the sintered
material is positioned in the electrodeposition tank and the tank is
filled with a nitric acid solution of dissolved nickel and cobalt
salts. An electrical current is applied to the tank causing nickel
and cobalt hydroxides to precipitate on the sintered material. The
presence of cobalt in the nickel active material aids in the charge
efficiency. After deposition of the desired amount of nickel
hydroxide, the material is submerged in potassium hydroxide for
electrochemical formation. After formation is completed, the cathodes
are removed from the tank for subsequent rinsing and the spent
formation caustic is dumped. Waste streams resulting from this process
are: (1) spent formation caustic removal; and (2) post-formation rinse
discharge. Wastewater from this operation was characterized by
sampling. Table V-18 (Page 272) presents the verification analysis
results of the post-formation rinse discharge (on a daily basis).
Table V-19 (Page 273) presents the daily pollutant mass loadings based
on the weight of active nickel applied to produce the cathode.
Nickel Impregnated Cathode - The impregnation process involves
submerging porous sintered stock in an aqueous solution of nickel
salts. Afterwards the product is immersed in a caustic solution to
precipitate the nickel as nickel hydroxide. The material is sub-
sequently rinsed to remove caustic, excess nitrate, and poorly
adherent particles. The entire impregnation cycle is repeated several
times until the appropriate weight gain of active materials is
achieved. During impregnation and precipitation, an electric
potential may be applied to the sintered stock to enhance nickel
deposition and reduce residual nitrate levels in the impregnated
product. In addition to nickel nitrate, impregnation solutions may
contain cobalt nitrate to modify electrode voltage characteristics and
increase electrical capacity. In some cases, impregnation with nickel
salt is accompanied by impregnation with a smaller quantity of cadmium
nitrate to introduce an anti-polar mass (see Section III) into
electrodes intended for use in sealed cells.
After impregnation has been completed, the cathode material is cleaned
to remove excess deposited material. The electrodes are then either
formed or assembled into cells for subsequent formation in the battery
case. Electrodes formed prior to assembly are typically subjected to
several charge-discharge cycles to develop the desired physical
structure and electrical characteristics and to remove impurities.
These electrodes are customarily rinsed after the formation process
resulting in a process wastewater discharge. Formation may be
accomplished either by application of electric current to the
electrodes in a caustic solution or by chemical oxidation and
reduction.
Preparation of the sintered stock required for impregnation using
nickel powder is also considered part of this process function. This
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operation may result in a process wastewater discharge from the clean-
up of tools used to prepare and apply nickel powder paste to support-
ing grids prior to sintering.
Figure V-6 (Page 198) is a flow diagram of the process for producing
impregnated nickel cathodes. As shown in the figure, a total of
eleven different sources of process wastewater are associated with
this process. These wastewater sources include: (1) nickel paste
clean-up; (2) spent impregnation caustic; (3) impregnation rinses;
(4) impregnation scubbers (used for nitric acid fume control); (5)
impregnated stock brushing; (6) pre-formation soak water, (7) spent
formation caustic; (8) post-formation rinses; (9) impregnation
equipment wash; (10) nickel recovery filter wash; and (11) nickel
recovery scrubber.
Seven facilities reported the manufacture of impregnated nickel
cathodes. One of these has subsequently moved their production. Of
the remaining six facilities, four plants, A, B, C, and D,- were
visited for on-site data collection and wastewater sampling. These
facilities represented a variety of process options and collectively
produced all of the wastewater streams identified. Total wastewater
discharges from nickel cathode production were characterized for each
day of sampling at each facility by summing the discrete waste streams
characterized above. This approach was required because waste streams
from individual process steps are frequently treated separately (and
directed to different destinations) or combined with wastewater from
other process functions. As a result, a single total process raw
wastewater stream was not generally available for sampling. The
calculated total wastewater characteristics for the production of
impregnated nickel cathodes are presented in Table V-20 (Page 274).
Table V-21 (Page 275) presents corresponding pollutant mass loadings.
Statistical analyses of these data are presented in Tables V-22 and V-
23 (Pages 276 and 27:7).
Ancillary Operations
Cell Wash - This process operation addresses washing either assembled
cells or batteries following electrolyte addition. The caustic
electrolyte consisting primarily of potassium hydroxide may be spilled
on the cell case during filling. The cells are washed to remove the
excess electrolyte and other contaminants.
Three plants (A, B, and C) in the subcategory reported cell wash
operations. Other facilities produce comparable products without the
need for cell washing. The quantity of water used to wash cells
ranges from 3,032.0 to 15,745.6 liters per day (7520.8 I/day mean and
3784.8 I/day median). The normalized discharge flows based on the
weight of finished cells range from 1.24 to 10.3 liters per kilogram
(4.93 I/kg mean and 3.34 I/kg median). The discharge flow rate
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reported by plant B, however, reflects the combined wastewater from
cell washing and floor area clean-up.
The cell wash wastewater at these facilities was not sampled and no
historical sampling data specifically representing wastewater from the
wash operations was provided. However, no materials were reported to
be used in the cell wash operation and the electrolyte addition to the
cells prior to washing is not expected to contribute pollutants to the
waste stream which are not present in process wastewater streams
previously sampled.
Characteristics of cell wash wastewater streams resulting from the
manufacture of alkaline electrolyte batteries are expected to vary
little among different battery types. Sampling data from cell wash
operations in the zinc subcategory, Tables V-100 and V-101 (Pages 360
and 361), are considered indicative of cadmium subcategory cell wash
effluent characteristics. Cadmium subcategory cell wash discharges,
however, are expected to contain nickel and cadmium rather than
mercury, manganese, and zinc.
Electrolyte Preparation - Electrolyte addition to assembled cells
involves pumps and other equipment which are intermittently cleaned.
Two plants reported wastewater discharge from electrolyte preparation.
The flows based on weight of finished cells are 0.13 and 0.02 I/kg,
respectively. The clean-up wastewater was not sampled, and no
historical sampling data was provided specifically representing the
waste stream. The only raw materials involved are potassium hydroxide
and lithium hydroxide which are not expected to contribute any
priority pollutants to the waste stream. The volume and pollutant
loads contributed by this wastewater source are minimal.
Floor Wash - Some facilities use water for floor maintenance in
process and assembly areas. Three plants in the data base reported
using water to clean floor areas. The discharge flow from this source
ranges from 0.25 to 33.4 liters per kilogram of finished cells.
The floor wash water for maintaining both impregnation and electrode-
position process areas as well as the assembly area was sampled at one
plant. The analysis results in units of mg/1 are presented in Table
V-24 (Page 278). In addition, Table V-25 shows the pollutant mass
loadings in units of mg/kg of cells produced. Pollutants in the floor
wash discharge include nickel, cobalt, cadmium, and zinc. Both nickel
and cobalt are present due to cleaning the nickel cathode process
floor areas. Floor maintenance in the vicinity of the cadmium anode
production is the primary contributor of cadmium in the wastewater.
The source of zinc is not readily determined.
Employee Wash - For purposes of health and safety, some plants require
employees to wash hands prior to lunch and at the end of the work
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shift to remove process chemicals. Hand-wash water was sampled at one
plant. These samples primarily reflect wash water that was used to
clean the hands of employees assembling nickel-cadmium batteries as
opposed to wash water used by process operators who handle the active
material. The analysis results presented in Table V-26 show that the
wastewater contains primarily oil and grease and TSS which are present
due to the nature of the assembly operations. On the first sampling
day, all pollutant levels are low since the sample was taken during
the second shift when there were only a few employees assemblng
batteries. The other two samples were taken during the first shift
when approximately fifteen times the employees washed their hands.
Table V-27 (Page 281) presents the pollutant mass loadings based on
weight of finished cells produced for each sample day.
Cadmium Powder Production - Cadmium powder production involves
chemical precipitation of cadmium. The cadmium may be returned to the
initial mixing step when the powder does not meet specifications.
Wastewater discharge from cadmium powder production results from
product rinsing and from air scrubbers used to control fumes from
process solutions. Wastewater from product rinsing was characterized
by sampling. The resulting concentrations together with corresponding
pollutant mass loadings based on the total discharge flow are shown in
Table V-28 (Page 282).
Silver Powder Production - The production of silver powder used
specifically for battery cathodes is produced primarily for silver
oxide-zinc batteries, and also for silver-cadmium batteries.
Discussion of this operation is under ancillary operations in the zinc
subcategory, on page 191. Analysis results from wastewater samples
collected on three successive days are presented in Table V-118 (Page
378). Production normalized discharge volumes and corresponding
pollutant mass loading for each sampling day are shown in Table V-119
(Page 379).
Nickel Hydroxide Production - Nickel hydroxide for use in battery
manufacture is produced by preparation of a solution containing nickel
and cobalt sulfates, precipitation of hydroxides from the solution,
and washing and drying the precipitate. In addition, graphite may be
added to the precipitated hydroxides. Wastewater discharge from this
process results from washing the precipitate. The reported discharge
volume from this source is 110 I/kg.
This operation was observed during data collection for this study, but
the resultant wastewater discharge was not characterized by sampling.
At that facility the wastewater from product washing is treated by ion
exchange to recover nickel prior to discharge. Characteristics of the
resultant effluent as supplied by the plant are presented in Table V-
12 (Page 266).
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Cadmium Hydroxide Production - Cadmium hydroxide for battery
manufacture is produced by thermal oxidation, addition of nickel
sulfate, hydration, and drying of the product. Process wastewater
results only from contamination of seal cooling water on slurry pumps
used in hydration. The total volume of this waste amounts to 0.9 I/kg
based on the weight of cadmium contained in the cadmium hydroxide
produced.
As discussed for nickel hydroxide production, this operation was
observed but its effluent was not characterized by sampling.
Wastewater from cadmium hydroxide production is combined with other
process waste streams prior to treatment by chemical precipitation and
clarification (by sedimentation and polishing filtration). Reported
characteristics of the resultant discharge are presented in Table V-12
(Page 266).
Total Process Wastewater Discharge Characteristics
Total process wastewater characteristics were determined by sampling
at four plants in the cadmium subcategory. These characteristics,
reflecting the combined raw waste streams from all cadmium subcategory
process operations at each site on each of three days of sampling, are
summarized statistically in Table V-29 (Page 283). Prevailing
discharge and treatment patterns in this subcategory generally
preclude directly sampling a total raw waste stream because wastes
from indivi-dual process operations are often treated or discharged
separately. In other cases, individual process wastes are mixed with
other waste streams such as non-contact cooling wastes and
electroplating wastewater prior to combination with other cadmium
subcategory waste streams. Consequently, the total process wastewater
characteristics shown in Table V-29 were determined for each plant by
mass balance calculations from analyses of wastewater samples from
individual process operations.
As Table V-29 shows, concentrations of some pollutants were observed
to vary over a wide range. These variations may generally be related
to variations in manufacturing processes discussed in the preceding
pages. Despite the observed variations, it may be seen that the most
significant pollutants are generally consistent from plant to plant
and that waste treatment requirements of all of the sampled plants are
quite similar.
CALCIUM SUBCATEGORY
Introduction
This subcategory encompasses the manufacture of thermal batteries for
military applications. These batteries are designed for long term
inactive storage followed by rapid activation and delivery of
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relatively high currents for short periods of time. This is
accomplished by the use of solid electrolytes which are heated to
above their melting point to activate the cell. Heat is supplied by
chemical reactants incorporated in the cell distinct from the anode
and depolarizer. Because calcium, the cell anode material, reacts
vigorously with water, water use and discharge in manufacturing these
batteries is quite limited. Production volumes are generally small
and manufacturing specifications vary depending upon military
specifications for particular batteries. The most significant
pollutants found in the limited volumes of wastewater generated in
this subcategory are asbestos and chromium.
Manufacturing Processes
In general, the manufacture of calcium anode thermal batteries
involves the preparation of the cell anode, depolarizer, electrolyte,
and the cell activator (heating element). This is followed by
mechanical assembly of these elements together with current
collectors, insulators, initiators, and containers to produce cells
and multicell batteries. Process water using steps are limited to
heating component production and, in some cases, testing and plating
of the completed battery assembly. Water may also be used and waste-
water generated in the disposal of calcium scrap. A generalized
process flow diagram is shown in Figure V-7 (Page 199 ). The
relationship between the process elements and discrete wastewater
sources reported at battery facilities is illustrated in Figure V-8
(Page 200 ).
Calcium anode material is generally produced by vapor deposition on a
metallic substrate such as nickel or iron which serves both as a
current collector and support for the calcium durir- eel! operation.
Because of the high reactivity of metallic calcium with water, this
process and all subsequent assembly operations involving the anode are
accomplished without the use of water and, in fact, must be performed
in areas of reduced humidity.
Depolarizers for these cells include calcium chromate, tungstic oxide,
and potassium dichromate. They may be prepared for use in the cells
in a variety of ways including impregnation of fibrous media,
pelletization of powders, and glazing. All are accomplished without
the use of process water. Electrolyte processing is similar and some
cell designs in fact combine the depolarizer and electrolyte.
Essentially all cells presently produced employ a lithium chloride-
potassium chloride eutectic mixture as the depolarizer.
Impregnation of fibrous media such as glass tape is accomplished by
dipping the fibrous material in a fused bath of electrolyte,
depolarizer, or mixture of electrolyte and depolarizer. The
impregnated material is subsequently allowed to cool and cut to shape
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for the specific cell design being constructed. Alternatively, the
depolarizer or electrolyte may be ground to powder, mixed with a
binder such as kaolin or silica, and pressed to form a pellet of
suitable size and shape. In general, pellets containing the
depolarizer contain electrolyte as well to ensure adequate
conductivity, and multi-layer pellets containing both depolarizer and
electrolyte layers are produced. Pellets are also produced which
contain a homogeneous mixture of electrolyte and depolarizer
throughout.
The heating component containing highly reactive materials is an
essential part of a thermal cell. Two basic types of heating
components are reported in present use, heat paper containing zir-
conium powder and barium chromate, and heat pellet containing iron
powder and potassium perchlorate. Heat paper is produced in a process
which involves process water use and wastewater discharge. Initially
zirconium powder, barium chromate (which is only sparingly soluble),
and asbestos fiber are mixed as an aqueous slurry. The slurry is then
filtered to produce a damp paper containing the zirconium and barium
chromate as well as the asbestos fiber. The filtrate is generally
treated by settling and discharged. Heat pellets are prepared by
mixing potassium perchlorate and iron powders and pressing the mixture
to form a pellet. This process involves no water use or discharge.
Heat paper is non-conductive during cell operation and must be used in
cells designed to accommodate this insulating layer. Heat pellets
become conductive during operation and may be used as the cathode
current collector as well as the source of heat to activate the cell.
Assembly of batteries from these components frequently involves the
creation of stacked multi-cell structures to provide voltages
considerably above the single cell output (generally 2.5-3 volts).
Assembly is under rigid quality control specifications and is
accomplished primarily by hand with frequent intermediate tests and
inspections. No water is used.
After assembly has been completed, and the cells are hermetically
sealed, they may be immersed in a water bath to test for leakage. The
contents of this bath may be discharged on an infrequent basis. It is
also common to tin or cadmium plate the case of assembled thermal
batteries. Wastewater discharges resulting from these operations are
not regulated under effluent guidelines for the battery manufacturing
category.
Subcategory Data Summary
Calcium anode batteries are produced at three plants. All production
is of specialty products governed by military specifications, and
products at different plants are not, in general, interchangeable.
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Raw materials used in manufacturing these batteries include: calcium,
iron, lithium chloride, potassium chloride, calcium chromate, silica,
kaolin, asbestos, zirconium, barium chromate, glass fiber, and
potassium dichromate. Specific materials vary somewhat from site to
site although the use of calcium, iron, lithium and potassium
chloride, calcium chromate, zirconium, barium chromate, and asbestos
is common to all manufacturers of these batteries. Present trends are
to eliminate the use of calcium chromate and barium chromate in new
designs by substituting alternative depolarizers and heat sources.
Military specifications for existing designs, however, make it
unlikely that use of these materials in manufacturing will be
discontinued altogether. Because of the limited use of water in
manufacturing batteries in this subcategory, only zirconium, asbestos,
barium chromate, calcium, and iron are likely to contact process water
or enter process wastewater at these facilities. Other process raw
materials may enter area wash water during infrequent shut down and
maintenance periods, but since normal clean-up is dry, the total
volume of water used in clean-up and the amount of these materials
discharged are very small.
Wastewater flows in this subcategory result only from the production
of heat paper as discussed above. The highest volume reported by any
plant in the subcategory is 60.7 1/hr (16 gal/hr). When normalized on
the basis of the weight of reactants used (barium chromate and
zirconium), the highest wastewater flow is 24.1 I/kg (2.9 gal/lb).
Present treatment practice is limited to settling and process
wastewater is either contract removed or discharged to a POTW. One
plant presently reports no process wastewater from the manufacture of
calcium subcategory batteries.
Effluent characteristics reported by one plant in this subcategory are
presented in Table V-30 (Page 284). Data reported by this plant are
specifically for the effluent from heat paper production.
LEAD SUBCATEGORY
Batteries manufactured in this subcategory employ lead anodes, lead
peroxide cathodes, and acid electrolytes. Lead subcategory products,
however, vary significantly in physical configuration, size, and
performance characteristics. They 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
produced from lead electroplated on steel and an acid electrolyte.
Process wastewater is generated only from the electroplating
operations which are not considered under battery manufacturing. The
SLI and industrial batteries are manufactured and shipped as "dry-
charged" and "wet-charged" units. Dry-charged batteries are shipped
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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.
Process water use and wastewater discharge varies widely among lead
subcategory plants reflecting differences in water use control and
wastewater management practices as well as 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 are also observed to vary widely resulting in
significant variability in effluent quality. Most plants in the
subcategory presently discharge process wastewater to POTW, and many
provide little or no pretreatment.
Manufacturing Process
The manufacture of lead batteries is illustrated in the generalized
process flow diagram presented in Figure V-9 (Page 201). 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 manufacture; (3) pasting
processes designed 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) charging or formation which
further binds the paste to the grid and renders the plate
electrochemically active; (8) final assembly; (9) testing; (10)
washing; and (11) final shipment. Each of these process steps may be
accomplished in a variety of ways. They may also be combined in
different overall process sequences depending on use and desired
characteristics of the batteries being produced. These process steps,
and their various implementations form the basis for analysis of lead
subcategory process wastewater generation and control as shown in
Figure V-10 (Page 202).
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 in dcp's
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 and
silver may be added to grids. Newly developed grid 'structures
discussed in the literature use ABS plastic grids coated with lead or
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polystyrene interwoven with lead strands for the negative plate, but
no plant reported commercial manufacture of these grid types.
Pure lead grids are used in the manufacture of batteries designed
especially for applications requiring low self-discharge rates. Their
use is limited in most batteries by the relatively low strength
provided by pure lead per unit of grid weight.
Lead-antimony has long been considered a most desirable alloy for grid
manufacture because of its ability to form easily molded castings
capable of sustained strength under charging cycle conditions while
providing a low expansion coefficient relative to lead. Antimony
retards positive grid growth and corrosion. It migrates from the
positive grid into the positive (lead peroxide) paste increasing paste
adhesion during cycling to prolong plate life. Unfortunately, when
antimony leaves the grid, it can also enter the electrolyte to plate
out onto the negative plate (lead) increasing self discharge during
open circuit stand and liberating hydrogen in preference to the
reduction of lead sulfate (local action) during charging. This effect
is diminished by the addition of trace amounts of selenium.
The use of lead-calcium alloy grids has allowed the development of
sealed maintenance-free batteries. Increased production of calcium
alloy grid batteries has resulted from improvements in techniques for
casting calcium-lead grids. Batteries with calcium-alloy grids were
originally developed by the telephone companies for float service
where the battery is maintained in a charged condition to
automatically take care of power required by a fluctuating load.
Current required for this application is 1/5 to l/8th that needed by
batteries with lead-antimony grids. For these stationary
applications, calcium alloy grids compete with pure lead grids.
Recently, sealed batteries using calcium alloy grids have become
increasingly popular for automotive use. Lead-strontium alloys may be
used for similar reasons and are easier to cast. Calcium alloy grids
are also manufactured by punching or perforating, by the expanded
metal process, and by wire forming techniques.
Among other additives to lead alloys, arsenic and silver inhibit grid
growth on overcharge and reduce postive grid corrosion, tellurium
provides finer grain and corrosion resistance, tin produces well
defined castings, and cadmium improves mechanical properties of the
lead. Impurities common to grid lead include copper, cuprosilver,
zinc, bismuth, and iron. Water discharge from this step is not
included in the battery manufacturing category but process wastewater
is rarely produced as a result of grid casting operations.
Active Material, Oxide Manufacture - 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
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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 exothermic oxidation 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
the oxidizing air flow and by non-contact cooling of the ball mill.
In the Barton process, molten lead is fed into a pot and vigorously
agitated to break lead into fine droplets by aspiration. 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 electrodes
used. Recycled lead recovered by remelting scrap is normally used in
casting grids, straps, and terminals.
Wastewater from lead oxide production (except for leady oxide) is not
included for regulation under the battery manufacturing category.
While the production of leady oxide is included in the battery
manufacturing category, only non-contact cooling water is used at most
sites, although some plants reported having contact wastewater and
scrubber discharge wastewater.
Pasting Processes - The process of pasting lead oxides on the grid
produces electrode plates with a porous, high area, reactive surface.
The pores allow maximum contact of ions present in the 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, in some cases red lead, binders such as acrylic fibers,
sulfuric acid, arid 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 ligninsulfonic acid. Addition
of expanders amounting to an aggregate 1 or 2 percent of the paste can
increase negative plate effective area by several hundred percent.
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While hardeners have been added to pastes (e.g. glycerine and
carboxylic acid), prevailing present practice is to control these
properties 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 added to the paste functions to produce proper consistency and
increase paste adhesion. During acid addition, considerable heat is
evolved requiring temperature control to provide a paste with the
proper cementing action.
Paste is applied to the grids by hand or machine. Water is required
to clean the equipment and the area. This water is usually recycled
after settling to remove particulates. It contains large
concentrations of lead as well as the various additives used in the
paste and, where discharged to treatment, greatly increases raw waste
pollutant loads. Process wastewater may also be generated by wet
scrubbers in the pasting areas.
Drying and Curing - The drying and curing operations are very
important in providing electrodes with the porosity and mechanical
strength required for adequate battery performance and service life.
The purpose of this step 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 or placing in humidity controlled rooms for several days
to convert free lead particles in the plates to lead oxide. In this
process the free lead is reduced from 24-30 percent to the desired
level (5 percent or less). Proper conditions of temperature and
humidity cause the formation of small crystals of tribasic lead
sulfate which convert easily to a very active lead peroxide (positive
plate) during formation. Too 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 formation. Too little or too much moisture in the plate
retards the rate of oxidation. The rate of curing may be increased by
providing controlled humidity at higher temperatures. This process
(steam curing) results in process wastewater.
After curing and prior to formation of plates, they may be soaked in
sulfuric acid solution to enhance sulfation and improve mechanical
properties. This may occur directly in the battery case or formation
tank or in a separate vessel. In either case, no significant process
wastewater results from this practice.
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Semi-Assembly (Stacking, Grouping, Separator Addition) - Following
curing, dry pasted 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.
Where formation is accomplished in the battery case (closed
formation), positive and negative plates are stacked together with
separators and welded to produce elements of an appropriate size for
the batteries being produced. Separators may be interleaved between
the positive and negative plates or wrapped around the positive
plates.
Where formation is accomplished in open tanks, positive and negative
plates are commonly grouped separately, spaced, and welded without
separators. After formation, separators are added and positive and
negative plates combined to form elements which are then inserted into
the battery case.
Separators serve to prevent short circuiting between the anode and
cathode while at the same time permitting electrolyte conduction
between them. They also may serve to provide physical support to the
positive plate. Both the configuration and material of separators
vary depending on the specific properties desired. Materials used for
separators in lead acid storage batteries include paper, plastic,
rubber, and fiberglass. Sheet type separators which are interleaved
between positive and negative plates are usually ribbed on one side.
The ribbed side is placed against the cathode to provide for improved
electrolyte transport. Other separators are flexible and are wrapped
around the positive plate or are in the form of envelopes enclose the
positive plates. Some separators are highly absorbent and retain
large quantities of electrolyte preventing it from spilling from the
battery.
Water use in the semi-assembly operation is limited to noncontact
cooling water associated with welding of elements and groups. No
process wastewater is produced.
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
commonly proceeds in two steps. Initially the acid is cut to an
intermediate concentration (about 45 percent acid) which may be used
in paste preparation. Subsequently 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. Acid cutting generates heat and generally
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requires non-contact cooling. Process wastewater, however, is not
generally produced although wet scrubbers are used at some sites to
control acid fumes. Since water is consumed in cutting acid, some
facilities use this process as a sink for process wastewater
contaminated with acid and lead, reducing or eliminating the volume
requiring treatment and discharge.
For some batteries, sodium silicate is added to the electrolyte prior
to addition to the battery to produce a thixotropic gel. The 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.
The addition of electrolyte to batteries for formation and for
shipment is frequently a source of wastewater discharge both directly
in the form of acid spillage and indirectly in discharges from battery
rinsing necessary to remove spilled acid from the battery case.
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 facilities, batteries are filled by immersion in tanks of acid.
Overfilling or filling by immersion result in significant
contamination of the battery case with acid and necessitate rinsing
prior to further handling or shipment, generating significant volumes
of process wastewater.
Formation (Charging) - Although lead peroxide is the active material
of the finished positive plate, it is not used in preparing paste for
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 in open tanks prior to battery assembly (open
formation) or within the battery case after assembly has been
completed (closed formation). Open formation is most often practiced
in the manufacture of dehydrated plate batteries.
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Open Formation. Open formation has the advantage of allowing access to
the battery plates during and after formation. This permits visual
inspection of the plates during formation and closer control of
formation conditions than is possible during closed formation. More
significantly, however, after open formation, plates may conveniently
be rinsed thoroughly to remove residual electrolyte and efficiently
dried as required for the manufacture of dehydrated plate batteries.
Most open tank formation is immediately followed by rinsing and
dehydrating of the formed plates. These operations are particularly
important for the (lead) negative plates which would oxidize rapidly
if acid and moisture were not eliminated. Rinsing is accomplished by
a variety of techniques and may involve the use of deionized water in
some cases. Multi-stage rinses are frequently employed to achieve the
required degree of electrolyte removal. Drying often involves the use
of both heat and vacuum to achieve dehydration of the plates.
Wastewater discharges result from vacuum pump seals or ejectors used
in drying as well as from rinsing. Wastewater may also result from
wet scrubbers used to control acid mist and fumes from charging tanks,
but this source is generally small in comparison to rinsing and drying
discharges.
Open tank formation may also be used in the manufacture of some wet
batteries. Because problems in formation associated with
inhomogeneity in the plates are most pronounced in larger plate sizes,
open tank formation for the manufacture of wet batteries is most often
encountered in the manufacture of industrial batteries with large
electrodes. Since these electrodes do not require rinsing and drying
however, open tank formation in these instances differs little from
closed formation in terms of wastewater generation and entails only
losses from drips and spills and, in some instances, discharge from
wet scrubbers used for fume control.
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. In general terms, as
the electrolyte concentration is increased, the rate at which
formation of positive plates proceeds is decreased, but durability of
the product is improved. The rate of formation of negative plates is
increased by increasing acid concentration.
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. The rate
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at which formation proceeds may vary appreciably with formation
periods ranging from about one to seven days. During formation heat
is generated in the batteries which must be dissipated. At the higher
charging rates this may be accomplished using contact cooling water on
the outside of the battery cases. This water is normally applied as a
fine spray and may be recirculated reducing the volume of the
resultant wastewater discharge. At lower charging rates, air cooling
is sufficient, and this process water use is eliminated. Since
hydrogen gas is often evolved during formation, wet scrubbers may be
used to control sulfuric acid fumes and mist carried out by the gas.
At lower charging rates, electrode over-voltage and consequently
hydrogen generation is reduced minimizing the need for wet scrubbers.
Double fill formation processes involve the use of a more dilute
formation electrolyte, formation of the battery in about 24 hours,
removal of the formation electrolyte for reuse, and addition of more
concentrated fresh electrolyte suitable for battery operation. Double
fill-double charge batteries are subsequently given a second boost
charge prior to shipment. As for single fill formation, contact
cooling water is commonly used, and wet scrubbers may be required to
control mist and fumes. Both filling and emptying battery cases may
result in contamination of the case with acid necessitating subsequent
rinsing. The extent of this contamination depends on the filling and
emptying techniques applied.
The fill and dump process includes damp batteries which are a part of
the group of batteries commonly called dry-charged by manufacturers.
These differ from dehydrated plate batteries in the degree of
electrolyte removal and dehydration. This causes the degree of charge
retention during long-term storage to be less than the dehydrated
plate type. These 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
removal of the formation electrolyte, some manufacturers add chemicals
to the battery in a second acid solution which is then 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.
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, installation of
elements in battery cases, 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, rubber cement, or with a bitu-
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minous sealer; vents are installed; and the battery posts are welded
or "burned" in place. Partial assembly prior to closed formation is
contiguous with semi-assembly and involves the same operations
described above except that the creation of elements proceeds as
described under semi-assembly. Final sealing of the case and
installation of vent covers is accomplished after formation. In
either case, no process water is used in assembly, and no process
wastewater discharge results.
Testing - Most finished batteries are tested prior to shipment to
ascertain correct voltage and current capacity. At some facilities a
small volume of process wastewater may result. In addition, selected
batteries may undergo more extensive tests including capacity, charge
rate acceptance, cycle life, over-charge, and accelerated life tests.
The conduct of these tests and subsequent disassembly and inspection
operations may also yield a very small volume of wastewater which is
similar in character to discharges from formation operations.
Batteries which are found to be faulty in testing may be repaired on
site. These repair operations generally requiring disassembly of the
battery and replacement of some component(s) may also generate a
limited volume of process wastewater although this source is minor in
relation to the total process wastewater flow.
Battery Wash - At most facilities batteries are washed prior to
shipment to remove electrolyte slops resulting from spilling and
splashing during filling and formation, and other contaminants
resulting from assembly operations. Washing may be accomplished by
hand or by battery wash machines and may involve the use of detergents
to achieve more complete removal of dirt, oil and grease. Where
detergents are used, the final battery wash containing the detergent
may be preceded by a water rinse to remove lead and acid. Wastewater
from battery rinses and from battery wash operations in which
detergents are not used are treated and reused, or used in electrolyte
preparation at some sites.
Process Integration - The differing means of implementing each of the
basic process steps discussed above may be combined to produce a large
number of distinct process flow sheets. Each facility will combine
these process elements in a pattern suited to its age, type of
product(s), degree of automation, and production volume. Further, not
all facilities perform all process operations on-site. A significant
number of plants purchase pasted battery plates from other facilities.
Conversely, some battery manufacturing plants produce only battery
plates and do not assemble finished batteries.
When plates are formed by the plate manufacturer prior to shipment
only assembly and electrolyte addition are performed on-site by the
battery manufacturer. Alternatively, the plates may be sold "green"
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(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 sheets of Figures V-ll through V-15 (Pages 203 -
207). In many cases, single facilities produce multiple product types
and therefore have process flow sheets combining operations of more
than one of these figures.
Subcategory Data Summary
Production - Lead acid battery production reported in dcp's totalled
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. Reported
annual production of batteries at individual facilities 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 dry 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.
Water Use and Wastewater Discharge - Production normalized flows
discharged (I/kg of total lead) from various process operations are
presented in Figure V-16 (Page 208). This figure shows the
distribution of production normalized flows for each process operation
at those plants which produce a wastewater discharge for a process
operation. Plants which report no process wastewater from the process
are not represented on the curves as shown- The insert on the figure
presents for each process the median of the non-zero flows, the median
of all flow 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 (plants supplying specific process flow data).
As the regression lines on the figure indicate, the dispersion in the
flow data (as indicated by the slopes of the lines) showed no
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significant differences among different process operations. 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 indicated by these data. Consequently the data indicate that any
plant active in any of these process operations can achieve wastewater
flows demonstrated for that process by other facilities without any
major process change.
As the insert on Figure V-16 shows, there are significant differences
among different process operations in the frequency with which zero
wastewater discharge results. Five of the eight processes shown are
reported to produce zero process wastewater by over half of the plants
supplying data. Zero process wastewater is reported by fewer than 20
percent of the plants supplying data for the other three process
operations.
In open case formation for batteries which are shipped wet, five
plants reported no formation process wastewater, while the other two
showed very high process discharges comparable to those from plate
formation and dehydration processes used in producing dehydrated
batteries. An examination of manufacturing process information at
these two facilities reveals that they are in fact, producing formed
dehydrated electrodes prior to including them in wet-charged
batteries. Thus, all facilities practicing open case formation
without rinsing and dehydrating the formed electrodes presently report
zero process wastewater discharge from this operation.
Closed formation of wet batteries was reported to produce a process
wastewater discharge at 31 of 88 plants supplying information. Both
single fill and double fill formation are included. Data from those
facilities from which data specific to these two formation processes
was obtained are summarized in Figure V-17 (Page 209). As these data
show, 90 percent of all plants reported zero discharge from single
fill formation while over 75 percent reported wastewater discharge
from double fill formation. The median flow at discharging plants,
however, was approximately equal for both processes. The more
frequent discharge of process wastewater from double fill formation is
attributable to more frequent use of contact cooling water in
formation as well as rinsing of batteries after dumping formation
electrolyte.
Process water from leady oxide production was reported by twelve
facilities, ten of which were operated by two companies. Waste was
reported to originate in leakage and "shell cooling" on ball mills,
contact cooling in oxide grinding, and wet scrubbers used for air
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pollution control. Most plants perform these processes using only
noncontact cooling water and dry bag-houses for air pollution control
and consequently produce no process wastewater.
Fifty-one of seventy plants supplying data produce no process
wastewater discharge from electrode pasting operations. This is
accomplished by treatment and recycle of pasting wastewater which is
common practice through the subcategory.
Process wastewater discharge from curing operations is reported by
fewer than 10 percent of the plants supplying data (8 of 89
facilities) and results from steam curing processes. Predominant
industry practices of curing in covered stacks or in humidity
controlled rooms achieve equivalent results to steam curing and
produce no wastewater. Mean and median discharge flows for each
process operation in this subcategory are presented in Table V-31
(Page 285).
Total plant discharge flows range from 0 to nearly 62,000 1/hr with a
median value of 3,500 1/hr. Production normalized discharge flows
range from 0 to 100 I/kg with a median of 2.8 1/kkg. Discharge flow
from each plant in the subcategory is shown in Table V-32 (Page 286 ).
Approximately 27 percent (50 plants) of all plants in the subcategory
reported zero process wastewater discharge to POTW or surface waters.
These zero discharge facilities were primarily either plants which
purchased plates and assembled batteries only (17 plants) or plants
which produced only wet batteries and generally employed single-fill
formation (18 plants). Of the 50 plants, 26 plants indicated that no
process wastewater was generated. Six others indicated that
wastewater was recycled and reused. The remaining facilities employ
evaporation or holding ponds (5 plants),' discharge to dry wells,
sumps, septic tanks or cesspools (9 plants), contract removal of pro-
cess wastewater (2 plants), disposal of wastes in a sanitary landfill
(1 plant), or did not specify the disposition of process wastes (1
plant). Among discharging plants, only sixteen were direct
dischargers. All others introduce process wastewater into POTW.
Wastewater Treatment Practices and Effluent Characteristics - Plants
in the lead subcategory employ a variety of end-of-pipe treatment
technologies and in-process control techniques and achieve widely
varying effluent quality. End-of-pipe treatment practices employed
include pH adjustment, chemical precipitation, settling in a variety
of devices, filtration, flotation, and reverse osmosis. In-process
control techniques include segregation and treatment or recycle of
specific waste streams and process modifications to eliminate points
of water use and discharge. Discharge to POTW is performed by most
plants in the subcategory which produce a process wastewater
discharge. Dcp responses showed some significant differences between
plants discharging to POTW and direct dischargers both in terms of
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treatment practices and effluent performance achieved. Direct
dischargers generally provide more extensive wastewater treatment'and
control facilities 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-seven
plants reported the use of pH adjustment and settling while nineteen
others reported the use of filtration for solids removal. Reported
filtration units generally serve as primary solids removal and are not
polishing filters designed to achieve very low effluent pollutant
concentrations.
Effluent quality data provided in dcp's for plants practicing pH
adjustment and settling are presented in Table V-33 (Page 289 ). While
the dcp's did not in general provide sufficient data to allow
meaningful evaluation of treatment system design and operating
parameters, some characterises 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's indicates that few discharges
are at 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 in 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-33 clearly indicate that the
sedimentation systems employed by some facilities 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 these two groups
of plants corresponds to differences in the severity of regulations
presently applied to direct and indirect discharges, indicating that
the variations in the data reflect variations in treatment design and
operating practice rather than difference in attainable levels of
pollutant reduction at these facilities.
Table V-34 (Page 290 ) presents effluent quality data from dcp's 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.
Twenty-two plants reported the introduction of process wastewater into
POTW after pH adjustment without the removal of suspended solids.
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Effluent quality data were provided by eleven of these facilities as
shown in Table V-35 (Page 291 ). This table also shows effluent data
from one facility which reported process wastewater discharge to a
POTW without treatment.
Several plants provided data in dcp's indicating the use of wastewater
treatment systems other than those discussed above. These included
sulfide precipitation, flotation separation, and reverse osmosis. One
facility 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, in-process controls were often not clearly shown and were
only indicated by process line descriptions and identified wastewater
sources similar to those of plants visited for on-site data
collection. As a result, the present extent of practice of such
techniques as low-rate charging without the use of contact cooling
water cannot be defined from the dcp's. One in-process control
technique which could be identified in many dcp's was segregation of
process wastewater from pasting area and equipment washdown and
subsequent settling and reuse of this waste stream. Approximately 30
percent of the plants reporting wastewater discharges indicated this
practice. Those facilities using this in-process technique are
identified in Tables V-33, V-34, and V-35. The data in Tables V-33
and V-34 do not show significantly lower effluent lead concentrations
from plants recyling pasting wastewater although raw waste
concentrations and pollutant loads are significantly reduced by this
practice as demonstrated by the data in Table V-35. This further
substantiates the observation that effluent quality at existing lead
subcategory plants is primarily determined by treatment system design
and operating parameters.
Additional in-process control techniques which are indicated in the
dcp's 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; slow 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's and is presumed to
exist at other facilities 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 30 percent of those facilities which
practiced dehydrated plate manufacture and supplied process diagrams
in their dcp's. The production normalized flow resulting from these
rinses are not generally significantly lower than those resulting from
single stage or unspecified rinses. Since the spillage of electrolyte
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on battery cases necessitates removal of the spilled acid prior to
shipment to allow safe handling of the battery, it may be concluded
where wet batteries are shipped and battery wash discharges are not
reported, that 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 slow-rate
charging is indicated at a number of battery manufacturing facilities
which did not indicate process contact wastewater from wet-charge
formation processes. Finally, approximately 50 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 facilities either achieve satisfactory plate drying without the
use of seal or ejector water or recirculate water used for these
purposes.
Process Water Uses and Wastewater Characteristics
Process wastewater was characterized by sampling at five facilities
manufacturing lead acid batteries. These plants collectively
represent the production of both SLI and industrial batteries and
manufacturing processes including single and double fill closed
formation processes and the formation of damp and dehydrated plate
batteries. They also embody a variety of in-process control
techniques including pasting washdown recirculation, low rate
formation, and recirculation of treated process wastewater, and
several different wastewater treatment technologies. Sampling at
these facilities provides the basis for characterizing total battery
manufacturing process wastewater and wastewater resulting from
specific process operations. Interpretation of sampling results is
enhanced by reference to additional information obtained from industry
dcp's and in visits to eleven additional lead acid battery
manufacturing facilities at which wastewater samples were not
obtained.
Total Process Wastewater Characteristics - Total process wastewater
characteristics determined from the analysis of samples collected at
Plants A, B, C, D, and E are presented in Table V-36 (Page 292).
Pollutant loads determined by sampling at each of these faciltties are
presented in Table V-37 (page 294 ). These data represent the process
wastewater stream discharged to treatment at each facility. All
process waste sources flowing to treatment are included, but streams
which are totally recycled such as pasting wastewater are not included
in these data. Considerable variations in wastewater volume and in
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pollutant concentrations and loadings among these facilities are
evident. They may be understood on the basis of the manufacturing
processes and wastewater management practices at these sites.
Plant A manufactures wet and damp batteries and practices extensive
in-process control of wastewater. Pasting equipment and area washdown
at this facility is treated in a multistage settling system and
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 using 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 for 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 in a reject battery repair area. The total
waste from this facility which is represented in Tables V-65 and V-66
includes wastewater flowing to waste treatment, the battery rinses and
wash water, and the repair area clean-up waste, 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 facility. Significantly, the wastewater treatment system
includes an evaporation pond allowing the achievement of zero
pollutant discharge from this facility.
Plant B manufactures a high percentage of dehydrated plate batteries
but also practices significant in-process control techniques. 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 filling area and battery case washing. Open-case
formation and plate dehydration operations account for most of the
process wastewater generated which results from plate rinsing, fume
scrubbers, formation area washdown, and from a vacuum ejector used in
dehydrating the formed, rinsed plates. Partially treated wastewater
is recycled from the waste treatment system for use in the wet
scrubbers, area washdown, and rinsing 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 facility is only
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46 percent of the raw waste volume shown in the table or approximately
4.0 I/kg.
The raw waste 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 lead 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 facility. The relatively
high production normalized flow results 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 controls. Pasting area wash water is collected in a sump
and pumped to the plants' central wastewater treatment facility.
Aside from limited settling of the heaviest material in the sump, this
waste stream is neither recycled nor treated separately prior to
combining with other process waste streams. Wet 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 waste
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 are dumped
after formation and 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 waste at this facility was sampled as it entered
wastewater treatment and includes all sources discussed above. The
pasting wastewater is represented in process wastewater charac-
teristics presented for this plant. This, together with differences
in water conservation practices, appears to account for the
differences observed in pollutant concentrations and waste loads
between this facility and Plant A. Lead pollutant loadings, for
example, are significantly higher at Plant C as a result of the
introduction of pasting wastewater and wastewater from battery
centrifuges into waste treatment, but raw waste concentrations are low
due to the dilution afforded by the much higher wastewater volume at
this facility (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 control
techniques at this facility resulted in the generation of a relatively
low volume of process wastewater. Pasting area and equipment wash
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water is not recycled at this facility, but is separately treated by
settling before introduction into the plant's 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 were formed during
sampling at this facility. Open formation is followed by a two-stage
countercurrent rinse of the formed plates. They are dried in an oven
without the use of any 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, reject battery repair operations, and wastewater from
an on-site laboratory.
Plant E manufactures only wet industrial batteries. In-process
control techniques at this site reduce the ultimate discharge volume
essentially 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 facility results
only from washing pasting equipment and floor areas. This wastewater
is treated and recycled for use in washing pasting area floors.
Equipment is washed using deionized water resulting in a gradual
accumulation of wastewater in the recycled system and necessitating
occasional contract removal of some wastewater. The total process
wastewater characterized in Tables V-36 and V-37 includes the
wastewater from pasting equipment and area washdown. The sample used
to characterize this waste was obtained from a waste collection pit in
which settling of paste particles occurred resulting in the reduced
lead and TSS concentrations observed. The total process wastewater
characteristics presented in Tables V-36 and V-37 were calculated from
analyses of all of the individual waste streams described above
including the pasting wastewater before settling.
A statistical summary of the total raw waste characteristics observed
at these facilities is presented in Table V-38 (Page 296). 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-39 (Page 297 )•
Wastewater From Specific Process Operations - Wastewater samples
obtained at a number of facilities provide characterization of
wastewater from specific process operations which contribute to the
total wastewater stream addressed in the preceding discussion. Major
process wastewater sources characterized include pasting, closed
formation for wet batteries, closed formation for damp batteries, open
formation and plate dehydration for dry charged batteries and battery
wash operations. Wastewater from battery repair operations and
general plant floor washing was also characterized in sampling
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although these sources constitute minor contributions to the total
process wastewater flow.
Characteristics of individual process waste streams from the major
wastewater sources are summarized in Table V-40 (Page 298) which also
provides the range and median values of concentrations in these
individual waste streams.
Pasting. Wastewater samples were taken at three plants. Analysis
results are shown in Table V-41 (Page 299). As indicated on the
table, wastewater samples at two facilities were obtained from sumps
or holding tanks in which some settling of solids from the pasting
waste evidently 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 solids and lead is attained by settling. Since the waste
stream sampled at Plant A has minimum settling effects, it was chosen
as typical of raw wastes developed by this process for the
determination of typical raw waste characteristics as shown in Table
V-69. Pollutant loads from pasting based on sampling results at that
facility are shown in Table V-42 (Page 300). This process is
potentially a major contributor to total raw waste loads but may be
eliminated by recycle as presently practiced at many sites.
Closed Formation of_ Wet Batteries. Wastewater samples were obtained
at Plant A and represent the post formation rinse of double fill wet
batteries. Contact cooling water used in formation was included in
the total process wastewater at Plant C but was not separately
characterized. Production normalized wastewater flows associated with
formation of wet batteries at Plant A are comparable to the median
value found in the dcp's. Formation wastewater characteristics and
pollutant loads observed in sampling at this site are presented in
Tables V-43 and V-44 (Pages 301 and 302 ) respectively.
Closed Formation of Damp Batteries. Wastewater samples were also
obtained at Plant A. 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 discharge is
associated with a spray rinse similar to that used for wet formation.
Loadings are somewhat higher than those for wet formation, 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 of these units is included in the total raw waste stream
sampled at that facility. Formation wastewater at that site results
from contact cooling of batteries during a high rate formation
process.
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Formation and Dehydration of Plates. Plant D uses countercurrent
rinsing of the open case formed electrodes and uses no ejector or pump
seal water in plate dehydration. Despite those practices, wastewater
discharge from plate formation and dehydration at this site is higher
than the median value from dcp's. This may be attributed to the low
volume of dehydrated plate production and inefficient control of water
used in the plate rinse. Concentrations observed in wastewater from
this step (shown in Table V-45, Page 303 ) are similar to those
observed in wastewater from other processes. Pollutant loads from
open formation and dehydration of electrodes are shown in Table V-46
(Page 304). An indication of discharge characteristics from open
formation where water is used both in rinsing and dehydration may be
derived from the total process wastewater at Plant B which is
dominated by discharges from open formation processes.
Battery Wash. Battery wash wastewater sample results from Plants A
and D are presented in Table V-47 (Page 305). Sampling at Plant D
included both a battery rinse and a final detergent wash. Samples
from Plant D also include small flow contributions from battery
testing and area washdown. Table V-48 (Page 306) presents pollutant
loads observed in sampling at these sites.
Battery Repair and Floor Wash. Wastewater samples were obtained at
Plant A. Analysis results are shown in Table V-49 (Page 307), and
corresponding waste loads are shown in Table V-50 (Page 308). The
samples represent waste from a floor washing machine and from cleanup
associated with a battery repair area. As the data show, con-
tributions of these waste sources to the total plant process
wastewater are minimal.
Additional Wastewater Sources. Battery manufacturers reported some
process wastewater streams which were not characterized by sampling.
Some, such as lead casting wastewater and wastewater from plastic
molding operations, were excluded from consideration because they are
not included in the battery manufacturing category. Process contact
wastewater from leady oxide production in ball milling is a rare
occurrence, resulting from inadequate maintenance or air scrubbers.
This process wastewater stream was not specifically characterized by
sampling, however, contributions to total wastewater flow are
minimal.
Wastewater from curing pasted plates by steaming is reported at a
number of facilities but was not observed at any plants visited for
wastewater sampling. This wastewater stream is, however, small in
volume and will have little effect on wastewater treatment design and
performance. It is anticipated that chemical characteristics of
wastewater from this source will be similar to those found in rinse
wastewater from dehydrated plate manufacturing.
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Treated Effluent Characteristics - The characteristics of treated
effluent discharges at three visited battery manufacturing plants are
presented in Table V-51 (Page 309 ). These facilities all employ waste
treatment systems based on chemical precipitation and solids removal
but have implemented three different solids removal techniques.
Plant B employs a tubular cloth filter from which solids are
continuously removed by the flow of the waste stream which becomes
progressively more concentrated as clarified water permeates through
the filter. This system is reported to be highly effective as
indicated in dcp data from this facility. During sampling, however,
excessive solids levels had been allowed to build up in the system and
were observed to be 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 and produced the lowest
lead levels observed in 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 facility.
Data from these facilities illustrate the importance of pH as an
operating parameter for the removal of lead by chemical precipitation.
Both plants B and D were observed to provide treatment at pH values
considerably lower than is desireable for lead precipitation, a
condition reflected in the poor effluent performance observed in
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 effluent lead and TSS values shows clearly that the effluent
contained considerable concentrationsof dissolved lead.
LECLANCHE SUBCATEGORY
This subcategory encompasses the manufacture of all batteries
employing both a zinc anode and a zinc chloride or zinc chloride-
ammonium chloride electrolyte. Presently there are 19 active plants
in the subcategory, 17 of which manufacture cells with zinc anode,
carbon-manganese dioxide (Mn02) cathode, and zinc chloride or zinc
chloride-ammonium chloride electrolyte. The remaining two plants use
a silver cathode. There are several distinct variations both in form
and in manufacturing process for the Leclanche cell, with
corresponding variation in process water use and wastewater discharge.
Wastewater discharge results only from separator production and from
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cleanup of miscellaneous equipment. After a discussion of the
manufacturing processes employed in the subcategory and a summary of
available data characterizing Leclanche subcategory facilities, the
process elements that produce wastewater are discussed in greater
detail regarding specific wastewater sources, flow rates, and chemical
characteristics.
Manufacturing Processes
As shown in the generalized process flow diagram of Figure V-18 (Page
210), the manufacture of batteries in this subcategory comprises the
preparation of the anode and cathode, the preparation or application
of the separator, assembly of these components into cells and
batteries, and ancillary operations performed in support of these
basic manufacturing steps. Process water is used in separator
preparation, electrolyte formulation, and in a variety of ancillary
operations. Process wastewater results from ancillary operations
including the preparation of some types of separators.
The observed variations in anode, cathode, and separator manufacture
and the combinations of these processes carried out at existing plants
and ancillary operations that have been observed to generate
wastewater are shown in Table V-52 (Page 311). These variations
provide the framework for analysis of process wastewater generation in
the Leclanche subcategory as indicated in Figure V-19 (Page 211). Of
twelve identified process elements in this subcategory, only four
generate process wastewater. Three of these were characterized by
wastewater sampling at two facilities in the subcategory. Wastewater
discharge from the fourth is believed to be similar in character, and
is eliminated by recycle in present practices.
Anode Manufacture - The Leclanche anode is produced either from zinc
sheet or powdered zinc. The zinc sheet is most often formed into a
can, which contains the other components of the cell. This can is
either purchased, or formed at the battery plant. The forming
processes may involve cleaning and chromating steps that generate
wastewater; however, these processes are not considered to be part of
battery manufacturing. The other form of zinc sheet metal anode is a
flat zinc plate.
Preparation of powdered zinc anodes includes formulation of an anode
paste of zinc dust, carbon, and binders. The paste is applied to
specific areas on a conductive vinyl film.
Cathode Manufacture - Four distinct types of cathodes are produced in
the Leclanche subcategory; cathodes molded from mixed manganese
dioxide and carbon with several variations in electrolyte form, porous
carbon cathodes (which also contain manganese dioxide), silver
chloride cathodes, and cathodes in which manganese dioxide is pasted
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on a conductive substrate. These cathode types are combined with zinc
anodes and electrolyte to yield cells with a variety of configurations
and performance characteristics.
Powdered Mn02 cathodes are produced by blending manganese dioxide with
other powdered materials consisting primarily of carbon. The
resulting mixture is then combined with electrolyte solution before
insertion into the cell. Manufacture of this type of cathode is
reported by 14 plants. One of these discontinued operations during
1979, leaving 13 active plants. Based on both the survey and visit
data, the list of raw materials added to the manganese dioxide ore to
form the cathode may include acetylene black, carbon black, graphite,
magnesium oxide, mercury, and ammonium chloride. Typically, ammonium
chloride is added to the electrolyte solution prior to blending with
the depolarizer material; however, one plant reported that ammonium
chloride is added directly to the depolarizer material. After
preparation of the depolarizer material, the electrolyte solution,
which may or may not contain mercury, is added. (In Leclanche cells,
mercury is added to either the electrolyte, cathode mix, or the
separator). Five out of the thirteen plants reported adding mercuric
chloride to the electrolyte solution. Nine plants reported combining
the depolarizer material with an electrolyte solution which does not
contain mercury. One plant is counted in both groups because both
manufacturing systems are used in the plant.
Porous carbon cathode manufacture consists of blending carbon,
manganese dioxide, and water; molding this mixture around a porous
carbon rod; wrapping in a nylon net separator; and drying in an oven.
This agglomerate electrode is sometimes called an "agglo".
The silver chloride cathode is prepared by molding silver chloride
around a silver wire to form a bobbin. After wrapping, the cathode
bobbin is ready for insertion into the zinc anode can. Two plants
reported the manufacture of silver chloride cathodes.
For the pasted Mn02 cathode, a paste consisting of -manganese dioxide,
carbon, and latex is applied to a conducting film. The steps used to
prepare similar to the steps this film are described above for the
zinc powder anode. The cathode paste material is applied on the film
in rectangular spots, directly opposite the anode spots. Anode and
cathode preparation utensil washwaters are combined, and the resulting
wastewater is included under ancillary operations.
Ancillary Operations
Separator Manufacture - Separators are used to isolate the cathode
from the anode, while providing a conductive path between them.
Separators consist of gelled paste, treated paper, or plastic sheet.
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Wastewater is directly associated with the manufacture of some of the
Leclanche separators.
Cell Assembly - Cell assembly processes differ for paper separator
cells, paste cells, flat cells, carbon cathode cells, silver cathode
cells, and pasted cathode cells. In making paper separator cells, a
pre-coated paper separator is first inserted into the zinc can. The
depolarizer mix is compacted into a cylinder, the carbon rod (current
collector) inserted into the mix and the subassembly inserted into the
paper-lined can. Additional electrolyte and paper washers are added
before the cell is sealed. A cap and paper collar are attached to the
cell, and the cell is tested and aged. Cells are then either sold
separately or combined and assembled into batteries, tested again, and
packed for shipment.
In paste cell production, a paste containing water, flour, starch,
zinc chloride, mercuric chloride, and ammonium chloride is inserted
into a zinc can. The depolarizer-electrolyte mix, molded around a
central carbon rod, is inserted into the zinc can. After the paste
sets into a gel, the cell is sealed. The cell then goes through
testing, finishing, aging, and retesting before being packed and
shipped. The processes of conveying the cathode bobbin to the cell
assembly and of setting the separator paste result in the generation
of process wastewater in one type process. These processes are
discussed in greater detail in subsequent portions of the section.
In flat cell production, the major operations include the manufacture
of the duplex electrodes and depolarizer-electrolyte mix cake, cell
assembly, and battery assembly. The duplex electrode is made by
coating one side of a zinc sheet with conductive carbon. Manganese
dioxide, carbon, ammonium chloride, zinc chloride, and water are mixed
and pressed into a cake which serves as a depolarizer and electrolyte.
The duplex electrode and the cake are then stacked together with a
paper separator in between and a plastic envelope around the four
sides of the cell. The cells then undergo a quality control
inspection and are assembled into stacks with a final flat zinc
electrode and tin plated steel end boards. The stacks are inspected,
dipped in wax, aged, and inspected again for quality assurance.
Stacks are then assembled into finished batteries.
In assembling the porous carbon cathode cell, the porous carbon
cathode is inserted into the zinc anode container. An electrolyte-
separator paste is then added, and the cells are sealed and
interconnected to form batteries.
In the silver chloride cathode cell, the wrapped cathode bobbin is
inserted into a zinc can containing the electrolyte-separator paste.
The cell is then sealed.
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The powdered zinc anode-pasted Mn02 cathode foliar cell is assembled
by interleaf ing separator sheets between the duplex electrodes and
adding electrolyte before sealing the cells into a stack. The sealed
stack of cells is tested and wrapped to form a finished battery.
Equipment and Area Cleanup - In the Leclanche subcategory, there are
equipment cleanup practices that cannot be associated with production
of only one of the major cell components, anode, cathode, or
separator. They include the clean-up of equipment used in assembling
cells as well as in the preparation and delivery of electrolyte.
Because wastewater results from some of these operations, they are
discussed as ancillary operations.
Subcateqory Data Summary
Nineteen plants are currently producing cells in the Leclanche
subcategory. Most of the cathodes are made from Mn02 and carbon,
although two plants make cells with silver chloride cathodes. Cells
with silver chloride cathodes, however, comprise less than 0.01
percent of the total production in the subcategory. Nearly all of the
production is in the form of standard, round "dry cells". Other
products are cells of various shapes for special purposes, flat cell,
batteries, foliar film pack batteries, and air-depolarized batteries.
Production - Annual production reported in the subcategory totaled
96,260 kkg (106,108 tons). This total includes all except two plants
(making carbon cathode and silver cathode cells, respectively) for
which production is judged to be far below average for the
subcategory. The total production also includes one high production
plant which has discontinued operation (the production is believed to
have been shifted to another plant owned by the company). Reported
production is based on 1976 annual production rates, except for one
plant which was not in production until 1977. Annual production at
individual plants in the subcategory ranges from 1.4 kkg (1.5 tons) to
24,000 kkg (26,000 tons) with a median value of 2,700 kkg (3,000
tons).
Geographically, plants in the Leclanche subcategory are in the eastern
United States, with a single exception in Texas. There are eight
active facilities in EPA Region V, three each in Regions I and III,
two each in Regions II and IV, and one in Region VI. The age of these
facilities ranges from three years to many decades.
Raw Materials - Raw materials common to many of the plants in the
Leclanche subcategory are zinc for anodes, Mn02 and carbon for the
cathode mix, carbon for the cathode current carrier, ammonium chloride
and zinc chloride for the electrolyte, paper for the separator and
paperboard washers, mercuric chloride for anode amalgamation, and
asphalt for sealing. Other reported raw materials are zinc oxide,
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titanium, ammonium hydroxide, phenolics, manganese, adhesives,
ammonia, polystyrene, steel, brass, ethyl cellulose, polyvinyl
chloride, toluene, polycyclopentadiene, monochlorobenzene,
cyclohexanone, silica, starch, solder, wax, grease, magnesium
perchlorate, barium chromate, lithium chromate, latex, vinyl film,
aluminum, magnesium oxide, and others.
Water Use and Wastewater Discharge - Process water use and wastewater
discharge among Leclanche subcategory plants were generally observed
to be very low or zero, with a maximum reported process water
discharge rate of 2,158 1/hr. The only discrete cell component with
which wastewater could be associated was with the separator. At
several Leclanche plants, water is used for cleaning utensils or
equipment used in the production of cell components rather than for
cleaning the components themselves.
Eleven of the nineteen Leclanche subcategory plants reported zero
process wastewater discharge. Two of the remaining plants did not
report process wastewater flow rates. Process wastewater flow rates
reported by the remaining six plants follow:
Observed Flow
Rate (I/day)
Mean Visit
Plant Number Survey Data Data
A 30.4
B 9,900 5,340
C 0.47
D 187 653
E 34,500
F 1,910
Mean and median discharge flows for each of the process operations or
functions included in this subcategory are shown in Table V-53 (Page
xxx). This table also presents the production normalizing parameters
upon which the reported normalized flows are based.
Wastewater Treatment Practices and Effluent Quality - Only five of the
19 active plants in the Leclanche subcategory have wastewater
treatment systems. The most frequent technique was filtration, which
was reported at four plants. Three plants reported pH adjustment, two
reported coagulant addition, two reported settling, two reported
equalization, two reported coagulant addition, one reported skimming,
and one reported carbon adsorption.
Table V-54 (Page 313 ) shows reported effluent quality at the Leclanche
plants. Comparing this table with the treatment system information
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shows that treatment, as practiced, has not always been very
effective. Plant F, which reported high mercury and zinc effluent
concentrations as shown in this table, also reported one of the more
substantial treatment systems including amalgamation, pH adjustment,
coagulant addition, and filtration.
Specific Process Water Uses and Wastewater Characteristics
Anodes - There is no process wastewater associated specifically with
Leclanche anode manufacture.
Cathodes - There is no process wastewater associated specifically with
Leclanche cathode manufacture.
Ancillary Operations
Cooked Paste Separator - In cells produced using this process, the
paste temperature is elevated to achieve optimum setting conditions
for the paste formulation. The raw materials for producing the paste
include starch, zinc chloride, mercuric chloride, and ammonium
chloride and water. After the paste and cathode are inserted into the
zinc can, the can is passed through a hot water bath with the water
level approximately one inch above the bottom of the can, heating the
can and causing the paste to gell. After setting the paste, the can
is removed from the hot water bath and final assembly operations are
conducted.
Only one plant reported producing "cooked" paste separator cells.
Wastewater from the paste separator manufacture was sampled at this
facility. The only source of direct process discharge is from the hot
bath paste settling. At this facility, no wastewater is discharged
from either the paste preparation or paste clean-up operations, due to
in-process controls. The paste preparation water supply tank holds
water previously used for cleaning. The sources of water reused in
mixing the paste include floor wash water from the paste preparation
room, paste pipeline system wash water, and paste cleanup water used
during mechanical difficulties. An example of mechanical difficulties
is bobbin insertion failure which results in the paste being washed
out of the cans for the purpose of recovering the cans for reuse. All
of the water that contacts the paste is collected for reuse in paste
formulation, and this closed system limits mercury contamination of
the wastewater.
The source of direct process wastewater discharge is the hot bath used
for setting the separator paste which becomes contaminated from
contact with the outside of the can, from an occasional spill of one
or more cans into the bath and wastes from the operating machinery.
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Total discharge rates measured during the sampling visit ranged from
0.03 to 0.05 liters per kilogram of finished cells, with a mean value
of 0.04 and a median value of 0.05 I/kg. Composite samples were taken
which include wastewater from each of the three discharge sources and
the analytical results are presented in Table V-55 (Page 314). Table
V-56 (Page 315 ) presents the pollutant mass loadings basea on the
weight of finished cells for each of the three sample days. Three
significant pollutants found in this flow-proportioned combined waste
stream are mercury, manganese and zinc. Also, TSS is present in
significant concentrations which indicates material contamination from
both paste and bobbin application. An additional significant
pollutant in the paste setting wastewater is oil and grease. The
primary source of this pollutant is drag-out water that contacts the
lubricated gears that drive the tank conveyor.
Uncooked Paste Separator - Paste formulations are currently used in
which the paste separator material sets at room temperatures. The
wastewater from preparing these paste mixtures is substantially less
than for the cooked paste method, and the separator characteristics
are adequate for the cell types being produced. One plant
manufactures carbon-zinc cells with an uncooked paste separator.
The paste formulation includes zinc chloride, ammonium chloride,
mercuric chloride, cornstarch, and flour. The resulting paste is held
in cold storage until injected into the zinc anode cans. After the
insertion of the compressed cathode, the paste is then allowed to set.
Next, the final assembly operations are performed to prepare the cells
for shipping. No wastewater is generated from this process for
producing paste separator material. All of the water added to form
the paste mixture is incorporated in the finished cells, and the
equipment used to blend the paste is not washed. Also, the floor in
the paste preparation area is vacuum cleaned, eliminating floor wash
water.
Two plants produce paste separator material for use in silver
chloride-zinc cells. Flour, zinc chloride and ammonium chloride are
used in formulating the separator paste. The cathode is inserted into
an anode can containing separator paste; spacers and support pieces
are added; and the can is sealed. The only source of wastewater
discharge is paste tool cleaning. This waste stream estimated at less
than 5 I/day was not sampled. The components of the paste, which does
not contain mercury, are the only pollutants in the wastewater.
Pasted Paper (With Mercury) Separator Preparation - Production of
pasted paper separators involves blending a paste-like material;
applying it to the surface of paper; and oven drying the resultant
pasted paper. The raw materials used to form the paste consist of
starch, methanol, mercuric chloride, methocel, silica, and water.
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The manufacture of pasted paper separator material containing mercury
is specific to battery manufacturing and is included under battery
manufacturing. When purchased the separator material is inserted
directly into the zinc can, followed by cathode mix. Therefore, no
wastewater is associated with separator application by these Leclanche
cell manufacturers.
The only source of wastewater discharge during pasted paper
manufacture is hand washing and washing of equipment used to handle
the paste. This wastewater was sampled. The measured flows ranged
from 0.11 to 0.17 I/kg of applied dry paste material (0.14 I/kg mean
and 0.15 I/kg median). The analytical results for this waste stream
are presented in Table V-57 (Page 316 )• Table V-58 (Page 317 )
presents the daily pollutant mass loadings of the paste equipment
clean-up operation wastewater. Significant pollutants observed
include zinc, manganese, mercury, TSS, and oil and grease.
Among these significant pollutants, zinc and manganese dioxide are not
raw materials in paste formulation. They are presumed to derive from
adjacent areas in which zinc chloride and manganese dioxide are
handled.
The presence of TSS in significant concentrations results from washing
equipment surfaces to remove process material accumulations. Oil and
grease is also present in significant concentration due to the removal
of equipment lubricants during the wash operation. There is
considerable variability in pollutant concentrations during the three
sampling days because of the nature of the hand wash and cleaning
operations.
One plant which manufactures and sells mercury containing pasted paper
separators (but does not make batteries) was visited. In-process
controls and contract hauling are used to eliminate process wastewater
discharge.
Pasted Paper (Without Mercury) Separator - Some of the Leclanche cell
manufacturers use pre-pasted paper separator materials which does not
have a mercury component. The wastewater resulting from manufacturing
the paper separator material which does not contain mercury is not
specific to the battery industry since the product has other
industrial uses in addition to Leclanche cell manufacturing.
Equipment and Area Cleanup - Equipment and area cleanup (including
handwash) wastewater in the Leclanche subcategory is that which cannot
be associated solely with anode, cathode, or separator production.
The operations generating this wastewater are:
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PLANT OPERATION
A Electrolyte preparation equipment wash
B Cathode carrier wash
C Hand washing
C Miscellaneous equipment wash
D Electrode preparation equipment wash
E Electrolyte preparation equipment wash
F Electrolyte preparation equipment wash
Out of the nineteen active Leclanche plants, thirteen reported no
discharge of process wastewater: four of the 13 reported neither
process water use nor wastewater discharge, while nine reported water
use but no discharge. The six remaining plants listed above reported
both water use and water discharge. Water use at the nine plants
reporting use but no discharge is for electrolyte preparation.
Table V-59 (Page 31&) indicates the best available information on
equipment and area cleanup wastewater discharges for the nineteen
Leclanche plants. The flow is normalized in terms of weight of
finished product, and is expressed in liters discharged per kilogram
of finished product.
Equipment and area cleanup wastewater samples were taken at Plants B
and C. Pollutant concentrations from these sampled plants and also
plant supplied data are included in Table V-60 (Page 319:). Table V-61
(Page 320) presents pollutant mass loads expressed as milligrams
discharged per kilogram of cells produced. Table V-62 presents
statistics based on the values in Table V-60, and Table V-63 (Page
322) presents statistics based on the values in Table V-61.
Total Process Wastewater Characteristics - A statistical summary of
total process wastewater characteristics from Leclanche subcategory
plants is presented in Table V-64 (Page 323).
LITHIUM SUBCATEGORY
This subcategory encompasses the manufacture of batteries combining
lithium anodes with a variety of depolarizer materials. Because
lithium reacts vigorously with water, electrolytes used in these
batteries are generally organic liquids or solids or solid inorganic
salts which are fused during activation of thermal batteries. While
manufacturing processes vary considerably among the different battery
types included in this subcategory, they have in common limited use of
process water and relatively low volumes of process wastewater.
Manufacturing Processes
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The manufacture of batteries in this subcategory is illustrated in the
generalized process diagram shown in Figure V-20 (Page 212). The
manufacture of lithium anodes generally involves only mechanical
forming of metallic lithium to the desired configuration and is not
reported to involve process water use at any facility. Depolarizers
used with the lithium anodes are frequently blended with or dissolved
in the cell electrolyte and include iodine, iron disulfide, lead
iodide-lead sulfide-lead (mixed), lithium perchlorate, sulfur dioxide,
thionyl chloride and titanium disulfide. Preparation and handling of
three of these depolarizers, iron disulfide, sulfur dioxide, and
thionyl chloride, is reported to yield process wastewater. Cell
assembly techniques differ with specific cell designs, but are
universally accomplished without the use of process water or the
generation of process wastewater. Usually, cell assembly is
accomplished in special humidity controlled "dry" rooms. Thermal
batteries manufactured in this subcategory include a heating component
in addition to the anode, depolarizer, and electrolyte discussed
above. The manufacture of one type of heating component, "heat
paper", results in process wastewater as described previously in the
calcium subcategory. One additional ancillary operation reported in
this subcategory which produces process wastewater is the disposal of
scrap lithium by reaction with water. The relationship between the
process elements and discrete wastewater sources reported at battery
facilities is illustrated in Figure V-21 (Page 213).
Anode Manufacture
All cells manufactured in this subcategory employ a lithium anode
which is metallic lithium in the charged state. The anode is
generally prepared from purchased metallic lithium sheet or foil by
mechanical forming operations only, although one facility reported the
preparation of a lithium alloy for use in high temperature batteries.
In some cases the anode may also include a support structure of non-
reactive metal such as aluminum screen. The use of pasted or powder
anodes as observed in other subcategories is not reported, apparently
because the high reactivity of lithium and relatively low current
drains for which most lithium cells are designed do not necessitate
maximized anode surface areas. No manufacturer in this subcategory
reported process wastewater resulting from anode preparation.
Cathode Manufacture
Iodine Cathode Manufacture - The depolarizer for lithium iodine
batteries is created by the mixture of iodine with an organic solid,
poly-2-vinyl pyridine. This mixture is added to the cells in a molten
state and, upon cooling, yields a conductive solid mass containing the
reactive iodine. The electrolyte in these cells is solid lithium
iodide which forms at the interface between the anode and depolarizer
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after assembly of the cell. No process water is used in manufacturing
these cathodes, and no process wastewater results.
Iron Disulfide Cathode Manufacture - Iron disulfide is used as a
depolarizer in thermal batteries which use lithium anodes. Production
of battery quality iron disulfide depolarizer may generate a process
wastewater stream.
Lead Iodide Cathode Manufacture - This cathode is reported to be a
mixture of lead iodide, lead sulfide and lead. Specific manufacturing
processes employed were not identified, and points of process water
use are uncertain although water use in fume scrubbers was indicated.
(To be resolved during plant visits and follow-up).
Lithium Perchlorate Cathode Manufacture - Manufacture of this type of
cathode was reported only on a small scale in sample quantities.
Manufacturing process details were not supplied, but no process
wastewater discharge from the production of this type of cathode was
indicated.
Sulfur Dioxide Cathode Manufacture - The manufacture of cathodes for
cells using sulfur dioxide as the depolarizer begins with the
preparation of a porous carbon electrode structure, generally by
pasting on a metallic grid. Binders such as teflon may be added to
the carbon paste. The sulfur dioxide is mixed with an organic solvent
(generally acetonitrile) and one or more inorganic salts such as
lithium chloride or lithium bromide. The resultant liquid organic
electrolyte-depolarizer mixture is subsequently added to the cells,
and they are sealed. Wastewater produced in the manufacture of these
cathodes results from wet scrubbers used primarily to control S02
emissions, and from wet clean-up in case of spills. Industry data
indicates that spills are very infrequent.
Thionyl Chloride Cathode Manufacture - Manufacturing processes for the
production of cells using thionyl chloride as the depolarizer are
similar to those discussed above for sulfur dioxide depolarized
cathodes except that the organic electrolyte acetonitrile is not used.
The production of these cathodes also results in process wastewater
from fume scrubbers and (potentially) from the clean-up of spills of
process materials.
Titanium Disulfide Cathode Manufacture - Titanium disulfide cathodes
are made by blending the active material (as a powder) with a binder
and inserting the mixture in a metal can. Electrolyte, which is
formed from dioxolane and sodium tetraphenyl boron, is added
separately after insertion of the cell separator and anode. No
process water use or wastewater discharge is reported from this
process.
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Ancillary Operations
Heating Component Production
Heat Paper Production - Wastewater is generated by the manufacture of
heat paper for use in thermal cells manufactured in this subcategory.
The heat paper production process is identical to that previously
discussed in the calcium subcategory.
Heat Pellet Production - No process water use or discharge is
generated from this process which is used in the manufacture of
thermal batteries. Heat pellet production is identical to that
discussed under the calcium subcategory discussion.
Scrap Disposal. Lithium scrap is disposed at some sites by reacting
it with water. Although no discharge of the resultant solution is
reported at present, this scrap disposal process is a potential source
of process wastewater.
Subcategory Data Summary
Seven plants reported the manufacture of-a total of eight different
types of batteries within this subcategory. These facilities range in
production from less than 50 kg per year (100 Ibs/yr) to 14 metric
tons (15.5 tons) and in employment from 4 to 175. While plants differ
significantly in products, manufacturing processes, production volume,
and employment, all report little or no wastewater discharge and
relatively few process wastewater sources. Consequently, existing
wastewater treatment and available effluent monitoring data are
limited.
Production - Because lithium battery technologies are rapidly
changing, production patterns are also undergoing rapid change. Three
of seven identified producers were not manufacturing in this
subcategory during 1976 and submitted production data for more recent
years. Consequently, it is not possible to compare plant production
figures, on any single annual basis. Based on the submitted figures,
one plant accounts for more than half of the total subcategory output.
However, several facilities reported only prototype, sample, or start-
up production with larger scale operations anticipated in the near
future.
At present, lithium subcategory production is heavily concentrated in
the northeastern U.S. with one facility in EPA Region I, two in Region
III and three in Region II. The other producer was a small operation
in Region IX.
Water Use and Wastewater Discharge - As previously indicated, water
use and process wastewater discharge in this subcategory is quite
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limited. Only three of seven plants in the subcategory reported
process wastewater discharges. These ranged from 3.9 1/hr (1 gal/hr)
to 150 1/hr (39 gal/hr). Process operations identified as sources of
process wastewater discharge and reported production normalized
wastewater flow rates for each are identified in Table V-65 (Page
324).
Wastewater Treatment Practices and Effluent Quality - Present
wastewater treatment practices within this subcategory are limited to
pH adjustment and settling at one facility and pH adjustment at
another. Effluent monitoring data were submitted by only one
facility. These data, already presented in the discussion of the
calcium subcategory, characterized the wastewater discharge resulting
from heat paper production.
MAGNESIUM SUBCATEGORY
The magnesium subcategory includes manufacturing operations producing
cells combining magnesium anodes with a variety of depolarizer
materials. Many of the cell types produced are reserve cells which
are activated by electrolyte addition or by initiation of a chemical
reaction to raise the cell temperature to operating levels. One type
of cell, magnesium-carbon, presently accounts for over 85 percent of
the total production in the subcategory. A number of different
process operations in the subcategory are observed to yield process
wastewater. These waste streams vary significantly in flow rates and
chemical characteristics.
Manufacturing Process
The manufacture of magnesium anode batteries is illustrated in the
generalized process flow diagram of Figure V-22 (Page 214). Anode
manufacture generally involves mechanical forming and cutting of
magnesium metal, and cleaning and chromating of the formed product.
Cathodes are prepared by a variety of techniques including blending
and pressing of powdered materials, and processes involving chemical
treatment operations. Material used as a cell separator is chemically
treated at one facility producing a process wastewater stream.
Heating components (heat paper) are manufactured at one plant in the
subcategory for assembly into magnesium anode thermal batteries. One
facility reported testing assembled cells with a subsequent wastewater
discharge. The relationship between the process elements and discrete
wastewater sources reported at battery facilities is illustrated in
Figure V-23 (Page 215).
Anode Manufacturing
Anodes used in this subcategory are primarily mechanically formed
metallic magnesium, except for thermal cells where the anode is
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magnesium powder. In the case of magnesium-carbon cells, the anode
may form the can in which the cell is assembled. In other cell types
and in some magnesium-carbon cells, the anode is cut from magnesium
sheet or foil. Magnesium anodes used in magnesium-carbon cells are
generally cleaned and chromated before assembly into the cells. The
chromate conversion coating on the magnesium anode serves to suppress
parasitic reactions during storage and reduce self-discharge of these
cells. These operations as well as the metal forming operations to
produce magnesium cans may be performed on-site at the battery
manufacturing plant or by a separate supplier.
The cleaning and chromating processes involve subsequent rinse
operations which produce a wastewater discharge. These processes as
well as the metal forming steps, however, are common mechanical
operations. As a result, the wastewater effluents produced are not
considered under battery manufacturing. No battery manufacturing
process wastewater results from the production of these anodes.
Cathode Manufacturing
Carbon Cathode Manufacturing - The manufacture of cathodes for
magnesium-carbon cells involves the separate preparation of a carbon
current collector and of a depolarizer mix. The carbon current
collector is formed by blending carbon with binder materials to
produce a solid cathode structure. This may take the form of a solid
rod to be inserted in the center of a formed magnesium can or of a
carbon cup within the cell is assembled.
The depolarizer for these cells, manganese dioxide, is blended with
carbon and other inorganic salts such as barium and lithium chromate
to enhance conductivity through the depolarizer mix. Magnesium
perchlorate electrolyte may also be added to this mixture before
assembly into the cell. No process wastewater discharge was reported
from the manufacture of carbon cathodes or depolarizer material by any
plant in the subcategory.
Copper Chloride Cathode Manufacturing - The production of copper
chloride cathodes for use in reserve cells is reported to proceed by
forming the powdered material into pellets which are subsequently
inserted into the cell assembly. No process wastewater results.
Copper Iodide Cathode Manufacturing - The manufacture of this cathode
type involves mixing cuprous iodide, sulfur, and carbon and sintering
the mixture. The sintered material is subsequently ground and pressed
on a supporting copper grid to form the cathode which is dipped in an
aqueous alcohol solution prior to insertion in the battery. Only
noncontact cooling water is used in this process, and no process
wastewater results.
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Lead Chloride Cathode Manufacturing - Lead chloride cathodes are
reported to be produced by pressing lead chloride on a copper screen.
No process wastewater is generated.
M-Dinitrobenzene Cathode Manufacturing - Cathodes in which this
material serves as the depolarizer are produced by mixing m-dinitro-
benzene with carbon or graphite, ammonium thiocyanate, and glass
fiber. The mixture is subesquently molded or pasted to produce a thin
sheet which is in contact with a flat stainless steel current
collector in the assembled cell. No process wastewater is reported to
result.
Silver Chloride Cathode Manufacturing - Three different processes are
reported for the production of silver chloride cathodes for use in
reserve cells. Two of these involve chemical processing and result in
process wastewater streams, while the third is strictly a physical
process involving no water use and no process wastewater discharge.
Silver chloride cathodes are produced by one manufacturer by forming
silver chloride powder into pellets which are subsequently assembled
into reserve cells. The manufacturing process is reported to be
similar to that for the production of copper chloride cathodes.
In another process, silver chloride is calendered into strips and
punched. The resultant material is then treated with photo developers
to reduce the surface to metallic-silver. The cathode material is
then rinsed, yielding a process wastewater stream, and subsequently
sent to cell assembly.
Alternatively, silver is electrolytically oxidized in hydrochloric
acid to produce silver chloride. The product of this operation is
subsequently rinsed, dried, and used in assembling cells. Process
wastewater results from rinsing the electrolytic silver chloride.
Vanadium Pentoxide Cathode Manufacturing - Vanadium pentoxide, used as
the depolarizer in magnesium anode thermal batteries, is blended with
electrolyte (lithium chloride and potassium chloride) and kaolin as a
dry powder and pressed to form pellets which are used in cell
assembly. No water is used directly in this process, but wastewater
is discharged from fume scrubbers on dehumidifiers used to dry
manufacturing areas.
Cell Assembly
Details of the cell assembly process vary significantly among the
different types of cells manufactured in this subcategory. None of
the cell assembly processes, however, are reported to generate process
wastewater.
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For magnesium carbon cells, the separator, depolarizer mix, and
cathode are inserted in the magnesium anode can, electrolyte is added,
and assembly is completed by sealing and adding contacts and a steel
outer case. Alternatively, magnesium carbon cells are assembled by
insertion of the anode in the annular carbon cathode cup and placement
of cathode mix in the spaces between anode and cathode. After this,
electrolyte is added, the cell is sealed, and contacts and a steel
outer case are added to complete assembly. The electrolyte used is an
aqueous solution of magnesium perchlorate.
In assembly of ammonia activated magnesium reserve cells, the ammonia
which forms the electrolyte is placed in a sealed reservoir within the
battery assembly from which it is pumped into the cells upon
activation of the battery. Solid electrolyte is incorporated in
pellets containing the depolarizer in magnesium anode thermal
batteries. In seawater activated cells, the saline seawater itself
serves as the electrolyte, and none is added during assembly of the
cells.
Ancillary Operations
Heating Component Manufacture - Magnesium anode thermal batteries are
activated by heat generated in a chemically reactive element (heat
paper) incorporated within the cell structure. The production of this
cell component produces process wastewater as previously described for
the calcium subcategory.
Separator Processing - One manufacturer reported the use of glass
beads as the separator in magnesium reserve cells. These glass beads
are reportedly etched using hydrofluoric acid and ammonium fluoride as
a part of the manufacturing process. A subsequent rinse results in a
process wastewater discharge. This process is not presently active,
although resumption of production is possible.
Cell Test Operation - After assembly, quality control tests on
magnesium reserve cells may include activation to verify satisfactory
performance. Water used in this operation (destructive testing) was
reported to constitute a source of process wastewater by one
manufacturer of magnesium reserve cells.
Floor Wash Operation - The removal of contaminants from production
area floors is frequently required for hygiene and safety. This may
be accomplished in many cases by dry techniques such as sweeping and
vacuuming but may also require the use of water in some instances.
One plant in this subcategory reported floor washing and indicated a
resultant process wastewater discharge.
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Subcategory Data Summary
Production - Total 1976 annual production of batteries in this
subcategory as reported in dcp's was 1220 metric tons (1340 tons).
Over 85 percent of this total was produced as magnesium-carbon
batteries. Thermal batteries and ammonia activated reserve batteries
together accounted for less than 1 percent of the total. The
remainder comprises a variety of magnesium reserve cells generally
intended for seawater activation.
Eight facilities reported production of batteries in this subcategory.
Two of the eight facilities account for 84 percent of the total
production. These two plants manufacture magnesium-carbon batteries
as does the third largest facility. None of these plants reported the
production of any battery manufacturing wastewater.
Six of the eight facilities manufacturing magnesium anode batteries
report production in other battery manufacturing subcategories as
well. Magnesium-carbon battery production is co-located with
Leclanche subcategory production in two of three instances. This
association is logical since cathode materials and cell assembly
techniques are quite similar for these cell types. Other
subcategories represented on-site with magnesium subcategory pro-
duction include the cadmium subcategory, lead subcategory, lithium
subcategory, and zinc subcategory. In most cases, magnesium sub-
category production accounts for less than 30 percent of the total
weight of batteries produced at the facility. Because of the limited
use of water and wastewater discharge associated with magnesium
subcategory operations, combined wastewater discharge and treatment
are rare despite the high incidence of common-site production.
Wastewater from magnesium subcategory production is combined with
wastes from other subcategories at only one facility. Since no
production operations are common at that site, segregation of wastes
at that facility is feasible.
Geographically, producers in this subcategory are scattered. One
plant is located in each of U.S. EPA Regions I, III, VI and VIII, two
in Region IV, and two in Region V. No two facilities are located in
the same state.
Water Use and Wastewater Discharge - Process water use varies con-
siderably among manufacturers in this subcategory. As shown in the
preceeding manufacturing process discussion, most process operations
are accomplished without the use of process water. In addition, many
of the cell types produced either use non-aqueous electrolytes or are
shipped without electrolyte.
Process operations which result in battery manufacturing wastewater
are reported at four of the eight plants in the subcategory. Pro-
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duction normalized wastewater flows from each of these process
operations are presented in Table V-66 (Page 325). Total process
wastewater flow rates are reported to range from 0 to 5200 1/hr (1370
gal/hr) with an average of 670 1/hr (180 gal/hr). Wastewater
discharges from plants in this subcategory are equally split between
direct and indirect discharge. Total process wastewater discharge
from magnesium subcategory processes at individual plants is presented
in Table V-67 (Page 326 ).
Wastewater Treatment and Effluent Quality - Present wastewater treat-
ment practice within this subcategory is limited. Treatment practices
at most facilities are limited to pH adjustment and removal of sus-
pended solids. One plant reported the use of settling tanks followed
by filtration for this purpose. No effluent analyses specifically
characterizing treated wastewater from this subcategory were supplied
in dcp's.
ZINC SUBCATEGORY
Batteries manufactured in this subcategory all employ a zinc anode
which is amalgamated to reduce anode corrosion and self-discharge of
the cell. They also have in common the use of an alkaline aqueous
electrolyte which is primarily composed of potassium or sodium
hydroxide. The zinc anodes employed, however, vary considerably in
physical configuration and in production techniques depending upon the
desired operational characteristics of the cells produced. This
subcategory encompasses batteries manufactured for a variety of uses
with different performance characteristics and physical dimensions.
Six different depolarizers are used in these cells, and cathodes for
cells using some of these depolarizers may be produced by several
different techniques.
Process water is used in many of the operations performed in the
manufacture of batteries in this subcategory, and flow rates are
sometimes high. Process wastewater is discharged from most plants and
characteristically results from a number of different manufacturing
processes. Because of the large number of different wastewater
producing operations in the subcategory and the variety of patterns in
which they are combined at individual plants, plant wastewater
discharges are observed to vary widely in wastewater flow rates and in
chemical characteristics. Wastewater treatment practices and effluent
quality are also observed to vary significantly within the
subcategory. However, the flow rates and chemical characteristics of
wastewater from specific process operations performed at different
sites are generally observed to correspond. Observed differences can
usually be accounted for by observed variations in plant water
conservation practices.
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Manufacturing Process
The manufacture of zinc subcategory batteries may be represented by
the generalized process flow diagram presented in Figure V-24 {Page
216). The anode and cathode variations observed in this subcategory
together with ancillary operations which generate process wastewater
formed the basis for analysis of process wastewater generation as
illustrated in Figure V-25 (Page 217). As shown in the figure,
several distinct waste streams frequently result from a single process
operation or function.
Not all operations shown on this diagram are performed at each plant
in the subcategory, and in some cases, the order in which they are
performed may vary, but in most cases the overall sequence of process
operations is similar. Few plants generate process wastewater from
all of the process operations indicated on the diagram. At most
facilities some of these production steps are accomplished without
generating a waste stream. The specific operations performed by these
"dry" techniques varies from site to site and each of the indicated
wastewater sources is observed at one or more plants in the
subcategory.
Anode Operations
Amalgamation - Zinc anodes used in these cells commonly corrode by
reactions with the cell electrolyte in which hydrogen gas is evolved.
Hydrogen overvoltage and thus anode corrosion in the cell is
suppressed by zinc anode amalgamation. This reduction in the rate of
anode corrosion is essential to the achievement of acceptable battery
life, and anode amalgamation is universal in this subcategory.
Because many of the cells produced are designed for high discharge
rates, powdered zinc and porous structures are used in anodes to
maximize electrode surface area. Mercury requirements for
amalgamation are consequently increased, and mercury consumption in
amalgamating anodes in this subcategory is typically 0.05 kg per kg of
zinc as compared to 0.00035 kg per kg of zinc in the Leclanche
subcategory. This increase in mercury requirements influences the
amalgamation techniques which may be employed as well as the severity
of mercury pollutant discharge problems encountered.
Amalgamation is presently accomplished by six distinct techniques
depending in part on the anode configuration produced and in part on
the preference of the manufacturer. Present practice includes
amalgamation by inclusion of mercury (alloying with zinc) during
casting of anode material; amalgamation by mixing zinc and mercury
salts or mercury in an aqueous solution from which the product is
removed (wet amalgamation) with subsequent rinsing of product; mixing
zinc, mercury, electrolyte and a gelling agent to form amalgam gel
(gelled amalgam); blending mercury and dry zinc powder (dry
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amalgamation); mixing zinc and mercuric oxides prior to pressing or
pasting the material on a supporting grid; and amalgamation by
immersing the anode in a solution of mercury salts. The processes of
wet amalgamation of zinc powder, production of gelled amalgam, and
anode immersion cause mercury to be present in plant wastewater
directly through wastewater discharges resulting from these
operations. Other amalgamation processes may result in the presence
of mercury in the plant wastewater streams as a result of subsequent
process water contact with the amalgamated anode materials.
Amalgamation by incorporation of mercury in the zinc casting is
employed in the production of cast anodes for use in air-depolarized
cells. Because of their relatively low surface area per unit weight,
these cast anodes are not suitable for use in cells designed for high
discharge rates. This amalgamation process does not result in the
generation of any process wastewater.
The process of wet amalgamation of zinc powder is used by facilities
producing alkaline manganese cells and a variety of button cells with
mercury and silver cathodes. In this process, zinc and mercury are
mixed in an aqueous solution which generally contains either ammonium
chloride or acetic acid to enhance the efficiency of amalgamation.
Subsequently, the solution is drained away and the amalgam product is
rinsed, usually in several batch stages. A final alcohol rinse is
frequently used to promote drying of the product. Binders such as
carboxymethyl cellulose (CMC) are commonly added to the dry
amalgamated zinc powder which aid in compaction of the anode in the
cells. Wastewater from this process results from discharge of the
spent amalgamation solution and from subsequent rinses as well as from
washing of amalgamation equipment and floor areas. The final alcohol
rinse is generally retained and reused until ultimately contractor re-
moved .
The gelled amalgam process results in production of moist anode gel in
a single operation. Zinc powder, mercury and electrolyte are combined
with a gelling agent such as carboxymethyl cellulose and mixed to
achieve the desired anode mix characteristics. Mixing equipment used
in this operation and process floor areas are washed with water to
minimize mercury exposure to workers and to limit equipment corrosion
by the electrolyte added to the gel.
In the dry amalgamation process zinc powder and metallic mercury are
mixed for an extended period of time to achieve amalgamation. The
resultant material may subsequently be mixed with a binder such as CMC
and moistened with electrolyte to aid in compaction of the anodes in
the cells. -Amalgamation equipment used for this process may generally
be cleaned by dry techniques eliminating all process water use and
wastewater discharge. Discussions with industry personnel have
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indicated that this process is less costly than wet amalgamation and
has resulted in satisfactory anode performance.
Amalgamation of anodes prepared from zinc oxide powder is accomplished
by mixing mercuric oxide powder with the zinc oxide. An amalgam is
produced upon subsequent reduction of the zinc oxide to zinc during
electrode formation. This amalgamation process does not produce any
direct wastewater discharge but results in the presence of mercury in
wastewater resulting from pasting or pressing electrodes and from
subsequent formation steps unless these are accomplished within the
battery case.
Electrodeposited zinc anodes are amalgamated by immersion in a
mercuric chloride solution. In present practice, amalgamation is
sometimes followed by a rinsing step. The amalgamation solution is
periodically dumped generating process wastewater containing extremely
high concentrations of mercury and zinc.
Amalgamation by inclusion of mercury in the cell separator or
electrolyte as observed in the manufacture of Leclanche subcategory
batteries is not practiced by any manufacturer in the zinc subcate-
gory. This may be attributed to the higher surface areas of elec-
trodes used in these cells (and correspondingly higher mercury
requirements) as well as the fact that many cells are designed to
contain minimal electrolyte. These conditions may make it impractical
to include sufficient mercury in either the separator or electrolyte.
Further, the lack of mixing involved in this method of addition could
make the rate of mercury transport through the porous anode volume
(and hence of amalgamation) unacceptably low.
Anode Preparation - The nature and extent of anode preparation
operations varies considerably. Cast anodes may be used directly or
subjected only to physical cutting or machining. As previously
indicated, amalgamated zinc powder may be mixed with binders and
electrolyte and is then generally simply pressed in place during
assembly with no further preparation required. In the manufacture of
anodes from zinc oxide, the zinc oxide is mixed with mercuric oxide
and a binding agent such as polyvinylalcohol (PVA) and then pasted or
pressed onto supporting metal grids. These electrodes may be
subsequently formed by electrolytic reduction of zinc oxide to zinc
and rinsed producing a process wastewater discharge. The preparation
of electrodeposited anodes involves electrolytic deposition of zinc on
a metallic grid and subsequent rinsing of the resultant anode. In
this case, anode preparation precedes amalgamation.
Cathode Operations
Depolarizer Material Preparation - Depolarizers used in this
subcategory are primarily metal oxides which are purchased from
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manufacturers of inorganic chemicals. In some cases, however, de-
polarizer material is chemically prepared on-site because special
characteristics are required for battery manufacture. Commercially
available depolarizer materials may also be prepared on site at
battery plants in processes equivalent to those used in inorganic
chemicals manufacturing operations which are not considered part of
battery manufacturing.
Mercuric oxide, which serves as the depolarizer in mercury cells, is
commonly purchased by battery manufacturers. One plant, however,
produces this material on-site from metallic mercury in a chemical
process which produces process wastewater containing considerable
quantities of mercury. This process is located in a separate building
from the actual battery manufacturing operations and its wastewater
discharge is treated in a separate system. Since the mercuric oxide
product is available commercially, this process is considered
inorganic chemicals manufacture and its effluent is not considered
under battery manufacturing.
Silver peroxide, used as the depolarizer in batteries manufactured in
this subcategory, is produced on-site. The production process
includes wet oxidation of monovalent silver oxide by either of two
alternative chemical processes and subsequent rinsing of the product.
Because this operation is unique to battery manufacturing operations,
the resultant wastewater discharge is addressed as a battery manufac-
turing effluent. Silver powder is also produced on site at battery
manufacturing plants for use in cathode manufacture. It is produced
by electrolytic deposition, mechanical removal from the substrate, and
rinsing. Rinsing the powder produces a wastewater discharge which is
regulated under the zinc subcategory. Silver peroxide and silver
powder production are addressed as separate ancillary operations in
this subcategory.
Cathode Preparation - Variations in cathode preparation techniques are
similar to those described for anode manufacture except that in
addition to differences in configuration, differences in depolarizer
material are also significant in this case. Ten distinct cathode
manufacturing processes are observed in this subcategory producing the
following types of cathodes:
1) Porous Carbon
2) Manganese Dioxide
3) Mercuric Oxide
4) Mercuric Oxide-Cadmium Oxide
5) Pressed Silver Powder
6) Pressed and Electrolytically Oxidized Silver
7) Pressed Silver Oxide Powder
8) Pressed, Reduced and Electrolytically Oxidized
Silver Oxide Powder
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9) Pasted and Pressed Silver Peroxide Powder
10) Impregnated Nickel
Porous carbon cathodes are used in air depolarized cells and are
produced by blending carbon, manganese dioxide and water and pressing
and drying the mixture to produce an agglomerated cathode structure or
"agglo" which serves a current collector for the cathode reaction and
as a porous medium to carry atmospheric oxygen to the electrolyte.
Control of the porosity and surface characteristics of the agglo is
essential since the cathode must permit free flow of oxygen through
the pores, but not become flooded with the electrolyte in which it is
immersed. Flooding of the agglo would reduce the surface area over
which reaction with oxygen could occur to such an extent that
practical cell operation could not occur. The manufacture of this
cathode type is not reported to result in process wastewater.
Manganese dioxide serves as the depolarizer in alkaline manganese
cells. Manganese dioxide cathodes are prepared by blending manganese
dioxide with carbon and binders such as cement (and in some cases
sufficient electrolyte to wet the mixture). The cathode is formed by
pressing the mixture into a steel cell container which serves as
current collector and support. The carbon in the cathode mix serves
to provide conductivity through the cathode since manganese dioxide
itself conducts poorly. Although water is used in wetting the cathode
mix, no process wastewater discharge associated with production of
this type of cathode is reported.
The manufacture of mercuric oxide cathodes reported by five facilities
(production atone facility has ceased since submittal of dcp), is
accomplished in a process similar to that described above for
manganese dioxide cathodes. Mercuric oxide as a dry powder is blended
with graphite and sometimes with manganese dioxide, pressed into
shape, and inserted in steel cell containers. No process wastewater
is generated.
The mercuric oxide-cadmium oxide cathode is closely related to the
mercuric oxide cathode and is manufactured by the same process except
that cadmium oxide is included in the depolarizer mix. The function
of the cadmium oxide is to provide continued cell operation at a
reduced voltage for an interval after the mercuric oxide in the
cathode is depleted. This characteristic is exploited in devices such
as battery powdered smoke detectors to provide a warning of impending
battery failure. Production of this type of cathode was reported by
one plant in the subcategory. No process wastewater results.
The manufacture of pressed silver powder cathodes begins with the
production of silver powder which is prepared on-site by
electrodeposition. The resultant powder is pressed on the surface of
a silver screen or other support and sintered to achieve mechanical
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integrity. These electrodes may then be assembled with unformed
(oxidized) zinc anodes and the resultant batteries charged prior to
use. The only process wastewater resulting from the manufacture of
these cathodes is associated with the production of silver powder
which is addressed as a separate ancillary operation.
Cathodes may also be produced from silver powder as described above
and subsequently formed prior to cell assembly. Silver powder used in
producing cathodes of this type may be produced on-site or purchased.
The formation process is accomplished by electrolysis in a potassium
hydroxide solution and generally involves several charge-discharge
cycles with the final state of the electrode being the charged silver
oxide state. Formation of the cathodes is followed by rinsing which
results in the generation of process wastewater.
The preparation of cathodes using silver oxide powder proceeds simply
by blending solid constituents and pressing them to produce cathode
pellets for use in silver oxide-zinc button cells. Depending upon
desired cell characteristics, manganese dioxide, magnesium oxide, and
mercuric oxide may be added to change the cell voltage and the shape
of the discharge curve. Manganese dioxide provides a period of
gradual voltage decline after exhaustion of the silver oxide allowing
cells used in devices such as hearing aids to "fail gracefully" and
giving the owner time to replace them. Graphite is added to provide
additional conductivity within the cathode while the silver is in the
charged (oxide) state, and binders are typically added to improve
mechanical integrity.
Cathodes may also be produced by applying a paste of silver oxide
powder and water to a supporting silver grid. This material is then
thermally reduced to silver metal and sintered. Afterwards, the
sintered material is charged to the oxide state by electrolysis in
potassium hydroxide solution and rinsed. Rinse water and spent
formation solutions constitute sources of process wastewater.
The production of silver peroxide cathodes begins with the oxidation
of silver oxide to produce silver peroxide. Subsequently, the
resultant material may be processed in two ways depending upon cell
configuration. Silver peroxide may be mixed as a slurry and applied
to a supporting silver grid to create the cathode structure or it may
be blended with other materials and formed into pellets for use in
button cells. In the first case, wastewater results from washing
paste mixing and application equipment. In the latter case,
subsequent chemical treatment of the pellet cathodes results in the
generation of process wastewater discharges. The production of silver
peroxide is addressed as a separate ancillary operation in this
subcategory.
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Nickel hydroxide cathodes used in this subcategory are prepared by
sintering, impregnation and formation processes as described for the
cadmium subcategory.
Ancillary Operations
Electrolyte Preparation - The electrolytes used in cells in this
subcategory are primarily aqueous solutions of either potassium or
sodium hydroxide but may in some cases contain zinc oxide as well. In
general, they fre added to the batteries in solution form during cell
assembly and must first be prepared from purchased solid constituents.
The preparation of these electrolyte solutions sometimes results in
the generation of some process wastewater, particularly where
different cell types requiring a variety of electrolyte compositions
are produced, and electrolyte mixing equipment is rinsed or washed
between batches of electrolyte.
Cell Assembly - The specific operations involved in cell assembly in
this subcategory are as varied as the physical configurations of the
cells produced. These include button cells, cylindrical cells with
pressed cathodes and powdered zinc anodes, and rectangular cells with
stacked flat electrodes. In general terms assembly of all of these
cells involves placement of the cell separator(s) between the anode(s)
and cathode(s), insertion of the electrodes and separator in the cell
case, addition of electrolyte, sealing the cell, and application of
cell contacts involving both intercell connections and outer battery
housing as required. Process wastewater is not produced directly from
cell assembly operations although some facilities report spillage of
small volumes of electrolyte which is collected and either reused or
disposed.
Cell separators used in this subcategory vary widely in materials and
configuration. Materials used include nonwoven cellulose, paper,
cellophane, and nylon. However, manufacture or handling of separators
is not reported as a source of process wastewater.
Cell Washing - Many of the cells produced in this subcategory are
washed prior to assembly or shipment. These cell wash operations
serve to remove spilled electrolyte, oils and greases, and general
soil from the cell case and minimize the probability of corrosion of
the battery case and contacts or of devices into which the battery is
placed. As described in more detail in connection with process
wastewater characteristics, cell washing procedures vary significantly
among plants and frequently involve multiple cleaning steps using
different process chemicals. Both organic and inorganic cleaning
solutions are used, but most cell cleaning processes include one or
more water rinses resulting in wastewater discharge.
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Reject Cell Handling - Because of the high energy content of cells
produced in this subcategory, cells rejected for defects during
assembly could pose a fire or explosion hazard if shorted out during
handling for disposal. For this reason, they are frequently placed in
containers of water to provide a relatively high resistance short
circuit and dissipate the cells energy safely. The water in these
containers is exposed to all cell constituents for an extended period
of time and is thus potentially contaminated with all battery
component materials. However, the total volume of this wastewater is
very small.
Employee Wash-up - Since mercury, zinc, cadmium, and other materials
used in manufacturing batteries are toxic, washing of the hands and
persons of workers who contact these materials is frequently required
as a part of industrial hygiene procedures. Wastewater from these
washing procedures contains process materials and is thus deemed
battery manufacturing process wastewater.
Equipment Wash - The equipment used in manufacturing batteries may
become contaminated with spilled electrolyte or electrode materials
and require washing as a part of maintenance procedures. Four plants
in the subcategory reported process wastewater from such equipment
washing procedures.
Floor Wash - Production area floors require cleaning as a matter of
industrial safety and hygiene. This may be accomplished in many cases
by dry techniques such as sweeping and vacuuming, but three
manufacturers in this subcategory reported floor washing operations
with a resultant wastewater discharge.
Silver Etch - Silver foil is prepared for use in electrode manufacture
by etching with nitric acid and subsequently rinsing the etched foil.
Wastewater from this process constitutes another battery manufacturing
waste stream requiring consideration.
Silver Peroxide Production - Silver peroxide for use in cathode
manufacture is produced on-site at battery manufacturing plants by
chemical oxidation of purchased silver oxide. Process wastewater
discharges result both from spent process solutions and from water
used in rinsing the silver peroxide product.
Silver Powder Production - The production of silver powder for use in
battery cathodes by electrodepositon and mechanical removal from the
substrate, can be produced for both zinc anode batteries and cadmium
anode batteries as discussed under the cadmium subcategory.
Wastewater is generated in rinsing the product.
Process Integration - The different process operations discussed above
may in principle be combined in many ways for the manufacture of
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batteries. Table V-68 (Page 327 ) presents the combination of anode
and cathode manufacturing processes observed in the subcategory at the
present time. The extent of practice of the ancillary process
operations discussed above is also indicated in the table. Of twenty-
six distinct process operations or functions identified in the
subcategory, seventeen are reported to result in process wastewater
discharges. All of these discharge sources were represented in
sampling at zinc subcategory plants.
Subcategory Data Summary
Five battery product types: alkaline manganese, mercury-zinc, silver
oxide-zinc, nickel-zinc and carbon-zinc-air, are manufactured within
this subcategory. In addition, silver oxide-zinc cells are produced
using two different oxides of silver, silver oxide (monovalent) and
silver peroxide. The silver peroxide yields a higher cell voltage and
greater energy density. Plants in the subcategory vary widely in
production volume, process wastewater generation, and manufacturing
processes. Many produce more than one type of cell. Wastewater
treatment practices and effluent quality are highly variable.
Production - Annual production in the subcategory totaled 22,300
metric tons (24,500 tons) broken down among battery product types as
shown below:
Battery Type
Alkaline Manganese
Carbon-zinc-air
Silver oxide-zinc
Mercury-zinc
Nickel-zinc
No. of
Producing
Plants
8
2
9
5
1
Estimated
Annual Production
Metric Tons Tons
17800 19600
2010 2210
1240 1360
1230 1350
0.23 0.25
Water Use and Wastewater Discharge - Wastewater discharge from zinc
subcategory manufacturing operations as shown in Table V-69 (Page 329 )
varies between 0 and 26,000 1/hr (7,000 gal/hr). This variation may
be understood on the basis of the variations among these plants in the
mix of production operations employed, and the observed variability in
water conservation practices in the subcategory. The impact of
variations in manufacturing process is indicated in the data presented
in Table V-70 (Page 339) which presents normalized wastewater
discharge flows from both visit and dcp data, for each major process
operation in this subcategory.
Wastewater Treatment and Effluent Characteristics - The plants in this
subcategory reported the practice of numerous wastewater treatment
technologies including pH adjustment, sulfide precipitation, carbon
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adsorption, amalgamation, sedimentation, and filtration. Several
indicated the recovery of some process materials from wastewater
streams. The effectiveness of these treatment techniques varies
widely as indicated in the effluent data presented in Table V-71 (Page
331 ). In addition to the wastewater treatment systems reported in
dcp's, a complete system combining in-process controls with ion
exchange and wastewater recycle has recently been installed which will
ultimately eliminate the discharge of wastewater effluent from one
plant. Process changes at another plant have also eliminated process
wastewater discharge since the data presented in the dcp were
developed.
Specific Process Water Uses and Wastewater Characteristics
Anode Operations
Zinc Cast or_ Fabricated Anode - Anodes in this group are produced by
casting or by stamping or forming of sheet zinc. In producing cast
anodes, zinc and mercury are alloyed, and the mixture is cast to
produce an amalgamated anode.
Two plants in the data survey reported using cast anodes for
carbon-zinc-air cell manufacture. No process wastewater is generated
in producing anodes by this procedure.
Zinc Powder - Wet Amalgamated Anode - The amalgamation process is
conducted to reduce the corrosion of the zinc anode thereby increasing
the cell shelf life. Anode material in this group is produced by
amalgamation in aqueous solutions and subsequently rinsed. This
process is consequently termed a wet amalgamation process. Wastewater
discharges also result from both floor area and equipment clean-up
operations occurring in conjunction with the amalgamation processes.
Six plants in the data base reported using wet amalgamated powdered
zinc processes for anode formulation. Two plants have discontinued
these operations. The amalgamation process starts with mixing zinc
and mercury in an aqueous solution contained in a large blending tank.
Some plants use an ammonium chloride solution whereas other plants mix
zinc and mercury powders in an acetic acid solution. For both of
these processes, the aqueous solutions used to amalgamate the zinc and
mercury are drained, and the resulting product is rinsed. Both the
process solution and the rinse wastewater are discharged. After
sufficient rinsing, the moist amalgam is next rinsed in alcohol, and
the excess alcohol is decanted from the product. The amalgam is
removed from the tank and dried to a powdered form prior to adding
binding agents which aid in compacting the anode material into the
steel cans. Finally, cleaning procedures are conducted to remove
impurities from the tank and other equipment in preparation for
processing the next batch of amalgam material. The water used to
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clean the equipment and floor area is also discharged. Figure V-26 is
a schematic diagram of the zinc powder-wet amalgamation process. When
the dried amalgamated product is found to be unacceptable for use in
assembling batteries, it may be returned to the amalgamation area for
reprocessing and further rinsing.
In summary, there are four spurces of wastewater from the wet
amalgamation process: (1) spent aqueous solution discharge; (2)
amalgam rinses; (3) reprocess amalgam rinses; and (4) floor area and
equipment wash discharge. The discharge from amalgamation (total of
above four streams) ranges from 1.4 to 10900.8 liters per day at the
seven plants which reported using the wet amalgamation process (2890.2
I/day mean and 1211.2 I/day median). The production normalized
discharge from both dcp and visit data ranges from 0.69 to 10.09 I/kg
(3.8 I/kg mean and 2.2 I/kg median).
The wastewaters from wet amalgamation processes at two plants were
sampled. The normalized discharge flow during sampling ranges from
1.88 to 6.82 I/kg (4.2 I/kg mean and 3.8 I/kg median). The entire
amalgamation process wastewater was sampled at both facilities.
Wastewater from amalgam preparation and equipment cleaning was
combined. Another waste stream at one plant is associated with
reprocessing amalgamated material. During the sampling visit amalgam
that had been previously stored was being reprocessed intermittently
throughout the three sample days because the oxidation level was
unacceptable for further processing. This material is first submerged
in acetic acid to alleviate the oxidation problem and the subsequent
processing is the same for "virgin" amalgam batches; however, the
mercury concentration in the wastewater of the "virgin" amalgam
process will be substantially greater than that of the reprocessed
amalgam since no additional mercury is mixed into the latter material.
After completion of the amalgamation process, the amalgamated powdered
zinc is either compacted or mixed with gelling materials to form semi-
rigid anodes. One plant reported combining the amalgam with an
unspecified gelling agent for the manufacture of button cells. No
further specifics on this amalgamation process were provided. Three
of the four remaining plants report adding a binding agent,
carboxymethylcellulose, to the amalgam powder prior to compacting the
resulting material into steel cans. The remaining plant did not
specify the binding agent in either the raw material listing or
process diagram.
Table V-72 (Page 332) presents the daily analysis results in units of
mg/1 for both sampled amalgamation processes. Higher zinc
concentrations observed in wastewater from one plant result from the
malfunctioning of the amalgam mixer. Each load of amalgam did not
completely empty out of the tank which required manually scraping the
residue from the mixer and washing the remaining material from the
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tank by using a hose. This cleaning procedure increases the volume of
water used in the amalgamation process and contributes to the zinc
concentrations of the wastewater. Mercury was detected in all the
amalgamation samples, and was measured at relatively high
concentrations in samples at Plant B.
Table V-73 (Page 333 ) presents the pollutant mass loading in the
amalgamation samples taken daily at both Plants B and A. The range,
mean, and median values in units of mg/1 and mg/kg are presented in
Tables V-74 and V-75 (Pages 334 and 335:), respectively.
Gelled Amalgam Anode - The production of gelled amalgam as illustrated
in Figure V-27 (Page 220) begins with the combination of zinc and
mercury powder in the appropriate proportions and the addition of
potassium hydroxide solution to this mixture. The gelling agent,
which is either earboxymethylcellulose or carboxypolymethylene, is
blended in the amalgam mixture to achieve the appropriate gel
characteristics. No wastewater discharge is directly associated with
processing the gelled amalgam; however, both equipment and floor area
are washed to remove impurities resulting from the amalgam processing.
These maintenance procedures result in wastewater discharges.
Wastewaters from two plants (B and A) were sampled. Table V-76 (Page
33t ) presents the analysis results of these waste streams. The
discharge flows on a daily basis range from 0.21 to 1.67 I/kg (0.69
I/kg mean and 0.48 I/kg median). The discharge flows measured at
Plant B include the combined wastewater from both equipment and floor
areas wash operations whereas the flow measurements at Plant A involve
wastewater from floor washing only.
At Plant A, the water used to wash the amalgamation equipment is
recirculated and dumped only once every six months. As a result,
wastewater from this source amounts to approximately 0.001 I/kg, a
negligible contribution to the total discharge volume.
All of the waste streams from amalgamation at these sites were sampled
including the recirculating blender wash water at Plant A even though
this water was scheduled for dumping one and a half months after the
sampling visit was completed. The significant pollutants in these
alkaline waste streams include TSS, mercury, and zinc which result
from the removal of residual amalgam in the cleaning of utensils and
equipment. In addition, spillage resulting from the bulk handling of
raw materials for conducting the amalgamation process are removed
during floor washing.
Zinc concentrations in amalgamation wastewater on the first sampling
day at Plant B could not be calculated. Pollutant concentrations in
this waste stream were not measured directly but were determined by
mass balance using two wastewater samples representing wastewater
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resulting from scrap cell deactivation and the mixed scrap cell
deactivation and amalgamation wastewater. On the first day extremely
high zinc concentrations in the scrap cell deactivation wastewater
prevented meaningful determination of zinc concentrations in the
amalgamation waste stream.
Another parameter that is present in significant concentrations in the
anode room floor wash samples taken at Plant A is arsenic. The source
of this pollutant is unknown although it may be a trace contaminant of
the zinc used in the amalgamation process. The waste streams
generated from washing both the amalgamation equipment and floor areas
are highly alkaline resulting from the potassium hydroxide addition in
gelled amalgam formulation and inclusion of utensil wash water from
electrolyte preparation.
Table V-77 (Page 337) shows the daily pollutant mass loadings in units
of mg/kg for both clean-up processes. Statistical analysis of these
data are presented in Tables V-78 and V-79 (Pages 338 and 339) for
both mg/1 and mg/kg analysis results, respectively.
Three plants produce gelled amalgam. The resultant wastewater
discharges range from 0.25 to 1.13 I/kg with a mean of 0.69 I/kg.
Dry Amalgamated Zinc Powder Anodes - The production of dry amalgamated
powder proceeds simply by mixing mercury metal and zinc powder for an
extended period of time. To control mercury vapor exposure of
production workers, the mixing is commonly performed in an enclosed
vented area separate from the material preparation areas. This
process is truly dry and involves no process wastewater discharge.
This process element also includes the production from zinc powder
amalgamated off-site.
Two plants obtain amalgam produced off-site and one produces dry,
amalgamated powder.
Zinc Oxide Powder - Pasted or Pressed Anodes - The manufacture of
these anodes involves the preparation of a slurry consisting of zinc
oxide and mercuric oxide. The mixture is then layered onto a grid.
The resultant product is allowed to dry, and finally the dried
material is compressed to eliminate irregularities such as jagged
edges. The anode plaques are assembled with cathode plaques to
manufacture batteries which are shipped unformed and later formed by
the customer. Since the formation operation is not conducted on-site,
there is no wastewater associated with anode formation. No other
sources of wastewater associated with the production of this anode
type were reported. Only one plant reported manufacturing slurry
pasted anodes which are assembled with uncharged cathodes to produce
cells to be later charged by the customer.
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Zinc Oxide Powder - Pasted or Pressed, Reduced Anodes - The production
of anodes in this group involves mixing zinc oxide and mercuric oxide
in either a slurry or dry powder form and applying the mixture onto
grids. The pasted or pressed product is electrochemically formed in
potassium hydroxide solution to convert zinc oxide to the zinc state
and reduce mercuric oxide to mercury to amalgamate with the active
zinc. After completion of formation, the anode material is rinsed to
remove residual caustic.
The pressed powder technique for zinc anode formulation as illustrated
in Figure V-28 (Page 221) first involves preparing a dry powder
mixture of both zinc oxide and mercuric oxide. A binding agent such
as PVA is added to the mixture prior to application on the grids which
are held in place by separate molds. Both the grids and powder
mixture are compressed and the resulting plaques are immersed in
potassium hydroxide solution. The plaques are electrochemically
formed and subsequently rinsed and dried.
The slurry paste processing method as illustrated in Figure V-29 (Page
222) involves preparing a slurry of zinc oxide, mercuric oxide, and
either water or dilute potassium hydroxide. A binding agent such as
CMC may be combined with the slurry. Once the slurry is prepared, it
is layered on the surface of either a silver or copper screen and the
material is allowed to dry prior to formation. The plates are
immersed in a potassium hydroxide solution and formed against either
positive electrodes or nickel dummy electrodes. After completion of
formation, the anodes are thoroughly rinsed to assure removal of
potassium hydroxide. The plaques are dried and later compressed to
eliminate irregularities such as jagged edges.
Four plants reported using either the pressed powder or pasted slurry
technique for zinc anode manufacture. The only source of discharge is
the post-formation rinse operation. Since the raw materials are
comparable for both techniques of preparing the plaques, the pollutant
characteristics for the rinse water discharges are similar. The
discharge flow rate of the post-formation rinse based on weight of
zinc applied in anode formulation ranges from 33.3 to 277.3 I/kg
(142.4 I/kg mean and 116.7 I/kg median). The rinse water waste stream
was sampled at two of these facilities, Plants A and B. One plant, C,
is excluded from the flow analysis because the required data were not
provided in the dcp. At Plant B, plaques are rinsed in a multistage
countercurrent rinse after formation.
As previously mentioned, the post-formation rinse wastewater was
sampled at both Plants A and B. The analysis results for each sample
day are presented in Table V-80 (Page 340.)'. Table V-81 (Page 341)
presents the pollutant mass loadings from anode preparation on a daily
basis. Tables V-82 and V-83 (Pages 342 and 343 ) show the statistical
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analysis of the raw waste data in units of mg/1 and mg/kg,
respectively.
Electrodeposited Zinc Anode - This process involves electrodepositing
zinc on a grid and rinsing prior to amalgamation by deposition of
mercuric salts. Afterwards, the plaques are either immediately dried
or rinsed and then dried.
The most common grid materials used in the electrodeposition process
include silver and copper expanded sheets. The grids are immersed in
an aqueous solution of potassium hydroxide and zinc, and an electrical
current is applied causing the zinc to deposit onto the grids. When
the appropriate weight gain of active material on the grids is
achieved, the grids are removed from the caustic solution and
subsequently rinsed in a series of tanks. At an intermediate point in
the rinsing procedure, the moist material may be compressed resulting
in wastewater which combines with the rinse wastewater. After
completion of the rinse operation, the prepared plaques are dipped in
an acidic solution containing mercuric chloride. Mercury is reduced
and deposits on the surface forming an amalgam with the zinc. The
amalgamated plaques are either rinsed and subsequently dried or
immediately dried following amalgamation. Figure V-30 (Page 223 ) is a
schematic diagram of the entire electrodeposition process.
Two plants (A and B) in the data base reported using the zinc electro-
deposition process. The resultant wastewater was sampled at Plant A.
Based on the data received in the survey for Plant B and the visit
data for Plant A, the discharge flows range from 1420.7 to 4966.9
liters per kilogram of zinc applied during the electrodeposition
operation. The process waste streams associated with the manufacture
of electrodeposited anodes include (1) post-electrodeposition rinses,
(2) amalgamation solution dump, and (3) post-amalgamation rinse. The
first two waste streams were sampled at Plant A, and the remaining
waste stream was not sampled because the process at that facility does
not require a rinse following the amalgamation step.
At Plant A, the post-electrodeposition rinse flows are higher than at
Plant B because the latter plant has implemented a countercurrent
rinse system. The post-electrodeposition rinse operation which was
sampled at Plant A has a discharge flow ranging from 4655.6 to 5368.3
I/kg (4965.3 I/kg mean and 4871.9 I/kg median) which exceeds by at
least a factor of four the discharge flow for the same rinse operation
at Plant B. Ninety-seven percent of the total electrodeposition
process wastewater at both facilities results from post-electrode-
position rinsing. The most significant pollutant in the sampled rinse
waste stream is zinc resulting from poorly-adherent zinc particles
which are removed from the product by rinsing and compressing between
the rinsing phases.
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The other waste stream at Plant A which is associated with the zinc
electrodeposition process is the amalgamation solution dump. At this
facility, the amalgamation solution is dumped after sixteen hours of
operation of a single electrode-position line. The resulting
normalized discharge flow averages one liter per kilogram of zinc
applied. Table V-84 (Page 344 ) presents chemical characteristics of
the total wastewater discharge resulting from the production of
electrodeposited zinc anodes. For the first and third days, these
characteristics were determined by mass balance calculations from the
measured characteristics of the electrodeposition rinse and
amalgamation solution waste streams. In addition, the pollutant mass
loadings on each sample day are presented in Table V-85 (Page 345.).
Cathode Operations
Porous Carbon Cathode - The production of porous carbon cathodes
involves the combination of powdered carbon, manganese dioxide, and
water to form "agglos" or agglomerates of active cathode material.
These agglos are assembled with cast zinc anode plates to manufacture
carbon-zinc air cells.
Two plants reported manufacturing porous carbon cathodes. No
wastewater is discharged from this cathode manufacturing process at
either of these plants.
Manganese Dioxide-Carbon Cathode - Cathodes in this group are produced
by blending manganese dioxide with carbon black, graphite, cement, and
for some special cells, mercuric oxide. Typically the cathode mixture
is inserted in steel cans along with separator material, and
electrolyte solution consisting of potassium hydroxide is subsequently
added to the partly assembled cells. At some plants, electrolyte
solution is blended with the cathode material, and the resulting
mixture is molded into cylindrical structures prior to insertion in
the steel cans. The separator material is placed into the interior of
each can, and additional electrolyte solution is then applied.
Nine plants reported producing manganese dioxide carbon cathodes for
alkaline-manganese cell manufacture. Three of these plants have since
discontinued the production of alkaline-manganese cells.
The processes used to formulate the cathode material do not generate
any wastewaters.
Mercuric Oxide (And Mercuric Oxide-Manganese Dioxide-Carbon) Cathodes
- Mercuric oxide is the principle depolarizer material for cathodes in
this element. The cathode mixture is pelletized and placed in steel
containers to produce mercury (Ruben) cells.
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The four plants presently producing this cathode are mercury cell
manufacturers that blend mercuric oxide with other raw materials in
formulating cathodes. Depending on battery specifications, the
mercuric oxide is blended with a variety of other materials including
graphite and manganese dioxide. The cathode formulation process
generates no process wastewater since the blended and pelletized
materials are in dry powdered forms.
Mercuric Oxide-Cadmium Oxide Cathode - The cathodes assigned to this
element are produced by blending mercuric oxide, manganese dioxide,
graphite, and cadmium oxide. The mixture is then pelletized and
placed in steel cans. One plant reported using this method to
manufacture cathodes. No wastewater is generated from this cathode
process.
Silver Powder Pressed Cathode - This grouping includes cathodes
produced by the application of silver powder onto grids. Cathodes in
this group are formed after assembly into cells. Silver powder
(sometimes produced on-site) is pressed on the surface of a silver
screen or other support material and the pressed product is sintered
to prepare the plaques for assembly. No process water is used and no
wastewater discharge results from the production of these cathodes.
Silver Powder Pressed and Electrolytically Oxidized Cathode - The
manufacture of these cathodes involves the use of silver powder which
ts either purchased or produced on-site. Once the silver powder is
prepared, the material is pressed on the surface of a silver grid or
other support material and subsequently sintered. Next, the sintered
plaques are immersed in potassium hydroxide solution and subjected to
an electrical charge-discharge operation which converts the silver
material to a silver oxide state. After completing this process, the
formed plaques are rinsed to remove any residual caustic. Figure V-31
(Page 224) is a schematic diagram of this process.
Three plants reported pressing silver powder on grids to produce
sintered plaques which are subsequently formed. The post-formation
rinse wastewater was sampled at both Plants A and B. Table V-86
presents the normalized discharge flows which range from 79.7 to
1135.5 liters per kilogram of silver powder applied to the grid
material. With the value for the second day at Plant A eliminated
because of variability observed with floor area maintenance water use,
the mean and median normalized flow is 196.25 I/kg. The post-
formation rinse is the only source of wastewater from the manufacture
of these cathodes. Analysis results are presented in Table V-87 (Page
347).
Table V-88 (Page 348 ) presents the daily pollutant mass loadings of
both facilities and statistical analyses in units of mg/1 and mg/kg
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are presented in Table V-89 and V-90 (Pages 349 and 350),
respectively.
Silver Oxide (Ag?0) Powder Cathodes - This process involves blending
powdered raw materials to formulate cathodes used in button cell
manufacture. The cathode powder mixture depends on engineering
specifications and may include such materials as manganese dioxide,
graphite, magnesium oxide, mercuric oxide, and binders blended with
silver oxide powder. When the cathode mixture is prepared, the
material is pelletized and inserted into the cell containers.
Four plants reported manufacturing cathodes in this group. No
wastewater is generated from this process since the materials are
combined in the dry powdered state and further processing, involving
pelletizing and insertion in the cell container, is executed under dry
conditions.
Silver Oxide (Ag?0) Powder - Thermally Reduced O£ Sintered,
Electrolytically Formed Cathode - Cathode formulation using this
process involves preparing a slurry paste of silver oxide powder and
deionized water and layering the mixture on silver metal grids. The
reinforced material is thermally reduced to silver by applying heat
sufficient for sintering. The resulting plaques are positioned in
tanks containing dilute potassium hydroxide solution, electrically
formed, rinsed and soaked until the engineering specifications are
met. Figure V-32 is a schematic diagram of this process which
indicates the wastewater discharge locations.
Two plants reported using this process. The normalized wastewater
flow rates for these plants ranged from 25.0 to 237.1 liters per
kilogram of silver in the silver oxide applied to the grid material.
These plants reported that wastewater discharges result from slurry
paste preparation, formation, and post-formation rinsing. However,
Plant A reported data only for post-formation rinsing (corresponding
to the 25.0 I/kg), and Plant B reported data only for spent formation
solutions and post-formation rinses (corresponding to the 237.1 I/kg).
Two samples were taken which together represent an entire post-
formation rinse cycle. The rinse cycle at Plant B has two phases.
The first phase involves rinsing the plaques for approximately an hour
while they are still positioned inside the formation tanks, and the
second phase involves removing the plaques from the tanks and
subsequently submerging them in water to soak for approximately 24
hours. The analysis results of the post-formation rinse wastewater
(both phases) are presented in Table V-91 (Page 351:) and the pollutant
mass loading estimates are presented in Table V-92 (Page 352). The
wastewater of the first phase of the post-formation rinse operation
was sampled on the second day and the discharge flow was 437.3 I/kg.
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This waste stream is highly alkaline due to the residual formation
caustic.
The second phase of the rinse cycle was sampled on the third day
during which the normalized discharge flow was 100.9 I/kg. The
significant pollutants in this waste stream are mercury and silver.
The higher silver concentration in the wastewater of the second rinse
phase compared to that reported for the first phase is due to the fact
that a smaller volume of water is contacting the surface of the
plaques for a considerably longer time span.
Silver Peroxide (AqO) Cathodes - Cathode preparation follows the
manufacture of silver peroxide powder, which is a separate ancillary
operation. Two cathode preparation processes are in current practice.
Two plants use a chemical treatment process, and one plant uses a
slurry pasting process.
The chemical treatment process starts with pelletizing of the silver
peroxide powder. These cathode pellets are then chemically treated in
two-phases; first in a concentrated potassium hydroxide solution; and
then in a concentrated potassium hydroxide-methanol mixture. After
rinsing and extended soaking in potassium hydroxide, the pellets are
treated with a solution of hydrazine and methanol for the purpose of
metallizing the surface. Figure V-33 (Page 226) is a schematic
diagram of the process involving chemical treatment of silver peroxide
pellets.
Process waste streams are associated with the first phase of chemical
treatment. The wastewater results from (1) spent potassium hydroxide
and methanol bath dumps, (2) rinsing, and (3) soaking. Two plants (A
and B) reported chemically treating silver peroxide pellets. The
normalized discharge flow from this chemical treatment phase range
from 5.6 to 12.8 liters per kilogram of silver processed. The latter
value represents the average discharge flow observed during the
sampling visit at Plant B. Observed daily discharge flow range from
5.5 to 22.4 I/kg. Table V-93 (Page 353) presents the analysis results
of the wastewater sampled at Plant B which is a combination of both
the spent solution dump and subsequent rinse wastewater. Analytical
results vary throughout the three sampling days due to the batch
discharge nature of the processes and the one-hour sampling interval.
Another method currently used to produce silver peroxide cathodes
involves mixing a slurry of silver peroxide powder, deionized water,
and a binding agent such as carboxymethylcellulose. The slurry paste
is layered on the surface of a silver metal grid and subsequently
dried. The only wastewater from this process is from the clean-up of
utensils used to mix the slurry and apply the material on support
material. Figure V-34 (Page 227) is a schematic diagram of this
process.
185
-------
Plant C reported manufacturing reinforced silver peroxide cathodes.
The resultant wastewater was sampled at this facility which produced a
normalized discharge flow for the sample day of 76.0 liters per
kilogram of silver processed. This flow varies according to the
operator's discretion in the amount of water used to wash the
utensils. Table V-93 (Page 353) presents the results of analysis of
the wastewater from the utensil wash operation at Plant C.
Table V-94 (Page 354 ) presents the pollutant mass loadings in the
process waste streams of both Plants C and B. These data are the
basis for the statistical summary of wastewater characteristics from
processes for producing silver peroxide cathodes. The waste streams
resulting from both pellet chemical treatment and slurry application
on support material are summarized in the statistical analyses
presented in Tables V-95 and V-96 (Pages 355 and 355).
Nickel Impregnated Cathodes - Sintered cathodes which are then
impregnated and formed are used to manufacture nickel-zinc batteries.
Discussion and analyses of the impregnated nickel cathode is under the
cadmium subcategory. Table V-22 (Page 276) and Table V-23 (Page 277)
present the results of the analyses in terms of concentrations and
mass loadings.
Ancillary Operations
Cell Wash - After completion of both anode and cathode manufacture,
the cells are assembled; washing alkaline electrolyte is added; the
cells are sealed; and the cells are washed to remove residual electro-
lyte and clean the metallic cell surface of other contaminants. There
are a variety of cell washing systems including both manual and
automatic types and cleaning agents including solvents, compounds and
plain water.
Cell wash operations presently conducted at the seven facilities
reporting cell wash operations can be assigned to one of five groups
based on the chemicals used to wash the cells. This scheme is used as
a framework for describing each of the cell wash operations. These
groups are (1) acetic acid cell wash, (2) cleaning compounds (usually
chromic acid containing) cell wash, (3) methylene chloride cell wash,
(4) freon cell wash; and (5) plain water cell rinse. Within each
group there is at least one plant in which the cell wash operation
wastewater was sampled.
The first grouping listed involves the use of acetic acid in the
preliminary phase of the cell wash operation. The sealed cells are
immersed in a solution consisting of acetic acid with an unspecified
detergent. Afterwards, the cells are transferred from the acidic
solution to a potassium hydroxide solution; thoroughly rinsed to
remove any remaining chemical used to clean the cells; and dipped in a
186
-------
solution containing an oil base additive. Two plants reported using
this technique for cleaning cells.
The second general grouping involves the use of cleaners; usually
containing chromic acid. Rinsing occurs after washing these cells.
Four plants in the data base reported using cleaners containing
chromic acid and wastewater from three of these cell wash operations
was sampled.
The third cell wash grouping involves submerging the cells in a series
of tanks containing methylene chloride, methyl alcohol and ammonium
hydroxide. The wastewater from one plant which used this process to
wash cells was sampled.
The fourth cell wash group uses freon to clean cell surfaces. Two
plants presently use freon in the cell wash operations.
In the fifth cell wash group, only water (no chemical) was reported to
be used to clean the cell container surfaces. Two plants are in this
group, and samples were taken at one plant.
A total of seven plants reported using a cell wash operation in the
manufacture of zinc subcategory cells. The production normalized
discharge flows are determined for each of the seven plants by using
data either obtained in the dcp's or during sampling visits. Table V-
97 (Page 357 ) presents the normalized discharge flows from cell wash
operations at Plants A-G. Based on these data, the range is 0.09 to
34.1 liters per kilogram of finished cells (6.35 I/kg mean and 0.34
I/kg median). The large observed discharge flow variations from cell
wash operations may be related primarily to differences in plant water
conservation practices although cell size and plant specific washing
procedures are also observed to have an influence.
Table V-98 (Page 358) presents the data from sampling cell wash
operation wastewaters at four plants. All of the cell wash groups are
represented. In the table all of the waste streams from cell wash
operations that were sampled at each facility are combined on a flow-
proportioned daily basis to achieve complete plant-by-plant raw waste
characterizations from cell washing.
Table V-99 (Page 359 ) presents the pollutant mass loadings on a daily
basis for each facility. Statistical summaries are presented in
Tables V-100 and V-101 (Page 360 ). The normalized discharge flows
range from 0.085 to 1.8 liters per kilogram. The low value reflects a
recirculating wash operation and the high value is a composite of
wastewaters from three cell wash operations at one plant.
Electrolyte Preparation - Wastewater is generated from washing
equipment used to prepare and apply electrolyte to the zinc
187
-------
subcategory cells. Nine plants reported using water to formulate
electrolyte solution which generally consists of dilute potassium
hydroxide. One plant reported using sodium hydroxide solution as a
substitute electrolyte for potassium hydroxide solution in the
manufacture of certain cells. Two facilities both reported adding
zinc oxide to the electrolyte solution.
Five plants reported no wastewater discharge from electrolyte
processing. However, the remaining four plants did report wastewater
discharges from electrolyte formulation primarily resulting from
utensil washing. Table V-102 (Page 362 ) presents the analytical
results of the waste stream sampled at Plant A. The measured flow is
0.37 liters per kilogram of finished cells processed during the
sampling day.
Based on both the visit and dcp data, the wash-up operation associated
with the preparation of electrolyte solution generates minimal
wastewater (mean normalized flow of 0.12 I/kg and median normalized
flow of 0.0 I/kg). The observed pollutant mass loadings of the
sampled waste stream at Plant A as presented in Table V-103 (Page 363)
do not contribute substantially to the total cell manufacture raw
waste.
Silver Etch Process - The silver etch process prepares silver basis
material for use in the zinc electrodeposition process. The silver foil
is etched with nitric acid, rinsed and dried prior to electrodeposition.
After use in the process, the nitric acid is collected in containers for
contractor remove. Squeegees are used to wipe the etched silver foil
surfaces before rinsing, and only residual acid contaminates the rinse
wastewater.
The only wastewater discharge results from rinsing the etched silver
foil. This waste stream was sampled at Plant A. The process is
conducted on an intermittent basis depending on the production of
silver oxide-zinc cell types requiring the etched material. The
observed discharge flow is 49.1 liters per kilogram of silver
processed.
Tables V-104 and V-105 (Pages 364: and 365 ) present the analytical
results in units of mg/1 and mg/kg for the silver etch process
wastewater. The pollutant characteristics of this acidic waste stream
include zinc and silver. The presence of zinc probably results from
process material contamination. The concentration of silver in the
wastewater is high reflecting the absence of effective silver recovery
measures.
Mandatory Employee Wash - For the purpose of ensuring health and
safety, some facilities require the employees to wash before each
break and at the end of each work day. Since process materials are
188
-------
removed during the wash operation, the resultant waste stream is
considered process wastewater from the zinc subcategory.
Two plants (A and B) reported mandatory employee washing. Employee
wash wastewater from both facilities was sampled. The composited
sample taken at Plant B is a combination of wastewaters generated from
washing clothes previously worn by process employees and from employee
showers. However, a flow measurement was not obtained due to pipe
inaccessibility. The analytical results are presented in Table V-106
(Page 366).
The employee wash wastewater was separately sampled at Plant A. The
observed discharge flow is 0.27 liters per kilogram of finished cells.
Table V-107 (Page 367 ) presents the analytical results of the wash
waste stream. The most significant pollutants are suspended solids
and oil and grease which are expected due to the employees handling
both process materials and lubricated machinery. Table V-108 (Page
368) presents the pollutant mass loadings of the employee wash waste
stream only from Plant A.
Reject Cell Handling - Inspections are performed throughout the cell
assembly process. When a cell .does not meet quality control
specifications, it is removed from the process line for future repairs
or disposal. If a cell can not be repaired, it is disposed as scrap.
The disposal techniques implemented by the zinc subcategory cell
manufacturers vary according to whether the materials - composing the
rejected cells require inactivation. By submerging certain cells in
water, the active materials are discharged which lessens the potential
fire hazard in both handling and disposal of these cells.
Three plants (B, C, and A) reported using water for handling reject
cells. The discharge flows are minimal ranging from 0.002 to 0.03
liters per kilogram of finished cells (0.01 I/kg mean and 0.002 I/kg
median). One plant contractor hauls the wastewater with the rejected
cells to a landfill site whereas the other two plants treat the
wastewater on-site.
At Plant A, the discharge flow was observed to be 0.03 liters per
kilogram of finished cells. Table V-109 (Page 369 ) presents the
analysis results of the reject cell handling waste stream. The
significant pollutants are silver, zinc, and mercury.
The reject cell wastewater was also sampled at Plant B/ Analytical
results for Plant B only are presented in Table V-110 (Page 370).
This waste stream is characterized by a low discharge flow (0.003
liters per kilogram). The most significant pollutants observed are
suspended solids, zinc, and mercury which are constituents of the
alkaline cells being processed. Table V-lll (Page 371 ) presents the
189
-------
pollutant mass loadings of the data attained from sampling the reject
cell wastewater at Plant B.
Floor Wash - Some facilities maintain process floor areas by using
water to remove wasted process materials and other dirt. Only three
plants reported using water for floor maintenance whereas the other
plants generally use other means to clean the floors. These methods
which do not involve water usage include vacuuming, dry sweeping, and
applying desiccant materials in instances of solution spillages.
Each of the three plants that reported using water to clean process
floor areas has a wastewater discharge from the cleaning operation.
Two plants reported discharge flow estimates reflecting both floor
area and equipment cleaning wastewater in their dcp's. Based on dcp
estimates and the discharge flows observed during the sampling visit
at Plant A which represents floor cleaning only, the range of
discharge flows is 0.0008 to 0.30 liters per kilogram of finished
cells (0.13 I/kg mean and 0.10 I/kg median).
Table V-112 (Page 372 ) presents the analytical results of the
wastewater resulting from the floor wash operation at Plant A. Table
V-113 (Page 373:) presents the pollutant mass loadings based on the
data obtained at Plant A.
Lead is a significant pollutant which apparently results from
contamination with solder constituents used to attach tabs to the
electrode substrate materials. In addition, suspended solids are high
in the floor wash wastewater as is ammonia which is a chemical used to
clean the floors.
Equipment Wash
Four plants in the data base reported using water to clean equipment
used to manufacture zinc subcategory cells. All of these plants have
wastewater discharges resulting from cleaning equipment used to handle
process materials. As was previously cited in the floor wash
discussion, two plants reported wastewater discharge estimates
representing both equipment and floor cleaning. Separate equipment
cleaning discharge flow estimates have been obtained in sampling the
resultant wastewater at Plants A and B. At these two plants, the
observed discharges range from 5.1 to 9.0 liters per kilogram of
finished cells.
The significant pollutants in the equipment wash waste streams at
Plant B include suspended solids, zinc, and mercury which result from
the formation operation. Table V-114 (Page 374 ) presents the
analytical results for equipment wash. The relatively high discharge
flow occurred on the first sampling day because all of the equipment
was washed.
190
-------
The same table shows the analytical results from the sample visit of
Plant A. The wastewater at this facility is generated from equipment
wash operations with occasional employee hand washing. The observed
flow is 5.1 liters per kilogram of finished cells. The significant
pollutants in this waste stream are suspended solids, mercury, and
zinc which result from process material contamination.
Table V-115 (Page 375 ) presents the pollutant mass loading calculated
from the analysis data from both Plants A and B. Statistical
summaries of both the concentration and loading data are presented in
Table V-116 and V-117 (Pages 376 and 377 ), respectively.
Silver Powder Production - Silver powder for use in battery cathodes
is manufactured by electrodeposition and mechanical removal. The
slurry which results is filtered to recover the silver powder, and the
filtrate is returned for continued use in the electrodeposition
process. The wet silver powder is rinsed to remove residual acid and
dried prior to storage or use in cathode manufacture.
Process wastewater from the product rinse step was characterized by
sampling at Plant A. Observed wastewater discharge flows range
between 19.8 and 23.7 I/kg (21.2 I/kg mean and 20.1 I/kg median). The
results of analyses of samples from this wastewater source are
presented in Table V-118 (Page 378 ). Table V-119 (Page 379 ) presents
corresponding pollutant mass loading data.
Silver Peroxide Production - Silver peroxide is produced by two
chemical oxidation processes from silver oxide or silver nitrate.
Oxidants used are ozone and potassium persulfate.
The results of analysis of wastewater samples from peroxide production
are presented in Table V-120 (Page 380:) and corresponding pollutant
mass loadings in Table V-121 (Page 381 ).
Total Subcategory Wastewater Characteristics
Total process wastewater characteristics have been estimated for the
zinc subcategory by chemical analysis of waste streams from each
process element. These wastewater values are summarized in a single
table weighted according to the amount of each element manufactured in
the subcategory.
191
-------
Electrolyte Raw
Materials
Electrolyte
Preparation
Wastewater
Anode
Preparation
Anode
Asseirtuy
Zathod
Cathode
Preparation
5
10
jj ro
Wastewater
Cell
Wash
Wastewater
Product
Cells
Floor
Wash
Wastewater
Erployee
Wash-up
Special
Chemicals
and
Metals
Production
Wastewater
Wastewater
FIGURE V-l
GENERALIZED CADMIUM SUBCATEGORY MANUFACTURING PROCESS
192
-------
FIGURE V-2
CADMIUM SUBCATEGORY ANALYSIS
Grouping
Anode
Manufacture
Cathode
Manufacture
Element
Pasted and Pressed Powder
Electrodeposited
Impregnated
Silver Powder Pressed
Nickel Pasted and Pressed
Powder
Specific Wastewater Sources ( Subelements )
. Process Area Clean-up
. Product Rinses
. Spent Caustic
. Scrubbers
. Sintered Stock Preparation Clean-up
. Impregnation Rinses
. Spent impregnation Caustic
. Product Cleaning
. Pre-forraation Soak
. Spent Formation Caustic
. Post-formation Rinse
. No Process Wastewater
. No Process Wastewater
Ancillary
Operations
Nickel Electrodeposited
Nickel Impregnated
Cell Wash
. Spent Caustic
. Post-formortion Rinse
. Sintered Stock Preparation Clean-up
. Impregnation Rinses
. Impregnation Scrubbers
. Product Cleaning
. Pre-formation Soak
. Spent Formation Caustic
. Post-formation Rinses
. Impregnation Equipment Wash
. Nickel Recovery Filter Wash
. Nickel Recovery Scrubber
. Cell Wash
193
-------
FIGURE V-2 (CON'T)
CAEMILM SIBCATEOORY ANALYSIS
Grouping
Ancillary
Operations
Element
Electrolyte Preparation
Floor Wash
Employee Wash
Cadmium Powder Production
Specific Wastewater Sources ( Subelements
. Equipment Wash
. Floor Wash
. Bnployee Wash
. Product Rinses
. Scrubber
Silver Powder Production
Nickel Hydroxide Production
Cadmium Hydroxide Production . Seal Cooling Water
Refer to Zinc Subcategory
Analysis (Figure V-26)
Product Rinses
194
-------
Cadmium Nitrate, .
Hydrogen Peroxide
Solution
Preparation
Grid
Electro-
deposition
Water-
Rinse
Rinse Wastewater
Discharge
Caustic Solution •*-
Formation
Caustic Solution Process
Reuse or Discharge
Water
Rinse
Rinse Wastewater
Discharqe
Finished Anode
To
Assembly
FIGURE V-3
PRODUCTION OF
CADMIUM ELECTRODEPOSITED ANODES
195
-------
Scrubbers
Cadmium Nitrate
Sintered Grids
Solution
Preparation
Wastewater
Impregnation
Caustic Solution-»-
Water
Eisners ion
Rinse
^ To Reuse or Spent
Caustic Dischar:
Rinse Wastewater
Discharae
Water
Caustic Solution
Cleaning
Formation
lb Reuse or Rinse
Wastewater Discharae
Spent Caustic
Discharge
Water
Rinse
Rinse Wastewate:
Discharge
Finished Cathodes'
Assembly
FIGURE V-4
PRODUCTION OF
CADMIUM IMPREGNATED ANODES
196
-------
wicKex Nitrate,
Cobalt Nitrate
Grids
Caustic
Solution
Water
Solution
Preparation
t
Electrode
position
»
Formation
|
Rinse
Caustic Solution Process
Reuse Or Discharge
Rinse Wastewater
Discharge
Finished Cathodes
To Assembly
FIGURE V-5
PRODUCTION OF
NICKEL ELECTRODEPOSITED CATHODES
197
-------
Nickel Nitrate,,
Cobalt Nitrate
Solution
Preparation
Sintered Grids
Caustic Solution'
Water
Impregnation
Immersion
Rinse
Ib Reuse or Spent
Caustic Discharge
Rinse Wastewater
Discharge
Water
Cleaning
To Reuse or Rinse
Wastewater Discharge
Caustic Solution
Formation
Spent Caustic
Discharge
Water
Rinse
Rinse Wastewater
Discharge
Finished Cathodes-
To
Assembly
FIGURE V-6
PRODUCTION OF
NICKEL IMPREGNATED CATHODES
198
-------
Blend De-
polari zer
And Elec-
trolyte
Depolarizer
Preparation
Heating Component
Preparation
Wastewater
Assenfcly
Anode
Manufacture
Ship
Cell
Testing
Wastewater
FIGURE V-7
GENERALIZED CALCIUM SUBCATEGORY
MANUFACTURING PROCESS
199
-------
FIGURE V-8
CALCIUM SUBCATEGORY ANALYSIS
Grouping Element Specific Wastewater Sources
(Subelements)
Anode Vapor Deposited . No Process Wastewater
Manufacture Fabricated
Cathode Calcium Chromate . No Process Wastewater
Manufacture Tungstic Oxide
Potassium Dichromate
Ancillary Heating Component Production:
Operations Heat Paper . Slurry Preparation
. Filtrate Discharge
Heat Pellet . No Process Wastewater
200
-------
PbO
TU:
Leady
LL"_ r Oxide -• i
Production
"•Wt« |^r
1 ^
P&O • Pi
HECYCIL3 TO
MUER
JLPOUTOW— *—
Open Formation
Dehydrated Line
t
. >• row
KjiC,
t EVA?
DRV |— »
f
?AJ/^ ASSL-.K.
t
IURN POST
t
COVES » | SEAL J
VAT if. •
SCRt'lIEK
1 WASTE
MATE!)
PASTING
HACHUIE
WITH BKKtS fbC
t
STOIUCE
0» CUKE 1
or PLATES j
i atJEc
f , »u-«
STACKER
f
UEL:
AiStMLSS
ELD1ENTS
REJECT *
PUIES BAnEKY
CASE "
& COVES
FRESH AtlB )— •
1 n,SO^
,
!
y '• i
T
TEST f— — •
T
Sr.i?
PIC LtAC
1 MACHINE ! I m
IT'"'" «~ Df
CLEA.S-U? ™ TUATSET:
3RY SAC
HOC SI
i- ",L>
Wet Battery Line
~[ Ajsi-j-.y
T
[_ SI&S POST
»
-[ ACID rill.
f
1 row | ,
{C'J^T
-. , , ,: _,
J FILL
!
_J_ECOST CHAR:E
— ».Ej:rrs
» unrein rs SMELTIK
Mot Regulated under
Battery Manufacturing
FIGURE V-9
LEAD BUBCATEGORY
GENERALIZED MANUFACTURING PROCESSES
201
-------
FIGURE V-10
LEAD SUBCATEGORY ANALYSIS
Process
Anodes and Cathodes
Leady
Oxide Production
Paste Preparation and
Application
Curing
Closed Formation (In Case)
Single Fill
Double Fill
Fill and Dump
Open Formation (Out of Case)
Wet
Dehydrated
Ancillary Operations
Final Battery Wash
Floor Wash
Sinks and Showers
Battery Repair
Specific Wastewater Sources
.Ball Mill Shell Cooling
.Scrubber
.Product Soak
.Equipement and Floor Area
Clean-up
.Scrubber
.Steam Curing
.Contact Cooling
.Scrubber
.Contact Cooling
.Scrubber
.Product Rinse
.Formation Area Washdown
.Formation Area Washdown
.Product Rinse
.Scrubber
.Contact Cooling
.Scrubber
.Formation Area Washdown
.Formation Area Washdown
.Product Rinse
.Vacuum Pump Seals and Ejectors
.Scrubber
.Battery Wash
.Floor Wash
.Employee Wash
.Battery Repair Area Wash
202
-------
Lead
Water
Leady
Oxide
Production
Acid
Cutting
Paste
Preparation
Pasting
Lead Alloy
_*
Grid Castinq
Or Rolling
Curing
Stackino
And
Welding
Separators
Case, Covers
Teminals
FIGURE V-ll
PRODUCTION OF
CLOSED FORMATION WET BATTERIES
203
-------
Acid Water
Acid
Cutting
Lead
J_
Leaoy
Oxide
Production
Paste
Preparation
Pastinq
Seoarators
Case, Covers
Terminals
Acid Fill
Closed
Formation
Lead Alloy
I
Grid Castinq
Or Rolling
Wastewater
Dome Acid
Seal
Wash
Wastewste:
Test
t
Ship
FIGURE V-l2
PRODUCTION OF
DAMP BATTERIES
204
-------
Lead
Acid Water
t t
Leady
Oxide
Production
Lead Alloy
Acid
Cuttinq
Paste
Preparation
«_
Pasting
t
Curing
t
Weld
Groups
t
Open
Formation
Grid Cast-
ing Or
RDllino
Separators, Cases,
Covers, Terr.inals
Rinsing
And
Dehydration
Assenblv
Wastewater
Wash
Wastewater
Test
T
Ship
FIGURE V-l3
PRODUCTION OF
DEHYDRATED BATTERIES
205
-------
Purchased Green
Plates
;
Double
toid Wate
1 t
Acid
Cutting
l_
r
•_JL
Dunp And
Refill
Pill ,
'Boost
Charae
Stacking
And
Welding
t
Assenbly
t
Acid Fill
t
Closed
Formation
-*- Separators
--_Case, Cover
Terminals
Wastewater
, Single Fill
Wash
Wastewater
Test
t
Ship
FIGURE V-14
PRODUCTION OF BATTERIES
FROM GREEN (UNFORMED) ELECTRODES
206
-------
Formed Plate
Groups
Acid Water
it
Acid
Cutting
Assembly
Acid
Fill
Separators, Cases
Covers, Terminals
Wash
Wastewater
Test
Ship
FIGURE V-15
PRODUCTION OF BATTERIES
FROM PURCHASED FORMED PLATES
207
-------
100
90
80
70
60
50
40
30
20
10
Production Normalized Flow ( I/kg
...!_• K) u> ,tk m .
&
&
/
/
//
/
/
'/
/
sample
Median Number
(Zeros Of
Included) Values
0 7
9.0 35
0.83 11
0 88
0.715 60
0 34
0 95
0 89
M
Af/X^
m
'
%
L_/>^
Vl*
/
' /
/
fr
^J
•o/
^
^
A
rs r\T cm R tv^r" c>tjr«( fBrCent OI fiOt
^ f^iV -L f f^*/LS\f W ^ A N^» » »-w-^f»m - ™^— ^^— —
LEAD SUBCATEfOFOr PROCESS OPERATIONS
208
-------
kg
8 1
\& iH
Cb
•D
«
N
•ft
•-«
«
K
u
o
z
o
•ft
4i
u
3
•o
o
u
o.
6
'
A
1
NurabcT Nu
in be r
Sample Ot Ot
Process Median Values Zeros
( I/kg )
Single Fill Formation 0 40 36
Double Fill Formation 0.305 30 9
" -o — er
-tr-o^
DC
Fc
-
^r
•
iuble Fill
>r mat ion
^
/
/'°
I
y
/
7
Single Fi
Formation
P
1—
1
J
1
0 1
1
/
11 /
/
10 20 30 40 50 60 70 80 90 10(
CUMULATIVE PERCENT OF PLANTS
FIGURE V-l7
PRODUCTION NORMALIZED DISCHARGE FROM DOUBLE AND SINGLE FILL FORMATION
-------
Electrolyte Raw
Materials
Separator
Raw
Materials
Electrolyte
Fornulation
Zinc
J_
Anode
Shaping
Separator
Preparation
Wastewater
(One Process)
Cathode Raw
Materials
Assembly
Cathode
Preparation
Product
Cells
Washed Tools
and Equipment
Miscellaneous
Tools And
Equiprrent
Fron All
Operations
Hand And
Equipment
Wash
Wastewater
FIGURE V-18
GENERALIZED SCHEMATIC FOR
I£CLANCHE CELL MANUFACTURE
210
-------
FIGURE V-19
LECLANCHE SUBCATEGORY ANALYSIS
Grouping
Anode
Manufacture
Cathode
Manufacture
Ancillary
Operations
Element
Zinc Powder
Manganese Dioxide - Pressed
(All Formulations)
Carbon (Porous)
Silver Chloride
Manganese Dioxide - Pasted
Separators
ooked Paste
Uncooked Paste
Pasted Paper
Equipment and Area
Cleanup
Specific Wastewater Sources
. No Process Wastewater
. No Process Wastewater
. No Process Wastewater
. No Process Wastewater
. No Process Wastewater
. Paste Setting
. Equipment Wash
. Equipment Wash
. Electrolyte Preparation
. Assembly Equipment Wash
. Employee Wash
. Electrode Preparation
Equipment Wash
. Miscellaneous Equipment
Wash
211
-------
Anode
Manufacture
Heating Component
Preparation
(Thermal
Cells Only)
Assenbly
Depolarizer
Preparation
Wastewater
Wastewater
Blend
Depolarizer
Electrolyte
Electrolyte
Shic
Lithium
Scrap
Disposal
Cell Testing
Wastewater
Wastewater
FIGURE V-20
GENERALIZED LITOIUV. SUBCATEGORY
MANUFACTURING PROCESS
212
-------
FIGURE V-21
LITHIUM SUBCATEGORY ANALYSIS
Grouping
Element
Specific Wastewater Sources
(Subelements)
Anode
Manufacture
Cathode
Manufacture
Ancillary
Formed and Stamped
Iodine
Iron Disulfide
Lead - Iodide
Lithium Perchlorate
Sulfur Dioxide
Thionyl Chloride
Titanium Disulfide
.No Process Wastewater
-No Process Wastewater
.Product Treatment
.To Be Resolved
.No Process Wastewater
.Scrubbers
.Cleanup
.Scrubbers
.Spills
.No Process Wastewater
Heating Component Production:
Heat Paper .Filtrate Discharge
.Slurry Preparation
Heat Pellets .No Process Wastewater
Scrap Disposal .Scrap Disposal
Testing .Leak Testing
213
-------
Wastewater
r "~1
1 Anode 1
J Pbrm |
1 , 1
i
i
J
i ' 1
I Clean f, 1
^ Chroma te ,
t
Wastewater
Sop.
Anorle
Cell
Ttst
Separator
Preparation
irator
As.sentil e
S^
up
-^-Was tewater
•^*-
Depolarizer
Preparation
}
Cathode
Manufacture
Heating
Component Prep.
(Thermal
Cells Only)
*- Wastewater
-^- Support
-*- Wastewater
Floor
Wash
Wastewater
Scrubber
>Wastewater
Operations Not Regulated In Battery
Manufacturing Point Source Category
FIGURE V-22
GENERALIZED MAGNESIUM SUBCATEXDKY
MANUFACTURING PROCESS
-------
FIGURE V-23
MAGNESIUM SUBCATEGORY ANALYSIS
Grouping
Element
Specific Wastewater Source
(Subelements)
Anode
Manufacture
Cathode
Manufacture
Ancillary
Operations
Magnesium Powder
Carbon
Copper Chloride
Copper Iodide
Lead Chloride
M-Dinitrobenzene
Silver Chloride -
Surface Reduced
Silver Chloride - Electro-
lytic Process
Silver Chloride
Vanadium Pentoxide
Heating Component Production:
Heat Paper
Testing
Separator Processing
Floor Wash
Scrubbers
.No Process Wastewater
.No Process Wastewater
.No Process Wastewater
.No Process Wastewater
.No Process Wastewater
.No Process Wastewater
.Product Rinsing
.Product Rinsing
.No Process Wastewater
.Scrubbers
.Filtrate Discharge
.Slurry Preparation
.Activation of Sea-Water
Reserve Batteries
.Etching Solution
.Product Rinsing
.Floor Wash
.Air Dehumidifiers
215
-------
Anode Raw
Materials
Cathode Raw
Materials
i
Amalgamation
1
Wastewater
I
Chemical
Preparation
Of
Depolarizer
Anode
Preparation
Wastewater
Electrolyte
Raw Materials
Anode
Formation
Wastewater
I
Wastewater
Cathode
Preparation
Electrolyte
Preparation
Wastewater
Wastewater
Cathode
Formation
Anode
Assembly
Employee
Wash
Cathode
Wastewater
Cell
Wash
Wastewater
I Rejects
__i
Reject
Cell
Handling
Wastewater
Wastewater
Product Cells
-^Wastewater
Bquionent
"wash
VJastewater
FIGURE V-24
GENERALIZED ZINC SUBCATEGORY MANUFACTURING
PROCESSES
216
-------
FIGURE V-25
ZINC SUBCATEOORY ANALYSIS
Grouping
Anode
Manufacture
Cathode
Manufacture
Element
Cast or Fabricated
Zinc Powder - Wet Amal-
gamated
Zinc Powder - Gelled
Amalgam
Zinc Powder - Dry Amal-
gamated
Zinc Oxide Powder - Pasted
or Pressed
Zinc Oxide Powder - Pasted
or Pressed, Reduced
Zinc Electrodeposited
Porous Carbon
Specific Wastewater Sources
. No Process Wastewater
. Floor Area and Equipment Clean-up
. Spent Aqueous Solution
. Amalgam Rinses
. Reprocess A-nalgam Rinses
. Floor Area and Equipment Clean-u?
. No Process Wastewater
. No Process Wastewater
. Post-formation Rinse
. Post-electrodeposition Rinses
. Spent Amalgamation Solution
. Post-amalgamation Rinse
. No Process Wastewater
Manganese Dioxide - Carbon . No Process Wastewater
Mercuric Oxide (and mercuric . No Process Wastewater
oxide - manganese dioxide
carbon)
Mercuric Oxide - Cadmium
Oxide
Silver Powder Pressed
. No Process Wastewater
. No Process Wastewater
Silver Powder Pressed and.
Electrolytically Oxidized"
. Post-formation Rinse
217
-------
FIGURE V-25 (CON'T)
ZINC SUBCATEQDRY ANALYSIS
(Grouping
Cathode
Manufacture
(con't)
Ancillary
Operations
Element
Silver Oxide (Ag.O)
Powder *
Specific Wastewater Sources
. ND Process Vbstewater
Silver Oxide (Ag-O)
Powder - ttiermally Reduced
or Sintered, Electrolytically
Formed
Silver Peroxide (AgO)
Nickel Impregnated
Cell Wash
Electrolyte Preparation
Silver Etch
Mandatory Employee Wash
Reject Cell Handling
Floor Wash
Equipment Wash
Silver Powder Production
Silver Peroxide Production
. Slurry Paste Preparation
. Spent Caustic Formation
. Post-formation Rinse
. Utensil Wash
. Spent Solution
. Product Rinse
. Product Soak
Refer to Cadmium Subcategory Analy-
sis (Figure V-2)
. Acetic Acid Cell Wash
. Chromic Acid Containing Cell Wash
. Methylene Chloride Cell Wash
. Freon Cell Wash
. Non-chemical Cell Wash
. Equipment Wash
. Product Rinse
. Employee Wash
. Reject Cell Handling
. Floor Wash
. Equipment Wash
. Product Rinse
. Product Rinses
. Spent Solution
218
-------
Zinc, Mercury
Solution
Mix
Water
i
Rinse
Rinse Wastewater
Discharqe
Methanol
Methanol
Rinse
1
Drv
Contractor Removal
Of Spent Methanol
Dry powdered
To
Assenblv
FIGURE V-26
PRODUCTION OF
ZINC POWDER - WET AMALGAMATED ANODES
219
-------
Zinc, Mercury
Electrolyte
Mix
Gellina Aaent
Blend
I
Gelled Amalgam
To
Asserblv
Water
Equipment
And Floor
Area Wash
Wash Wastewater
Discharge
FIGURE V-27
PRODUCTION OF GELLED AMALGAM ANODES
220
-------
Zinc Oxide And
Mercuric Oxide
Bswders
Bindinq Aaent
Mix
1
Blend
Grids
Caustic Solution
Press On
Grids
I
Electroly-
tically
Reduced
Water
Rinse
Rinse waste water
Discharqe
Dry
Finished Anodes
FIGURE V-28
PRODUCTION OF PRESSED ZINC OXIDE
ELECTROLYTICALLY REDUCED ANODES
221
-------
Zinc Oxide. Mercuric
Oxide Slurry
Mix
Bindinq Agent
I
Blend
Grids
I
Layer on
Grids
Caustic Solution
Water
I
Electro-
lytically
reduced
I
Rinse
I
Dry
Rinse Wastewater
Discharge
Compress
Finished Anodes
To Assenblv
FIGURE V-29
PRODUCTION OF PASTED ZINC OXIDE
ELECTROLYTICALLY REDUCED ANODES
222
-------
Zinc Caustic
Solution
Solution
Preparation
Grids
i
Electrode
position
Water
Rinse
Rinse Wastewater
Discharae
Mercuric Chloride
Acidic Solution
I
Analqana-
tion
Drv
Spent Analgaretion
Solution Disposal
Water
1
Rinse
Rinse Wastewater
Discharae
I
Dry
i
Finished Anodes ^
FIGURE V-30
PRODUCTION OF ELECTRODEPOSITED
ZINC ANODES
223
-------
Silver Powder
Mix
Grids
I
Press On
Grids
Caustic Solution
I
Electroly-
tically
Bormed
Water
Rinse
Rinse Wastewater
Discharge _
Dry
\
Finished Cathodes
1 ^
To Assembly
FIGURE V-3 1
PRODUCTION OF SILVER POWDER PRESSED
ELECTROLYTICALLY OXIDIZED CATHODES
224
-------
Silver Oxide
Fowder, water
Mix
Grids
1
Layer On
Grids
i
Sinter
Caustic Solution _
Electroly-
tically
Formed
To Reservoir Or Spent
Caustic Discharge
Water
Rinse
Rinse Wastewater
Discharge
Water
Soak (One
Point)
water
1
Equipment
And Floor
Area Wash
1
Soak Wastewater
Discharge
Drv
Wash Wastewater
Discharge
Finished Cathodes
ID Assembly
FIGURE V-3 2
PRODUCTION OF SILVER OXIDE (Ag20) POWDER
THERMALLY REDUCED OR SINTERED,
ELECTROLYTICALLY FORMED CATHODES
225
-------
Silver Peroxide
»i
Pelletize
Solution
i
Chenical
Treatment
Water
i
.Spent Solution
Discharge
Rinse
Containers
1
Rinse Wastewater
Discharge
Dry And Place
In Container
Methanol-Hydraz ine
Solution _
Chenical
Treatment
Methanol
i
Contractor Reroval
Of Spent Solution
Methanol
Rinse
Contractor Removal
of Methanol
I
Dry
Finished Cathodes
To Assenblv
FIGURE V-3 3
CHENICAL TREATMENT OF SILVER
PEROXIDE CATHODE PELLETS
226
-------
Silver Oxide Powder
And Water
•#•
Binding Agent
Grids
Water
Mix
1
Blend
I
layer On
Grids
i
Dry
Finished Cathodes
Tto Assenfcly
Eouipnent
Wash
Wash Wastewater
Discharge
Figure V-34
PRODUCTION OF PASTED
SILVER PEROXIDE CATHODES
227
-------
TABLE V-l
SCREENING ANALYSIS RESULTS
CADMIUM SUBCATEGORY
DCP Data Plant Raw
KTBP, BTBP Influent Waste
Cone. Cone.
mg/1 ng/1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride
Chlorobenzene
1,2,4 Trichlordbenzene
Hexachlorobenzene
1, 2 Dichloroethane
1,1,1 Trichlorethane
Hexachloroethane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetr^chloroethane
Chloroethane
Bis Chloromethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinly Ether
2-Chlorona0ithalene
2,4,6 Trichlorophenol
Parachlorometacresol
Chloroform
2 Chlorophenol
1,2 Dichlorobenzene
1,3 Dichlorobenzene
1,4 Dichlorobenzene
3,3 Dichlorobenzidine
1,1 Dichloroethylene
1,2 Trans-Dichloroethylene
2,4 Dichlorophenol
1,2 Dichloropropane
1,2 Dichloropropylene
2,4 Dimethylphenol
2,4 Dinitrotoluene
2,6 Dinitrotoluene
1,2 Diphenylhydrazine
Etnylbenzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
4 Brcmophenyl Phenyl Ether
•Bis (2 Chloroisopropyl ) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride
Methyl Chloride
Methyl- Bronide
BrcRoform
Dichlorobronone thane
Trichlorofluoronethane
Dichlorodifluorcmethane
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.530
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.024
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
0.061
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.027
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
ND
ND
ND
ND
ND
0.013
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.61
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mq/1
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
ND
NA
NA
ND
ND
ND
ND
NA
ND
NA
NA
NA
*
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
ND
NA
NA
NA
NA
ND
NA
NA
NA
NA
0.044
ND
ND
ND
ND
ND
ND
228
-------
TABLE V-l
SCREENING ANALYSIS RESULTS (CONT.)
CADMIUM
DCP Data
KTBP, BTBP
51. Oilorodibronomethane
52. Hexachlorobutadiene
53. Hexadilorccyclopentadiene
54. Isophorone
55. Naphthalene
56. Nitrobenzene
57. 2 Nitrophenol
58. 4 Nitrophenol
59. 2,4 Dinitrophenol
60. 4,6 Dinitro-o-cresol
61. N-Nitrosodinethylamine
62. B-Nitrosodiphenylamine
63. N-Nitrosodi-N-propylamine
64. Pentadilorophenol
65. Phenol 0,2
66. Bis (2-Ethylhexyl) Phthalate
67- Butyl Benzyl Phthalate
68. Di-N-butyl Phthalate
69. Di-N-octyl Phthalate
70. Diethyl Phthalate
71. Dimethyl Phthalate
72. 1,2 Benzanthraoene
73. Benzo (A) Pyrene
74. 3,4 Benzofluoranthene
75. 11, 12-Benzofluoranthene
76. Chrysene
77. Acenaphthylene
78. Anthracene
79. 1,12-Benzoperylene
80. Fluorene
81. Phenanthrene
82. 1,2,5,6 Dibenzanthracene
83. Indenopyrene
84. Pyrene
85. Tetrachloroethylene
86. Toluene
87. Trichloroethylene 0,1
88. Vinyl Chloride
89. Aldrin
90. Dieldrin
91. Chlordane
92. 4,4 DDT
93. 4,4 DDE
94. 4,4 DDD
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
SUBCATEGORY
Plant Raw
Influent Waste
Cone. Cone.
mg/1 mg/1
ND
ND
ND
ND
ND
WD
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
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
ND
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
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.025
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
ND
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
ND
*
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
229
-------
TABLE V-l
SCREENING ANALYSIS RESULTS (CONT.)
CADMIUM SUBCATEGORY
DCP Data Plant Raw
RTBP, BTBP Influent Waste
Cone. Cone.
mq/1 mq/1
101. Heptachlor Epoxide
102. Alpha-BHC
103. Beta-BHC
104. Garma-BHC (Lindane)
105. Delta-BHC
106. PCB-1242
107. PCB-1254
108. PCB-1221
109. PCB-1232
110. PCB-1248
111. PCB-1260
112. PCB-1016
113. Toxaphene
114. Antimony
115. Arsenic
116. Asbestos
117. Beryllium
118. Cadmium
119. Chromium
120. Copper
121. Cyanide
122. Lead
123. Mercury
124. Nickel
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,7,8 TCDD (Dioxin)
130. Xylenes
131. Alkyl Epoxides
Aluminum
Ammonia
Barium
ROTTWl
^^i 1 i WI A
Calcium
Cobalt
Fluoride
Gold
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttrium
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1,0 ND
1,0 ND
NA
< 0.001
4,0 0.009
2,0 0.007
0.010
1,0 0.020
0.020
0.0003
7,0 < 0.005
ND
< 0.0001
ND
0.090
NA
NA
NA
< 0.090
0.12
0.020
< 0.080
18.0
< 0.002
1.20
<0.001
7*.8
0.03
<0.006
6.0
<0.005
ND
-,- 8.8
NA
<5.0
0.05
< 0.006
<0.002
<0.002
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
<0.01
70
.08
<0.09
0.07
0.40
0.0003
100
ND
<0.01
ND
<0.5
NA
NA
NA
<0.90
5.76
<0.06
<0.80
<50
<0.02
1.15
ND
1.00
7.00
0.10
<0.06
<5.00
< 0.009
0.05
400
NA
368
0.30
<0.06
<0.02
<0.02
Effluent
Cone.
mq/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND'
ND
ND
ND
ND
NA
<0.01
100
<0.05
<0.09
0.04
0.40
0.0003
70
ND
<0.01
ND
<0.5
NA
NA
NA
<0.90
3.57
<0.06
<0.80
<50
<0.02
1.15
ND
7.00
0.09
<0.06
<5.00
< 0.009
ND
510
NA
338
<0.08
<0.06
<0.02
<0.02
Analysis
Blank
Gone.
mq/1
NA
NA
NA
NA
VTA
NA
VTJl
NA
NA
%TK
NA
ItTk
NA
m
NA
vra
NA
XTK
NA
%TM
NA
NA
NA
tTH
NA
NA
NA
NA
NA
NA
NA
NA
NA
ITK
NA
NA
&m
NA
NA
NA
MH
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
NA
NA
NA
230
-------
TABLE V-l
SCREENING ANALYSIS RESULTS (CONT.)
CADMIUM SUBCATEGORY
DCP Data Plant Raw Effluent Analysis
KTBP, BTBP Influent Waste Gone. Blank
Gone. Gone. Cone.
mg/1 rag/1 mg/1 mg/1
ND Not detected
NA Not analyzed (includes Xylenes & Alkyl Epcxides since laboratory analysis 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 less than .01 mg/1.
** Indicates less than .005 mg/1.
231
-------
TABLE V-2
SCREENING ANALYSIS RESULTS
CALCItM SUBCATEGORY
Plant Raw
Influent Waste
DPC Data Cone. Cone.
KTBP, BTBP mg/l mg/1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
Acenaphthene
Acrole in
Acrylontirile
Benzene
Benzidine
Carbon Tetrachloride
Chi orobenzene
1,2,4 Trichl orobenzene
Hex achl orobenze ne
1,2 Dichloroethane
1,1,1 Trichl oroe thane
Hex achl oroe thane
1,1 Dichloroethane
1,1,2 Trichl oroe thane
1,1,2,2 Tetrachloroethane
Chi oroe thane
Bis Chlorcmethyl Ether
Bis 2-Chl oroethyl Ether
2-Chloroethyl Vinyl Ether
2-Cnl oronapt hal ene
2,4,6 Trichl orophenol
Pa rachl orone tacresol
Chloroform
2 Chi orophenol
1,2 Dichlorobenzene
1,3 Dichlorobenzene
1,4 Dichlorobenzene
3,3 Dichlorobenzidine
1,1 Dichl oroethyl ene
1,2 Trans-Dichloroethylene
2,4 Dichl orophenol
1,2 Dichl oropropane
1,2 Dichl oropropyl ene
2,4 Diirtethylphenol
2,4 Dinitrotoluene
2,6 Dinitrotoluene
1,2 Diphenylhydrazine
Ethylbenzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.055
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
0.013
ND
ND
ND
ND
ND
ND
ND
ND
0.038
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
nq/1
NA
ND
ND
ND
NA
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
ND
NA
ND
NA
NA
NA
*
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
ND
NA
NA
232
-------
TABLE V-2
SCREENING ANALYSIS RESULTS (CONT.)
CALCIUM SUBCATBGORY
Plant Raw
Influent Waste
DPC Data Cone. Cone.
KTBP, BTBP ing/I mg/1
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
4 Bromophenyl Phenyl Ether
Bis (2 Chloroisopropyl) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride
Methyl Chloride
Methyl Bromide
Bromoform
Dichl orobronoroe thane
Tr ichl orof 1 uorone thane
Dichl orod i f 1 uorome thane
Chi orod ibrcmome thane
Hexachl orobu t ad i ene
Hexachl orocyclopentadi ene
Isophorone
Naphthalene
Nitrobenzene
2 Nitrophenol
4 Nitrophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Ni trosod ime thyl am ine
N-Ni trosod iphenyl amine
N-Nitrosodi-N-propylamine
Pentachl orophenol
Phenol
Bis (2-Ethylhexyl) Phthalate
Butyl Benzyl Phthalate
Di-N-butyl Phthalate
Di-N-octyl Phthalate
Diethyl Phthalate
Dijnethyl Phthalate
1,2 Benzanthracene
Benzo (A) Pyrene
3,4 Benzofluorathene
11, 12-Benzofluoranthene
Chrysene
Acenaph thyl ene
Anthracene
1 , 1 2-Benzoperylene
Fluorene
ND
ND
ND
0.011
ND
ND
ND
ND
ND
15D
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
0.014
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
0.024
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
TO
Analysis
Blank
Cone.
mg/1
NA
NA
NA
*
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
N?V
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
233
-------
TABLE V-2
SCREENING ANALYSIS RESULTS (CONT.)
81. Phenanthrene
82. 1,2,5,6 Dibenzanthracene
83. Indenopyrene
84. Pyrene
85. Tetrachloroethylene
86. Toluene
87. Trichloroethylene
88. Vinyl Chloride
89. Aldrin
90. Dieldrin
91. Chlordane
92. 4,4 DDT
93. 4,4 DDE
94. 4,4 ODD
95. Alpha- Endosul fan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
101. Heptachlor Epoxide
102. Alpha-BHC
103. Beta-BHC
104. Gamma-BBC (Lindane)
105. Delta-BBC
106. PCB-1242
107. PCB-1254
108. PCB-1221
109. PCB=1232
110. PCB-1248
111. PCB-1260
112. PCB-1016
113. Toxaptene
114. Antimony
115. Arsenic
116. Asbestos
117. Beryllium
118. Cadmium
119. Qironium
120. Copper
CALCIIM SUBCATBGORY
Plant
Influent
DPC Data Cone.
KTBP, BTBP ing/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
-------
TABLE V-2
SCREENING ANALYSIS RESULTS (COOT.)
CALCIIW SUBCATEGORY
Plant Raw
Influent Waste
DPC Data Cone. Cone.
KTBP, BTBP mg/1 mg/1
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8 TCDD (Dioxin)
Xylenes
Alkyl Epoxides
Aluminum
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
Gold
Iron
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttrium
ND
0.025
<0.001
0.060
<0.005
0.003
<0.050
0.018
ND
NA
NA
-,- 0.086
-,- NA
-,- 0.016
-,- 0.040
-,- 15.4
-,- 0.011
1.7
-,- NA
-,- 0.091
3.47
-,- 0.007
-,- <0.001
-,- ND
-,- ND
-,- ND
-,- 5.73
-,- NA
-,- ND
-,- 0.012
-,- 0.001
-,- 0.030
-,- <0.001
ND
0.044
<0.001
0.067
<0.005
0.012
<0.050
0.045
ND
NA
NA
0.104
NA
2.67
0.116
15.9
0.006
1.7
NA
0.122
3.66
0.008
0.001
ND
ND
ND
6.06
NA
21
0.006
0.001
0.030
0.001
Analysis
Blank
Cone.
mg/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
235
-------
TABLE V-2
SCREENING ANALYSIS RESULTS (OONT.)
CALCIUM SUBCATEX30RY
Plant Raw Analysis
Influent Waste Blank
DPC Data Cone. Cone. Cone.
KTBP, BTBP rog/1 mg/1 mg/1
ND Not detected
NA Not analyzed (includes Xylenes & Alkyl Epoxides since laboratory analysis
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 less than 0.01 mg/1.
** Indicates less than 0.005 mg/1.
236
-------
TABLE V-3
SCREENING ANALYSIS RESULTS
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27-
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
LEAD
DCP Data
KTBP, BTBP
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetradhloride
Chlorobenzene
1,2,4 Trichlorobenzene
Hexachlorobenzene
1, 2 Dichloroethane 0,1
1,1,1 Trichlorethane 0,5
Hexachloroethane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetrachloroethane
Chloroethane
Bis Chlorcmethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinyl Ether
2-Chloronaphtnalene
2,4,6 Trichlorophenol
Parachlorometacresol
Chloroform
2 Cnlorophenol
1,2 Dichlorobenzene
1,3 Dichlorobenzene
1,4 Dichlorobenzene
3,3 Dichlorobenzidine
1,1 Dichloroethylene
1,2 Trans-Dichloroethylene
2,4 Dichlorophenol
1,2 Dichloropropane
1,2 Dichloropropylene
2,4 Dimethylphenol
2,4 Dinitrotoluene
2,6 Dinitrotoluene
1,2 Diphenylhydrazine
Ethylbenzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
4 Brcnophenyl Phenyl Ether
Bis (2 Chloroisopropyl ) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride 6,0
Methyl Chloride
Methyl Brcru.de
Bronoform
Dichlorobromoniethane
Trichlorofluoronethane
Dichlorodifluoranethane 0,4
SUBCATEGORY
Plant
Influent
Cone.
mg/1
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
ND
*
ND
ND
Raw
Waste
Cone.
mg/1
*
ND
ND
*
ND
ND
ND
ND
ND
ND
0.025
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
Effluent
Cone.
mg/1
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
0.029
*
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
*
*
ND
ND
ND
ND
*
ND
ID
ND
*
ND
ND
Analysis
Blank
Cone.
mg/1
NA
NA
NA
NA
*
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
ND
NA
ND
NA
NA
NA
*
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
ND
NA
NA
NA
NA
NA
0.012
ND
ND
ND
ND
ND
ND
237
-------
TABLE V-3
SCREENING ANALYSIS RESULTS (OONT.)
LEAD
DCP Data
"KTBP, BTBP
51. Chlorodihroraotnethane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
54. Isophorone
55. Naphthalene 0,6
56. Nitrobenzene
57. 2 Nitrophenol
58. 4 Nitrcphenol
59. 2,4 Dinitrophenol
60. 4,6 Dinitro-o-cresol
61. N-Nitrosodimethylamine
62. B-Nitrosodiphenylamine
63. N-Nitrosodi-N-prcpylanine
64. Pentachlorophenol
65. Phenol
66. Bis (2-Ethylhexyl) Phthalate
67. Butyl Benzyl Phthalate
68. Di-N-butyl Phthalate
69. Di-N-octyl Phthalate
70. Diethyl Phthalate
71. Dimethyl Phthalate
72. 1,2 Benzanthracene
73. Benzo (A) Pyrene
74. 3,4 Benzofluoranthene
75. 11, 12-Benzofluoranthene
76. Chrysene
77. Acenaphthylene
78. Anthracene
79. 1,12-Benzoperylene
80. Fluorene
81. Phenanthrene
82. 1,2,5,6 Dibenzanthracene
83. Indenopyrene
84. Pyrene
85. Tetrachloroethylene
86. Toluene 0,1
87. Trichloroethylene
88. Vinyl Chloride
89. Aldrin
90. Dieldrin
91. Chlordane
92. 4,4 DDT
93. 4,4 DDE
94. 4,4 DDD
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
SUBCATEGORY
Plant
Influent
Cone.
mg/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
ND
ND
ND
ND
ND
Raw
Waste
Cone.
mg/1
*
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
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
*
0.016
ND
*
ND
ND
ND
*
ND
ND
ND
*
ND
0.007
ND
ND
0.007
ND
ND
*
ND
*
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
ND
NA
NA
'NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
NA
NA
NA
NA
HA
NA
NA
HA
NA
NA
NA
ND
*
*
ND
NA
NA
NA
MA
NA
NA
NA
NA
NA
NA
NA
NA
238
-------
TABLE V-3
SCREENING ANALYSIS RESULTS (OONT.>
LEAD SUBCATEGORY
DCP Data Plant Raw
KTBP, BTBP Influent Waste
Gone. Gone.
mcT/1 nq/1
101. Heptachlor Epo5d.de
102. Alpha-BHC
103. Beta-BHC
104. Gartna-BHC (Lindane)
105. Delta-BHC
106. PC&-1242
107. PCB-1254
108. PCB-1221
109. PCB-1232
110. PCB-1248
111. PCB-1260
112. PCB-1016
113. Tbxaphene
114. Antiinony
115. Arsenic
116. Asbestos
117- Beryllium
118. Cadmium
119. Chronium
120. Copper
121. Cyanide
122. Lead
123. Mercury
124. Nickel
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,7,8 TCDD (Dioxin)
130. Xylenes
131. Alkyl Epoxides
Aluminum
Armenia
Barium
Boron
Calcium
Cobalt
Fluoride
Gold
Iron
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttrium
0,1
0,1
0,1
38,8
30,7
24,2
15,2
14,32
65,9
0,6
20,8
6,0
6,5
21,7
0 3
0
—
—
—
-
—
-
-
—
—
—
-
-
-
-
—
—
_
•
2
—
—
-
-
-
—
—
-
-
-
—
-
"•
-
-
_
— r~
"t~
~f"*
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
ND
< 0.001
ND
0.300
NA
NA
NA
0.060
NA
0.007
NA
11.000
< 0.005
0.820
ND
< 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
**
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
ND
.033
ND
0.40
NA
NA
NA
0.20
NA
0.03
NA
26.0
< 0.005
0.8
ND
2.00
2.20
0.06
0.008
36.5
0.008
0.58
100
NA
57.8
0.02
<0.02
<0.01
<0.02
Effluent
Gone.
mg/1
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
.92
ND
<0.2
2.10
0.03
< 0.005
10.0
<0.005
0.04
260
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
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
239
-------
TABLE V-3
SCREENING ANALYSIS RESULTS (OONT.)
LEAD
DCP Data
KTBP, BTBP
SUBCATEGORY
Plant
Influent
Cone.
mg/1
Raw
Waste
Gone.
mg/1
Effluent
Cone.
rag/1
Analysis
Blank
Cone.
mg/1
ND Not detected
NA Not analyzed (includes Xylenes & Alkyl Epoxides since laboratory analysis 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 less than .01 mg/1.
** Indicates less than .005 ng/1.
240
-------
TABLE V-4
SCREENING ANALYSIS RESULTS
LECLANCHE SUBCATEGORY
DCP Data Plant
KIBP, BTBP Influent
Cone.
mg/1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride
Chlorcbenzene
1,2,4 Trichlorobenzene
Hexachlorcbenzene
I, 2 Dichloroethane
1,1,1 Trichlorethane
Hexachloroethane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetrachloroethane
Chloroethane
Bis Chloronethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinyl Ether
2-Chloronaphthalene
2,4,6 Trichlorophenol
Parachloranetacresol
Chloroform
2 Chlorophenol
1,2 Dichlorobenzene
1,3 Dichlorobenzene
1,4 Dichlorobenzene
3,3 Dichlorobenzidine
1,1 Dichloroethylene
1,2 Trans-Dichloroethylene
2,4 Dichlorophenol
1,2 Dichloropropane
1,2 Dichloropropylene
2,4 Dimethylphenol
2,4 Dinitrotoluene
2,6 Dinitrotoluene
1,2 Diphenylhydrazine
Ethylbenzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
4 Bronophenyl Phenyl Ether
Bis (2 Chloroisopropyl ) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride 1,0
Methyl Chloride
Methy Bromide
Branoform
Dichlorobramomethane
Trichlorofluoronethane
Dichlorodifluoranethane
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.043
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
0.010
ND
ND
Raw
Waste
Cone.
mg/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
ND
ND
ID
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
ND
NA
ND
ND
NA
ND
NA
NA
NA
ND
ND
NA
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
ND
NA
NA
NA
NA
NA
ND
NA
NA
ND
ND
ND
NA
NA
NA
ND
NA
NA
NA
NA
NA
0.006
ND
ND
ND
ND
ND
ND
241
-------
TABLE V-4
SCREENING ANALYSIS RESULTS (OONT.)
LECLANCHE SUBCATEGOKY
DCP data Plant Raw
KTBP, BTBP Influent Waste
Cone. Cone.
mq/1 tng/1
51. Chlorodibrariome thane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
54. Isophorone
55. Naphthalene
56. Nitrobenzene
57. 2 Nitrophenol
58. 4 Nitrophenol
59. 2,4 Dinitrophenol
f f\ A f r~i * ' i *l
ou. 4,0 Dinitro—G—cresoi
61. N-Nitrosodinethylarnine
62. B-Nitrosodipehnylanane
63. N-Nitrosodi-N-propylafnine
64. Pentachlorophenol
65. Phenol
66. Bis (2-Etnylhexyl) Phthalate
67. Butyl Benzyl Phthalate
68. Di-N-butyl Phthalate
69. Di-N-octyl Phthalate 0,1
70. Diethyl Phthalate
71. Dimethyl Phthalate
72. 1,2 Benzanthracene
73. Benzo (A) Pyrene
74. 3,4 Benzofluoranthene
75. 11, 12-Benzofluoranthene
76. Chrysene
77. Acenaphthylene
78. Anthracene
79. 1,12-Benzoperylene
80. Fluorene
81. Phenanthrene
82. 1,2,5,6 Dibenzanthracene
83. Indencpyrene
84. Pyrene
85. Tetrachloroethylene 0,1
86. Toluene 0,2
87. Trichloroethylene 0,1
88. Vinyl Chloride 0,1
89. Aldrin
90. Dieldrin
91. Qilordane
92. 4,4 DDT
93. 4,4 DDE
94.. 4,4 ODD
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
*
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
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
*
*
*
ND
.016
*
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
Analysis
Blank
Cone.
mg/1
ND
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
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
242
-------
TABLE V-4
SCREENING ANALYSIS RESULTS (CONT.)
LECLANCHE SUBCATEGORY
DCP Data Plant Raw
KTBP, BTBP Influent Waste
Cone. Gone.
mg/1 mg/1
101. Heptachlor Epoxide
102. AlphaBHC
103. BetaBHC
104. GammaBHC (Lindane)
105. DeltaEHC
106. PCB1242
107. PCB1254
108. PCB1221
109. PCB1232
110. PCB1248
111. PCB1260
112. PCB1016
113. Toxaphene
114. Antimony
115. Arsenic
116. Asbestos
117. Beryllium
118. Cadmium
119. Chromium
120. Copper
121. Cyanide
122. Lead
123. Mercury
124. Nickel
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,7,8 TCDD (Dioxin)
130. Xylenes
131. Alkyl Epoxides
Aluminum
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
Gold
Iron
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttrium
0,3
0,4
0,5
1,2
4,2
4,3
5,1
1,3
1,0
0,2
~,~
*~,~
"~,~
™,"™
~,~
~i~
— —
- -
- -
— —
- -
- -
- -
- -
- -
~/""
","*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.001
<0.002
<0.005
<0.009
ND
<0.02
0.020
<0.005
ND
<0.001
ND
0.080
NA
NA
NA
<0.09
NA
0.010
0.100
52.000
<0.002
1.200
ND
< 0.1
7.500
0.02
< 0.006
ND
1.600
0.240
66.00
NA
ND
<0.008
<0.006
<0.002
< 0.002
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.00
ND
ND
<0.01
Q..10
0.20
1.00
.018
6.00
6.00
4.00
ND
<0.01
ND
2000
NA
NA
NA
<0.09
ND
0.40
2.00
150
<0.02
2.20
ND
5.00
33.0
10.0
0.20
ND
14.9
.82
180
NA
1630
3.00
ND
ND
ND
Analysis
Blank
Cone.
mg/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
NA
NA
NA
NA
NA
NA
NA
243
-------
TABLE V-4
SCREENING ANALYSIS RESULTS (OONT.)
LECLANCHE SUBCATEGORY
DCP Data Plant Raw Analysis
KTBP, BTBP Influent Waste Blank
Cone. Cone. Cone.
mg/1 mg/1 mg/1
ND .Nbt detected
NA Not analyzed (includes Xylenes & Alkyl Epoxides since laboratory analysis 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 less than .01 mg/1.
** Indicates less than .005 mg/1.
244
-------
TABLE V-5
SCREENING ANALYSIS RESULTS
ro
-e»
en
LITHIUM SUBCATEGORY
Plant Raw
Influent Waste
DPC Data Cone. Cone.
KTBP, BTBP nxj/1 mg/1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
Acenaphthene
Acrole in
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride
Chlorobenzene
1,2,4 Trichlorobenzene
Hexachlorobenzene
1,2 Dichloroethane
1,1,1 Trichloroethane
Hexachloroethane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetrachloroethane
Chloroe thane
Bis Chloromethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinyl Ether
2-Chloronaphthalene
2,4,6 Trichlorophenol
Parachlorome tacresol
Chloroform
2 Chlorophenol
1,2 Dichlorobenzene
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.055
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.013
ND
ND
ND
ND
ND
ND
ND
ND
0.038
ND
ND
Analysis
Blank
Cone.
mg/1
NA
ND
ND
ND
NA
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
ND
M
ND
NA
NA
NA
*
NA
NA
Raw
Waste
Cone.
mg/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.012
ND
ND
Analysis
Blank
Cone.
mg/1
NA
ND
ND
ND
NA
ND
ND
m
NA
ND
ND
NA
ND
ND
ND
ND
ND
NA
ND
NA
NA
NA
*
NA
NA
-------
TABLE V-5 (CON'T)
SCREENING ANALYSIS RESULTS
ro
LITHIIM SUBCATEGORY
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
DPC Data
KIBP, BTBP
1,3 Dichlorobenzene
1,4 Dichlorobenzene
3,3 Dichlorobenzidine
1,1 Dichloroethylene
1,2 Trans-Dichloroethylene
2,4 Dichlorophenol
1,2 Dichloropropane
1,2 Dichloropropylene
2,4 Dimethylphenol
2,4 Dinitrotoluene
2,6 Dinitrotoluene
1,2 Diphenylhydrazine
Ethylbenzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
4 Bromophenyl Phenyl Ether
Bis ( 2-Chloroisopropyl ) Ether
Bis (2-Chloroethoxy) Methane
Methylene Chloride
Methyl Chloride
Methyl Bromide
Bronoform
Dichlorobronome thane
Trichlorofluorome thane
Dichlorod if luororoe thane
Plant
Influent
Cone.
rog/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.011
ND
ND
ND
ND
ND
ND
Raw1
Waste
Cone.
mg/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.014
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
ND
NA
NA
NA
NA
NA
*
ND
ND
ND
ND
ND
ND
Raw2
Waste
Cone.
nrj/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.016
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
n
-------
TABLE V-5 (CON'T)
SCREENING ANALYSIS RESULTS
LITHIUM SUBCATECORY
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
Chlorod ibromome thane
Hexachlorobutad iene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2 Nitrophenol
4 Nitrophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Ni trosodime thy lamine
N-N i trosod iphenylamine
N-Ni trosorl i-N-propylamine
Pentachlorophenol
Phenol
Bis (2-Cthylhexyl) Phthalate
Butyl Benzyl Phthalate
Di-N-butyl Phthalate
Di-N-oetyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthracene
Benzo (A) Pyrene
3,4 Benzofluoranthene
11, 12-Benzofluoranthene
Plant
Influent
DPC Data Cone.
RIBP, BTBP roq/1
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.
mq/i
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
0.024
ND
*
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
n>g/l
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
MA
NA
NA
NA
NA
NA
Raw2
Waste
Cone.
mq/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.013
*
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
ItKJ/l
ND
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-5 (CON'T)
SCREENING ANALYSIS RESULTS
LITHIUM SUBCATEOORY
Plant Raw
Influent Waste
DPC Data Cone. Cone.
KTBP, BTBP mq/1 roq/1
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
rv, 86.
S 87-
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
Chrysene
Acenaph thylene
Anthracene
1 , 12-Benzoperylene
Fluorene
Phenanthrene
1,2,5,6 Dibenzanthracene
Indenopyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride
Aldrin
Dieldrin
Chlordane
4,4 DDT
4,4 DDE
4,4 ODD
Alpha-Endosulfan
Beta-Endosulfan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
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
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
- roq/1
NA
NA
NA
FA
NA
NA
NA
NA
NA
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Raw2
Waste
Cone.
mq/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
Analysis
Blank
Cone.
TO/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
TABLE V-5 (CON'T)
SCREENING ANALYSIS RESULTS
ro
LITHIUM SUBCATEGORY
Plant Raw
Influent Waste
DPC Data Cone. Cone.
KTBP, BTBP mq/1 mg/1
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
Heptachlor Epoxide
Alpha-BHC
Beta-BHC
Gamma-BHC (Lindane)
Delta-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chrcruum
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.005
<0.005
<0.001
0,1 0.001
0,1 0.005
0.068
ND
0,1 0.025
<0.001
0.060
<0.005
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.005
<0.005
<0.001
0.002
2.06
0.118
0.00
0.044
<0.001
0.067
<0.005
Analysis
Blank
Cone.
mg/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
Raw2
Waste
Cone.
mg/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.005
<0.005
<0.001
0.025
0.015
0.109
0.14
4.93
<0.001
0.235
<0.005
Analysis
Blank
Cone.
mg/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
-------
TABLE V-5 (CON'T)
SCREENING ANALYSIS RESULTS
ro
en
o
LITHIUM SUBCATEGORY
126.
127.
128.
129.
130.
131.
Silver
Thallium
Zinc
2,3,7,8 TCDD (Dioxin)
Xylenes
Alkyl Epoxides
Aluminum
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
Gold
Iron
Lithium
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
JLUt-J
Tin
JL AI •
Titanium
Vanadium
Yttrium
Plant
Influent
DPC Data Cone.
RIBP, BTBP mq/1
0.003
<0.050
0.018
ND
NA
NA
-,- 0.086
-,- NA
-,- 0.016
-,- 0.040
-,- 15.4
-,- 0.011
1.7
-r-
-,- 0.091
<0.050
-,- 3.47
-,- 0.007
-,- <0.001
-,- ND
-,- ND
-,- 0
-,- 5.73
-,-
-,- ND
-,- 0.012
-,- 0.001
-,- 0.030
-r- <0.001
Raw
Waste
Cone.
mq/1
0.012
<0.050
0.045
ND
NA
NA
0.104
NA
2.67
0.116
15.9
0.006
1.7
0.122
<0.050
3.66
0.008
0.001
0
0.00
0
6.06
21.0
0.006
0.001
0.030
<0.001
Analysis
Blank
Cone.
mg/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
2
Raw
Waste
Cone.
mg/1
0.001
<0.050
0.473
ND
NA
NA
0.287
NA
0.059
0.193
22.8
0.176
3.05
54.9
<0.050
3.78
1.60
0.021
ND
ND
1.56
6.44
39.0
0.023
0.001
0.035
0.023
Analysis
Blank
Cone.
mq/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
-------
TABLE V-5 (CON'T)
SCREENING ANALYSIS RESULTS
LITHIUM SUBCATEGORY
ND
NA
Plant
Influent
DPC Data Cone.
KTBP, BTBP mg/1
Not detected
Mot analyzed (includes Xylenes & Alkyl Epoxides
Raw
Waste
Cone.
mg/1
Analysis
Blank
Cone.
roq/1
Raw
Waste
Cone.
mq/1
Analysis
Blank
Cone.
mq/1
since laboratory analysis were not final iz<
for these parameters).
KTBP Known to be present indicated by number of plants.
BTBP Believed to be present indicated by number of plants.
ro
J2 -,- Not investigated in DCP survey.
* Indicates less than .01 mg/1.
** Indicates less than .005 mg/1.
1. Heat Paper Production Wastewater
2. Cathode Process Wastewater
-------
Table V-6
SCREENING ANALYSIS RESULTS
MAGNESIUM SUBCATEGORY
Plant
Influent
DPC Data Cone.
KTBP, BIBP mg/1
1.
2.
3.
4.
5.
6.
7.
6.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
-40.
Acenaphthene
Ac role in
Acrylontirile
Benzene
Benzidine
Carbon Tetrachloride
Chlorobenzene
1,2,4 Trichlorobenzene
Hex achl orobenze ne
1,2 Dichloroe thane
1,1,1 Trichloroe thane
Hexachl oroethane
1,1 Dichl oroethane
1,1,2 Trichl oroethane
1,1,2,2 Tetr achl oroethane
Chi oroethane
Bis Chlorcmethyl Ether
Bis 2-Chl oroethyl Ether
2-Chloroethyl Vinyl Ether
2-Chl oronapthalene
2,4,6 Trichlorophenol
Parachl orone tacresol
Chloroform
2 Chlorophenol
1,2 Dichlorobenzene
1,3 Dichlorobenzene
1,4 Dichlorobenzene
3,3 Dichl orobenz id ine
1,1 Dichl oroethyl ene
1,2 Trans-Dichl oroethyl ene
2,4 Dichl orophenol
1,2 Dichl oropropane
1,2 Dichl oropropyl ene
2,4 Diirethylphenol
2,4 Dinitrotoluene
2,6 Dinitrotoluene
1,2 Diphenylhydrazine
Ethyl benzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.055
ND
NO'
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Raw
Waste
Cone.
mg/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.013
ND
ND
ND
ND
ND
ND
ND
ND
0.038
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
NA
ND
ND
ND
NA
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
ND
NA
ND
NA
NA
NA
*
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
ND
NA
NA
252
-------
TABLE V-6
SCREENING ANALYSIS RESULTS (CONT.)
MAGNESIUM SUBCATEGORY
Plant
Influent
DPC Data Cone.
KTBP, BTBP rog/1
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78-.
79.
80.
4 Brcmophenyl Phenyl Ether
Bis (2 Chloroisopropyl) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride
Methyl Chloride
Methyl Bromide
Bromoform
Dichl orobromome thane
Tr ichl orof 1 uorome thane
Dichl orodi f 1 uorome thane
Chi orod ibromome thane
Hexachl orobutad i ene
Hexachl orocyclopentadi ene
Isophorone
Naphthalene
Nitrobenzene
2 Nitrophenol
4 Nitrophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Ni trosod ime thyl am ine
N-Ni trosodiphenylaiTiine
N-Ni trosodi-N-propylamine
Pentachl orophenol
Phenol
Bis (2-Ethylhexyl) Phthalate
Butyl Benzyl Phthalate
Di-N-butyl Phthalate
Di-N-octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthracene
Benzo (A) Pyrene
3,4 Benzofluorathene
11, 12-Benzofluoranthene
Cnrysene
Acenaphthylene
Anthracene
1 , 12-Benzoperylene
Fluorene
ND
ND
ND
0.011
ND
ND
ND
ND
ND
TJD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
*
NT)
ND
NT)
ND
ND
ND
ND
ND
ND
TID
ND
ND
Raw
Waste
Cone.
mj/1
ND
ND
ND
0.014
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
0.024
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
TJD
Analysis
Blank
Cone.
nq/1
JA
NA
NA
*
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
ra
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ffc
NA
NA
N£
Nft
NA
NA
NA
N^
NA
NA
NA
NA
NA
253
-------
TABLE V-6
SCREENING ANALYSIS RESULTS (COOT.)
MAGNESIUM SUBCATEGORY
Plant
Influent
DPC Data Cone.
KTBP, BTBP mg/1
81. Phenanthrene
82. 1,2,5,6 Dibenzanthracene
83 . Indenopyrene
84. Pyrene
85. Tetrachloroethylene
86. "toluene
87. Irichloroethylene
88. Vinyl Chloride
89. Aldrin
90. Dieldrin
91. Chlordane
92. 4,4 DDT
93. 4,4 DDE
94. 4,4 DDD
95. Alpha- Endosul fan
96. Beta- Endosul fan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
101. Heptachlor Epoxide
102. Alpha-BHC
103. Beta-BHC
104. GamiTB-BHC (Lindane)
105. Dslta-BHC.
106. PCB-1242
107. PCB-1254
108. PCB-1221
109. PCB=1232
110. PCB-1248
111. PCB-1260
112. PC9-1016
113. Tbxaptene
114. Antimony
115. Arsenic
116. Asbestos
117. Beryllium
118. Cadmium
119. Chromium
120. Copper
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
<0.005
<0.005
<0.001
0,1 0.001
0,2 0.005
0.068
Raw
Waste
Cone.
ing/I
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.005
<0.005
<0.001
0.001
2.06
0.118
Analysis
Blank
Cone.
mg/1
m
Ift
m
m
ND
ND
ND
ND
m
tft
ra
m
NR
m
m
ra
m
m
wv
N^
m
v&
m
m
m
m
N\
i&
m
M^
m
i&
w.
NA
NA
TV,
NA
NA
NA
NA
254
-------
TABLE V-6
SCREENING ANALYSIS RESULTS (COOT.)
MAGNESIUM SUBCATEGORY
Plant
Influent
DPC Data Cone.
KTBP, BIBP rog/1
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
Qranide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8 TCDD (Dioxin)
Xylenes
Alkyl Epoxides
Aluminum
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
Gold
Iron
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttriur.
ND
0.025
0.001
0.060
<0.005
0.003
<0.050
0.018
TJD
NA
NA
-,- 0.086
NA
-,- 0.016
-,- 0.040
-,- 15.4
-,- 0.011
1.7
-,- NA
-,- 0.091
-,- 3.47
-,- 0.007
-,- <0.001
-,- ND
-,- ND
-,- ND
-,- 5.73
-,- NA
-,- ND
-,- 0.012
-,- 0.001
-,- 0.030
-,- <0.001
Raw
Waste
Cone.
mg/1
ND
0.044
0.001
0.067
<0.005
0.012
<0.050
0.045
ND
NA
NA
0.104
NA
2.67
0.116
15.9
0.006
1.7
NA
0.122
3.66
0.008
0.001
ND
ND
ND
6.06
NA
21
0.006
0.001
0.030
0.001
Analysis
Blank
Cone.
fig/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
255
-------
TABLE V-6
SCREENING ANALYSIS RESULTS (OONT.)
MAGNESIUM SUBCATEGORY
Plant Raw Analysis
Influent Waste Blank
DPC Data Cone. Gone. Gone.
KTBP, BIBP rog/1 mg/1 mg/1
ND Not detected
NA Not analyzed (includes Xylenes & Alkyl Epoxides since laboratory analysis
vrere not finalized for these parameters).
JCTBP 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 less than 0.01 mg/1.
** Indicates less than 0.005 mg/1.
256
-------
TABU? V-7
SCUEQIING ANALYSIS KKSULTS
ro
1 Acenaphthena
2 Acrolcln
3 Acrylonitrile
4 Benzene
5 Benzidine
6 Carbon Totradiloririe
7 Chlorcbenzeno
8 1,2,4 Tridilorobenzene
9 Hexadilorubunzene
10 2 Didtloroethane
11 1,1 Trichlorocthana
12 texachloroethane
13 1 nichloroethano
14 1,2 Tridiloroothane
15 1,2,2 Tetradiloroethane
16 Ohloroothane
17 Bis Chlromethyl Ether
18 Bis 2-Chloroetnyl Ether
19 2-Chlorocthyl Vinyl Ether
20 2-Chlorona|jhthalune
21 2,4,6 Tridilorqjhcnol
22 Parachloronet aerosol
23 Chloroform
24 Ohlorophcnol
25 ,2 Dichlorcbenzeno
26 ,3 OidilordienzoiKi
27 ,4 DidilordMiizene
28 ,3 Dichlorcbeiizidine
29 ,1 Didiloroothylene
30 ,2 Trans-Oidiloroethylene
31 ,4 Didilorojihonol
32 ,2 Diohloropropane
33 ,2 Didiloropropylene
34 2,4 Diinethylphnnol
35 2,4 Dinitrotolumio
36 2,6 Dinitrotoluene
37 1,2 Diplienylhydrazine
38 Bthylbonzcne
DCP Data Plant
KTBP, DIBP Influent
Cone.
ma/1
ND
ND
ND
ID
ND
ND
ID
ND
ND
ND
1,0 ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.086
ND
ND
ID
ID
ND
ID
ID
ND
ND
ND
ND
ND
ND
ND
ID
ZINC SUDCATBOORY
Raw Effluent
Uaste Gone.
Gone.
TO/1 TO/1
NA
ND
ND
*
NA
ND
ND
NA
NA
ND
4.2
NA
0.018
ND
ND
ND
ND
ND
ND
NA
HA
NA
ID
NA
NA
NA
NA
NA
0.64
0.016
NA
ND
ID
NA
NA
NA
NA
*
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
6.4
ND
0.079
*
ND
ND
ND
ID
ND
ND
•
ND
ID
*
ND
ND
ND
ND
0.42
ND
ID
ND
ND
ID
ND
ND
ND
0.032
Analysis
Blank
Gone.
TO/1
NA
ND
ID
ND
NA
ND
ND
NA
NA
ND
ND
NA
ND
ID
ND
ND
ND
NA
ND
NA
NA
NA
ND
HA
NA
NA
HA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
IID
Plant
Influent
Gone.
TO/1
ND
ID
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ID
ND
ND
ND
ND
ND
ND
ND
ID
ND
ND
ND
ND
ND
ND
ID
ID
ND
ND
ND
ND
ND
ID
ID
ND
Raw
Waste
Cone.
ID
ID
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
ID
ND
ND
ID
ND
ID
ID
ND
ND
Effluent
Oboe.
mil
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ID
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
TO/1
NA
ND
ND
ID
NA
ID
ID
NA
HA
ND
ND
HA
ND
ID
ID
ND
ND
NA
NA
NA
NA
NA
ND
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
ND
-------
TABU; v-7
SCREENING ANALYSIS RESULTS (OONT.)
ro
01
oo
39 Fluoranthene
40 4 Chlorophenyl Phenyl Ether
41 4 Branoplienyl Phenyl Ether
42 Bis(2 Chloroiaopropyl) Ether
43 Bisl 2 Chloroethoxy) Methane
44 Methylene Chloride
45 Methyl Chloride
46 Methyl Bromide
47 Bromoform
48 Didilorobrcmonothano
49 Tridilorof luoronethane
50 Dichlororlifluoranethane
51 Chlorodilirojnoniethane
52 llexachlorobutadicno
53 Itexadilorocyclopcntadlene
55 Naphthalene
56 Nitrobenzene
57 2 Nitrophcnol
58 4 Nitroplienol
59 2,4 Dinitrophenol
60 4,6 Dinitro-o-cresol
61 N-Nitroandimethylamine
62 N-Nitroaodiphenylamine
63 N-Nitroaodi-N-prctiylamine
64 Pentachlorcphenol
65 Phennl
66 Bis (2-Ethylhexyl) Ph thai ate
67 Butyl Benzyl Phthalate
68 Di-N-butyl Phtlialatc
69 Di-H-octyl Phthalate
70 Diothyl Phtltalate
71 Dimethyl Phthalate
72 1,2 Bonzanthraocne
73 Benzo (A) Pyrene
74 3,4 Benzofluorantliene
75 11,12-BenzoflHoranthene
76 Chryaone
77 Acena|ththylcni:
POP Data Plant
KTBP, BTBP Influent
Cone.
ND
ND
ND
ND
ND
1,1 ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
kafl
ImJ
ID
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
*
ND
ND
ND
ND
ND
ND
rr>
ND
HI)
ZINC SUBCATTOOKY
Raw Effluent
Waste Cone.
Cone.
mg/1 mg/1
NA
NA
NA
NA
NA
0.35
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
ND
8.4
ND
ND
ND
ND
ND
ID
ND
try
ND
0.190
ND
ND
ND
ro
ID
ND
ND
ND
ND
0.06
*
ND
*
ND
*
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
NA
NA
NA
NA
NA
ND
ND
ID
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
MA
NA
in
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
Plant
Influent
Cone.
mg/l
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
un
T9J
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
ND
II)
ND
Raw
Haste
Cone.
ND
ND
ID
ND
ND
0.022
ND
ND
ND
ND
ID
ND
ND
ND
ND
ND
ND
ND
ND
ND
ID
ID
ND
ND
0.040
ND
0.012
*
*
HD
ND
ND
ND
ND
ND
ND
ND
ND
Effluent
Cone.
M9/1
ND
ND
ND
ND
ND
0.031
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.027
*
0.031
*
*
ND
ND
ND
ND
ND
ND
ND
ND
NA
Analysis
Blank
Gone.
mg/1
NA
NA
NA
NA
NA
0.018
ND
ND
ID
ND
ND
ND
ND
NA
NA
KA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
TABIJ3 V-7
SCREENIHG ANALYSIS RESULTS (OONT.}
ZINC SUBCATBOORY
Ol
VO
DCP Data
KTBP, BreP
Plant
Influent
Oonc.
mg/1
Raw
Haste
Oonc.
ma/1
Effluent
Oonc.
iwj/1
Analysis
Blank
Oonc.
mq/1
Plant
Influent
Oonc.
TO/1
Raw
Waste
Cone.
mg/1
Effluent
Cone.
TO/1
Analysis
Blank
Gone.
mg/1
78 Anthracene
79 1,12-Bcnzoperylene
80 Fluorene
81 Phenanthrene
82 1,2,5,6 Dibenzanthracene
83 Indonopyrene
84 Pyrene
85 TBtrachloracthylene
86 Toluene
87 Tritiiloroethylene
88 Vinyl Chloriite
89 Aldrin
90 Dieldrin
91 Ohlonlane
92 4,4 nor
93 4,4 DOE
94 4,4 COD
95 Alpha-Endosulfan
96 Beta-Endoeulfan
97 Endosulfan Sulfate
98 Endrin
99 Erelrin Aldehyde
100 Iteptachlor
101 llcptachlor Epoxido
102 Alpha-HC
103 Beta-BIC
104 Garana-UlC (Lindane)
105 Dclta-DIC
106 PCB-1242
107 PCB-1254
108 PCD-1221
109 PCU-1232
110 PCB-1248
111 PCB-1260
112 PCB-1016
113 Woxaphune
114 Antimony
115 Arsenic
116 Asbestos
0,1
2,0
1.0
1.0
ND
ND
to
to
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
to
to
to
to
ND
ND
ND
ND
ID
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
0.025
0.11
0.39
ND
NA
HA
NA
HA
NA
NA
HA
HA
HA
NA
NA
Iff,
HA
HA
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
0.07
ND
ID
ND
ID
ND
ND
ND
ND
ID
*
0.055
0.045
ND
ID
ID
ND
ND
ID
to
ND
ID
ID
ID
ID
ND
ND
ND
to
ID
ND
ND
ND
ND
ND
ID
MO
ND
to
ND
ND
ND
NA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ND
NA
HA
HA
NA
NA
NA
NA
NA
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
NA
NA
NA
NA
ND
ND
ND
ID
ID
ID
ND
to
ND
ND
ID
ID
to
to
to
to
to
to
ND
ND
ND
ID
ND
ID
ND
ID
ID
ND
ID
ND
ID
ND
ID
ID
ID
ND
ND
to
to
*
10
to
*
to
to
to
*
*
*
ND
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
ND
ND
ND
ND
ND
ND
ND
*
ID
ID
ND
ND
ID
ID
ND
tf)
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
NA
NA
NA
NA
NA
NA
HA
ND
ID
ND
ND
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
-------
TABLK V-7
SCREENING AHftLYSIS RESULTS (OONT.)
ro
CT>
o
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
DCP Data Plant
KTBP, BTOP Influent
Cone.
mg/l
Beryl Him <0.001
Cadmiun 0,1 <0.002
Chranium 5,0 <0.005
dapper <0.006
Cyanide 1,2 NT)
Lead 0,1 <0.02
Mercury 12,0 0.0060
Nickel 1,0 < 0.005
Selenium ND
Silver 6,0 < 0.001
Thallium ND
Zinc 13,2 0.170
2,3,7,8 TCDD (Dioxin) NA
Xylenes NA
Alkyl Epoxides NA
Aluminum 0.068
Amonia
Bariim
Boron -
Calcim -
Cobalt
Fluoride
Gold
Iron
Magnesium
Manganese
Molybdenum -
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium -
Vanadium ~
Yttrium
HA
0.026
<0.05
<5.0
< 0.005
1.10
ND
0.17
2.600
< 0.005
< 0.005
3.3
0.018
ND
18.80
NA
HD
< 0.005
< 0.015
<0.012
<0.016
ZINC SUBCATEOORY
Raw Effluent
Haste Cone.
done.
mg/1 mg/1
< 0.001
0.16
2.13
0.078
ND
<0.02
110
< 0.005
HD
0.192
U>
21.0
NA
NA
NA
0.387
NA
0.029
0.316
<5.0
< 0.005
2.65
to
2.06
1.50
0.45
0.015
6.00
0.110
1.73
1570
NA
270
< 0.005
<0.015
<0.12
<0.16
< 0.001
< 0.002
< 0.005
0.047
ND
<0.02
0.06
< 0.005
0.08
0.036
ND
0.226
MA
NA
HA
0.217
NA
0.358
0.321
<5.0
< 0.005
1.90
ND
62.8
1.90
.377
< 0.005
3.7
0.180
1.54
J580
NA
38.0
< 0.005
< 0.015
<0.12
<0.16
Analysis
Blank
Cone.
mg/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
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
tlA
Plant
Influent
Cbnc.
ng/1
< 0.001
< 0.002
0.020
0.030
< 0.005
<0.02
0.100
< 0.005
HD
.< 0.001
ND
0.200
NA
NA
NA
<0.09
0.12
<0.006
<0.08
66.0
< 0.002
0.13
ND
<0. 1
30.00
< 0.006
< 0.006
1.0
ND
0.11
4.20
NA
5.0
< 0.008
< 0.006
< 0.002
< 0.002
Raw
Waste
Cone.
mg/1
ND
0.060
0.020
0.100
0.001
0.100
0.800
0.010
0.080
0.010
ND
10
NA
NA
HA
3.00
11.3
< 0.006
<0.08
25.0
0.003
0.44
MO
0.50
5.90
2.00
0.04
8.00
ND
410
428
0.07
0.02
< 0.002
< 0.002
Effluent
Cbnc.
rag/1
<0.001
0.030
0.020
0.100
0.001
0.100
0.800
0.050
MR
0.020
in
40
NA
UA
NA
2.00
1.81
< 0.006
< 0.08
14.0
0.004
0.23
ND
0.30
3.10
0.80
0.02
8.00
0.001
260
476.6
0.05
0.01
0.004
0.003
Analysis
Blank
Cbnc.
ng/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
-------
TABLE V-7
ZI1C SUBCATBGORY
DCP Data
tfTBPjBTBP
Plant
Influent
Cone.
mg/1
Raw
Waste
Cone.
wj/1
Effluent
Oonc.
mg/1
Analysis
Blank
Cone.
mg/1
Plant
Influent
Gone.
ng/1
Raw
Waste
Cone.
mg/1
Effluent
Cone.
mg/1
Analysis
Blank
Cone.
ng/1
Not a^ilyLd (includes Xylenes fc Alkyl Epoxides since laboratory analysis were not finalized for these parameters).
KTBP Known to be present indicated by number of plants.
ro BTOP Believed to be present indicated by nunber of plants.
-------
TABU; v-8
VERIFICATION PARAMETERS
91
11
13
23
20
30
38
44
55
64
65
66
67
68
69
70
78
81
84
85
86
87
114
115
118
119
120
121
122
123
124
125
126
128
pannrnviiR
1,1, 1-Triohlorethano
1 , 1-Dichlorothano
Chloroform
1 , 1-Oichloroothylene
1,2 Trans-dichlorocthylenc
Ethylbenzcnc
Mcthylene Chloride
Naphthalene
Pentachlorophenol
fticnol
Bis(2-othyl hoxyDPhthalate
Butyl Benzyl Phthalatc
Di-H-butyl Fhthalate
Di-N-octyl Fhthalate
Dicthyl Phtlialatc
Anthracene
fticnanthrcno
lyrene
Tbtradiloroethylenc
•toluene
Tr ichloroothylone
Ant irony
Arsenic
Cadmium
Chromium
Chppcr
Cyanide
Lead
ffcrcury
Nickel
Sclcniun
Silver
Zinc
Aluminum
Arronia
Calcium
Ccfcalt
Iron
I.ithiun
llagncsiun
Manganese
Phenols (Total)
Strontiiwi
Oil and firoaso
TSS (Total SuspRndnd Solids)
pll
CADMIUM
SUDCATFnORY
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CALCIUM LEAD
SUBCATEOORSf SUUCATTOORY
X
X
)(
x
x
X
x
X
x
x
X
x
x
x
X
x
(X)
1 " /
X
(X) X
t" I
x
x
ivl X
|A| *
(X) X
LEOJtflCHE LITHIUM MAGNESIUM
SUBCATEQCHW SUBCATEOOfW SUBCATEOOW
x
X
X
X
X
X
X
X
X
X
X
(X)
(X)
X
X (X) (X)
X
X (X)
-------
TABLE V-9
CADMIUM SUBCATEGORY PROCESS ELEMENTS
(Reported Manufacture)
Cathodes
Mercuric Oxide
Powder Pressed
Silver Powder Pressed
Nickel
Powder Pressed
Nickel Electro-
deposited
Nickel Impregnated
Cadmium Pasted
and Pressed
Powder
x
x
Anodes
Cadmium
Electrodeposited
Cadmium
Impregnated
Ancillary Operations
Cell Wash
Electrolyte
Preparation
Floor and Equipment
Wash
Employee Wash
Cadmium Powder
Production
Silver Powder Production
Nickel Hydroxide Pro-
duction
Cadmium Hydroxide Pro-
duction
x
x
263
-------
TABLE V-10
CADMIUM SUBCATEGORY EFFLUENT FLOW RATES
FROM INDIVIDUAL FACILITIES
PLANT FLOW RATE
ID I/day
A 15700
B >450000
C 145000
D >450000
E 0
F 54500
G 3780
H 0
I 1890
j 67000
264
-------
TABLE V-ll
NORMALIZED DISCHARGE FLOWS
CADMIUM SUBCATEGORY ELEMENTS
Ul
Mean
Discharge
Elements UAg)
Anodes
Pasted & Pressed
Powder
Electrodeposited
Impregnated
Cathodes
Nickel Electrode-
Posited
Nickel Impregnated
Ancillary Operations
Cell Wash
Electrolyte Prepa-
ration
Floor Wash
Employee Wash
Cadmium Powder
Production
Silver Powder
Cadmium Hydroxide
Production
Nickel Hydroxide
Production
2.7
697.
998.
569.
1640.
4.93
0.08
12.0
1.5
65.7
21.2
0.9
110.
Median
Discharge
UAg)
1.0
697.
998.
569.
1720.
3.3
0.08
2.4
1.5
65.7
21.2
0.9
110.
Production Total Production
Weighted Mean Raw Waste Normalizing
Raw Waste (lAg) ^folume (1/yr) Parameter
4.63
690.
960.
569.
1140.
3.67
0.068
28.0
1.5
65.7
21.2
5.15
417.
9.5xl05
S.OxlO7
1.7xl08
6.8xl05
2.6xl08
4.7xl06
3.7xl04
7.6xl06
6.8xl04
2.7xl07
S.OxlO5
1.6xl08
1.7xl08
Weight of Cadmium in Anode
Weight of Cadmium in Anode
Weight of Cadmium in Anode
Weight of Applied Nickel
Weight of Applied Nickel
Weight of Cells Produced
Weight of Cells Produced
Weight of Cells Produced
Weight of Cells Produced
Weight of Cadmium Used
Weight of Silver Powder
Produced
Weight of Cadmium Used
Weight of Nickel Used
-------
TABLE V-12
CADMIUM SUBCATEOORY EFFLUENT QUALITY
(FROM DCP'S)
TOTAL DISCHARCS
PLANT FLOW pH Oil&Greai
ID NO. 1/hr (gal/hr) (mg/1)
A
B
C
D
E
F
G +
G++
H
114
114,000*
27250
33160*
23
7880
4630
7040
AQ>;nn
(30)
(30000)
(7200) 7-14
(8760) 12.4 3
(6.1)
(2081) 7.5
(1220)
(1860)
se TSS Cd
(mg/1) (mg/1)
1.1
0.01
8.1
150 41
0.1
0.04
0.26
3.73
Go Nl flg &n
(mg/1) (rag/1) (mg/1) (mg/1)
6.7
0.034
18.5
46
<0.08 <0.02
0.09
0.08 0.54
0.34
3.06 75
* Combined discharge includes wastewater from other subcategories
+ Effluent from pH adjustment and clarification
++ Effluent from ion exchange
-------
TABLE V-13
POLLUTANT CONCENTRATIONS IN CADMIUM
PASTED AND PRESSED POWDER
ANODE ELEMENT WASTE STREAMS
POLLUTANT
Temperature (Oeg C)
44 Methylene chloride
87 Trichloroethylene
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Aim. to Chlor.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
29.0
0.00
0.00
285.
0.01
0.00
0.10
0.10
0.05
0.00
40.5
0.53
2.
0.
0.
5,
90
00
04
00
808.
10.0
10.0
mg/1
DAYS
2
29.0
0.00
0.00
365.
0.00
0.00
0.00
0.00
0.00
0.00
2.78
0.35
0.67
0.00
0.01
1960.
1040.
9.6
9.6
31.0
0.00
0.00
151.
0.00
0.00
9.45
9.40
0.02
0.00
5
35
15
13,
0,
1,
0.00
0.06
500.
1270.
9.0
9.0
NOTE: VALUES IN ALL SAMPLING TABLES
HAVE BEEN ROUNDED TO TWO DECIMAL
PLACES FOR DRAFT REPORT
267
-------
TABLE V-14
POLLUTANT MASS LOADINGS IN THE CAM-HUM PASTED
AND PRESSED POWDER ANODE ELEMENT
WASTE STREAMS
mg/kg
POLLUTANT DAYS
123
Flow (I/kg) 1.53 1.78 2.68
Temperature (Deg C) 29.0 29.0 31.0
44 Methylene chloride 0.00 0.00 0.00
87 Trichloroetnylene 0.00 0.00 0.00
118 Cadmium 437. 650. 405.
119 Chromium, Total 0.00 0.00 0.00
Chranium, Hexavalent 0.00 0.00 0.00
121 Cyanide, Total 0.16 0.00 25.3
Cyanide, Amn. to Chlor. 0.15 0.00 25.2
122 Lead 0.08 0.00 0.05
123 Mercury 0.00 0.00 0.00
124 Nickel 62.1 4.95 36.2
128 Zinc 0.81 0.62 0.94
Ammonia 4.45 1.19 3.08
Cobalt 0.00 0.00 0.00
Phenols, Total 0.06 0.02 0.17
Oil & Grease 7.67 3490. 1340.
Total Suspended Solids 1240. 1850. 3400.
pH, mininum 10.0 9.6 9.0
pH, maximum 10.0 9.6 9.0
268
-------
Table V-15
POLLUTANT CONCENTRATIONS IN THE CADMIUM
ELECTRODEPOSITED ANODE ELEMENT
WASTE STREAMS
mg/1
POLLUTANT DAYS
123
Tenperature (Deg C) 24.6 21.6 24.7
44 Methylene chloride 0.00 0.00 0.00
87 Trichloroethylene 0.00 0.00 0.00
118 Cadmium 108. 130. 46.2
119 Chromium, Total 0.00 0.00 0.00
Chromium, Hexavalent 0.00 0.00 0.00
121 Cyanide, Total 0.02 0.02 0.02
Cyanide, Amn. to Chlor. Ill
122 Lead 0.00 0.00 0.00
123 Mercury 0.00 0.00 0.00
124 Nickel 0.08 0.08 0.05
128 Zinc 0.01 0.01 0.00
fcratDnia 2.27 2.49 4.07
Cobalt 0.00 0.00 0.00
Phenols, Total 0.01 0.01 0.01
Oil & Grease 5.05 5.09 5.48
Total Suspended Solids 188. 178. 14.9
pH, minimum 2.9 4.5 3.7
pH, maxijnum 11.9 11.8 11.7
I - Interference
269
-------
Table V-16
POLLUTANT MASS LOADINGS IN THE CADMIUM
ELECTRODEPOSITED ANODE ELEMENT
WASTE STREAMS
POLLOTANT
Flow (I/kg)
Temperature (Deg C)
44 Methylene chloride
87 Trichloroethylene
118 Cadmium
119 Qironium, Total
Chrcmium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
I - Interference
1
691.
24.6
0.00
0.07
74700.
0.00
0.00
14.3
I
0.00
0.41
55.3
6.04
1570.
0.00
8.24
3490.
130000.
2.9
11.9
rag/kg
DAYS
2
697.
21.6
0.00
0.07
90200.
0.42
0.00
14.1
I
0.00
0.21
58.3
4.48
1730.
0.00
8.29
3550.
124000.
4.5
11.8
3
697.
24.7
0.00
0.07
32200.
0.09
0.00
16.5
I
0.07
0.39
33.6
1.54
2830.
0.00
8.29
3820.
10400.
3.7
11.7
270
-------
POLLDTANT
Table V-17
POLLUTANT CONCENTRATIONS AND MASS
LOADINGS IN THE CADMIUM IMPREGNATED
ANODE ELEMENT WASTE STREAMS
mg/1
DAYS
2
Flow (I/kg)
Temperature (Deg C) 21.6
44 Methylene chloride 0.00
87 Trichloroethylene *
118 Cadmium 63.3
119 Chromium, Total 0.19
Chromium, Hexavalent I
121 Cyanide, Total 0.06
Cyanide, Amn. to Chlor. 0.02
122 Lead 0.00
123 Mercury 0.001
124 Nickel 3.30
128 Zinc 0.06
Ammonia 3.20
Cobalt 0.11
Phenols, Total 0.03
Oil & Grease 2.70
Total Suspended Solids 354.
pH, minijTTum 5.2
pH, maximum 13.5
I - Interference
* - Less than 0.01
3
14.2
0.00
0.00
0.11
0.10
I
0.02
0.00
0.00
0.03
1.20
0.02
1.40
0.04
0.01
2.30
54.0
7.0
13.0
rag/kg
DAYS
2
800.3
21.6
0.00
0.00
50700.
152.
I
48.0
16.0
0.00
0.56
2640.
48.0
2560.
88.0
24.0
2160.
283000.
5.2
13.5
3
1283.9
14.2
0.00
0.00
141.
128.
I
25,7
0.00
0.00
38.5
1540.
25.7
1800.
51.4
12.8
2930.
69300.
7.0
13.0
271
-------
Table V-18
POLLUTANT CONCENTRATIONS IN THE NICKEL
ELECTRODEPOSITED CATHODE ELEMENT
WASTE STREAMS
mg/1
POLLUTANT DAYS
123
Temperature (Deg C) 11.0 12.0 10.0
44 Methylene chloride 0.00 * 0.00
87 Trichloroethylene 0.00 0.00 0.00
118 Cadmium 0.05 0.09 0.01
119 Qircmium, Total 0.00 0.00 0.01
Chronium, Hexavalent 0.00 0.00 0.00
121 cyanide, Total 0.04 0.04 0.01
cyanide, Amn. to Chlor. 0.04 0.02 0.00
122 Lead 0.00 0.00 0.00
123 Mercury 0.02 0.00 0.03
124 Nickel 1.98 6.01 1.55
128 Zinc 0.00 0.00 0.00
Ammonia 0.00 0.00 0.00
Cobalt 0.00 0.25 0.05
Phenols, Total 0.01 0.04 0.01
Oil & Grease 1.00 2.00 2.00
Total Suspended Solids 0.00 5.00 0.00
pH, minimum 7.1 5.2 7.0
pH, maximum 7.1 5.8 7.2
* Less than 0.01
272
-------
Table V-19
POLLUTANT MASS LOADINGS IN THE NICKEL
ELECTRODEPOSITED CATHODE ELEMENT
WASTE STREAMS
mg/kg
POLLUTANT DAYS
1 2 3
Flow (I/kg) 97.7 416. 1180.
Tatperature (Deg C) 11.0 12.0 10.0
44 Methylene chloride 0.00 0.04 0.00
87 Trichloroethylene 0.00 0.00 0.00
118 Cadmium 4.69 37.5 15.2
119 diranium, Total 0.00 0.00 8.20
Chronium, Hexavalent 0.00 0.00 0.00
121 Cyanide, Total 4.10 16.7 12.8
Cyanide, Aim. to Chlor. 4.10 6.70 0.00
122 Lead 0.00 0.00 0.00
123 Mercury 1.56 0.00 37.3
124 Nickel 193. 2500. 1810
128 Zinc 0.00 0.00 0.00
Ammonia 0.00 0.00 0.00
Cobalt 0.00 104. 61.9
Phenols, Total 0.59 17.5 16.3
Oil & Grease 97.7 833. 2330.
Total Suspended Solids 0.00 2080. 0.00
pH, minijnum 7.1 5.2 7.0
pH, maximum 7.1 5.8 7.2
273
-------
Table V-20
POLLUTANT CONCENTRATIONS IN THE NICKEL
IMPREGNATED CATHODE ELEMENT
WASTE STREAMS
44
87
118
119
121
122
123
124
128
ro
POLLUTANT
Temperature (Deg C)
Methylene chloride
Trichloroethylene
Cadmium
Chromium, Total-
Chromium, Hexavalent
Cyanide,
Cyanide,
Lead
Mercury
Nickel
Zinc
Anronia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended
Solids
pH, minimum
pH, maximum
Total
Amn. to Chlor.
1
28.6
0.00
*
79.2
0.18
0.00
0.03
>r. 0.02
0.01
0.00
514.
0.05
8.64
0.00
0.01
27.6
1163.
4.1
13.1
PLANT A
2
16.7
0.00
0.00
25.5
0.09
0.00
0.03
0.02
0.00
0.01
189.
0.03
9.39
0.00
0.01
7.44
342.
4.0
13.0
3
30.2
0.00
0.00
10.7
0.05
0.00
0.02
0.02
0.00
0.00
120.
0.06
9.03
0.00
0.01
6.16
185.
5.2
12.8
1
51.5
0.00
0.00
0.02
0.05
0.00
O.Q5
0.05
0.00
0.00
21.1
0.12
8.50
0.26
0.01
0.99
2690.
9.7
12.0
mg/1
PLANT C
DAYS
2
38.7
0.00
0.00
0.04
0.14
I
0.07
*
0.01
0.00
9.20
0.34
8.10
0.21
0.02
1.30
644.
6.5
10.0
PLANT D
3
43.9
0.00
0.00
0.14
0.11
I
0.01
0.00
0.00
0.02
44.7
0.03
8.50
1.30
0.01
6.90
92.5
8.0
11.5
1
16.0
0.00
0.00
0.03
0.00
0.00
0.00
0.00
0.00
0.00
59.0
0.22
NA
4.70
0.02
2.40
96.0
7.7
10.9
2
16.0
0.00
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
1.96
0.15
NA
0.08
0.00
3.00
28.0
8.5
10.5
PLANT B
1
71.9
0.00
0.00
13.4
*
0.00
0.29
0.00
0.00
0.00
199.
0.30
86.6
0.10
0.03
6.10
87.9
1.0
14.0
2
69.9
0.00
0.00
0.77
*
0.00
0.05
0.00
0.00
0.00
14.5
0.71
18.9
0.00
0.09
6.06
64.8
1.0
14.0
I - Interference
NA - Not Analyzed
* - Less than 0.01
-------
r\j
Table V-21
POLLUTANT MASS LOADINGS IN THE NICKEL
IMPREGNATED CATHODE ELEMENT WASTE STREAMS
PLANT A
mg/kg
PLANT C
PLANT D
PLANT B
DAYS
44
87
118
119
121
122
123
124
128
POLLUTANTS
1
Flow (I/kg) 1820.
Temperature (Deg C) 28.6
Msthylene chloride 0.00
Trichloroethylene 0.00
Cadmium 41400.
Chronium, Total 139.
Chromium, Hexavalent 0.00
Cyanide, Total 54.1
Cyanide, Aim. to
Chlor.
Lead
Mercury
Nickel
Zinc
Ammonia
fhhalt
VJLAJUX \*
Phenols, Total
Oil & Grease
Total Suspended
Solids
pH, minimum
pH, maximum
26.1
18.2
18.3
307000.
44.0
15300.
0.00
8.99
12100.
2
1630.
16.7
0.00
0.04
144000.
323.
0.00
45.5
33.3
0.00
1.48
934000.
82.1
15700.
0.00
12.3
50200.
556000. 2110000.
4.0
13.0
4.1
13.1
3
1621.
30.2
0.01
0.16
17400.
72.9
0.00
37.2
28.4
0.00
0.60
195000.
90.0
14600.
0.00
9.24
9990.
300000.
5.2
12.8
1
1360.
51.5
0.00
0.00
27.1
67.8
0.0
67.8
67.8
0.00
1.40
28600.
163.
11500.
353.
10.9
1340.
3640000.
9.7
12.0
2
2000.
38.7
0.00
0.00
78.2
274.
I
137.
15.6
20.0
0.59
18000.
644.
15800.
410.
39.1
2540.
1300000.
6.5
10.0
3
1530.
43.9
0.00
0.00
228.
179.
I
13.0
0.00
0.00
32.5
72700.
48.8
5690.
2110.
16.3
11200.
150000.
8.0
11.5
1
2000.
16.0
0.00
0.20
51.7
0.00
0.00
0.00
0.00
0.00
0.00
117000.
438.
9350.
29.8
4780.
191000.
7.7
10.9
2
4000.
16.0
0.00
0.40
15.9
0.00
0.00
0.00
0.00
0.00
0.00
7800.
597.
322.
0.00
11900.
111000.
8.5
10.5
1
228.
71.9
0.00
0.00
3050.
0.44
0.00
65.2
0.00
0.00
0.00
45400.
69.2
19700.
23.0
5.68
1390.
20000.
1.0
14.0
2
197.
69.9
0.00
0.00
152.
0.38
0.00
10.1
0.00
0.00
0.00
2850.
140.
3730.
0.12
16.9
1200.
12800.
1.0
14.0
I - Interference
-------
Table V-22
STATISTICAL ANALYSIS (rog/1) OF THE NICKEL
IMPREGNATED CATHODE ELEMENT WASTE STREAMS
POLLOTANT
Temperature (Deg C)
44 Methylene chloride
87 Trichloroethylene
118 Cadmium
119 Chronium, Total
Chronium, Hexavalent
121 Cyanide, Total
Cyanide, Arm. to Chlor.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
MINIMUM
16.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.96
0.03
3.50
0.00
0.00
0.99
28.0
1.0
10.0
MAXIMUM
71.9
0.00
*
79.2
0.18
0.00
0.29
0.05
0.01
0.02
514.
0.71
86.6
4.70
0.09
27.6
2690.
9.7
14.0
MEAN
38.4
0.00
0.00
13.0
0.06
0.00
0.05
0.01
0.00
0.00
117.
0.20
19.1
0.67
0.02
6.80
539.
5.6
12.2
MEDIAN
34.5
0.00
0.00
0.46
0.05
0.00
0.03
0.00
0.00
0.00
51.9
0.14
8.60
0.09
0.01
6.10
141.
5.9
12.4
#
VAL.
10
0
0
10
8
0
8
5
10
5
10
10
8
7
9
10
10
10
10
#
ZEROS
0
10
10
0
2
8
2
5
8
5
0
0
0
3
1
0
0
0
0
#
PTS
10
10
10
10
10
8
10
10
10
10
10
10
8
10
10
10
10
10
10
* - Less than 0.01
Number of values may include concentrations less than 0.005 shown
as 0.00 on tables.
276
-------
Table V-23
STATISTICAL ANALYSIS (rag/kg) OF THE NICKEL
IMPREGNATED CATHODE ELEMENT WASTE STREAMS
POLLUTANT
MINIMUM MAXIMUM MEAN
MEDIAN
Flow (I/kg)
Temperature (Deg C)
44 Methylene Chloride
87 Trichloroethylene
118 Cadmium
119 Chromium, Total
Chranium, Hexavalent
121 Cyanide, Total
Cyanide, Aim. to Chlor.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
197.
16.0
0.00
0.00
3980.
71.9
0.01
0.40
15.9 144000.
0.00
0.00
0.00
0.00
0.00
0.00
2850.
44.0
3730.
323.
0.00
137.
67.8
16.9
32.5
934000
644
19700
0.00
0.00
1200.
12800
1
9350.
39.1
50200.
3640000.
0 9.7
1661.
38.3
0.00
0.08
20600.
106.
0.00
43.0
17.1
93
50
10.0
14.0
173000.
232.
12800.
1260.
14.9
10700.
840000.
5.6
12.2
1630.
34.4
0.00
0.00
190.
70.4
0.00
41.4
7.80
0.00
0.59
59000.
115.
15000.
173.
11.6
7380.
246000.
5.9
12.4
277
-------
Table V-24
POLLUTANT CONCENTRATIONS IN THE FLOOR AND
EQUIPMENT WASH ELEMENT WASTE STREAMS
mg/1
POLLOTANT
Temperature (Deg C) 16.0
44 Methylene chloride NA
87 Trichloroethylene NA
118 Cadmium 29.2
119 Chronium, Total 0.08
Chromium, Hexavalent 0.00
121 Cyanide, Total NA
Cyanide, Amn. to Chlor. NA
122 Lead 0.00
123 Mercury 0.00
124 Nickel 9.08
128 Zinc 12.9
Ammonia NA
Cobalt 5.04
Phenols, Total NA
Oil & Grease NA
Total Suspended Solids NA
pH, miniiTtum 7.9
pH, maximum 7.9
NA - Not Analyzed
278
-------
Table V-25
POLLUTANT MASS LOADINGS IN THE FLOOR AND
EQUIPMENT WASH ELEMENT WASTE STREAMS
POLLOTANT
Flow (I/kg) 0 25
Temperature (Deg C) 16*0
44 Methylene chloride Na
87 Tridhloroethylene NA
118 Cadmium 7>18
119 Chromium, Total o!()2
Chromium, Hexavalent 0*00
121 Cyanide, Total fa
Cyanide, ton. to Chlor. NA
122 Lead 0>00
123 Mercury o;oo
124 Nickel 2.23
128 Zinc 3^7
Ammonia ^
Cobalt 1,24
Phenols, Total N^
Oil & Grease N&
Total Suspended Solids MA
pH, minimum 7.9
1*1, maximum 7.9
NA - Not Analyzed
279
-------
Table V-26
POLLUTANT CONCENTRATIONS IN EMPLOYEE WASH
ELEMENT WASTE STREAMS
ng/1
POLLUTANT DAYS
123
Temperature (Deg C) 31.0 32.0 32.0
44 Methylene chloride 0.00 0.00 0.00
87 Trichloroethylene 0.00 0.00 0.00
118 Cadmium 0.00 0.13 0.08
119 Orranium, Total 0.00 0.00 0.00
Chronium, Hexavalent 0.00 0.00 0.00
121 Cyanide, Total 0.00 0.03 0.04
Cyanide, Amn. to Chlor. 0.00 0.03 0.04
122 Lead 0.00 0.00 0.00
123 Mercury 0.00 0.00 0.00
124 Nickel 0.00 0.13 0.26
128 Zinc 0.19 0.24 0.05
Ammonia 0.00 0.00 0.00
Cobalt 0.00 0.00 0.00
Phenols, Total 0.01 0.01 0.00
Oil & Grease . 1.0 212. 288.
Total Suspended Solids 0.00 280. 312.
pH, minimum 7.3 6.8 7.9
pH, maximum 7.3 6.8 7.9
280
-------
Table V-27
POLLUTANT MASS LOADINGS IN EMPLOYEE WASH
ELEMENT WASTE STREAMS
rag/kg
POLLUTANT DAYS
123
Flow (I/kg) 1.48 1.48 1.48
Temperature (Deg C) 31.0 32.0 32.0
44 Methylene chloride 0.00 0.00 0.00
87 Trichloroethylene 0.00 0.00 0.00
118 Cadmium 0.003 0.19 0.11
119 Chronium, Total 0.00 0.00 0.00
Chronium, Hexavalent 0.00 0.00 0.00
121 Cyanide, Total 0.00 0.04 0.05
Cyanide, Amn. to Chlor. 0.00 0.04 0.05
122 Lead 0.00 0.00 0.00
123 Mercury 0.00 0.00 0.00
124 Nickel 0.00 0.19 0.38
128 Zinc 0.28 0.35 0.07
Ammonia 0.00 0.00 0.00
Cobalt 0.0 0.00 0.00
Phenols, Total 0.01 0.02 0.00
Oil & Grease 1.48 313. 425.
Total Suspended Solids 0.00 413. 460.
pH, minimum 7.3 6.8 . 7.9
pH, maximum 7.3 6.8 7.9
281
-------
TABLE V-28
MEAN CONCENTRATIONS AND POLLUTANT
MASS LOADINGS IN THE CADMIUM
POWDER ELEMENT WASTE STREAMS
POLLUTANT
Flow (I/kg)
Temperature (Deg C)
44 Methylene chloride
87 Trichloroethylene
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
Mean
(mg/1)
21,
0,
9
00
.00
0.
117.
0.004
0.00
0.03
0.00
0.00
0.01
0.06
4270.
5.
0,
0,
4,
20
00
02
40
17.5
1.3
3.3
Mean
(mg/kg)
65.7
21.9
0.00
0.00
7710.
0.26
0.00
1.70
0.00
0.00
0.53
3.90
281000.
342.
0.00
1
289.
1150.
1.3
3.3
30
282
-------
ro
oo
CO
Pollutants
Tenperature
44 Methylenc Chloride
87 Trichloroethylene
118 Cadnium
119 Chromium (total)
Chromium (hexavelont)
121 cyanide (total)
Cyanide (amenable)
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Ammonia
Cobalt
Phenols (total)
Oil and Grease
Total Suspended Solids
pH Mininum
pH Maximum
Table V-29
CADMIUM SUBCATEGORY - STATISTICAL ANALYSIS OF TOTAL
RAH WASTE CONCENTRATIONS
(mg/1)**
Minimum
14.0
Maximum
66.8
Mean
29.6
Median
25.4
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.57'
0.00
0.00
1.94
0.00
0.00
0.80
13.0
1.0
2.5
0.03
*
230
0.76
0.00
0.26
0.24
0.03
281.
23.9
3310.
77.7
1.57
0.08
17.4
2290.
7.1
14.0
*
*
41.9
0.20
0.00
0.07
0.03
0.00
61.0
8.47
391.
14.8
0.39
0.02
6.62
323.
3.4
11.6
*
*
18.3
0.09
0.00
0.02
0.00
0.00
19.2
9.98
0.15
6.69
0.05
0.01
5.73
64.2
2.6
12.9
No. df
Positive
Values
12
6
9
11
12
0
9
8
8
12
3
11
9
7
10
11
12
12
12
** Values of 0.00 in table with positive values indicated reflect measured values of
pollutant in seme samples, but calculated total raw waste concentration less than 0.005 ng/1.
» Not a cadmium subcategory verification parameter, analyzed only where silver cathodes produced.
No. of
Zeros
6
3
1
0
12
2
3
4
0
1
1
0
5
1
0
0
0
0
* Less than 0.01.
-------
Table V-30
EFFLUENT CHARACTERISTICS FROM CALCIUM SUBCATEGORY
MANUFACTURING OPERATIONS - DCP DATA
Flow Rate
1/hr (gal/hr)
1385. (366)*
Cd
mg/1
0.01
Ba
mg/1
20.0
Cr
mg/1
0.20
* Intermittent flow, average is <45 1/hr (2 gal/hr) on a monthly
basis.
re
oo
TABLE V- 3 0 A
NORMALIZED DISCHARGE FLOWS
CALCIUM SUBCATEGORY ELEMENTS
Elements
Heat Paper
Manufacture
Cell Leak
Testing
Mean
Discharge
(1/fcg)
276
0.014
Median
Discharge
U/kg)
24.1
0.014
Production
Weighted Mean
Raw Waste (I/kg)
16.9
0.010
Total
Raw Waste
Volume (1/yr)
1.3 x 105
200
Production
Normalizing
Parameter
Weight of Reactants
Weight of Cells Produced,
-------
Table V-31
NORMALIZED DISCHARGE FLOWS
LEAD SUBCATEGORY ELEMENTS!/
Element
Mean
Discharge
(I/kg)
Median
Discharge
(1/kg)
No. of Plants
Represented
in Data
Anodes and Cathodes
Leady Oxide Production 0.21
Paste Preparation and 0.57
Application
Curing 0.01
0.0
0-0
0.0
34
95
89
Closed Formation
(In Case)
Single Fill
Double Fill
Fill and Dump
Open Formation (Out of
Case)
Dehydrated
Wet
Ancillary Operations
Battery Wash
Floor Wash
Battery Repair
0.09
1.26
1.73
18.4
4.77
1.28
0.41
0.17
0.0
0.31
0.83
9.0
0.0
0.72
0.49
0.17
40
30
11
35
7
60
5
1
-' Production normalizing parameter is total weight of lead used.
285
-------
Table V-32
OBSERVED DISCHARGE FLOW RATES
FOR EACH PLANT IN LEAD SUBCATEGORY
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
288
295
299
Observed Flow
Rate U/hr)
1699
4883
2952
11640
0.4
NA
0.0
329
0.0
2725
8
9278
NA
0.0
0.0
57
0.0
8
NA
0.0
0.0
37320
10260
18850
NA
6813
454
9312
9372
11360
6086
NA
NA
2271
31385
15
5678
NA
NA
0.0
0.0
Plant Number
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
480
Observed Flow
Rate (1/hr)
20900
34450
0.0
2566
61910
0.0
7843
NA
0.0
6699
NA
0.0
NA
2184
0.0
454
0.0
2763
7949
43671
4269
NA
NA
NA
0.0
0.0
0.0
0.0
29042
0.0
6927
14630
27252
2574
NA
0.0
0.0
15
2892
22210
286
-------
TABLE V-32 (CON'T)
OBSERVED DISCHARGE FLOW RATES
FOR EACH PLANT IN LEAD SUBCATEGORY
Plant Number
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
704
Observed Flow
Rate (1/hr)
NA
MA
NA
7816
NA
11920
11128
0.0
1817
0.0
4542
0.0
0.0
22710
568
NA
0.0
47460
3429
3274
2725
0.0
NA
NA
1533
4360
22030
810
12692
NA
0.0
22500
0.0
2074
31794
6813
265
5450
9084
0.0
8849
Plant Nuntoer
705
706
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
820
828
832
852
854
857
863
866
877
880
883
Observed Flow
Rate (1/hr)
2725
0.0
1590
NA
6472
0.0
NA
0.0
443
2840
3588
NA
29080
NA
0.0
13073
3452
1363
11470
1135
4315
6624
41640
5110
0.0
0.0
NA
13110
598
0.0
3407
68
8327
16070
0.0
4201
11057
0.0
18573
0.0
0.0
287
-------
TABLE V-32(X)NIT
OBSERVED DISCHARGE FLOW RATES
FOR EACH PLANT IN LEAD SUBCATEGORY
Observed Flow Observed Flow
Plant Number Rate (1/hr) Plant Number Rate (1/hr)
893 2157 963 0.0
901 0.0 964 0.0
917 18849 968 0.0
920 NA 971 0.0
927 0.0 972 23846
936 3634 976 26800
939 NA 978 1226
942 0.0 979 0.0
943 17487 982 10537
947 18400 990 3180
951 1136
NA - Not Available
288
-------
Table V-33
EFFLUENT CHARACTERISTICS REPORTED BY PLANTS PRACTICING PH
ADJUSTMENT AND SETTLING TECHNOLOGY
Pollutant Parameter (n,g/l)
Direct/ Effluent Paste
Indirect I/kg pB O&G TSS Pe Pb Zn Recirc,
D 5.10 6.9 20
1.1-4.3 X
7.5
0.4
0.5
1.0
7 0.8
0.187
2.7 X
4 0.2 1.0 0.1 X
6 0.28
X
1.0
10 0.25
1.58 5.85 26.14 257.7
I
I
D
I
I
I
D
I
I
D
I
I
D
1.88
3.15
8.0
4.56
9.76
2.01
6.35
13.32
51.9
1.74
1.34
2.57
5.76
7.5
6.9 8.2
7 4.5
6.65
3
3
1
4
3
289
-------
Table V-34
EFFLUENT QUALITY DATA FROM PLANTS PRACTICING PH
ADJUSTMENT AND FILTRATION
Production
Normalized
Direct/ Effluent
Indirect I/kg pH
A
B
C
D
E
F
G
I
D
I
I
I
D
I
2.78
4.41
43.1
1.56
3.46
9.9
0.70
7.5
7.5
11.2
O&G
Pollutant Parameter (mg/1)
TSS Fe Pb
Zn
Paste
Recirc
1.0
0.3 0.05 0.1 X
.5 Filter&Settle
0.3
0.0
0.47
0.25
0.34
0.1
290
-------
table V-35
EFFLUENT QUALITY DATA FROM PLANTS PRACTICING
PH ADJUSTMENT ONLY
Production
Normalized
Direct/ Effluent
Indirect I/kg pH
6.07
22.9
3.73
81.7
13.5
5.35
51.9
10.1
A
B
C
D
E
F
G
H
I
J
K
I
I
I
I
I
I
I
I
I*
I
I
5.02
26.4
63.3
15.0
6.65
5.7
Pollutant Parameter (mg/1)
O&G TSS Fe Pb
29.8
10-15
2.77
6.0
27.5
1.4
33
32
.2
1.0
3.95
10-15
3.0
26.92
Zn
Paste
Recirc
0.4
0.24
* Reports no effluent treatment prior to release to POTW
291
-------
ro
\o
ro
Vaifierature (Deg C) 18.2
11 1,1,1-Trichloroethane 0.00
23 Chloroform o.OO
44 Hothyleno chloride *
55 Naplithalene *
65 Phenol NA
66 Bis(2-cthylhexyl(phthalate *
67 Butyl benzyl phthalate •
68 Di-n-butyl phthalate 0.00
69 Di-n-octyl phthalate 0.00
78 Anthracene o.OO
81 Phenanthrene o.OO
84 Pyrene o.OO
114 Antimony o.OO
115 Arsenic 0.00
118 Cadmium 0.03
119 Chronium, Total 0.12
Chronium, Itexavalent 0.00
120 Copper 0.44
122 Lear] 6.88
123 Mercury 0.00
124 Nickel 0.12
126 Silver 0.00
128 Zinc 0.31
Iron 6.64
Phenols, Total 0.02
Strontium 0.02
Oil & Grease 49.0
Total Suspended Solids 416.
pH, Minimum 2.0
pH, Maximum 11.9
NA-Not Analyzed
•-Less than 0.0I
Table V-36
TOTAL RAW VASTG FOR VISITS
PLANT
18.9
0.00
0.00
0.00
0.01
0.00
*
0.00
*
0.00
*
*
0.00
0.00
0.00
0.00
0.03
0.00
0.28
1.43
0.01
0.02
0.00
0.13
6.55
0.01
0.00
13.0
15.0
2.0
6.8
18.0
0.00
0.00
0.00
0.02
NA
0.01
*
*
0.00
*
*
0.00
0.00
0.01
0.01
0.05
0.00
0.38
1.17
0.03
0.03
0.00
0.19
5.52
0.05
0.00
9.24
16.4
2.0
5.7
17.0
0.03
*
*
*
*
0.14
0.02
*
0.14
0.03
0.03
*
0.00
0.00
0.01
0.01
0.00
0.08
13.0
IR
0.00
0.03
0.33
2.00
0.01
HA
36.5
57.8
2.2
3.6
PLANT
17.0
0.00
0.00
0.00
0.00
MA
0.04
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
NA
0.09
15.4
0.00
0.00
0.01
0.35
3.80
0.00
0.00
10.6
31.2
2.0
4.9
B
17.0
0.00
0.00
0.00
0.00
NA
0.03
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.02
NA
0.11
45.9
0.00
0.02
0.02
0.38
4.37
0.00
0.00
5.20
52.4
1.8
3.9
-------
Table v- 3 6 ( c o n ' t)
Temperature (Ocg C) 15.3
11 1,1,1-Trichloroethane 0.00
23 Chloroform 0.00
44 Mothylene chloride 0.00
55 Naphthalene 0.00
65 Phenol NA
3> 66 Bis(2-ethylhexyl)phthalate 0.04
<*> 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 0.00
115 Arsenic 0.00
118 Cadmium 0.00
119 Chrcmium, Total 0.10
Chromium, Itexavalent NA
120 Copper 0.06
122 Lead 1.00
123 Mercury 0.00
124 Nickel 0.08
126 Silver 0.00
128 Zinc 0.05
Iron 9.24
Phenols, -total 0.00
Strontium 0.03
Oil & Grease 3.10
Total Suspended Solids 6.00
pil, Minimm 2.1
pH, Maximum 2.9
NA-Not Analyzed
*-Lcss than 0.01
TOTAL RAW WVSTE FOR VISITS
(mg/D
PLANT
16.5
0.00
0.00
0.00
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.06
NA
0.08
1.36
0.00
0.04
0.00
0.12
15.5
0.00
0.03
4.00
14.0
2.0
2.4
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
0.00
0.00
0.07
NA
0.05
1.45
0.00
0.07
0.00
0.19
9.41
0.00
0.03
3.90
5.00
2.0
2.4
35.1
0.00
0.00
0.00
*
NA
0.03
*
*
*
0.00
0.00
0.00
0.00
0.02
0.00
0.67
NA
0.32
18.3
0.00
0.38
0.00
0.75
15.5
0.02
0.00
10.3
350.1
2.0
12.0
PLANT D
33.5
*
0.00
0.00
*
NA
0.04
*
*
*
0.00
0.00
0.00
0.09
0.00
0.00
0.73
NA
0.77
15.7
0.00
0.51
0.00
1.07
20.1
0.04
0.00
9.44
974.
2.0
12.0
PLANT
28.0
*
0.00
0.00
*
NA
0.05
*
0.00
*
0.00
0.00
0.00
0.19
0.12
0.00
3.27
NA
2.50
44.9
0.00
2.49
0.02
6.80
74.0
0.03
0.00
16.7
1300.
2.0
12.0
HA
0.00
0.00
0.00
0.00
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
0.13
NA
0.03
NA
0.00
NA
13.4
0.05
NA
0.01
3.88
390.
0.02
0.00
3.00
184.
NA
NA
-------
Table V-37
LEAD SUBCATBGORY TOTAL RAW WASTE LOADINGS
(rag/kg)
PLANT A
PLANT B
IV)
10
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
Mothylene chloride
Naphthalene
Phenol
Bis( 2-ethylhexyl )phthalate
Butyl benzyl phthalate
Oi-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrene
Antimony
Arsenic
Cadmium
Chromium, Total
Chremium, Hexavalent
Copper
Lead
Msrcury
Nickel
Silver
Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pll. Maximum
1.21
18.2
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.002
0.00
0.03
0.15
0.00
0.53
8.31
0.00
0.15
0.00
0.37
8.02
0.02
0.03
59.2
502.
2.0
11.9
1.21
18.2
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.002
0.00
0.03
0.15
0.00
0.53
8.31
0.00
0.15
0.00
0.37
8.02
0.02
0.03
59.2
502.
2.0
11.9
1.20
18.9
0.00
0.00
0.00
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.004
0.04
0.00
0.33
1.72
0.01
0.03
0.00
0.16
7.84
0.02
0.00
15.5
18.0
2.0
6.8
0.71
18.0
0.00
0.00
0.00
0.01
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.004
0.004
0.03
0.00
0.27
0.83
0.02
0.02
0.00
0.14
3.89
0.04
0.00
6.52
11.6
2.0
5.7
8.84
17.0
0.22
0.00
0.00
0.00
0.00
1.19
0.15
0.00
1.24
0.28
0.28
0.00
0.00
0.00
0.07
0.08
0.00
0.73
115.
NA
0.00
0.29
2.94
17.7
0.07
NA
323.
511.
2.2
3.6
9.87
17.0
0.00
0.00
0.00
0.01
NA
0.43
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.12
NA
0.89
152.
0.00
0.00
0.07
3.46
37.5
0.00
0.00
105.
308.
2.0
4.9
10.3
17.0
0.00
0.00
0.00
0.01
NA
0.31
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.12
0.18
NA
1.13
471.
0.00
0.21
0.15
3.90
44.9
0.00
0.00
53.4
538.
1.8
3.9
NA-Not Analyzed
-------
Table V-37 (DON'T)
LEAD SUBCATBOORY TOTAL RAW HBSTE LOADINGS
(rag/kg)
ro
10
Flow (I/kg)
Temperature (Dog 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 Phenanthrenc
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chranium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pll. Minimum
pfl. Maximum
6.68
15.3
0.00
0.00
0.00
0.00
NA
0.25
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.65
NA
0.42
6.68
0.00
0.52
0.00
0.36
61.8
0.00
0.18
20.7
40.1
2.1
2.9
PLANT C
6.59
16.5
0.00
0.00
0.00
0.00
NA
0.07
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.38
NA
0.51
8.96
0.00
0.24
0.00
0.79
102.
0.00
0.22
26.4
92.3
2.0
2.4
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
0.00
0.00
0.00
0.47
NA
0.37
10.1
0.00
0.48
0.00
1.33
65.7
0.00
0.23
27.2
34.9
2.0
2.4
1.35
35.1
0.00
0.00
0.00
0.00
NA
0.04
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.003
0.91
NA
0.44
24.7
0.00
0.52
0.001
1.01
20.9
0.03
0.00
14.0
473.
2.0
12.0
PLANT D
1.25
33.5
0.00
0.00
0.00
0.00
NA
0.05
0.00
0.00
0.00
0.00
0.00
0.00
0.11
0.00
0.01
0.92
NA
0.97
19.6
0.00
0.63
0.001
1.34
25.2
0.05
0.00
11.8
1220.
2.0
12.0
PLANT £
0.56
28.0
0.00
0.00
0.00
0.00
NA
0.03
0.00
0.00
0.00
0.00
0.00
0.00
0.11
0.07
0.002
1.84
NA
1.41
25.2
0.00
1.40
0.01
3.82
41.6
0.02
0.001
9.36
731.
2.0
12.0
0.22
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
0.03
NA
0.01
NA
0.00
NA
2.92
0.01
NA
0.002
0.85
85.0
0.004
0.00
0.65
40.1
NA
MA
NA-Not Analyzed
-------
Table V-38
11
23
44
ro 55
S 65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
POLLUTANTS
Tenperature (Deg C)
1,1, 1-Trichloroothane
Chloroform
Mothylene chloride
Naphthalene
Phenol
Bis( 2-othylhexyl (phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenan throne
Pyrene
Antimony
Arsenic
Cadmium
Chromium, Total
Chronium, Hexavalent
Copper
Lead
Mercury
Nickel
Silver
Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pfl. Minimum
pll. Maximum
Minimum
15.3
*
0.00
0.00
0.00
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.05
1.00
0.00
0.00
0.00
0.05
2.0
0.00
0.00
3.00
5.00
1.8
2.4
Maximum
35.1
0.03
*
A
0.01
*
0.14
0.02
*
0.14
0.03
0.03
*
0.19
0.12
0.03
3.27
0.00
2.50
45.9
0.05
2.49
0.03
6.80
390.
0.05
0.03
49.0
1300.
2.2
12.0
Mean
17.5
0.03
*
*
0.01
*
*
*
0.03
0.01
0.01
0.43
0.00
0.43
13.8
0.01
0.31
0.01
1.12
43.3
0.01
0.01
13.4
263.
2.0
6.7
STATISTICAL SUMMARY OF THE LEAD SUBCATEQORY
RAW WSTE
(rag/1)
Madian
17.5
*
0.00
*
*
0.00
0.03
0.00
*
*
0.00
0.00
0.00
0.00
0.06
0.00
0.19
13.0
0.00
0.05
0.00
0.33
9.24
0.01
0.00
9.44
52.4
2.0
5.3
I
Val.
12
13
6
8
10
1
13
7
8
6
7
7
5
4
4
10
12
0
12
13
4
10
8
13
13
8
5
13
13
12
12
*
Zeros
0
0
7
5
3
2
0
6
5
7
6
6
8
9
8
3
0
5
0
0
8
2
5
0
0
5
7
0
0
0
0
I
Pts.
12
13
13
13
13
3
13
13
13
13
13
13
13
13
12
13
12
5
12
13
12
12
13
13
13
13
12
13
13
12
12
* Loss than 0.01
-------
Table V-39
STATISTICAL ANALYSIS OF THE LEAD SUBCATBQORy
TOTAL RAW WASTE LOADINGS
(mg/kg)
POLLUTANTS
Flow (I/kg)
Tcrcperature (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
ro 69 Di-n-octyl phthalate
i° 78 Anthracene
81 Phenanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadnium
119 Chrcnium, Total
Chromium, Hexavalent
120 Capper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontiun
Oil & Grease
Total Suspended Solids
pH, Mininum
pll, Maximum
MINIMUM
0.22
15.3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.00
0.27
0.83
0.00
0.00
0.00
0.14
3.89
0.00
0.00
0.65
11.6
1.8
2.4
MAXIMUM
10.3
35.1
0.00
0.00
0.00
0.05
0.00
1.19
0.15
0.00
1.24
0.28
0.28
0.00
0.11
0.07
0.12
1.84
0.00
1.41
471.
0.02
1.40
0.29
3.90
102.
0.07
0.23
323.
1220.
2.2
12.0
MEAN
4.29
17.5
0.00
0.00
0.00
0.00
0.00
0.19
0.00
0.00
0.10
0.00
0.00
0.00
0.02
0.01
0.02
0.48
0.00
0.67
65.2
0.003
0.35
0.04
1.57
40.2
0.02
0.06
51.7
348.
2.0
6.7
MEDIAN
1.35
17.5
0.00
0.00
0.00
0.00
0.00
0.04
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.004
0.28
0.00
0.52
10.1
0.00
0.22
0.001
1.01
37.5
0.02
0.00
20.7
308.
2.0
5.3
NA-Not Analyzed
-------
Table V-40
Plow
IVxif lorature (Dog C)
11 1,1,l-Tr iohloroethane
23 Chloroform
44 ffctJiylenc chloride
55 Naphthalene
65 Phenol
66 Di&(2-etJiylhexyl|phthalate
[^ 67 Uutyl benzyl phthalate
00 68 ni-n-butyl phthalate
69 Di-n-octyl phtlialato
76 Aiitluraocne
81 Phcnantnrunc
84 Pyrcnc
114 Antimony
115 Arsunic
118 Cadmium
119 Chrunitm, Total
Chrunium, Hexavalent
120 Cn|jpcr
122 Lcail
123 Hircury
124 Nickel
126 Silver
128 Zinc
Iron
Phuiola, Total
Strontiim
Oil t Grease
Total Suspended Solids
til, MininuM
(II, HaxiMUM
LEAD SUUCATEOOKY CltAKACTORISTICS
PRUCISS WASTES
PASTING Wet Batteries
Closed Formation
I/kg lAg
nj/1
29.0
•
*
0.00
*
0.00
*
0.00
*
0.00
t
*
0.00
0.00
0.00
0.01
0.01
0.00
0.10
280.
0.00
0.01
0.18
0.51
2.03
0.08
0.00
35.0
11000.
6.7
8.9
0.22
rag/kg
29.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
16.3
0.00
0.001
0.01
0.05
0.25
0.01
0.00
2.22
1320.
6.7
8.9
n.j/i
18.5
0.00
0.00
*
0.00
0.00
*
*
*
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.05
0.00
0.17
0.96
0.00
0.02
0.00
0.08
5.10
0.02
0.00
1.10
6.00
2.0
2.6
0.45
ny/kg
18.5
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
0.02
0.00
0.08
0.50
0.00
0.01
0.00
0.04
2.03
0.01
0.00
0.52
3.12
2.0
2.6
OF INDIVIUUAI.
Dehydrated
Damp Batteries Batteries BATTEK*
Closed Formation °Pen Formation HASH
lAg lAg lAg
nq/1
19.3
0.00
0.00
0.00
0.00
0.00
*
0.00
•
0.00
0.00
0.00
0.00
0.00
0.03
0.01
0.12
0.00
0.40
1.84
0.00
0.09
0.00
0.14
6.88
0.02
0.00
1.25
10.5
2.0
3.9
1.30
nig/kg
19.3
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
0.02
0.01
0.13
0.00
0.49
2.33
0.00
0.10
0.00
0.16
7.97
0.03
0.00
1.64
12.7
2.0
3.9
roj/1
49.2
*
•
0.00
•
NA
0.06
0.00
*
0.00
*
*
0.00
0.00
0.00
0.00
0.05
NA
0.04
7.66
0.00
0.11
0.00
0.34
1.57
0.01
0.00
4.05
4.50
2.0
4.8
13.9
mg/kg
49.2
0.00
0.00
0.00
0.00
NA
0.92
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.05
0.66
MA
0.58
109.
0.00
1.54
0.00
4.76
20.5
0.16
0.00
60.0
72.5
2.0
4.8
mg/i
23.0
0.00
0.00
0.00
0.01
0.00
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.62
0.00
0.45
7.4
0.00
0.06
0.00
0.53
16.8
0.02
0.00
16.0
81.5
2.0
9.9
0.62
mg/kg
23.0
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.45
0.00
0.29
5.0
0.00
0.05
0.00
0.38
12.1
0.01
0.00
8.9
44.3
2.0
9.9
Nh-IJot Analyzed
-------
PUNT EPA ID
Table V-41
PASTING WASTE CHARACTERISTICS
(mg/1)
Strcan Identification
POLLUTANTS
Tcrf»rature (Deg C)
11 1,1.1-Trichloroethano
23 Chloroform
44 Methylcne 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 Fhenanthrone
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmiun
119 Chronicm, Total
Chroniun, Hexavalent
120 Copper
122 Leal
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontiim
Oil & Grease
Total Suspiended Solids
pH, Miniimwi
pi I, Maximim
I-Intorferencc
NA-Not Analyzed
*-Les.<3 than 0.01
Clean Up Hater Pron
Pasting Machine
In-Lino Sunp Under
Pasting Machine
NA
0.00
0.00
0.00
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.12
2700.
0.02
0.00
0.26
0.04
0.80
0.09
0.00
38.0
10900.
7.2
7.9
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
0.00
0.08
6000.
0.00
0.00
0.19
0.16
2.65
0.15
0.00
1620.
12500.
9.8
9.8
NA
0.00
0.00
0.00
*
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.67
0.00
0.18
0.00
0.00
0.58
3360.
I
0.00
0.71
0.51
7.23
0.11
0.00
1200.
42300.
11.4
11.4
29.0
0.00
0.00
0.00
0.02
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.03
NA
0.03
280.
0.00
0.03
0.01
0.78
0.76
0.06
0.00
9.30
6600.
6.1
6.1
NA
0.00
0.00
0.00
0.01
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.02
NA
0.03
208.
0.00
0.02
0.01
0.54
0.54
0.08
0.00
35.0
20900.
NA
NA
NA
0.00
0.00
0.00
0.02
NA
0.11
0.00
0.00
0.00
0.00
0.00
0.00
0.31
0.00
0.04
0.03
NA
0.19
254.
0.00
0.02
0.18
0.41
2.03
0.07
0.02
30.0
11000.
NA
in
NA
0.00
0.00
0.00
0.00
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
0.13
HA
0.03
HA
0.00
NA
13.4
0.05
NA
0.01
3.88
390.
0.02
0.00
3.00
184.
NA
IIA
-------
Table V-42
PLANT EPA ID
PASTING WASTE LOADINGS
(ng/kg)
A
CJ
o
o
Stream Identification
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Mothylenc 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 Pyrcne
114 Antimony
115 Arsenic
118 Cadmium
119 Chronium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 rfcrcury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontium
Oil & Crease
Total Suspended Solids
pH, Minimum
pH, Maximum
I-Interferonce
NA-Mot Analyzed
Clean-Up Water Fran
Pasting Machine
In-Line Sump Under
Pasting Machine
0.31
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
840.
0.01
0.00
0.08
0.01
0.25
0.03
0.00
11.8
3390.
7.2
7.9
0.35
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
0.00
0.00
0.03
2100.
0.00
0.00
0.07
0.06
0.93
0.05
0.00
568.
4370.
9.8
9.8
0.32
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.16
0.00
0.06
0.00
0.00
0.18
1060.
I
0.00
0.22
0.16
2.30
0.04
0.00
378.
13400.
11.4
11.4
0.06
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
0.00
0.00
0.00
0.002
NA
0.001
16.3
0.00
0.002
0.001
0.05
0.04
0.004
0.00
0.54
383.
6.1
6.1
0.06
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.001
NA
0.002
13.2
0.00
o.opi
0.001
0.03
0.03
0.01
0.00
2.22
1320.
NA
MA
0.06
NA
0.00
0.00
0.00
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.00
0.002
0.002
NA
0.01
16.2
0.00
0.002
0.01
0.03
0.13
0.004
0.001
1.93
704.
IIA
NA
0.22
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
0.03
NA
0.01
NA
0.00
NA
2.92
0.01
NA
0.002
0.85
85.0
0.004
0.00
0.65
40.1
HA
NA
-------
Table V-43
CLOSED FORMATION POLLUTANT
CHARACTERISTICS OF BOTH
WET AND DAMP BATTERIES
Plant A
(mg/1)
POLLUTANTS
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-oc±yl 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
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA-Not Analyzed
*-Less than 0.01
WET BATTERIES
DAMP BATTERIES
18.5
0.00
0.00
*
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.00
0.10
0.96
0.00
0.01
0.00
0.06
3.90
0.02
0.00
1.00
6.00
2.0
6.8
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
0.00
0.01
0.07
0.00
0.17
1.71
0.02
0.04
0.00
0.08
7.92
0.01
0.00
1.10
8.00
2.0
2.4
18.0
0.00
0.00
0.00
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.05
0.00
0.40
0.85
0.00
0.02
0.00
0.18
5.10
0.08
0.00
4.20
1.00
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
0.00
0.00
0.00
0.01
0.06
0.00
0.33
1.71
0.00
0.04
0.00
0.10
4.40
0.02
0.00
1.30
8.00
2.0
5.7
18.0
0.00
0.00
0.00
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.05
0.01
0.17
0.00
0.46
1.96
0.00
0.14
0.00
0.17
9.36
0.02
0.00
1.20
13.0
NA
2.0
301
-------
Table V-44
CLOSED FORMATION WASTE LOADINGS OF BOTH
WET AND DAMP BATTERIES
PLANT A
(ing/kg)
WET BATTERIES
DAMP BATTERIES
11
23
44
55
65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
1,1, 1-Trichloroethane
Chloroform
Methylene chloride
Naphthalene
Phenol
Bis( 2-ethylhexyl Jphthalate
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
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
0.52
18.5
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.05
0.50
0.00
0.004
0.00
0.03
2.03
0.01
0.00
0.52
3.12
2.0
6.8
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
0.00
0.00
0.002
0.03
0.00
0.08
0.78
0.01
0.02
0.00
0.04
3.60
0.01
0.00
0.50
3.63
2.0
2.4
0.38
18.0
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.002
0.02
0.00
0.15
0.32
0.00
0.01
0.00
0.07
1.93
0.03
0.00
1.59
0.38
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
0.00
0.00
0.01
0.11
0.00
0.55
2.87
0.00
0.07
0.00
0.17
7.39
0.03
0.00
2.18
13.4
2.0
5.7
0.91
18.0
0.00
0.00
0.00
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.05
0.01
0.16
0.00
0.42
1.79
0.00
0.13
0.00
0.16
8.54
0.02
0.00
1.10
11.9
NA
2.0
NA-Not Analyzed
302
-------
Table V-45
OPEN FORMATION DEHYDRATED BATTERY
WASTE CHARACTERISTICS
(mg/1)
POLLUTANTS Plant D
CAYS
1 2
Temperature (Deg C) 50.0 48.0
11 1,1,1-Trichloroethane NA 0.00
23 Chloroform NA 0.00
44 Methylene chloride NA 0.00
55 Naphthalene 0.00 0.00
65 Phenol NA NA
66 Bis(2-ethylhexyl)phthalate 0.08 0.05
67 Butyl benzyl phthalate 0.00 0.00
68 Di-n-butyl phthalate * *
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 0.00 0.00
115 Arsenic 0.00 0.00
118 Cadmium 0.00 0.01
119 Oironium, Total 0.05 0.05
Chromium, Hexavalent NA NA
120 Copper 0.05 0.04
122 Lead 8.59 6.72
123 Mercury 0.00 0.00
124 Nickel 0.10 0.13
126 Silver 0.00 0.00
128 Zinc 0.35 0.33
Iron 0.93 2.21
Phenols, Total 0.02 0.01
Strontium 0.00 0.00
Oil & Grease 5.70 2.40
Total Suspended Solids 9.00 0.00
pH, Minimum 2.0 2.0
pH, Maximum 4.1 5.4
NA-Not Analyzed
*-Less than 0.01
303
-------
Table V-46
OPEN FORMATION DEHYDRATED BATTERY
11
23
44
55
65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
POLLUTANTS
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
Chronium, Total
Chromium, Hexavalent
Copper
Lead
Mercury
Nickel
Silver
Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
WASTE LOADINGS
(mg/kg)
PLANT D
CAYS
1
16.1
50.0
NA
NA
NA
0.01
NA
1.24
0.00
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.76
NA
0.74
138.
0.00
1.55
0.00
5.64
15.0
0.26
0.00
91.8
145.
2.0
4.1
NA-Not Analyzed
2
11.7
48.0
0.00
0.00
0.00
0.01
NA
0.60
0.00
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.11
0.56
NA
0.42
78.9
0.00
1.53
0.00
3.88
26.0
0.06
0.00
28.1
0.00
2.0
5.4
304
-------
Table V-47
BATTERY WASH WASTEWATER CHARACTERISTICS
(mg/1)
CO
o
en
Temperature (Deg C) 18.0
11 1,1,1-Trichloroethane 0.00
23 Chloroform 0.00
44 Methylene chloride 0.00
55 Naphthalene 0.01
65 Phenol NA
66 Bis(2-ethylhexyl)phthalate *
67 Butyl benzyl phthalate *
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 0.00
115 Arsenic 0.00
118 Cadmium 0.00
119 Chromium, Total 0.07
Chromium, Hexavalent 0.00
120 Copper 0.57
122 Lead 6.39
123 Mercury 0.00
124 Nickel 0.06
126 Silver 0.00
128 Zinc 0.24
Iron 6.93
Phenols, Total 0.02
Strontium 0.04
Oil & Grease 18.0
Total Suspended Solids 120.
pH, Minimum 2.0
pH, Maximum 7.7
NA-Not Analyzed
*-Less than 0.01
PLANT
18.0
0.00
0.00
0.00
0.03
0.00
*
0.00
0.00
0.00
It
*
0.00
0.00
0.00
0.00
0.00
0.00
0.28
1.20
0.01
0.00
0.00
0.13
3.90
0.01
0.00
23.0
19.0
2.0
6.8
18.0
0.00
0.00
0.00
0.04
NA
0.02
*
0.00
0.00
*
*
0.00
0.00
0.00
0.00
0.02
0.00
0.33
1.37
0.07
0.01
0.00
0.16
5.00
0.02
0.00
17.0
29.0
2.0
5.7
28.0
0.00
0.00
0.00
0.00
NA
0.01
*
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
1.16
NA
0.29
8.42
0.00
0.63
0.00
0.81
26.8
0.02
0.00
14.0
160.
2.0
12.0
PLANT D
28.0
*
*
0.00
*
NA
0.05
0.00
0.00
*
0.00
0.00
0.00
0.19
0.00
0.00
1.45
NA
1.47
9.69
0.00
0.91
0.00
1.77
40.0
0.02
0.00
10.4
70.0
2.0
12.0
28.0
*
*
0.00
0.00
NA
0.04
*
0.00
*
0.00
0.00
0.00
0.18
0.13
0.00
3.67
NA
2.79
18.9
0.00
2.80
0.00
7.60
83.0
0.02
0.00
15.0
93.0
2.0
12.0
-------
Table V-48
co
o
en
POLLUTANTS
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 Phcnanthrene
84 Pyrene
114 Ant irony
115 Arsenic
118 Cadiniun
119 Chronium, Total
Chromium, Itexavalent
120 Copper
122 Leal
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pi I, Minimum
pi!, Maxinum
BATTERY WRSH JfflSTEWATER LOADINGS
(rag/kg)
PLANT A
PLANT D
0.65
18.0
0.00
0.00
0.00
0.01
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.05
0.00
0.37
4.16
0.00
0.04
0.00
0.16
4.51
0.01
0.03
11.7
78.1
2.0
7.7
0.64
18.0
0.00
0.00
0.00
0.02
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
0.18
0.77
0.01
0.00
0.00
0.08
2.49
0.01
0.00
14.7
12.1
2.0
6.8
0.28
18.0
0.00
0.00
0.00
0.01
MA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.01
0.00
0.09
0.38
0.02
0.002
0.00
0.05
1.40
0.01
0.00
4.77
8.13
2.0
5.7
0.73
28.0
0.00
0.00
0.00
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.85
NA
0.21
6.15
0.00
0.05
0.00
0.59
19.6
0.01
0.00
10.2
117.
2.0
12.0
0.60
28.0
0.00
0.00
0.00
0.00
NA
0.03
0.00
0.00
0.00
0.00
0.00
0.00
0.11
0.00
0.004
0.87
NA
0.88
5.81
0.00
0.55
0.00
1.06
24.0
0.01
0.00
6.24
42.0
2.0
12.0
0.50
28.0
0.00
0.00
0.00
0.00
NA
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.09
0.08
0.00
1.84
NA
1.40
9.45
0.00
1.40
0.003
3.80.
41.5
0.01
0.00
7.50
46.5
2.0
12.0
NA-Mot Analyzed
-------
Table V-49
BATTERY REPAIR AND FLOOR VfflSH WASTE CHARACTERISTICS
(mg/D
CO
o
11
23
44
55
65
66
67
68
69
78
81
84
114
115
118
119
120
122
123
124
126
128
POLLUTANTS
DAYS
Temperature (Deg C)
1,1,1-Trichloroethane
Oilorofoim
Mcthylenc chloride
Naphthalene
Phenol
Bis(2-ethylhexyl)phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Anthracene
Phenanthrene
Pyrenc
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Leal
Mercury
Nickel
Silver
Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Mininum
pH, Maximum
NA-Not Analyzed
*-Less than 0.01
NA
0.00
0.00
*
0.00
NA
*
*
0.00
0.00
0.00
0.00
0.00
0.94
0.00
0.04
0.03
0.00
0.29
251.
0.00
0.03
0.00
0.94
9.76
0.15
0.00
NA
NA
NA
MA
FLOOR WASH
PLANT A
2
22.0
0.00
0.00
0.00
*
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.02
0.00
0.21
107.
0.00
0.02
0.00
0.71
6.82
0.09
0.00
25.0
1120.
NA
10.2
NA
0.00
0.00
0.00
*
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.02
0.00
0.32
51.0
0.00
0.00
0.00
0.47
6.45
0.16
0.00
28.0
952.
NA
10.2
1
NA
0.00
0.00
0.00
NA
NA
NA
NA
NA
NA
NA
NA
HA
0.64
0.11
0.22
0.25
0.00
5.46
65.0
0.01
0.43
0.01
9.87
460.
0.04
0.00
62.0
624.
2.3
2.3
BATTERY REPAIR
PLANT A
2
NA
0.00
0.00
0.00
*
0.00
0.01
*
0.01
0.00
*
*
*
0.00
0.00
0.34
0.10
0.00
9.83
0.54
0.01
0.52
0.00
7.51
370.
0.17
0.00
46.0
362.
NA
2.0
3
NA
0.00
0.00
0.00
0.00
NA
0.01
*
0.01
0.00
*
*
0.00
0.00
0.00
0.01
0.01
0.00
0.28
0.27
0.01
0.01
0.00
4.21
8.05
0.13
0.00
54.0
572.
NA
NA
PLANT
1
32.0
0.00
0.00
0.00
0.00
NA
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.15
0.01
0.25
NA
1.22
1.02
0.00
0.13
0.00
1.41
5.94
0.01
0.00
6.00
1.30
2.9
3.9
D
2
31.0
0.00
0.00
0.00
0.00
NA
0.01
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.12
NA
0.25
0.83
0.00
0.17
0.00
0.50
2.31
0.09
0.00
9.30
12.0
3.4
5.6
-------
Table V-50
BATTER* REPAIR AND FLOOR tffiSH WASTE LOADINGS
(ng/kg)
00
o
00
POLLOTANTS
Flow (I/kg)
Tcnperature (Deg C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Methylcne chloride
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-toutyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Phcnanthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chrcnium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontium
Oil 6 Grease
Ibtal Suspended Solids
pll, Minimum
pH, Maxinum
1
0.03
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.00
0.001
0.001
0.00
0.01
6.62
0.00
0.001
0.00
0.03
0.26
0.004
0.00
NA
NA
MA
MA
FLOOR WASH
PLANT A
2
0.02
22.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.00
0.00
0.004
2.16
0.00
0.00
0.00
0.01
0.14
0.002
0.00
0.51
22.5
NA
10.2
3
0.03
NA
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
1.32
0.00
0.00
0.00
0.01
0.17
0.004
0.00
0.72
24.6
HA
10.2
1
0.003
NA
0.00
0.00
0.00
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.002
0.00
0.001
0.001
0.00
0.02
0.22
0.00
0.001
0.00
0.03
1.55
0.00
0.00
0.21
2.10
2.3
2.3
E
PLANT .A
2
0.004
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
0.001
0.00
0.00
0.04
0.002
0.00
0.002
0.00
0.03
1.44
0.001
0.00
0.18
1.41
NA
2.0
IATTEK* Her/UK
PLANT D
3
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
0.00
0.00
0.00
0.00
0.00
0.001
0.001
0.00
0.00
0.00
0.02
0.03
0.00
0.00
0.20
2.16
NA
NA
1
0.17
32.0
0.00
0.00
0.00
0.00
NA
0.002
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.002
0.04
NA
0.21
0.17
0.00
0.02
0.00
0.24
1.01
0.002
0.00
1.02
0.22
2.9
3.9
£
0.32
31.0
0.00
0.00
0.00
0.00
NA
0.004
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
NA
0.08
0.27
0.00
0.06
0.00
0.16
0.74
0.03
0.00
2.99
3.85
3.4
5.6
NA-Not Analyzed
-------
Table V-51
EFFLUENT FROM SAMPLED PLANTS
(mg/1)
co
o
<£>
POLLUTANTS
DAYS
Flow (I/kg)
Ttnperature (Dog C)
11 1,1,1-Trichloroethane
23 Chloroform
44 Mcthylenc chloride
55 Naphthalene
65 Wicnol
66 Dis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
78 Anthracene
81 Fncnanthrcnc
84 lyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chrcniun, Ifexavalent
120 Capper
122 Lead
123 Horcury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, "total
Strontium
Oil £ Grease
Total Suspended Solids
pH, Minijnum
pll, Maximum
llA-Not Analyzed
*-Less than 0.0I
1
5.60
17.0
*
0.03
*
0.00
*
0.02
0.00
*
0.00
*
»
*
0.00
0.00
0.00
0.00
0.00
0.00
1.35
MA
0.00
0.00
0.10
0.00
0.00
NA
10.0
90.6
6.5
8.5
Plant B
2
4.08
17.0
*
0.00
0.00
0.00
NA
*
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
NA
0.04
4.05
0.00
0.00
0.00
0.10
0.71
0.00
0.02
9.90
76.0
7.2
8.8
3
3.40
17.0
*
0.00
0.00
0.00
NA
*
0.00
0.00
*
0.00
0.00
0.00
0.00
0.00
0.00
0.01
in
0.03
3.58
0.00
0.01
0.00
0.08
0.59
0.00
0.01
5.00
39.8
6.6
7.9
1
6.58
7.60
*
0.00
0.00
0.00
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MA
0.02
0.11
0.00
0.01
0.00
0.00
0.76
0.00
0.03
1.40
13.0
9.0
9.3
Plant C
2
6.48
7.80
*
0.00
*
0.00
MA
*
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
tIA
0.01
0.13
0.00
0.01
0.00
0.00
0.92
0.00
0.03
2.70
11.0
8.7
9.1
3
6.87
8.50
0.27
*
0.00
*
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
HA
0.02
0.11
0.00
0.01
0.00
0.04
0.95
0.00
0.00
2.2fl
11.0
8.6
9.1
-------
TABLE V-51(CON'T)
EFFLUENT FROM SAMPLED PLANTS
(mg/1)
CO
t—>
o
COMPONENTS
DAYS
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 Phenenthrene
84 Pyrene
114 Antimony
115 Arsenic
118 Cadmium
119 Oironium, Total
Chromium, Ifexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Phenols, Total
Strontium
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA-Not Analyzed
*-Less than 0.01
1
1.89
32.0
0.00
NA
*
*
*
0.00
*
*
0.00
0.00
0.00
0.00
0.01
NA
0.06
.06
.00
6.
0.
0.11
0.00
0.17
0.42
0.00
00
,30
50
0
0.
2.
3.
6.
10.4
Plant D
2
1.84
31.0
*
0.00
NA
0.02
0.00
0.00
0.00
*
*
0.00
0.00
0.00
0.00
0.01
NA
0.05
3.88
0.00
0.07
0.00
0.00
0.28
0.00
0.00
1.70
11.0
7.7
9.2
3
1.21
NA
*
*
*
0.00
NA
0.00
0.12
*
0.00
*
*
0.00
0.00
0.00
0.00
0.06
NA
0.09
13.3
0.00
0.05
0.00
0.11
3.38
0.00
0.00
3.70
66.0
7.0
9.0
-------
Table V-52
LECLANCHE SUBCATEGORY ELEMENTS (REPORTED MANUFACTURE)
Anodes
Cathodes (and
Electrolyte Form)
Cooked
Paste
Separator
Zinc Sheet Metal
Uncooked
Paste
Separator
Paper
Separator
Zinc Powder
Plastic
Separator
Mn02 Cathode
(and Electrolyte
with Mercury)
Mn02 Cathodes
(and Electrolyte
without Mercury)
MnO- Cathode
(and Gelled
Electrolyte
with Mercury)
Carbon Cathode
Silver
Cathode
Pasted
Mn02 Cathode
Ancillary Operations
Equipment
Cleanup
311
-------
u>
»-«
to
TABLE V-53
NORMALIZED DISCHARGE FLOWS
LECIANCHE SUBCATEQORY ELEMENTS
Elements
Ancillary
Separator
Cooked
Separator
Pasted
Equipment
Operations
Paste
Paper with
and Area
Mean
Discharge
dAg)
0.04
0.14
Mercury
0.38
Median
Discharge
UAg)
0.04
0.14
0
Production
Weighted Mean
Raw Waste (I/kg)
0.137
0.14
0.103
Total
Raw Waste
Volume (1/yr)
3.2xl06
1.5xl04
9.65xl06
Production
Normalizing
Parameter
Weight of Cells
Produced
Weight of Dry Paste
Material
Weight of Cells
Produced
Cleanup
-------
Table V-54
LECLANCHE SUBCATEQOEY EFFLUENT QUALITY
(FROM DCP'S)
PARAMETER
Flow, l/kg
Oil & Grease, mg/1 24.6
Lead, mg/1 0.03
Mercury, mg/1 1.42 3.15
Nickel, mg/1 0.007
Zinc, mg/1 - 658.0
313
-------
Table V-55
POLLUTANT CONCENTRATIONS OF THE COOKED
PASTE SEPARATOR ELEMENT WASTE STREAMS
POLLUTANTS
Flow
Temperature (Deg C)
70 Dietnyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
*-Less than 0.01
1
59.9
*
0.00
0.00
0.01
0.00
0.00
0.08
0.00
0.13
0.03
0.00
85.0
2.97
0.01
13.0
119.
5.1
6.8
mg/1
Days
2
59.9
0.00
0.00
0.00
0.02
0.00
0.00
0.08
0.00
0.16
0.05
0.00
94.0
5.48
0.01
39.0
41.0
5.1
6.8
3
59.9
*
0.00
0.00
0.02
0.00
0.00
0.13
0.00
0.15
0.10
0.00
148.
14.2
0.01
11.0
62.0
5.9
6.3
314
-------
Table V-56
POLLUTANT MASS LOADINGS OF THE COOKED PASTE
SEPARATOR ELEMENT VJASTE STREAMS
mg/kg
Days
POLLUTANTS 12 3
Flow (I/kg) 0.05 0.05 0.03
Temperature (Deg C) 59.9 59.9 59.9
70 Diethyl phthalate 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.00 0.00 0.00
118 Cadmium 0.001 0.001 0.001
119 Chromium, Total 0.00 0.00 0.00
Chronium, Hexavalent 0.00 0.00 0.00
120 Copper 0.004 0.004 0.003
122 Lead 0.00 0.00 0.00
123 Mercury 0.01 0.01 0.002
124 Nickel 0.002 0.002 0.002
125 Selenium 0.00 0.00 0.00
128 Zinc 4.01 4.23 3.75
Manganese 0.14 0.25 0.36
Phenols, Total 0.001 0.00 0.00
Oil & Grease 0.61 1.75 0.28
Total Suspended Solids 5.62 1.84 1.57
pH, Minimum 5.1 5.1 5.9
pH, Maximum 6.8 6.8 6.3
315
-------
Table V-57
POLLUTANT CONCENTRATIONS OF THE PAPER
SEPARATOR (WITH MERCURY) ELEMENTS
WASTE STREAMS
POLLUTANTS
Temperature (Deg C)
70 Diethyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 Qircmium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
1
31.0
*
0.00
0.00
0.47
0.00
0.00
0.11
0.07
0.40
0.14
0.00
1.16
1.15
0.01
16.0
140.
8.3
8.3
ng/1
Days
2
31.1
*
0.00
0.00
0.02
0.00
0.00
0.08
0.00
0.16
0.02
0.00
0.41
1.25
0.09
7.00
7.00
7.5
8.5
3
30.0
*
0.00
0.00
0.02
0.00
0.00
0.09
0.00
0.14
0.03
0.00
0.23
0.43
0.05
83.0
96.0
8.5
8.6
316
-------
Table V-58
POLLUTANT MASS LOADINGS OF THE PAPER
SEPARATOR (WITH MERCURY) ELEMENT
WASTE STREAMS
Days
POLLUTANTS 12 3
Flow (I/kg) 0.11 0.17 0.15
Temperature (Deg C) 31.0 31.1 30.0
70 Diethyl phthalate * * *
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.00 0.00 0.00
118 Cadmium 0.05 0.003 0.004
119 Chromium, Total 0.00 0.00 0.00
Chromium, Hexavalent 0.00 0.00 0.00
120 Copper 0.01 0.01 0.01
122 Lead 0.01 0.00 0.00
123 Mercury 0.04 0.03 0.02
124 Nickel 0.02 0.003 0.004
125 Selenium 0.00 0.00 0.00
128 Zinc 0.13 0.07 0.04
Manganese 0.13 0.22 0.07
Phenols, Total 0.001 0.02 0.01
Oil & Grease 1.74 1.22 12.6
Total Suspended Solids 15.2 1.22 14.6
pH, Minimum 8.3 7.5 8.5
pH, Maximum 8.3 8.5 8.6
*-Less than 0.01
317
-------
Table V-59
FLOW RATES (I/kg) OP ANCILLARY OPERATION WASTE STREAMS
SAMPLING SURVEY
Plant DATA MEAN DATA, I/kg
Ref. No. VALUE, I/kg _
0.05
5(B) 0.01 0.04
I !
»»> °-01
»'" r
J*/r.» °'44
"(E) 0.44
0
18 0
19
318
-------
TABLE V-60
POLLUTANT CONCENTRATIONS OF THE
EQUIPMENT AND AREA CLEANUP ELEMENT
WASTE STREAMS
Co
i—«
V£>
flOIiUTANTS
CAYS
Tanperature (Deg C)
70 Diethyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 Oiromium, Total
Chrcnium, Itaxavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pi I, Minimum
pit, Maximum
I-Interfcrence
* Less than 0.01
1
59.9
*
0.00
0.07
0.04
0.25
0.00
0.22
0.07
I
0.78
0.070
220.
140.
0.06
33.0
2610.
7.5
10.4
Plant B
2
43.3
*
0.00
0.09
0.02
0.13
0.00
0.16
0.00
I
0.22
0.090
325.
3.82
I
482.
4220.
7.5
10.4
3
60.0
*
0.00
0.64
0.09
2.88
0.00
3.22
0.94
I
10.1
0.600
680.
383.
I
36.0
14200.
8.5
9.7
1
31.0
*
0.00
0.00
0.05
0.01
0.00
0.09
0.00
0.02
0.57
0.00
98.0
33.9
0.06
9.80
357.
6.2
8.6
Plant C
2
30.5
*
0.00
0.00
0.04
0.02
0.00
0.10
0.00
0.03
0.33
0.00
42.4
21.8
0.25
439.
395.
6.1
9.0
Plant E Plant B Plant D
30.1
*
0.00
0.00
0.19
0.28
0.00
0.11
0.00
0.03
0.37
0.00
33.8
13.3
0.04
96.1
471.
6.1
8.7
117.
1640.
0.03
410.
0.03
1.42
0.01
24.6
-------
Table V-61
POLLUTANT MASS LOADINGS OF THE
EQUIPMENT AND AREA CLEANUP ELEMENT
WASTE STREAMS
Plant B
Plant C
CO
rv>
o
POLLUTANTS
DAYS
Flow (I/kg)
Tenperature (Deg C)
70 Diethyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 (Titanium, Total
Chronium, Hexavalent
120 Capper
122 Leal
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pll. Maximum
1
0.01
59.0
0.00
0.00
0.001
0.00
0.002
0.00
0.002
0.001
I
0.01
0.001
1.84
1.17
0.00
0.28
21.8
7.5
10.4
2
0.01
43.3
0.00
0.00
0.001
0.00
0.001
0.00
0.002
0.00
I
0.002
0.001
3.55
0.04
I
5.27
46.1
7.5
10.4
3
0.01
60.0
0.00
0.00
0.01
0.001
0.03
0.00
0.04
0.01
I
0.11
0.007
7.66
4.32
I
0.41
160.
8.5
9.7
1
0.01
31.0
0.00
0.00
0.00
0.001
0.00
0.00
0.001
0.00
0.00
0.01
0.00
0.98
0.34
0.001
0.10
3.58
6.2
8.6
2
0.01
30.5
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.00
0.00
0.003
0.00
0.43
0.22
0.003
4.46
4.02
6.1
9.0
3
0.01
30.1
0.00
0.00
0.00
0.002
0.003
0.00
0.001
0.00
0.00
0.004
0.00
0.34
0.13
0.00
0.96
4.72
6.1
8.7
Plant E Plant B Plant D
0.44 0.04 6.37
51.5
722.
0.001
16.4
6.19
9.05
0.04
157.
I-Interferenoe
-------
Table V-62
STATISTICAL ANALYSIS (mg/1) OF THE
EQUIPMENT AND AREA CLEANUP ELEMENT WASTE
STREAMS
to
rv>
POLLUTANTS
Temperature (Deg C)
70 Dicthyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Itexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pi I, Minimum
pll, Maxinun
* Less than 0.01
Ntnfcer of values may include concentrations less than
0.005 shown as 0.00 on table.
Minimum
30.1
*
0.00
0.00
0.02
0.01
0.00
0.09
0.00
0.02
0.01
0.0
33.8
3.82
0.04
9.80
357.
6.1
8.6
Maximum
60.0
*
0.00
0.64
0.19
2.88
0.00
3.22
0.94
117.
10.1
0.60
1640.
383.
0.25
482.
14200.
8.5
10.4
Mean
45.1
*
0.00
0.13
0.07
0.60
0.00
0.65
0.15
19.8
1.80
0.13
431.
99.3
0.10
160.
3710.
6.98
9.47
Median
37.1
*
0.00
0.04
0.05
0.19
0.00
0.13
0.00
0.03
0.37
0.04
273.
27.9
0.06
36.0
1540.
6.85
9.35
1
Val
6
0
0
3
6
6
0
6
3
6
7
3
8
6
4
7
6
6
6
I
Zeros
0
6
6
3
0
0
6
0
4
0
0
3
0
0
0
0
0
0
0
I
Pts
6
6
6
6
6
6
6
6
7
6
7
6
8
6
4
7
6
6
6
-------
STATISTICAL ANALYSIS (mg/kg) OF THE
EQUIPMENT AND AREA CLEANUP ELEMENT
WASTE STREAMS
CO
ro
ro
POLLUTANTS
Flow
Temperature (Deg C)
70 Diethyl phthalate
114 Antijnony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
Minimum
Maximum
Mean
Median
0.01
30.1
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.00
0.00
0.002
0.00
0.34
0.04
0.00
0.10
3.58
6.1
8.6
6.37
60.0
0.00
0.00
0.01
0.002
0.03
0.00
0.04
0.19
51.5
0.11
0.007
722.
4.32
0.003
157.
160.
8.5
10.4
0.77
45.1
0.00
0.00
0.001
0.001
0.01
0.00
0.01
0.03
10.1
0.03
0.001
94.3
1.04
0.001
24.0
40.1
6.98
9.47
0.01
37.1
0.00
0.00
0.00
0.00
0.002
0.00
0.001
0.01
0.001
0.01
0.00
2.7
0.28
0.001
0.96
13.3
6.85
9.35
-------
Table V-64
STATISTICAL ANALYSIS OF THE LECLANCHE SUBCATAGORY
RAW WASTE CDNCENTRATIONS
CO
ro
co
MINIMUM
636.
30.1
*
0.00
0.00
0.02
0.01
0.00
0.10
0.00
0.04
0.09
0.00
30.6
5.16
0.01
10.2
342.
5.1
8.6
MAXIMUM
5880.
59.9
*
0.00
0.20
0.17
0.89
0.00
1.08
0.29
0.13
3.18
0.185
312.
128.
0.24
392.
4420.
6.2
10.4
MEAN
2640.
55.3
*
0.00
0.04
0.06
0.21
0.00
0.26
0.05
0.08
0.76
0.035
119.
36.6
0.06
110.
1150.
5.7
9.5
rEDIAN
1920.
43.8
*
0.00
0.01
0.04
0.03
0.00
0.10
0.00
0.07
0.32
0.01
98.2
21.6
0.03
56.8
464.
6.0
9.4
1
VAL
6
6
0
0
3
6
6
0
6
3
6
6
3
6
6
6
6
6
6
6
#
ZERO
0
0
6
6
3
0
0
6
0
3
0
0
3
0
0
0
0
0
0
0
*
PTS
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
POLLUTANTS
FLOW (I/day)
Temperature (Deg C)
70 Methyl phthalate
114 Antimony
115 Arsenic
118 Cadium
119 Oiranium,Total
Chrcmium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
Number of values may include concentrations less than 0.005
shown as 0.00 on table.
* Less than 0.01
-------
u>
TABLE V-65
NORMALIZED DISCHARGE FLOWS
LITHIUM SUBCATEGORY ELEMENTS
Mean Median Production Total Production
Discharge Discharge Weighted Mean Raw Waste tformalizing
Elements (I/kg) (I/kg) Raw Waste (lAg) \folume (1/yr) Parameter
Cathodes
Sulfur Dioxide 0 - + 2.83
Thionyl Chloride 108. 108. 108.
Iron Disulfide 7.54 7.54 7.54
Ancillary
Operations
Heat Paper + + + + + +
Production
1.1 x 104 Weight of
3.1 x 105 Weight of
1.7 x 105 Weight of
-i- + Weight of
Sulfur Dioxide
Thionyl Chloride
Iron Disulfide
Reactants
Lithium Scrap
Disposal
Leak Test
Weight of Cells Produced
Weight of Cells Produced
+ Cannot be determined from presently available data.
+ + See calcium anode discussion
-------
u>
rsj
Ui
TABLE V-66
NORMALIZED DISCHARGE FLOWS
MAGNESIUM SUBCATEGORY ELEMENTS
Mean
Discharge
Elements (lAg)
Cathodes
Silver Chloride 3310.
Cathode-Surface
Reduced
Silver Chloride 1637.
Cathode-Electro-
lytic
Vanadium Pentoxide 1652.
Cathode
Ancillary
Operations
Cell Test 52.6
Separator +
Processing
Floor Wash 2.9
Heat Paper -H-
Manufacture
Median Production
Discharge Weighted Mean
(lAg) Raw Waste (I/kg)
3310. 3310.
1637. 1637.
1652. 1652.
52.6 5.26
+ +
2.9 2.9
•H- 792.
Total
Raw Waste
\folume (1/yr)
8.8xl05
2.3xl05
3.6xl06
9.1xl04
3.6xl04
1.3xl04
6.8xl06
Production
Normalizing
Parameter
Weight of Depolarizer
Material
Weight of Depolarizer
Material
Weight of Depolarizer
Material
Weight of Cells Produced
Weight of Cells Produced
Weight of Cells Produced
Weight of Reactive
Materials
+ Cannot be calculated from present information.
4-fSee Calcium Anode
-------
Table V-67
MAGNESIUM SUBCATEGORY PROCESS
WASTEWATER FLOW RATES FROM
INDIVIDUAL FACILITIES
Plant ID #
A
B
C
D
E
F
G
H
Flow Rate
(I/day)
4.18 x 10'
0
872
0
2990
+
0
0
+ Not Available
326
-------
Table V-68
Cathodes
ZINC SUBCATEGORY PROCESS ELEMENTS
(REPORTED MANUFACTURE)
ZINC ANODES
Cast or
Fabricated
Zinc Powder
Wet Gelled
Amalgamated Analrjan
Zinc Oxide Powder
Dry Pasted or Pasted or
Amalgamated Pressed on Grid Pressed-Reduced
Electrodeposited
Agglo (Porous Carbon)
Manganese Dioxide-Carbon
co
r>o
Mercuric Oxide (and Mer-
curic Oxide-Manganese Dio-
xide-Carbon)
Mercuric Oxide-Cadmium Oxide
Silver Powder
Pressed Only
Pressed and Electrolytically
Oxidized
Silver Oxide
Reduced-Sintered and Electro-
lytically Fbrmed
Pressed
Blended (MnO_, Mg.O)
Blended (Incf. FlgO)
X
X
-------
Table v-68 (con't)
ZINC SUBCATEGORY PROCESS ELEMENTS
ZINC ANODES
Zinc Powder Zinc Oxide Povrier
Cast or Wet Gelled Dry Pasted or Pasted or
Cathodes Fabricated Amalgamated ftnalgan Amalgamated Pressed on Grid Pressod-Reduced Electrodeposited
X X
Silver Peroxide
Nickel-Sintered, Impregnated X
and Formed
Ancillary Operations
Cell Wash X
f^ Electrolyte Preparation X
oo
Silver Etch X
Mandatory Employee Wash ^
Reject Cell Handling X
Floor Wash X
Equipncnt Wash ^
Silver Powder Production X
Silver Peroixde Production X
-------
Table V-69
OBSERVED FLOW RATES FOR
EACH PLANT IN ZINC SUBCATEGORY
Plant Nuniber
A
B
c
D
E
F
G
H
I
J
K
L
M
N
O
P
+ Data not Available.
DCP Data
+
25,432.2
3,494.2
+
16,118.2
4,008.0
77,516.8
144,000
0
16.0
27,500
10,900.8
0
22,619.2
4,542.4
21,206.4
Observed Flow
Rate (I/day)
Ifean Visit
Data
3,722.9
101,892.2
27,271.2
23,305.5
54,186.1
11,506.4
9.687.1
13,471.6
329
-------
TABLE V-70
NORMALIZED DISCHARGE FLOWS
ZINC SUBCA1EOORY ELEMENTS
Mean
Discharge
Elements
Anodes
Zinc Powder-Wet
AmalgaTiated
Zinc Powder-Gelled
Amalgam
Zinc Oxide Sawder-
Pasted or Pressed,
Reduced
Zinc Electrodeposited
Silver Powder Pressed
and Electrolytically
Oxidized
Silver Oxide (Ag,0)
Powder-thermal ly
Reduced or Sintered,
Electrolytically
Formed
Silver Peroxide
Powder
Nickel Impregnated
and Formed
Ancillary Operations
Cell Wash
Electrolyte
Preparation
Silver Etch
Mandatory Employee
Wash
Reject Cell Handling
Floor Wash
Equipment Wash
Silver Peroxide
Production
Silver Powder
Production
dAg)
3.8
0.68
143.
3190.
196.
131.
31.4
1640.
6.35
0.12
49.1
0.27
0.01
0.1
7.1
52.2
21.2
Median
Discharge
(lAg)
2.2
0.68
117.
3190.
196.
131.
12.8
1720.
0.34
0.
49.1
0.27
0.002
0.1
7.1
52.2
21.2
Production
Weighted Mean.
Raw Waste (I/kg)
3.86
0.44
150.
2792.
141.
198.
8.78
1640.
1.47
0.071
49.1
0.27
0.002
0.026
5.88
15.9
21.2
Total
Raw Waste
UDlume (1/yr)
5.6xl06
4.8xl05
4.9xl06
l.SxlO7
7.5xl06
6.6xl04
2.3xl05
_
1.9xl07
1.3xl06
2.8xl03
2.6xl06
2.2xl04
2.4xl05
1.2xl06
3.7xl05
8.0xl05
Production
Normalizing
Parameter
Weight of Zinc
Weight of Zinc
Weight of Zinc
Weight of Deposited Zinc
Weight of Applied Silver
Weight of Applied Silver
Weight of Applied Silver
Weight of Deposited
Nickel
Weight of Finished Cells
Weight of Finished Cells
Height of Silver Processed
Weight of Finished Cells
Weight of Finished Cells
Height of Finished Cells
Weight of Finished Cells
Weight of Silver in
Peroxide Produced
Weight of Silver Powder
Produced
330
-------
Table V-71
TREAlWMr PRACTICES AND EFFLUENT QUALITY AT ZINC SUBCATBOORY PLANTS
EFFLUENT ANALYSIS
EPA ID
A
B
c
GJ
GJ
I-*
D
E
F
G
H
I
J
K
TOEATMJWT
pi! Adj-Settle-Filter
Settle
Settle
Filter-Carbon
Adsorption
Skim-Filter-Carbon
Adsorption
pH Adjust-Chon
Precipitation
Settle-Filter
pll Adjust-Chan
Precipitation-Settle
Filter-Carbon
Adsorption
Amalgamation-Settle
Amalgamation-Settle
Settle
Od Cr Cu CM Pb fig
0.8 .04
0.20 1.0 0.005 .01
0.10 8. 0.01 .8
ND 10. 10. .00017
.0086
.20
.10 .01
.21 .13
0.0005
0.076
.005 .047 .018 0.032
.0403 .006 .19
tli Ag Zn HHj Fe tti TSS pH
1.3
2.0 30. 6-9.5
.16 .02 274. 2.52 .84
10. 10. .37 10. .50 10.
2.1 4.1 11.7
.70
.74 10 2.9 92
ND .03
3.99
.005 1.24 .291 8. .281 200. 11.2
.143 .194 15. .235 8.2
-------
Table V-72
POLLUTANT CONCENTRATIONS IN THE ZINC POWDER
WET AMALGAMATED ANODE ELEMENT WASTE STREAMS
co
co
r\>
POLLUTANTS/DAYS
Ttepporature (Dog C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethyleno
38 Ethylbenzene
44 Methylenc chloride
55 Naphthalene
64 Pentachloroplienol
66 Bis(2-ethylhoxyl) phthalate
70 Dicthyl phthalate
85 Totrachloroethylene
86 Toluene
87 Trichlorocthylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Omnium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Ann. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Annonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pfl. Maximum
I-Interference
NA-IJot Analyzed
*-Less than 0.01
1
14.0
0.00
0.00
0.00
0.00
0.00
0.00
*
NA
NA
0.00
0.00
0.00
0.00
0.00
0.08
0.00
0.14
0.11
0.01
0.00
I
0.00
I
0.00
0.00
0.00
35.3
0.00
N7V
tIA
0.03
0.08
2.00
0.00
8.8
8.8
Plant
A
2
21.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.14
0.01
0.21
0.14
0.01
0.03
I
0.00
I
0.00
0.00
0.00
22.0
0.00
NA
MA
0.06
0.06
2.80
32.0
8.2
8.5
ng/i Plant
B
3
18.0
0.00
0.03
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.08
0.00
0.03
0.03
0.01
0.00
I
0.00
I
0.00
0.00
0.00
47.4
0.00
NA
NA
0.09
0.11
9.20
25.0
8.4
8.8
1
28.0
0.00
HA
NA
NA
NA
0.00
tIA
NA
0.04
MA
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.00
0.00
0.00
0.60
0.00
HA
0.02
450.
NA
NA
NA
0.04
0.00
10.0
5.00
4.3
6.5
2
28.0
0.00
NA
NA
HA
NA
0.00
NA
NA
*
NA
NA
NA
0.00
0.00
0.00
0.00
0.01
0.00
0.02
0.00
0.00
0.00
0.50
0.00
NA
0.01
1050.
NA
NA
NA
0.03
0.00
9.00
5.00
4.3
6.5
3
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.07
NA
NA
NA
0.00
0.00
0.00
0.00
0.02
0.00
0.00
0.00
0.00
0.00
0.26
0.00
NA
0.02
206.
NA
1IA
MA
0.01
0.00
22.0
5.00
4.3
6.5
-------
Table V-73
POLLUTANT MASS LOADINGS IN THE ZINC
POWDER-WET AMALGAMATED ANODE
ELEMENT WASTE STREAMS
(mg/kg)
co
co
oo
POLLUTANTS/DAYS
Flow (I/kg)
Temperature (Dog C)
11 1,1,1-Trlchloroethane
13 1,1-Dichloroethane
29 1,1-Dichlorocthylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naplithalcno
64 Bentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Dicthyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichlorocthylcne
114 Antimony
115 Arsenic
118 Cadmium
119 Omnium, Total
Chrcnium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Aral, to Chlor.
122 Lead
123 ftercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Anronia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pit, Minimum
pH, Maximum
I-Intorference
NA-Not Analyzed
1
5.17
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.41
0.01
0.72
0.57
0.03
0.00
I
0.00
I
0.00
0.00
0.00
182.
0.00
NA
NA
0.16
0.46
10.3
0.00
8.8
8.8
Plant
A
2
6.82
21.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.96
0.04
1.43
0.96
0.07
0.18
I
0.00
I
0.00
0.00
0.00
150.
0.00
NA
NA
0.38
0.38
19.1
218.
8.2
8.5
3
6.82
18.0
0.00
0.21
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.55
0.0
0.23
0.21
0.08
0.00
I
0.00
I
0.00
0.00
0.00
323.
0.00
NA
NA
0.61
0.75
62.7
171.
8.4
8.8
1
2.38
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.10
NA
NA
MA
0.00
0.00
0.00
0.0
0.01
0.00
0.09
0.00
0.00
0.00
1.43
0.00
NA
0.05
1070.
NA
NA
HA
0.10
0.00
23.8
11.9
4.3
6.5
Plant
B
2
1.88
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.00
NA
NA
NA
0.00
0.00
0.00
0.0
0.01
0.00
0.04
0.00
0.00
0.00
0.94
0.00
NA
0.03
1980.
NA
NA
HA
0.06
0.00
17.0
9.4
4.3
6.5
3
2.16
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.15
NA
NA
NA
0.00
0.00
0.00
0.0
0.04
0.00
0.00
0.00
0.00
0.00
0.56
0.00
NA
0.04
445.
NA
NA
NA
0.02
0.00
47.5
10.8
4.3
6.5
-------
Table V-74
STATISTICAL ANALYSIS (mg/1) OF THE ZINC
POWDER-WET AMALGAMATED ANODE ELEMENT
WASTE STREAMS
GO
POLLUfAHTS Minlmn
Taiperature (Dog C)
11 1,1,1-Trichloroethane
13 1,1-Dich loroathane
29 1,1-Dich loroethy lene
30 1,2-Trans-dichloroethylene
38 Ethylbenacne
44 Mothylene diloride
55 Naphthalene
64 Pentadiloroplwnol
66 Bis(2-cthyIhexyl) phthalate
70 Diethyl plithalate
85 Tetradiloroethylene
86 Toluene
87 Trich loroethy lene
114 Antimony
115 Arsenic
118 Cartiniun
119 Chromium, Total
Chromium, Ifexavalont
120 Copper
121 Cyanide, Total
Cyanide, Ann. to Chlor.
122 teal
123 Mercury
124 Nickel
125 Selcniin
126 Silver
128 Zinc
Aluminum
Arronia
Iron
Manganese
Phenols, Ttotal
Oil & Grease
Total Susimnclol Solids
pH, riinimun)
pFI, Maximn
NA-rtot Analyzed
*-T,oss tlian 0.01
Maximum
Mean
I
Median
*
Val
14.0
0.00
0.00
0.00
0.00
0.00
0.00
*
NA
0.01
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
0.26
0.00
0.00
0.00
22.0
0.00
NA
HA
0.01
0.00
2.00
0.00
4.3
6.r>
28.0
*
0.03
*
*
0.00
*
*
NA
0.07
*
*
0.00
*
0.00
0.14
0.01
0.21
0.14
0.04
0.03
0.00
0.00
0.60
0.00
0.00
0.02
1050.
0.00
NA
IA
0.09
0.11
22.0
32.0
8.8
8.8
22.6
*
*
*
*
0.00
*
*
NA
0.04
*
*
0.00
*
0.00
0.05
0.00
0.07
0.05
0.01
0.00
0.00
0.00
0.45
0.00
0.00
0.01
302.
0.00
NA
HA
0.04
0.04
9.20
12.0
6.4
7.6
24.5
*
0.00
0.00
0.00
0.00
0.00
*
NA
0.04
0.00
0.00
0.00
0.00
0.00
0.04
0.00
0.03
0.02
0.01
0.00
0.00
0.00
0.50
0.00
0.00
0.01
127.
0.00
NA
NA
0.04
0.03
9.10
5.00
6.1
7.5
6
3
1
1
1
0
1
3
3
1
1
0
2
0
3
2
6
3
5
1
0
0
3
0
0
3
6
0
6
3
6
5
f>
6
t
Zeros
0
3
2
2
2
3
5
0
0
2
2
3
4
6
3
4
0
3
1
5
3
6
0
6
3
3
0
3
Pts
6
6
3
3
3
3
6
3
3
3
3
3
6
6
6
6
6
6
6
6
3
6
3
6
3
6
6
3
-------
Table V-75
STATISTICAL ANALYSIS (rag/kg) OF THE ZINC
POWDER-WET AMALGAMATED ANODE ELEMENT
WASTE STREAMS
POLLUTANTS
Minirturi Plaxinun ftean Median
Flow (I/kg) 1.88 6.82 4.21 3.77
Temperature (Deg C) 14.0 28.0 22.6 24.5
11 l,i;I-TTichloroethane 0.00 0.00 0.00 0.00
13 1,1-Dichloroethane 0.00 0.21 0.07 0.00
29 1,1-Dichloroethylene 0.00 0.00 0.00 0.00
30 1,2-Trans-dichloroethylene 0.00 0.00 0.00 0.00
38 Ethylbenzene 0.00 0.00 0.00 0.00
44 Methylene chloride 0.00 0.00 0.00 0.00
55 Naphthalene 0.00 0.03 0.01 0.00
64 Pentachlorophenol NA NA NA NA
66 Bis(2-ethylhexyl) phthalate 0.01 0.15 0.09 0.10
70 Diethyl phthalate 0.00 0.00 0.00 0.00
85 Tetradiloroethylene 0.00 0.00 0.00 0.00
86 Toluene 0.00 0.00 0.00 0.00
- 1 :
•• :
119 £3£S£-- S:S : : :
ion rr^ner- 0.00 0.09 0.05 O.Ub
SSSe Total 0 00 0.18 0.03 0.00
S?to Chlor. 0.00 0.00 0.00 0.00
,„ .__., 0.00 0.00 0.00 0.00
l^ ieaa Q qg Q 94
l^T? S'oo u'.oo o.oo o.oo
SXSun S'-OO 0.00 0.00 0.00
126
125 Selenium ---- ^ Q>02 0>01
12H Zinc 150. 1980. 692. 384.
128 Zinc o.oo o.oo o.oo o.oo
NA I1A T1A NA
NA HA NA NA
0.02 0.61 0.22 0.13
0.00 0.75 0.26 O.I')
Oil & Grease 10.3 62.7 30.1 21.4
Total Suspended Solids 0.00 218. w.i "^
pH, Minimum 4.3 8.8 6.4 o-^
pH, Maximum 6-5 K*
Analyzed
335
-------
TABLE V-76
POLLUTANT CONCETRATIONS IN THE ZINC
POWDER-GELLED AMALGAM ANODE ELEMENT
WASTE STREAMS
(mg/1)
POLLWANTS/DAYS
CO
oo
01
e (D.>j C)
1,1,1-Trichloroothane
1, 1-nich loorxjthane
1,1-nidliloroethylene
l,2-Trans-didiloroet)iylene
Rthyllxsiizeno
Methylene diloride
Naphthalene
Pontndilorophenol
Bis(2-othylhoxyl) phtlialato
Diotliyl phthalate
Ttetradlloroothyloiie
'ftjliione
Trichloroethylene
Ant irony
Arsenic
Cadmium
ChraniiM, Total
Itexavaleiit
11
13
29
30
38
44
55
64
66
70
85
86
87
114
I 15
I U)
119
120 Dipper
121 Cyanide, Total
Cyanide, flrw. ho flilor.
122 fcart
123 rfcrwity
124 Nickel
125 Solon inn
126 Silver
128 Zinc
Aluminum
Anronid
Iron
rianganuso
Phenols, Total
Oil & Oronse
lot'il .Siisi>v>1.--l Sol bis
pil, Miniron
pll, Maxirioi
I-lnterforence
NA-tJot Analy»nl
* Less than 0.01
1
21.0
*
NA
NA
NA
NA
0.00
MA
0.00
0.01
NA
HA
rjA
*
0.00
1.06
o.on
0.00
0.00
0.67
MA
NA
0.00
I
0.00
riA
0.00
1100.
MA
10.4
NA
0.11
0.003
33.0
97.0
13.2
13.5
Plant
A
2
26.0
NA
NA
UA
MA
UA
NA
MA
0.00
0.01
NA
MA
HA
HA
0.00
1.05
0.12
0.04
0.00
0.54
NA
NA
0.00
I
0.00
NA
0.00
750.
NA.
5.30
MA
3.42
?to
MA
100.
13.2
13.2
3
22.0
0.03
NA
MA
MA
NA
0.00
NA
0.00
0.04
MA
MA
HA
*
0.00
0.81
0.07
0.07
I
0.62
NA
NA
0.00
I
0.00
NA
0.00
440.
NA
4.70
MA
4.65
0.00
26.0
NA
12.0
13.4
1
16.0
*
NA
MA
tR
MA
0.02
NA
0.04
0.01
MA
NA
MA
0.00
0.00
0.00
0.06
0.02
0.00
0.10
MA
0.01
0.10
O.Bl
0.01
NA
0.01
MA
NA
11.5
MA
2.09
0.00
7.77
414.
'to
NA
Plant
B
2
15.0
0.00
MA
NA
NA
MA
0.00
(A
0.00
0.00
NA
MA
NA
0.00
0.00
0.08
0.01
0.01
0.00
0.08
0.01
0.01
0.00
0.47
0.03
NA
0.00
133.
MA
1.57
MA
0.17
0.00
6.00
258.
m
HA
16.0
0.00
MA
NA
MA
MA
0.00
MA
0.00
*
MA
MA
NA
0.00
0.00
0.07
0.01
0.01
t
0.05
0.00
0.00
0.00
0.50
0.00
tIA
0.01
17.6
MA
0.17
NA
0.21
0.10
0.00
545.
HA
MA
-------
Table V-77
POLLIJTAHrrS/QAYS
POLLUTANT MASS LOADING IN THE ZINC
POWDER-GELLED AMALGAM ANODE ELEMENT
WASTE STREAM
(mg/kg)
Plant
A
123 1
Plant
B
to
CO
•vl
Flow (I/kg)
Tferjiorature (Dog C)
11 1,1,1-Trichloxoethanc
13 1,1-Dichloroothane
29 1,1-DichloroetJiylene
30 1,2-Traiis-dich loroothyleno
38 HtJiylbenzcno
44 Hethylenc chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-cthylhexyl) phthalatc
70 Dietnyl phthalatc
85 Totrachloroethylenc
86 Toluene
87 Tridilotnethylene
114 Ant irony
115 Arsenic
118 Cadmium
119 Chrcniun, Total
Chrmium, tlexavalcnt
120 Copper
121 Cyanide, Total
Cyanide, fim. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Sclcniun
126 Silver
128 Zinc
Aluminum
Arrtmia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspnndod Solids
pil, Minimum
pll, Maxirium
I-Interference
NA-Hot Analysed
0.23
21.0
0.001
HA
HA
NA
NA
0.00
NA
0.00
0.003
NA
NA
NA
0.001
0.00
0.24
0.02
0.00
0.00
0.15
NA
KA
0.00
I
0.00
NA
0.00
251.
NA
2.40
HA
0.03
0.001
7.52
22.1
13.2
13.5
0.21
26.0
NA
NA
NA
NA
NA
rev
NA
0.00
0.003
NA
NA
NA
NA
0.00
0.22
0.03
0.01
0.00
0.12
NA
NA
0.00
I
0.00
NA
0.00
159.
NA
1.12
NA
0.73
NA
MA
21.2
13.2
13.2
0.31
22.0
0.01
NA
NA
NA
NA
0.00
NA
0.00
0.01
NA
NA
NA
0.001
0.00
0.26
0.02
0.02
I
0.20
NA
NA
0.00
I
0.00
NA
0.00
138.
HA
1.50
NA
1.46
0.00
8.17
NA
12.9
13.4
0.65
16.0
0.001
NA
NA
NA
NA
0.02
NA
0.03
0.01
NA
NA
NA
0.00
0.00
0.00
0.04
0.01
0.00
0.07
NA
0.003
0.07
0.53
0.01
NA
0.01
NA
NA
7.47
NA
1.35
0.00
5.02
267.
HA
HA
1.08
15.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.00
0.09
0.01
0.02
0.00
0.09
0.01
0.01
0.00
0.51
0.03
NA
0.002
143.
NA
1.69
HA
0.18
0.00
6.46
277.
NA
NA
1.67
16.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.01
NA
NA
NA
0.00
0.00
0.12
0.01
0.01
I
0.09
0.00
0.00
0.00
0.83
0.00
NA
0.02
29.4
HA
0.28
HA
0.35
0.16
0.00
909.
NA
MA
-------
Table V-78
STATISTICAL ANALYSIS (mg/1) OF THE ZINC
POWDER-GELLED AMALGAM ANODE ELEMENT
WASTE STREAMS
POLLUTANTS
CO
CO
oo
Mininum
Terperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethanc
29 1,1-Dichloroethylenc
30 1,2-Trans-dichloroothyleno
38 Ethylbenzene
44 Methyleno chloride
55 Naphthalene
64 Pcntachlorophenol
66 Dis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chroniun, "total
Chroniun, Itexavalent
120 Copper
121 cyanide, Total
Cyanide, Aim. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil f> Grease
Total Suspended Solids
pll, Minimum
pll, maximum
NA-Not Analyzed
*-Less than 0.01
Maximun
Mean
15.0
0.00
*
NA
NA
NA
0.00
NA
0.00
*
NA
*
*
0.00
NA
0.00
0.01
0.00
0.00
0.05
0.00
0.00
0.00
0.47
0.00
0.06
0.00
17.6
3.13
0.17
0.52
0.11
0.00
0.00
97.0
12.9
13.2
26.0
.0.03
*
NA
NA
NA
0.02
NA
0.04
0.04
NA
*
*
*
NA
1.06
0.12
0.07
0.00
0.67
0.01
0.01
0.10
0.81
0.03
0.06
0.01
1100.
3.13
11.5
0.52
4.65
0.10
33.0
545.
13.2
13.5
20.3
0.01
*
NA
NA
NA
*
NA
*
0.01
NA
*
*
*
NA
0.51
0.06
0.02
0.00
0.34
0.00
0.00
0.02
0.59
0.01
0.06
0.00
488.
3.13
5.61
0.52
1.77
0.02
14.6
283.
13.1
13.4
an
18.5
*
*
NA
NA
NA
0.00
NA
0.00
0.01
NA
*
*
*
NA
0.45
0.07
0.02
0.00
0.32
0.00
0.00
0.00
0.50
0.00
0.06
0.00
440.
3.13
5.00
0.52
1.15
0.00
7.77
258.
13.2
13.4
*
Val
6
4
1
1
1
6
1
1
4
5
6
5
0
6
2
2
1
3
2
1
3
5
1
6
1
6
2
4
5
3
3
*
Zeros
0
1
0
5
0
0
0
1
1
0
1
4
0
1
1
5
0
4
0
3
0
0
0
0
0
3
1
0
0
0
I
Pts
6
5
1
6
6
1
1
5
6
6
6
4
6
3
3
6
3
6
1
6
5
1
6
1
6
5
5
5
3
3
-------
Table V-79
STATISTICAL ANALYSIS (mg/kg) OF THE ZINC
POWDER-GELLED AMALGAM ANODE ELEMENT
WASTE STREAMS
CO
co
vo
POLLWANTS Mininum
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichlorocthano
29 1,1-Dichlorocthylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Mcthylene chloride
55 Naphthalene
64 Pentachlorcphenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylenc
86 Toluene
87 Trichloroothylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chrcniun, Total
Chromium, Uexavalent
120 Copper
121 Cyanide, Total
Cyanide, Awn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluninum
Arwonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pll, Mininum
pll, Maxinuim
Maximum
Mean
Median
0.21
15.0
0.00
0.00
NA
NA
NA
0.00
NA
0.00
0.00
NA
0.00
0.00
0.00
NA
0.00
0.01
0.00
0.00
0.07
0.00
0.00
0.00
0.51
0.00
0.04
0.00
29.4
2.02
0.28
0.34
0.03
0.00
0.00
21.2
12.9
13.2
1.67
26.0
0.01
0.00
NA
NA
NA
0.02
NA
0.03
0.01
NA
0.00
0.00
0.00
NA
0.26
0.04
0.02
0.00
0.20
0.01
0.01
0.07
0.83
0.03
0.04
0.02
251.
2.02
7.47
0.34
1.46
0.17
8.17
909.
13.2
13.5
0.69
20.3
0.002
0.00
NA
NA
NA
0.00
NA
0.00
0.01
NA
0.00
0.00
0.00
NA
0.15
0.02
0.01
0.00
0.12
0.002
0.003
0.01
0.62
0.01
0.04
0.01
144.
2.02
2.40
0.34
0.68
0.03
5.44
299.
13.1
13.4
0.48
18.5
0.00
0.00
NA
HA
NA
0.00
NA
0.00
0.01
NA
0.00
0.00
0.00
NA
0.17
0.02
0.01
0.00
0.10
0.001
0.003
0.00
0.53
0.00
0.04
0.001
143.
.02
.58
.34
.54
0.00
6.46
267.
13.1
13.4
MA-Mot Analyzer!
-------
Table V-80
POLLUTANT CONCENTRATIONS IN THE ZINC OXIDE
POWDER-PASTED OR PRESSED, REDUCED ANODE
ELEMENT WASTE STREAMS
rag/1
POLLUTANTS
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
I-Interference
NA-Not Analyzed
*-Less than 0.01
Plant
A
2
15.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.08
0.07
0.03
0.00
0.30
NA
NA
0.08
0.10
0.00
0.00
0.12
53.0
0.00
NA
NA
0.01
NA
NA
122.
11.9
11.9
DAYS
3
13.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.11
0.06
0.06
I
0.61
NA
NA
0.14
0.16
0.02
0.00
0.27
129.
0.48
NA
NA
0.01
NA
NA
96.0
11.4
11.4
1
15.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.00
0.00
0.01
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.28
0.00
NA
NA
0.00
NA
NA
5.00
9.4
9.4
Plant
B
2
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.00
0.00
0.03
0.00
0.00
NA
NA
NA
NA
0.01
0.05
0.00
0.00
2.84
NA
NA
NA
0.00
NA
NA
5.00
9.4
9.4
340
-------
Table V-81
POLLUTANT MASS LOADINGS IN THE ZINC OXIDE
POWDER-PASTED & PRESSED, REDUCED ANODE
ELEMENT WASTE STREAMS
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1, 1-Dichloroethy lene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
I-Interference
NA-Not Analyzed
Plant mg/kg
2
81.9
15.0
0.00
0.00
0.00
0.00
0.00
0.01
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
6.56
5.82
2.05
0.00
24.6
NA
NA
6.39
8.20
0.00
0.00
9.83
4340.
0.00
NA
NA
0.82
NA
NA
10000.
NA
NA
A
3
151.
13.0
0.02
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
16.7
8.78
8.93
I
92.4
NA
NA
21.2
24.2
3.48
0.00
40.9
19500.
72.7
NA
NA
0.91
NA
NA
14500.
NA
NA
DAYS
1
315.
15.0
0.00
0.03
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
3.47
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
88.3
0.00
NA
NA
0.00
NA
NA
1580.
NA
NA
Plant
B
2
239.
10.0
0.00
0.02
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
8.13
0.00
0.00
NA
NA
NA
NA
3.35
12.0
0.00
0.00
679.
NA
NA
NA
0.00
NA
NA
1200.
NA
NA
341
-------
Table V-82
STATISTICAL ANALYSIS (mg/1) OF THE ZINC
OXIDE POWDER-PASTED OR PRESSED REDUCED
ANODE ELEMENT WASTE STREAMS
FOLUn-AHTS
riinijnuRi
(Deg C)
11 1,1,1-Trichloroethano
13 1,1-Dichlorocthane
29 1,1-Dichloroethylenc
30 1,2-Trans-dichlorocthyleno
38 Ethylbenzcnc
44 Mothylene chloride
55 Naphthalene
64 Pcntachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl Phthalate
85 Ttetrachloroethylene
86 Ttoluone
87 Trichloroethylene
114 Antirony
115 Arsenic
118 Cactadum
119 Chronium, Ttotal
Quronium, Ifexavalent
120 Copper
121 cyanide, -total
Cyanide, Amn. to Chlor.
122 liad
123 r^rcurv
126 Silver
128 ZinT
128 SSu«
Iron
Phenols, -total
Oil £, Grease
ftflld.
pH, Minimum
pH, Maxinum
Ilaximum
ftean
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.28
0.00
NA
NA
0.00
HA
NA
5.00
lift
NA
15.0
*
*
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
*
0.00
0.00
0.11
0.07
0.06
0.00
0.61
NA
NA
0.14
0.16
0.05
0.00
0.27
129.
0.48
NA
NA
0.01
NA
NA
122.
NA
NA
12.9
*
*
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
*
0.00
0.00
0.05
0.04
0.02
0.00
0.30
NA
NA
0.07
0.07
0.02
0.00
0.10
46.3
0.16
NA
NA
0.00
NA
NA
57.0
NA
NA
ttedian
NA-ftot Analyzed
Nutter of^lues nay include concentrations less than 0.005 shown as 0.00 on table.
Val
14.0
0.00
*
0.00
0.00
0.00
0.00
0.00
IIA
NA
0.00
0.00
*
0.00
0.00
0.04
0.05
O.Oi
0.00
0.30
NA
NA
0.08
0.06
0.01
0.00
0.06
27.9
0.00
NA
NA
0.00
NA
NA
50.5
4
1
2
0
0
0
1
0
0
0
2
0
0
2
4
2
0
2
2
3
2
0
2
4
1
2
4
Zeros
0
3
A
4
1
1
2
4
2
0
2
Pts
4
4
j
«
I
4
4
4
I
«
4
4
4
4
3
3
-------
Table V-83
STATISTICAL ANALYSIS (mg/kg) OF THE ZINC
OXIDE POWDER-PASTED OR PRESSED, REDUCED
ANODE ELEMENT WASTE STREAMS
POLLUTANTS Minimum
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Didiloroethane
29 1, 1-Dichloroethylene
30 1,2-Trans-didiloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antinony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA-Not Analyzed
Maxijnum
Mean
Median
81.9
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
3.47
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
88.3
0.00
NA
NA
0.00
NA
NA
1200.
9.4
9.4
315.
15.0
0.02
0.03
0.00
0.00
0.00
0.01
0.00
NA
NA
0.00
0.00
1.26
0.00
0.00
16.7
8.78
8.93
0.00
92.4
NA
NA
21.2
24.2
12.0
0.00
40.9
19500.
72.7
NA
NA
0.91
NA
NA
14500.
11.9
11.9
197.
12.9
0.00
0.01
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.38
0.00
0.00
5.80
6.55
2.75
0.00
39.0
NA
NA
9.20
8.94
3.86
0.00
12.7
6160.
24.2
NA
NA
0.43
NA
NA
6830.
10.5
10.5
195.
14.0
0.00
0.01
0.00
0.00
0.
0.
0.
,00
.00
.00
NA
NA
0.00
0.00
.12
.00
0.
0.
5.
1.
0.00
3.28
6.98
1.02
0.00
24.6
NA
NA
6.39
.77
.74
0.00
4.92
2510.
0.00
NA
NA
0.41
NA
NA
5790.
10.4
10.4
343
-------
Table V-84
POLLUTANT CONCENTRATIONS IN THE ZINC
ELECTRODEPOSITED ANODE ELEMENT WASTE
STREAMS (Plant A)
mg/1
POLLUTANTS DAYS _
123
Temperature (Deg C) 9.0 10.0 7.0
11 1,1,1-Trichloroethane 0.00 0.00 O.ou
13 1,1-Didiloroethane 0.00 0.00 0.00
29 1,1-Dichloroethylene 0.00 0.00 u.w
30 1,2-Traiis-dichloroethylene 0.00 0.00 u.uu
38 Ethylbenzene 0.00 0.00 0.00
44 Methylene diloride 0.00 0.00 0.00
55 Naphthalene 0.00 0.00 0 00
64 Pentachlorophenol NA NA NA
66 Bis(2-€thylhexyl) phthalate NA NA "J
70 Diethyl phthalate 0.00 0.00 0.00
85 Tetrachloroethylene 0.00 0.00 O.OU
86 Toluene 0.00 0.00 0.00
87 Trichloroethylene 0.00 0.00 0.00
114 Antirony 0.00 0.00 0.00
115 Arsenic 0-°° 0'00 0'00
i" ^^ s-ss TO? n°i
119 Chrmium, Total 0.02 0.02 0.01
Chroniun, Hexavalont 0.00 0.00 0.00
120 Conner °-01 °'02
121 C^Se, Total 0.01 0.01 0.01
|ani,e, a., to Cnlor. 0.01 0.01 0.01
123 25ury 30.8 0.00 13.3
° '
nno
125 Selenium 0.00 0.00 0.00
126 Silver 0.07 0.03 0.43
1 -7R 7inr 12.1 \.i.S. Lt.*
128 l^10. o oo o.oo o.oo
IF * °i? °-
Oil & Grease . . .
"otal Suspended Solids 10.1 10.0 3.40
pH Mndrun
NA-Ifot Analyzeci
*-Less than 0.005
344
-------
Table V-85
POLLUTANT MASS LOADINGS IN THE ZINC
ELECTRODEPOSITED ANODE ELEMENT WASTE
STREAMS (Plant A)
mg/kg
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Didhloroethylene
30 if2-Trans-dichloroethylene
38 Ethylbensene
44 Methylene chloride
55 Naphthalene
64 Pentaohlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroetliylene
86 Toluene
87 Trichloroethylene
114 Antinony
115 Arsenic
118 Cadniun
119 Chromium, Total
Chrcmiun, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Ann. to Chlor.
122 Lead
123 rfercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Miniinum
pH, Maxinun
NA-Not Analyzed
1
4660.
9.0
0.00
0.00
0.47
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
72.7
0.00
55.7
46.6
23.3
184.
143000.
23.9
0.00
303.
56600.
0.80
6520.
NA
2.27
32.6
4660.
47000.
NA
NA
DAYS
2
5370.
10.0
0.00
0.00
0.54
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
32.2
0.00
107.
26.8
26.8
0.00
0.00
0.00
0.00
166.
65500.
.0.00
1503.
NA
0.00
5.37
40800.
53700.
NA
NA
3
4870.
7.0
0.00
0.00
0.49
0.00
0.00
0.00
2.44
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.02
61.9
0.00
39.6
24.4
24.4
35.5
65100.
19.7
0.00
2100.
60600.
0.97
1360.
NA
2.12
4.87
20000.
16600.
NA
NA
345
-------
Table V-86
NORMALIZED FLOWS OF POST-FORMATION
RINSE HASTE STREAMS
Waste Stream
Post-formation Rinsing
Plant ID#
A
A
A
B
B
C
(Mean
(Median
I/kg
79.7*
1135. 5*1/
100.9*
262.6
341.8
*
Plant
Mean
90.3
302.2
196.25)
196.25)
* This flow rate reflects the combined wastewater from post-formation
rinsing, floor area maintenance, and lab analysis.
+ Data not provided in survey
1/ Value for this day eliminated from statistical analysis because
of extreme variablility in floor area maintenance water use.
346
-------
Table V-87
POLLUTANT CONCENTRATIONS IN THE SILVER
POWDER PRESSED AND ELECTROLYTICALLY
OXIDIZED ELEMENT WASTE STREAMS
Plant mg/1 Plant
A B
POLLUTANTS Days
12313
Temperature (Deg C) 14.0 15.0 15.0 15.0 15.0
11 1,1,1-Trichloroethane 0.00 0.00 * 0.00 0.00
13 1,1-Dichloroethane 0.00 0.00 0.00 0.00 0.00
29 1,1-Dichloroethylene 0.00 0.00 0.00 0.00 0.00
30 1,2-Trans-dichloroethylene 0.00 0.00 0.00 0.00 0.00
38 Ethylbenzene 0.00 0.00 0.00 0.00 0.00
44 Methylene chloride 0.00 0.00 0.00 0.00 0.00
55 Naphthalene 0.00 0.00 0.00 0.00 0.00
64 Pentachlorophenol NA NA NA NA NA
66 Bis(2-ethylhexyl) phthalate NA NA NA NA NA
70 Diethyl phthalate 0.00 0.00 0.00 0.00 0.00
85 Tetrachloroethylene 0.00 0.00 0.00 0.00 0.00
86 toluene 0.00 * 0.00 * *
87 Trichloroethylene 0.00 0.00 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00 0.00 0.00
115 Arsenic 0.11 0.00 0.00 0.00 0.00
118 Cadmium 0.08 0.01 0.07 0.06 0.00
119 Oironium, Total 0.01 0.01 11.6 0.00 0.00
Chratiium, Hexavalent I 0.00 0.00 0.00 0.00
120 Copper 1.21 4.11 4.73 0.00 0.00
121 Cyanide, Total NA NA NA NA NA
Cyanide, Amn. to Chlor. NA NA NA NA NA
122 Lead 0.69 0.20 0.82 0.00 0.00
123 Mercury 0.06 0.01 0.01 0.01 0.07
124 Nickel 0.25 0.05 0.59 0.05 0.00
125 Selenium 0.00 0.00 0.00 0.00 0.00
126 Silver 0.64 0.32 1.48 3.88 3.20
128 Zinc 235. 29.4 59.0 0.00 0.00
Aluminum 0.00 0.00 4.44 0.00 0.00
Ammonia NA NA NA NA NA
Iron NA NA NA NA NA
Manganese 0.01 0.02 0.04 0.00 0.01
Phenols, Total NA NA NA NA NA
Oil & Grease NA NA NA NA NA
Total Suspended Solids 362. 86.0 217. 5.00 49.0
pH, Minimum 10.6 11.8 10.6 11.0 10.8
pH, Maxijnum 11.8 11.8 10.6 11.0 11.0
NA-Not Analyzed
*-Less than 0.01
347
-------
Table V-88
POLLUTANT MASS LOADINGS IN THE SILVER
POWDER PRESSED AND ELECTROLYTICALLY
OXIDIZED CATHODE ELEMENT WASTE STREAMS
POLLUTANTS
Plow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
I-Interference
NA-Not Analyzed
1
79.7
14.0
0.00
0.00
0.00
0.00
0.00
*
0.04
NA
NA
0.04
0.00
0.00
0.01
0.00
8.77
6.53
0.56
I
96.4
NA
NA
55.0
4.78
19.9
0.00
51.0
18700.
0.00
NA
HA
0.72
NA
NA
28800.
10.6
11.8
Plant
A
2
1140.
15.0
0.11
0.00
0.00
0.00
0.00
0.11
0.57
NA
NA
0.00
0.00
2.27
0.11
0.00
0.00
9.08
7.95
0.00
4670.
NA
NA
227.
10.2
56.8
0.00
363.
33400.
0.00
NA
NA
27.3
NA
NA
97700.
11.8
11.8
mg/kg
Days
3
101.
15.0
0.06
0.00
0.00
0.00
0.00
0.01
0.51
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
6.56
1170.
0.00
477.
NA
NA
82.8
1.72
59.6
0.00
149.
5960.
488.
NA
NA
4.04
NA'
NA
21900.
10.6
10.6
Plant
1
263.
15.0
0.00
0.03
0.00
0.00
.0.00
0.00
0.00
NA
NA
0.00
0.00
0.26
0.00
0.00
0.00
14.4
0.00.
0.00
0.00
NA
NA
0.00
2.89
12.6
0.00
1020.
0.00
0.00
NA
NA
0.00
NA
NA
1310.
11.0
11.0
B
3
342.
15.0
0.00
0.03
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.68
0.00
0.00
0.00
1.37
0.00
0.00
0.00
NA
NA
0.00
24.3
0.00
0.00
1090.
0.00
0.00
NA
NA
2.74
NA
NA
16700.
10.8
11.0
348
-------
Table V-89
STATISTICAL ANALYSIS (mg/1) OF THE SILVER
POWDER PRESSED AND ELECTROLYTICALLY
OXIDIZED CATHODE ELEMENT WASTE STREAMS
co
4s»
vo
POLLUTANTS
Minimum
Temperature (Deg C) 14.0
11 1,1,1-Trichloroethane 0.00
13 1,1-nichloroethane 0.00
29 1,1-nichloroethylene 0.00
30 1,2-Trans-dichloroethylene 0.00
38 Ethylbenzene 0.00
44 Mcthylene chloride 0.00
55 Naphthalene 0.00
64 Pcntnchlorophenol NA
66 Bis(2-othylhexyl) phthalate NA
70 Diethyl phtJialate 0.00
85 Tetrachloroethylene 0.00
86 Toluene 0.00
87 Trichloroethylene 0.00
114 Antimony 0.00
115 Arsenic 0.00
118 Cadmium 0.00
119 Chromium, Total 0.00
Qiromiun, Itexavalent 0.00
120 Copper 0.00
121 Cyanide, Total NA
Cyanide, Amn. to Chlor. NA
122 Lead 0.00
123 Mercury 0.01
124 Nickel 0.00
125 Selenium 0.00
126 Silver 0.32
128 Zinc 0.00
Aluminun 0.00
Armonia MA
Iron HA
Manganese 0.00
Phenols, Total NA
Oil & Grease MA
Total Suspended Solids 5.00
pli, Minimum 10.6
pil, Maximum 10.6
NA-Not Analyzed
*-Less than 0.01
Maximum
15.0
0.00
0.00
0.00
NA
NA
*
0.00
Mean
Median
*
Val
15.0
0.00
0.00
0.00
NA
NA
*
0.00
0.00
0.11
0.08
11.6
0.00
4.73
NA
NA
0.82
0.07
0.59
0.00
3.88
235.
4.44
MA
tlA
0.04
NA
tlA
362.
11.8
11.8
0.00
0.02
0.04
2.32
0.00
2.01
NA
NA
0.34
0.03
0.19
0.00
1.90
64.7
0.89
NA
NA
0.02
NA
MA
144.
11.0
11.2
15.0
0.00
0.00
0.00
0.00
0.00
*
*
NA
MA
0.00
0.00
It
0.00
0.00
0.00
0.06
0.01
0.00
1.21
NA
NA *
0.20
0.02
0.05
0.00
1.48
29.4
0.00
HA
NA
0.01
HA
NA
86.0
10.8
11.0
5
2
2
0
0
0
3
3
1
0
3
2
0
1
5
3
0
3
3
5
4
0
5
3
1
4
5
5
5
t
Zeros
0
3
3
5
5
5
2
2
Pts
5
5
5
5
5
5
5
5
-------
Table V-90
STATISTICAL ANLYSIS (mg/kg) OF THE SILVER
POWDER PRESSED AND ELECTROLYTICALLY
OXIDIZED CATHODE ELEMENT WASTE STREAMS
POLLUTANTS
Minimum
Maximum
Mean
Median
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antiinony
115 Arsenic
118 Cadmium
119 Oircnium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide,
Cyanide,
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA-Not Analyzed
Total
Aim. to Chlor.
79.7
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
1.37
0.00
0.00
0.00
NA
NA
0.00
1.72
0.00
0.00
51.0
0.00
0.00
NA
NA
0.00
NA
NA
1310.
10.6
10.6
1135.5
15.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
8.77
14.4
1170.
0.00
4670.
NA
NA
227.
24.3
59.6
0.00
1090.
33400.
448.
NA
NA.
27.3
NA
NA
97700.
11.8
11.8
384.1
15.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
1.75
7.60
236.
0.00
1050.
NA
NA
73.0
8.78
29.8
0.00
535.
11600.
89.6
NA
NA
6.95
NA
NA
33300.
11.0
11.2
262.6
15.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
6.56
0.56
0.00
96.4
NA
NA
55.0
4.78
19.9
0.00
363.
5960.
0.00
NA
NA
2.74
NA
NA
21900.
10.8
11.0
350
-------
TABLE V-91
POLLUTANT CONCENTRATIONS IN THE SILVER
OXIDE (A920) POWDER-THERMALLY REDUCED
AND SINTERED, ELECTROLYTICALLY FORMED
CATHODE ELEMENT WASTE STREAMS
(Plant B)
mg/1
Days
POLLUTANTS 2 3
Temperature (Deg C) 10.0 16.0
11 1,1,1-Trichloroethane 0.00 0.00
13 1,1-Dichloroethane * 0.00
29 1,1-Dichloroethylene * *
30 1,2-Trans-dichloroethylene 0.00 0.00
38 Ethylbenzene 0.00 0.00
44 Methylene chloride * 0.00
55 Naphthalene * *
64 Pentachlorophenol NA NA
66 Bis(2-ethylhexyl) phthalate NA NA
70 Diethyl phthalate * *
85 Tetrachloroethylene 0.00 0.00
86 Toluene 0.00 0.00
87 Trichloroethylene 0.00 0.00
114 Antimony 0.00 0.00
115 Arsenic 0.00 0.00
118 Cadmium 0.00 0.00
119 Chromium, Total 0.01 0.01
Chromium, Hexavalent 0.00 0.00
120 Copper 0.00 0.00
121 Cyanide, Total 0.01 0.00
Cyanide, Amn. to Chlor. 0.01 0.01
122 Lead 0.00 0.00
123 Mercury 0.01 0.02
124 Nickel 0.00 0.00
125 Selenium 0.00 0.00
126 Silver 0.30 16.7
128 Zinc 0.02 0.01
Aluminum 0.35 0.00
Ammonia 0.84 0.28
Iron NA NA
Manganese 0.00 0.00
Phenols, Total 0.00 0.02
Oil & Grease 12.0 9.30
Total Suspended Solids 6.10 1.00
pH, Minimum 12.4 9.0
pH, Maximum 12.4 9.0
NA-Not Analyzed
*-Less than 0.01
351
-------
Table V-92
POLLUTANT MASS LOADINGS IN THE SILVER
OXIDE (Ag20) POWDER-THERMALLY REDUCED
AND SINTERED, ELECTROLYTICALLY FORMED
CATHODE ELEMENT WASTE STREAMS
(Plant B)
mg/kg
Days
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Didiloroethy lene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chronium,
120 Copper
121 Cyanide,
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
NA-Not Analyzed
Hexavalent
Total
437.4
10.0
0.00
0.00
0.
0.
0.
.04
.00
.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
.00
.00
4.37
0.00
0.88
0.
0.
.62
.19
.00
.69
.00
.00
^44
2
2
0
5
0
0
131
7
153.
367.
NA
0.00
1.75
5250.
2670.
12.4
12.4
100.9
16.0
0.00
0.00
0.01
0.00
0.00
0.00
0.00
NA
NA
0.00
.00
.00
.00
.00
.00
.00
.71
.00
.00
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.51
0.51
0.00
.02
.00
.00
2.
0.
0.
1690.
1.11
0.00
28.3
NA
0.00
1.72
939.
101.
9.0
9.0
352
-------
Table V-93
POLLUTANT CONCENTRATIONS IN THE SILVER
PEROXIDE (AgO) POWDER CATHODE ELEMENT
WASTE STREAMS
mg/1
POLLUTANTS
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorcphenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadnium
119 Chronium, Total
Chronium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Aim. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
I-Interference
NA-Not Analyzed
*-Less than 0.01
Plant B
38.0
0.00
0.00
*
0.00
0.00
0.00
*
NA
NA
*
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.00
45.2
0.45
0.00
1.10
NA
0.00
0.00
16.0
620.
NA
NA
Days
1
NA
0.00
0.00
0.00
0.00
0.00
*
*
NA
NA
0.00
0.00
0.00
0.00
0.00
5.75
5.99
0.22
I
0.00
NA
NA
0.00
I
0.00
3.87
71.0
0.01
0.00
NA
NA
0.00
NA
NA
310.
NA
NA
2
NA
0.00
0.00
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
3.95
2.25
0.09
I
0.00
NA
NA
0.00
I
0.00
2.87
48.6
0.05
0.00
NA
MA
0.00
NA
NA
178.
NA
NA
3
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
3.38
3.38
0.16
I
0.00
NA
NA
0.00
I
0.00
2.20
8.80
0.03
3.56
NA
NA
0.00
NA
NA
730.
NA
NA
353
-------
Table V-94
POLLUTANT MASS LOADINGS IN THE SILVER
PEROXIDE (AgO) POWDER CATHODE ELEMENT
WASTE STREAMS
nig/kg
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
I-Interference
NA-Not Analyzed
Plant C
541
75.7
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.61
0.00
0.98
0.53
0.38
0.00
0.53
0.61
0.00
3420.
34.1
0.00
83.3
NA
0.00
0.08
1210.
46900.
9.0
9.0
Days
1
5.54
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
31.8
33.2
1.22
I
0.00
NA
NA
0.00
I
0.00
21.4
393.
0.08
0.00
NA
NA
0.00
NA
NA
1720.
10.0
11.0
Plant B
2
22.4
NA
0.00
Q.OO
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
88.3
50.3
1.97
I
0.00
NA
NA
0.00
I
0.00
64.1
1090.
1.12
0.00
NA
NA
0.00
NA
NA
3980.
11.0
13.0
3
10.4
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
35.2
35.2
1.67
I
0.00
NA
NA
0.00
I
0.00
22.9
91.7
0.31
37.1
NA
NA
0.00
NA
NA
7610.
10.0
13.0
354
-------
Table V-95
STATISTICAL ANALYSIS (mg/1) OF THE SILVER
PEROXIDE (AgO) POWDER CATHODE ELEMENT
WASTE STREAMS
co
en
in
POLLUTANTS
Flow
Temperature (Dcg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethano
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 nthylbenzene
44 Hethylcne chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetradiloroethylene
86 Toluene
87 Trichloroethylene
114 Antinony
115 Arsenic
118 Cadniuri
119 Chronium, Total
Chronium, Ilexavalent
120 Copper
121 Cyanide, Total
Cyanide, Am. to Chlor.
122 Load
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Alininum
Arronia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pll, Minimum
pll, flaxinurn
NA-Not Analyzed
*-}jcss than 0.01
Mininun
Maxinun
Mean
Median
*
Val
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.01
0.00
0.01
0.00
0.00
8.80
0.01
0.00
1.10
HA
0.00
0.00
16.0
178.
9.0
9.0
38.0
*
0.00
*
0.00
0.00
*
*
NA
NA
*
0.00
0.00
0.00
0.00
5.75
5.99
0.22
0.00
0.01
0.01
0.01
0.00
0.01
0.01
3.87
71.0
0.45
3.56
1.10
NA
0.00
0.00
16.0
730.
11.0
13.0
38.0
*
0.00
*
0.00
0.00
*
*
NA
NA
*
0.00
0.00
0.00
0.00
3.27
2.91
0.12
0.00
0.00
0.01
0.01
0.00
0.01
0.00
2.24
43.4
0.14
0.89
1.10
NA
0.00
0.00
16.0
460.
10.0
11.5
38.0
0.00
0.00
0.00
0.00
0.00
*
*
NA
HA
0.00
0.00
0.00
0.00
0.00
3.67
2.82
0.12
0.00
0.00
0.01
0.01
0.00
0.01
0.00
2.54
46.9
0.04
0.00
1.10
NA
0.00
0.00
16.0
465.
10.0
12.0
1
1
0
1
0
0
2
2
1
0
0
0
0
3
3
4
0
1
1
1
0
1
1
3
4
4
1
1
0
1
1
4
4
4
*
Zeros
0
3
4
3
4
4
2
2
3
4
4
4
4
1
1
0
1
3
0
0
4
0
3
1
0
0
3
0
4
0
0
0
0
0
I
Pts
4
4
4
4
4
4
4
4
1
4
1
1
4
1
4
4
4
4
4
1
4
1
1
4
4
4
Number of values nay include concentrations less than 0.005 shown as 0.00 on table.
-------
Table V-96
STATISTICAL ANALYSIS (rag/kg) OF THE SILVER
PEROXIDE (AgO) POWDER CATHODE ELEMENT
WASTE STREAMS
CO
in
Foujmwrs
Plow (l)
Tonperature (Dog C)
11 1,1,1-Trichloroethanc
13 1,1-Dich loroethane
29 1,1-Dichloroethylenc
30 1,2-Trans-dichloroethylenc
38 Ethylbenzcne
44 Motnylone chloride
55 Naphthalene
64 Pcntaohlorophonol
66 Bis(2-cthylhexyl) phthalate
70 Dicthyl phthalate
85 Tetrachloroothylene
86 Toluene
87 Trichloroe£hylene
114 Antijnony
115 Arsenic
llfl Cadmium
Chrrmium, Total
Chromium, Hexavalent
120 CopfMr
121 Cyanide, Total
Cyanide, Aim. to Chlor.
122 tead
123 Hcrcury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Annemia
Iron
flanganese
Phenols, Total
Oil & Crease
Total Suspended Solids
pH, Minimum
pll, Haxunum
Minimum
Maximum
Mean
Median
5.54
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.61
0.00
0.00
0.53
0.38
0.00
0.53
0.00
0.00
91.7
0.08
0.00
83.3
HA
0.00
0.08
1210.
1720.
9.0
9.0
75.7
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
[ft
NA
0.00
0.00
0.00
0.00
0.00
88.3
50.3
1.97
0.00
0.98
0.53
0.38
0.00
0.53
0.61
64.1
3420.
34.1
37.1
83.3
MA
0.00
0.08
1210.
46900.
11.0
13.0
28.5
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
38.8
29.7
1.37
0.00
0.25
0.53
0.38
0.00
0.53
0.15
27.1
1250.
8.89
9.27
83.3
NA
0.00
0.08
1210.
15100.
10.0
11.5
16.4
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
33.5
34.2
1.44
0.00
0.00
0.53
0.38
0.00
0.53
0.00
22.2
740.
0.72
0.00
83.3
HA
0.00
0.08
1200.
5790.
10.0
12.0
NA-Not Analyzed
-------
Table V-97
PRODUCTION NORMALIZED DISCHARGES FROM
CELL WASH ELEMENTS
WASTE
STREAM
Cell Wash
Wastewater
PLANT
ID f
A
B
C
D
E
F
G
RAN<2
I/kg
DCP
DATA
I/kg
4.6
5.0
34.1
0.33
MEAN
I/kg
IEAN
SAMPLING
DATA
I/kg
0.09
0.34
0.21
MEDIAN
I/kg
0.09- 34.1
6.35 o.34
-------
TABLE V-98
POLLUTANT CONCENTRATIONS IN THE CELL WASH
ELEMENT WASTE STREAMS
mg/1
Plant E
co
in
00
Plant G
11
13
29
30
38
44
55
64
66
70
85
86
87
114
115
118
119
1 *3rt
120
121
122
123
124
125
126
128
PQLLOTANTS
Temperature (Deg C)
1,1,1 - Trichloroethane
1,1 - Dichloroethane
1,1 - Dichloreethylene
1,2 - Trans-dichloroethylene
Rthylbenzene
Mothylcne chloride
Naphthalene
Bentachlorophenol
Bis(2-ethylhexyl) phthalate
Diethyl phthalate
Tatrachloroothylene
Toluene
Tridiloroethylene
Antimony
Arsenic
Cadmium
Chromium, Total
Chronium, Hexavalent
Cyanide, Total
Cyanide, Amn. to Chlor.
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil fc Grease
Total Suspended Solids
pi!, minimum
pit, maximum
1
29.8
0.01
NA
NA
NA
NA
0.00
NA
0.00
0.04
NA
NA
NA
0.01
0.00
0.00
0.00
0.03
0.00
0.27
NA
NA
0.01
0.02
3.82
NA
0.00
3.67
NA
1.46
MA
im
17.6
0.02
41.4
21.6
80
• y
11.4
2
30.3
*
NA
NA
NA
NA
0.00
NA
NA
0.11
NA
NA
HA
*
0.00
0.00
0.00
0.04
0.00
0.28
NA
NA
0.02
0.02
6.49
NA
0.00
3.68
NA
8.37
NA
24.0
0.02
71.6
51.9
80
. u
11.0
3
31.1
0.02
NA
NA
NA
NA
0.00
NA
0.00
0.02
NA
NA
NA
*
0.00
0.00
0.01
0.15
0.00
0.63
NA
NA
0.14
0.29
24.4
NA
0.00
12.4
NA
2.25
NA
69.6
0.01
49.8
161.
9.7
11.9
1
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.01
9.68
8.60
0.03
0.01
I
0.00
0.97
0.21
0.00
0.02
0.43
0.00
NA
NA
0.07
0.09
3.00
33.0
NA
NA
DAYS
2
58.0
0.00
0.00
0.00
0.00
*
0.00
0.02
NA
NA
0.00
0.00
*
0.00
0.00
0.07
0.18
73.1
59.1
0.19
0.02
I
0.01
5.34
1.54
0.05
1.35
12.7
0.17
HA
NA
0.61
0.02
29.7
13.7
HA
NA
3
56.0
0.00
0.00
0.00
0.00
0.00
0.00
*
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.01
15.4
15.0
0.01
0.02
I
0.00
1.33
0.35
0.00
0.03
0.71
0.00
NA
NA
0.15
0.02
11.0
0.00
NA
NA
1
34.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.16
NA
• NA
NA
0.00
0.00
0.00
0.01
256.
I
0.37
3.90
3.90
0.00
I
4.68
NA
0.01
18.4
NA
NA
NA
14.8
0.00
104.
29.0
5.8
5.8
Plant A
2
34.0
0.00
NA
NA
NA
NA
0.00
HA
NA
0.06
NA
NA
NA
0.00
0.00
0.00
0.01
253.
I
0.54
7.20
4.90
0.00
I
8.64
NA
0.02
32.9
NA
NA
NA
38.4
0.00
205.
38.0
6.4
6.4
Plant C
3
34.0
0.00
NA
NA
NA
NA
0.00
NA
HA
0.03
NA
NA
NA
0.00
0.00
0.00
0.01
318.
I
0.43
2.10
2.10
0.00
I
6.86
NA
0.01
29.4
NA
NA
NA
25.2
0.00
134.
42.0
5.8
5.8
1
NA
0.00
0.00
*
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
2.50
0.10
0.03
0.00
0.10
NA
NA
0.00
0.20
0.88
1.71
0.49
1.90
0.00
NA
NA
0.06
NA
NA
29.5
8.0
11.5
2
NA
0.00
*
0.00
0.00
0.00
0.00
NA
HA
0.00
0.00
0.00
0.00
0.00
2.53
0.10
0.00
0.00
0.08
NA
NA
0.00
0.59
0.69
1.63
0.26
2.22
0.00
NA
NA
0.09
NA
NA
34.3
7.5
11.9
J
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
NA
0.00
0.00
0.00
0.00
0.00
3.45
0.12
0.03
0.00
0.12
NA
NA
0.00
0.41
1.05
2.01
0.26
1.44
0.00
NA
NA
0.06
HA
NA
28.7
7.5
12.0
I - Interference
NA - Not Analyzed
* - Less than 0.01
-------
TABLE V-99
POLLUTANT MASS LOADINGS IN THE CELL WASH
CO
en
vo
ELEMENT WASTE STREAMS
Plant E
mg/1
Plant G
11
13
29
30
38
44
55
64
66
70
85
86
87
114
115
118
119
120
121
122
123
124
125
126
128
POIJUirANTS
Flow (I/kg)
Tcnperature (Dog C)
1,1,1 - Trichlorocthane
1,1 - Dichloroethane
1,1 - Dichloroethylene
1,2 - Trans-dichloroethyleno
Ethylbonzcno
Mothylene chloride
Naphthalene
Pcntadilorophenol
Bis(2-cthylhexyl) phthalate
Diethyl phthalate
Tatrachloroothylene
Toluene
Trichlorocthylene
Antinony
Arsenic
Cadmium
Chronium, Total
Chroniin, Ilexavalent
Copper
Cyanide, Total
Cyanide, Am. to Chlor.
T/jfld
Mercury
Nickel
Selenium
Silver
Zinc
Aluninum
Anronia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pi!, minimum
pll, naxinum
1
0.19
29.9
0.002
NA
NA
NA
NA
0.00
NA
0.00
0.01
NA
NA
NA
0.00
0.00
0.00
0.001
0.01
0.00
0.05
NA
NA
0.002
0.004
0.74
NA
0.00
0.71
NA
0.28
NA
3.42
0.003
8.02
4.19
8.9
11.4
2
0.22
30.3
0.00
NA
NA
NA
NA
0.00
NA
NA
0.03
NA
NA
NA
0.00
0.00
0.00
0.00
0.01
0.00
0.06
NA
NA
0.01
0.01
1.46
NA
0.00
0.83
NA
1.88
NA
5.39
0.004
16.1
11.6
8.0
11.0
3
0.22
31.1
0.01
NA
NA
NA
NA
0.00
NA
0.00
0.01
NA
NA
NA
0.00
0.00
0.00
0.002
0.03
0.00
0.14
HA
NA
0.03
0.07
5.37
NA
0.00
2.73
NA
0.50
NA
15.3
0.003
11.0
35.5
9.7
11.9
1
0.58
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.01
5.57
4.95
0.02
0.08
I
0.00
0.56
0.12
0.00
0.01
0.25
0.00
NA
NA
0.04
0.05
1.73
19.0
NA
NA
DAYS
2
0.30
58.0
0.00
0.00
0.00
0.00
0.00
0.00
0.07
NA
NA
0.00
0.00
0.001
0.00
0.00
0.02
0.05
21.6
17.4
0.06
0.01
I
0.003
1.58
0.45
0.01
0.40
3.76
0.05
NA
MA
0.18
0.01
8.77
4.05
HA
NA
Plant A
3
0.60
56.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.01
9.29
9.05
0.06
0.01
I
0.00
0.80
0.21
0.00
0.02
0.43
0.00
NA
NA
0.09
0.01
6.64
0.00
NA
NA
1
0.09
34.0
0.00
HA
NA
NA
NA
0.00
NA
NA
0.01
NA
NA
NA
0.00
0.00
0.00
0.001
21.8
I
0.03
0.33
0.33
0.00
I
0.40
NA
0.001
1.57
NA
NA
NA
1.26
0.00
8.86
2.47
5.8
5.8
2
0.09
34.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.01
NA
NA
NA
0.00
0.00
0.00
0.001
22.6
I
0.05
0.64
0.44
0.00
I
0.77
NA
0.001
2.94
NA
NA
NA
3.43
0.00
18.3
3.39
6.4
6.4
3
0.09
34.0
0.00
NA
NA
NA
NA
0.00
NA
HA
0.005
NA
NA
NA
0.00
0.00
0.00
0.001
28.6
I
0.04
0.19
0.19
0.00
I
0.62
NA
0.001
2.64
NA
NA
NA
2.26
0.00
12.0
3.77
5.8
5.8
Plant C
i
1.48
NA
0.00
0.00
0.01
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
3.71
0.15
0.04
0.00
0.15
NA
NA
0.00
0.30
1.31
2.54
0.73
2.82
0.00
0.00
NA
0.09
NA
NA
43.7
8.0
11.5
2
1.56
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
3.95
0.16
0.003
0.00
0.12
HA
NA
0.00
0.92
1.07
2.55
0.41
3.46
0.00
0.00
IIA
0.15
NA
IIA
53.6
7.5
11.9
3
1.80
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
6.23
0.22
0.05
0.00
0.22
NA
NA
0.00
0.74
1.90
3.76
0.47
2.59
0.00
0.00
MA
0.11
NA
NA
51.7
7.5
12.0
I - Interference
HA - Not Analyzed
-------
Table V-100
STATISTICAL ANALYSIS (mg/1) OF THE CELL
WASH WASTE STREAMS
POLLUTANTS
Temperature (Deg C)
11 1,1,1 - Trichloroethane
13 1,1 - Dichloroethane
29 1,1 - Dichloroethylene
30 1,2 - Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalateO.02
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
NA - Not Analyzed
* - Less than 0.01
Number of values may include concentrations less than 0.005
shown as 0.00 on table.
MINIMUM
29.9
0.00
0.00
0.00
oie.OO
0.00
0.00
0.00
0.00
:e0.02
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
2.10
0.00
0.02
0.21
0.00
0.00
0.43
0.00
1.46
NA
0.06
0.00
3.00
0.00
5.8
5.8
MAXIMUM
58.0
0.02
*
*
*
*
*
0.02
0.00
0.16
*
*
*
0.01
0.00
3.45
0.18
318.
59.1
0.63
7.20
4.90
0.14
5.34
24.4
2.08
1.35
32.9
0.17
8.37
NA
69.6
0.09
205.
161.
9.7
12.0
MEAN
32.3
*
*
*
*
*
*
*
0.00
0.07
*
*
*
*
0.00
0.71
0.05
77.1
9.19
0.25
2.21
3.63
0.02
1.02
4.97
0.91
0.20
9.99
0.03
4.02
NA
15.9
0.02
72.2
40.2
7.5
9.7
MEDIAN
34.0
*
*
*
*
0.00
0.00
*
0.00
0.05
*
*
0.00
*
0.00
0.00
0.01
4.91
0.00
0.23
1.06
3.90
0.00
0.41
2.68
0.84
0.02
3.67
0.00
2.25
NA
7.70
0.01
49.8
31.2
7.5
11.4
#
VAL
8
9
4
4
3
1
4
5
0
6
6
3
1
8
0
4
12
12
3
12
6
3
4
9
12
4
9
12
1
3
12
6
9
11
9
9
#
ZEROS
0
3
2
2
3
5
8
1
2
0
0
3
5
4
12
8
0
0
6
0
0
0
8
0
0
2
3
0
5
0
0
3
0
1
0
0
#
PTS
8
12
6
6
6
6
12
6
2
6
6
6
6
12
12
12
12
12
9
12
6
3
12
9
12
6
12
12
6
3
12
9
9
12
9
9
360
-------
Table V-101
STATISTICAL ANALYSIS (mg/kg) OF THE
CELL WASH WASTE STREAMS
POLLUTANTS
Flow (I/kg)
Temperature (Deg C)
11 1,1,1 - Trichloroethane
13 1,1 - Dichloroethane
29 1,1 - Dichloroethylene
30 1,2 - Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorcphenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
NA - Not Analyzed
MINIMUM
0.09
29.9
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.003
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.003
0.00
0.01
0.01
0.19
0.00
0.004
0.12
0.00
0.00
0.25
0.00
0.28
NA
0.04
0.00
1.73
0.00
5.8
5.8
MAXIMUM
1.80
58.0
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.03
0.001
0.00
0.00
0.002
0.00
6.23
0.22
28.6
17.4
0.22
0.64
0.44
0.03
1.58
5.37
3.76
0.73
3.76
0.05
1.88
NA
15.3
0.05
18.3
53.6
9.7
12.0
MEAN
0.60
32.3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
1.16
0.05
9.13
3.49
0.08
0.20
0.32
0.003
0.56
1.20
1.48
0.17
2.06
0.01
0.89
NA
2.65
0.01
10.2
19.4
7.5
9.74
MEDIAN
0.26
34.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.003
2.81
0.00
0.05
0.10
0.33
0.00
0.56
0.76
1.27
0.01
2.62
0.00
0.50
NA
0.72
0.003
8.86
7.92
7.5
11.4
361
-------
Table V-102
POLLUTANT CONCENTRATIONS IN THE
ELECTROLYTE PREPARATION WASTE
STREAM
(Plant A)
iag/1
POLLUTANTS
Flow
Temperature (Deg C) ""
11 1,1,1 - Trichloroethane °'°o
13 1,1 - Dichloroethane °'°9
29 1,1 - Dichloroethylene 0.00
30 1,2 - Trans-dichloroethylene 0.00
38 Ethylbenzene °-°°
44 Methylene chloride 0.00
55 Naphthalene 0*r°
64 Pentachlorophenol "£
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate °-00
85 Tetrachloroethylene 0.00
86 Toluene °-°°
87 Trichloroethylene 0.00
114 Antimony 44-1
115 Arsenic nnn
118 Cadmium nnr\
119 Chromium, Total 0.00
Chrcmium, Hexavalent 0.00
120 Copper °-°0
121 Cyanide, Total ™?
Cyanide, Amn. to Chlor. NA
123 Mercury 9*04
124 Nickel \'22
125 Selenium jj.60
126 Silver °-^9
128 Zinc nnn
Aluminum *
Ammonia
Iron n nn
Manganese C
Phenols, Total ^
Oil 6 Grease "?
Total Suspended Solids 70«0
pH. minimum ~'°
pH, Maximum 12-8
NA - Not Analyzed
362
-------
Table V-103
POLLUTANT MASS LOADINGS IN THE ELECTROLYTE
PREPARATION WASTE STREAM (Plant A)
mg/kg
POLLUTANTS
Flow (I/kg) 0.36
Temperature (Deg C) NA
11 1,1,1 - Trichloroethane 0.00
13 1,1 - Dichloroethane 0.00
29 1,1 - Dichloroethylene 0.00
30 1,2 - Trans-dichloroethylene 0.00
38 Ethylbenzene 0.00
44 Methylene chloride 0.00
55 Naphthalene 0.00
64 Pentachlorophenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate 0.00
85 Tetrachloroethylene 0.00
86 Toluene 0.00
87 Trichloroethylene 0.00
114 Antimony 0.00
115 Arsenic 1.63
118 Cadmium 0.00
119 Chromium, Total 0.00
Chronium, Hexavalent 0.00
120 Copper 0.00
121 Cyanide, Total NA
Cyanide, Amn. to Chlor. NA
122 Lead 0.00
123 Mercury 0.02
124 Nickel 0.08
125 Selenium 1.31
126 Silver 0.29
128 Zinc 6.99
Aluminum 0.00
Ammonia NA
Iron NA
Manganese 0.00
Phenols, Total NA
Oil & Grease NA
Total Suspended Solids' 25.5
pH, minimum 12.8
pH, maximum 12.8
NA - Not Analyzed
363
-------
Table V-104
POLLUTANT CONCENTRATIONS IN THE SILVER
ETCH WASTE STREAM (Plant A)
mg/1
PQLLOTAWTS
Twperstur* (Dag C) 10.0
11 1,1,1 - Trichloroethane 0.00
13 1,1 - Dichloroethane 0.00
29 1,1 - Diefcloroethylene 0.00
30 1,2 - Tfani-dichloroethylene 0.00
38 Etfylberaene 0.00
44 M*thyl«ne chloride 0.00
55 Naphthalene 0.00
€4 I*ntachl<*qphenol NA
66 lis<2-et*ylhexyl) phthalate NA
70 Diethyl phthalate 0.00
85 Ttetrachloroethflane 0.00
86 toluene 0.00
8 7 Tficiiloixwthy Ian* 0.00
114 totixory 0.00
115 Arsenic 0.00
118 CMfecuxi 0.04
119 Oironiwn, fbtal 0.01
ChraRsiun, HKCwalent 0.00
120 Copper 0.09
121 Cyanide, Ttotal 0.01
Cyanide, An. to Chlor. 0.00
122 Lead 0.05
123 Mercury 0.01
124 Nickel 0.00
125 Selenium 0.00
126 SilMwr 36.3
128 line 1.06
Alywinitn 0.65
ftaenia 2.00
Iron NA
Manganese 0.01
Ihenols, total 0.01
Oil & Grease 1.00
total Suspended Solids 7.00
pH, minimum 2.60
pH, naxirun 3.60
NA - Not Analyzed
364
-------
Table V-105
POLLUTANT MASS LOADINGS IN THE SILVER
ETCH WASTE STREAM (Plant A)
mg/kg
POLLUTANTS
Flow (I/kg) 49.0
Temperature (Deg C) 10»°
11 1,1,1 - Trichloroethane 0-01
13 1,1 - Dichloroethane 0.00
29 1,1 - Dichloroethylene 0.01
30 1,2 - Trans-dichloroethylene 0.00
38 Ethylbenzene O-00
44 Methylene chloride 0.00
55 Naphthalene °-00
64 Pentachlorophenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate 0.00
85 Tetrachloroethylene O*00
86 Toluene °'JjJj
87 Trichloroethylene O-00
114 Antimony °-00
115 Arsenic °-00
118 Cadmium J-^
119 Chrcrnium, Total °-44
Chronium, Hexavalent 0-00
120 Copper jJ-32
121 Cyanide, Total O-4^
Cyanide, Arm. to Chlor. 0.25
122 Lead 2*^^
123 Mercury °-JJ
124 Nickel °-00
125 Selenium °-00
126 Silver 17°°-
128 Zinc 52.0
Aluminum 31-^
Ammonia 9^*1
Iron l*
Manganese °-64
Phenols, Total °-54
Oil & Grease 49-°
Total Suspended Solids 343.
pH, minimum 2>6
pH, maximum 3.6
NA - Not Analyzed
365
-------
Table V-106
POLLUTANT CONCENTRATIONS IN THE LAUNDRY
WASH AND EMPLOYEE SHOWER WASTE STREAMS
(Plant B)
POLLUTANTS
Temperature (Deg C) 27.0
11 1,1,1 - Trichloroethane *
13 1,1 - Dichloroethane 0.00
29 1,1 - Dichloroethylene 0.00
30 1,2 - Trans-dichloroethylene 0.00
38 Ethylbenzene 0.00
44 Methylene chloride 0.00
55 Naphthalene *
64 Pentachlorcphenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate *
85 Tetrachloroethylene 0.00
86 Toluene 0.00
87 Trichloroethylene *
114 Antimony NA
115 Arsenic NA
118 Cadmium NA
119 Chromium, Total NA
Chromium, Hexavalent NA
120 Copper NA
121 Cyanide, Total 0.03
Cyanide, Amn. to Chlor. I
122 Lead NA
123 Mercury NA
124 Nickel NA
125 Selenium NA
126 Silver NA
128 Zinc NA
Aluminum NA
Ammonia NA
Iron NA
Manganese NA
Phenols, Total 0.19
Oil & Grease 270.
Total Suspended Solids 42.0
pH, minimum 4.7
pH, maximum 7.7
I - Interference
NA - Not Analyzed
* - Less than 0.01
mg/1
DAYS
2
28.0
*
0.00
0.00
0.00
0.00
0.00
*
NA
NA
*
0.00
0.00
*
0.00
0.00
0.07
0.00
0.00
0.23
0.01
I
0.00
9.40
0.00
0.00
1.46
0.82
0.16
NA
NA
0.35
0.05
5.20
72.0
6.4
7.2
3
30.0
*
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
*
0.00
0.00
*
0.00
0.00
0.10
0.00
0.00
0.45
0.00
I
0.04
I
0.03
0.00
0.43
1.22
0.16
NA
NA
0.40
0.08
14.0
23.0
5.5
6.9
306
-------
Table V-107
POLLUTANT CONCENTRATIONS IN THE MANDATORY
EMPLOYEE WASH WASTE STREAM (Plant A)
mg/1
POLLUTANTS DAYS
1 2 3
Temperature (Deg C) 17.0 29.0 26.0
11 1,1,1 - Trichloroethane 0.00 0.00 0.00
13 1,1 - Dichloroethane NA NA MA
29 1,1 - Dichloroethylene NA NA NA
30 1,2 - Trans-dichloroethylene NA NA NA
38 Efchylbenzene NA NA UA
44 Methylene chloride 0.00 0.00 0.00
55 Naphthalene NA NA NA
64 Pentachlorophenol 0.00 0.00 0.00
66 Bis(2-ethylhexyl) phthalate 0.00 0.00 0.00
70 Diethyl phthalate NA NA NA
85 Tetrachloroethylene NA NA NA
86 Toluene NA NA NA
87 Tridhloroethylene 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.00 0.00 0.00
118 Cadmium 0.00 0.00 0.00
119 Chromium, Total 0.00 0.00 0.00
Chromium, Hexavalent 0.00 0.00 0.00
120 Copper 0.03 0.01 0.02
121 Cyanide, Total 0.01 0.00 0.00
Cyanide, Arm. to Chlor. 0.01 0.00 0.00
122 Lead 0.00 0.00 0.00
123 Mercury 0.00 0.00 0.00
124 Nickel 0.00 0.00 0.00
125 Selenium NA NA NA
126 Silver 0.00 0.00 0.00
128 Zinc 0.10 0.15 0.15
Aluminum NA NA NA
Ammonia 6.23 0.73 0.13
Iron NA NA NA
Manganese 0.23 0.10 0.36
Phenols, Total 0.22 0.04 I
Oil & Grease 8.30 2.00 42.0
Total Suspended Solids 133. 84.0 55.0
pH, minimum NA NA NA
pH, maximum NA NA NA
I - Interference
NA - Not Analyzed
367
-------
Table V-108
POLLUTANT MASS LOADINGS IN THE MANDATORY
EMPLOYEE WASH WASTE STPEAitfS
(Plant A)
mg/kg
POLLUTANTS DAYS
1 23
Flow (I/kg) 0.27 0.27 0.27
Temperature (Deg C) 17.0 29.0 26.0
11 1,1,1 - Trichloroethane 0.00 0.00 0.00
13 1,1 - Dichloroethane NA NA NA
29 1,1 - Dichloroethylene NA NA NA
30 1,2 - Trans-didiloroethylene NA NA NA
38 Ethylbenzene NA NA NA
44 Methylene chloride 0.00 0.00 0.00
55 Naphthalene NA NA NA
64 Pentachlorophenol 0.00 0.00 0.00
66 Bis(2-ethylhexyl) phthalate 0.00 0.00 0.00
70 Diethyl phthalate NA NA NA
85 Tetrachloroethylene NA NA NA
86 Toluene NA NA NA
87 Trichloroethylene 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.00 0.00 0.00
118 Cadmium 0.00 0.00 0.00
119 Chromium, Total 0.00 0.00 0.00
Chromium, Hexavalent 0.00 0.00 0.00
120 Copper 0.01 0.04 0.01
121 Cyanide, Total o.OO 0.00 0.00
Cyanide, Amn. to Chlor. 0.001 0.00 0.00
122 Lead 0.01 0.00 0.00
123 Mercury 0.00 0.00 0.00
124 Nickel 0.00 0.00 0.00
125 Selenium NA NA NA
126 Silver 0.00 0.00 0.00
128 Zinc 0.03 0.04 0.04
Aluminum NA NA NA
Ammonia 1.66 0.19 0.04
Iron NA NA NA
Manganese 0.06 0.03 0.10
Phenols, Total 0.01 0.01 i
Oil & Grease 2.21 0.53 H.2
Total Suspended Solids 35.5 22.3 14^6
pH, minimum NA NA NA
pH, maximum NA NA NA
I - Interference
NA - Not Analyzed
368
-------
Table V-109
POLLUTANT CONCENTRATIONS IN THE REJECT
CELL HANDLING (Plant A)
rag/1
POLLUTANTS
Flow °'03
Temperature (Deg C) NA
11 1,1,1 - Trichloroethane NA
13 1,1 - Dichloroethane NA
29 1,1 - Dichloroethylene NA
30 1,2 - Trans-dichloroethylene NA
38 Ethylbenzene NA
44 Methylene chloride NA
55 Naphthalene NA
64 Pentachlorophenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate NA
85 Tetrachloroethylene NA
86 Toluene NA
87 Trichloroethylene NA
114 Antimony NA
115 Arsenic NA
118 Cadmium 0.02
119 Chromium, Total 0.10
Chromium, Hexavalent NA
120 Copper 5.46
121 Cyanide, Total NA
Cyanide, Arm. to Chlor. NA
122 Lead 0.34
123 Mercury 17.0
124 Nickel 0.57
125 Selenium NA
126 Silver 3.59
128 Zinc 156.
Aluminum 106.
Ammonia NA
Iron 0.57
Manganese 0.18
Phenols, Total NA
Oil & Grease NA
Total Suspended Solids NA
pH, minimum NA
pH, maximum NA
NA - Not Analyzed
369
-------
Table V-110
POLLOTANT (X8SCENTRATICNS IN THE
REJECT CPT-T- HANDLING WASTE STREAMS
(Plant B)
mg/1
DAYS
POLLUTANTS 3
Temperature (Deg C) 18.0 19.0 18.0
11 l,lTl - Trichloroethane 0.00 0.00 0.00
13 1,1 - Dichloroethane NA NA NA
29 1,1 - Dichloroethylene NA NA J^
30 1,2 - Trans-dichloroethylene NA m
38 Ethylbenzene NA NA NA
44 Methylene chloride 0.00 0.00 0.00
55 Naphthalene NA NA NA
64 Pentachlorcphenol 0.00 0.00 0.00
66 Bis(2-ethylhexyl) phthalate 0.04 0.08 0.01
70 Diethyl phthalate NA NA NA
85 Tetrachloroethylene NA NA NA
86 Toluene NA NA NA
87 Trichloroethylene 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.10 0.19 0.15
ill SSSm 0.00 0.00 0.00
119 Chromium, Total 0.00 0.02 0.01
Chrcndutn, Hexavalent 0.00 I 0.00
120 CoDcer 0.08 0.30 0.32
ill gSSe, Total 0.10 0.01 0.07
Cyanide, Amn. to Chlor. 0.01 0.01 0.00
122 Lead 0.06 0.00 0.00
123 Mercury 0.47 1.00 0.37
124 Nickel 0.01 0.07 0.18
125 Selenium NA NA NA
126 Silver 0.00 0.00 0.00
128 Zinc 730. 495. 206.
Aluminum NA NA NA
Ammonia 5.57 8.89 1.37
Iron NA NA NA
Manganese 0.02 0.15 0.29
Phenols, Total 0.00 0.00 0.12
Oil & Grease 13.3 6.00 19.0
Total Suspended Solids 762. 500. 1310.
pH, ndnimum NA NA NA
pH, maximum NA NA NA
I - Interference
NA - Not Analyzed
370
-------
Table V-lll
POLLUTANT MASS LOADINGS IN THE
REJECT CFT.T. HANDLING WASTE STREAMS
(Plant B)
11
13
29
30
38
44
55
64
66
70
85
86
87
114
115
118
119
120
121
122
123
124
125
126
128
POLLUTANTS
Plow (I/kg)
Temperature (Deg C)
1,1,1 - Trichloroethane
1,1 - Dichloroethane
1,1 - Dichloroethylene
1,2 - Trans-dichloroethylene
Methylene chloride
Naphthalene
Pentachlorophenol
Bis(2-ethylhexyl) phthalate
Diethyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Cyanide, Total
Cyanide, Amn. to Chlor.
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
I - Interference
NA - Not Analyzed
0.003
18.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.00
0.00
0.00
.00
.00
0.00
0.00
0.00
0.00
0.001
0.00
NA
0.00
2.00
NA
0.02
NA
0.00
0.00
0.04
2.08
NA
NA
0.
0.
mg/kg
DAYS
2
0.002
19.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.00
0.00
0.00
0.00
I
0.001
0.00
0.00
0.00
0.002
0.00
NA
0.00
0.90
NA
0.02
NA
0.00
0.00
0.01
0.91
NA
NA
0.003
18.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.001
0.00
0.00
0.00
0.001
0.00
NA
0.00
0.56
NA
0.004
NA
0.001
0.00
0.05
3.58
NA
NA
371
-------
Table V-112
POLLUTANT ODNCEWTRATIONS IN THE FLOOR I'JASH WASTE STREAM
(Plant A)
mg/1
POLLUTANTS
Temperature (Deg C) NA
11 1,1,1 - Trichloroethane NA
13 1,1 - Dichloroethane NA
29 1,1 - Dichloroethylene NA
30 1,2 - Trans-dichloroethylene NA
38 Ethylbenzene NA
44 Metnylene chloride NA
55 Naphthalene NA
64 Pentachlorqphenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate NA
85 Tetrachloroethylene NA
86 Toluene NA
87 Trichloroethylene NA
114 Antimony 0.00
115 Arsenic 0.00
118 Cadmium 0.04
119 Chromium, Total 0.35
Chromium, Hexavalent 0.00
120 Copper 0.23
121 Cyanide, Total NA
Cyanide, Arm. to Chlor. NA
122 Lead 4.13
123 Mercury I
124 Nickel 0.38
125 Selenium 0.00
126 Silver 49.5
128 Zinc 600.
Aluminum 5.83
Ammonia 120.
Iron NA
Manganese 0.34
Phenols, Total NA
Oil & Grease NA
Total Suspended Solids 2800.
pH, minimum MA
pH, maximum NA
I - Interference
NA - Not Analyzed
372
-------
Table V-113
POLLUTANT MASS LOADINGS IN THE FLOOR WASH WASTE STREAM
(Plant A)
mg/kg
POLLUTANTS
Flow (I/kg) 0.30
Temperature (Deg C) NA
11 1,1,1 - Trichloroethane NA
13 1,1 - Dichloroethane NA
29 1,1 - Dichloroethylene NA
30 1,2 - Trans-dichloroethylene NA
38 Ethylbenzene NA
44 Methylene chloride NA
55 Naphthalene NA
64 Pentachlorophenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate NA
85 Tetrachloroethylene NA
86 Toluene NA
87 Trichloroethylene NA
114 Antimony 0.00
115 Arsenic 0.00
118 Cadmium 0.01
119 Chromium, Total 0.10
Chromium, Hexavalent 0.00
120 Copper 0.07
121 Cyanide, Total NA
Cyanide, Aim. to Chlor. NA
122 Lead 1.22
123 Mercury I
124 Nickel 0.11
125 Selenium 0.00
126 Silver 14.6
128 Zinc 177.
Aluminum 1.72
Ammonia 35.5
Iron NA
Manganese 0.10
Phenols, Total NA
Oil & Grease NA
Total Suspended Solids 828.
pH, miniinum NA
pH, maximum NA
I - Interference
NA - Not Analyzed
373
-------
Table V-114
POLLUTANT CONCENTRATIONS IN THE EQUIPMENT WASH WASTE STREAMS
PLANT mg/1 PLANT
POLLUTANTS B DAYS A
123
Teirperature (Deg C) 18.8 10.0 50.0 NA
11 1,1,1 - Trichloroethane 0.00 0.00 0.00 0.00
13 1,1 - Dichloroethane 0.00 0.00 0.00 0.00
29 1,1 - Dichloroethylene 0.00 0.00 0.00 0.00
30 1,2 - Trans-dichloroethylene 0.00 0.00 0.00 0.00
38 Ethylbenzene 0.00 0.00 0.00 *
44 Methylene chloride 0.00 0.00 0.00 *
55 Naphthalene 0.00 0.00 0.00 *
64 Pentachlorophenol NA NA NA NA
66 Bis(2-ethylhexyl) phthalate NA NA NA NA
70 Diethyl phthalate 0.00 0.00 0.00 *
85 Tetrachloroethylene 0.00 0.00 0.00 0.00
86 Toluene 0.00 * * 0.00
87 Trichloroethylene 0.00 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00 0.00
115 Arsenic 0.01 0.10 0.09 0.00
118 Cadmium 0.19 0.02 0.02 0.02
119 Chromium, Total 0.00 0.00 0.01 0.01
Chromium, Hexavalent 0.00 I 0.00 0.00
120 Copper 0.01 NA 0.03 0.04
121 Cyanide, Total NA NA NA NA
Cyanide, Amn. to Chlor. NA NA NA NA
122 Lead 0.01 NA 0.00 0.00
123 Mercury 0.12 0.40 0.04 0.22
124 Nickel 0.13 0.02 0.04 0.10
125 Selenium 0.00 0.05 0.07 0.00
126 Silver 0.03 0.00 0.35 0.96
128 Zinc 8.03 0.66 1.40 1.79
Aluminum 0.12 NA 0.00 0.00
Ammonia NA NA NA NA
Iron NA NA NA NA
Manganese 0.02 0.00 0.02 0.07
Phenols, Total NA NA NA NA
Oil & Grease NA NA NA NA
Total Suspended Solids 51.5 112. 68.0 98.0
pH, minimum 12.0 11.8 12.0 5.6
pH, maximum 12.2 11.8 12.2 6.5
I - Interference
NA - Not Analyzed
* - Less than 0.01
374
-------
Table V-115
POLLUTANT MASS LOADINGS IN THE EQUIPMENT WASH WASTE STREAMS
rag/kg
Plant DAYS
B
POLLUTANTS 1 2 3
16.6 6.79 3.47 5.09
121 Cyanide, Total
Flow ^ ^ ^
g i;i'iiSSS£™ o'-oj o:« juS Lo
o.oo o.oo o.oo o.oo
o.oo o.oo o.oo o.oo
S SgSSSLT1-1* Si? SS r r
64 Pentachlorophenol NA ™ ™ NA
S*£?32S2iphthalate o^o 0*0 o.oo o.oo
0.00 0.00 0.00 0.00
0.00 o.oo o.oo o.oo
o.oo o.oo o.oo o.oo
o.oo o.oo o.oo o.oo
0.10 0.68 0.31 0.00
*-• 3 13 0.10 0.07 0.12
118 Cadmium £•« Q(J 0>04 0>06
119 Chromium, Total "-"« • . OQ Q>00
Chronium, Hexavalent 0.00 I "•
120 Copper NA NA NA
NA »
NA
°-08 »
uyanxae, wwu. vm NA NA NA
Cyanide, Aim. to Chlor. NA NA
I22 ^^ ?'o8 2 72 0.13 1.12
123 Mercury I-98 2'|2 J 13 0.51
124 Nickel n'Jo 0 34 0.24 0.00
125 Selenium °-™ ' 1>21 4.89
126 Silver O-57 » J 4>86 9al
128 ZPC. 2 06 NA 0.00 0.00
NA NA NA NA
NA NA NA NA
0.34 0.00 0.07 0.37
- Km NA NA NA
Phenols, Total NA NA
Oil & Grease NA NA r«
Total Suspended Solids 856. 761. 236.^ «y.g
pH, minimum 12-° ^'° ,-*, 6 5
PH, maximum 12-2 H-8 i2'2 6'5
I - Interference
NA - Not Analyzed
375
-------
Table V-116
STATISTICAL ANALYSIS (mg/1) OF THE EQUIPMENT WASH WASTE STREAMS
mg/i
POLLUTANTS
Temperature (Deg C)
11 1,1/1 - Trichloroethane
13 1,1 - Dichloroethane
29 1,1 - Dichloroethylene
30 1,2 - Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Cnronium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
NA - Not Analyzed
* - Less than 0.01
Number of values may include concentrations less than 0.005
shown as 0.00 on tables.
MINIMUM
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.00
0.00
0.01
NA
NA
0.00
0.04
0.02
0.00
0.00
0.66
0.00
NA
NA
0.00
NA
NA
51.4
5.6
6.5
MAXIMUM
50.0
*
*
0.00
0.00
*
*
*
NA
NA
*
0.00
*
0.00
0.00
0.10
0.19
0.01
0.00
0.04
NA
NA
0.01
0.40
0.13
0.07
0.96
8.03
0.12
NA
NA
0.07
NA
NA
112.
12.0
12.2
MEAN
19.3
*
*
0.00
0.00
*
*
*
NA
NA
*
0.00
*
0.00
0.00
0.05
0.06
0.01
0.00
0.02
NA
NA
*
0.19
0.07
0.03
0.34
2.97
0.04
NA
NA
0.03
NA
NA
82.4
10.3
10.7
MEDIAN
18.8
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
*
0.00
*
0.00
0.00
0.05
0.02
0.01
0.00
0.03
NA
NA
0.00
0.17
0.07
0.03
0.19
1.60
0.00
NA
NA
0.02
NA
NA
83.0
11.9
12.0
#
VAL
3
1
1
0
0
1
1
1
3
0
3
0
0
3
4
2
0
3
1
4
4
2
3
4
1
3
4
4
4
#
ZEROS
0
3
3
4
4
3
3
3
1
4
1
4
4
1
0
2
3
0
2
0
0
2
1
0
2
1
0
0
0
#
PTS
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
4
4
4
4
4
3
4
4
4
4
376
-------
Table V-117
STATISTICAL ANALYSIS (ng/kg) OF THE EQUIPMENT 1*8! «ST6 STPEWB
POLLUTANTS
11
13
29
30
38
44
55
64
66
70
85
86
87
114
115
118
119
120
121
122
123
124
125
126
128
Flow (I/kg)
Temperature (Deg C)
1,1,1 - Trichloroethane
1,1 - Dichloroethane
1,1 - Dichloroethylene
1,2 - Trans-dichloroethylene
Ethylbenzene
Methylene chloride
Naphthalene
Pentachlorophenol
Bis(2-ethylhexyl) phthalate
Diethyl phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Antimony
Arsenic
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Cyanide, Total
Cyanide, Amn. to Chlor.
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
MINIMW!
3.47
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.07
0.00
0.00
0.08
NA
NA
0.00
0.13
0.13
0.00
0.00
4.48
0.00
NA
NA
0.00
NA
NA
236.
5.6
6.5
MAXIMUM
16.6
50.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MA
NA
0.00
0.00
0.00
0.00
0.00
0.61
3.13
0.0*
§.00
0.21
NA
NA
0.08
2.72
2.13
0.34
4.89
134.
2.M
NA
NA
0.37
NA
NA
856.
12.0
12.2
mm
8.00
19.3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
MA
0.00
0.00
o.oo
0.00
0.00
0.27
O.M
0.02
0.00
0.13
NA
0.03
1.49
0.73
0.15
1.67
38.0
0.69
NA
NA
0.19
NA
NA
S88.
10.4
10.7
KDIAK
5.94
18.8
0.00
0.00
0.00
0.00
c.oo
0.00
0.00
MA
OJVM
.00
0.00
0.00
0.00
0/^A
.00
0.21
0.11
0.02
0.00
0.09
NA
0.00
1.55
0.32
0.12
0.89
6.98
0.00
NA
NA
0.20
^n
Im
NA
630.
11.9
12.0
NA - Not Analyzed
377
-------
Table V-118
POLLUTANT CONCENTRATIONS IN THE SILVER
POWDER PRODUCTION ELEMENT WASTE STREAMS
(Plant A)
ng/1
POLLUTANTS DAYS _
123
Temperature (Deg C) 14.0 15.0 14.0
11 1,1,1-TridHoroethane 0.00 0.00 0.00
13 1,1-DiAloroethane 0.00 0.00 0.00
29 1,1-Dichloroethylene 0.00 0.00 0.00
30 1,2-Trans-didiloroethylene 0.00 0.00 0.00
38 Ethylbenzene 0.00 0.00 0.00
44 Methylene chloride 0.00 0.00 0.00
55 Naphthalene 0.00 0.00 0.00
64 Pentachlorophenol NA NA NA
66 Bis(2-ethylhexyl) phthalate NA NA NA
70 Diethyl phthalate 0.00 0.00 0.00
85 Tetrachloroethylene 0.00 0.00 0.00
86 Toluene 0.00 0.00 0.00
87 Trichlorcethylene 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.00 0.00 0.00
118 Cadmium 0.00 0.01 0.00
119 Chromium, Total 0.70 1.52 0.58
Chrcmium, Hexavalent 0.00 0.00 0.00
120 Copper 4.35 10.5 4.37
121 Cyanide, Total NA NA NA
Cyanide, Arm. to Chlor. NA NA NA
122 Lead 0.16 0.28 0.00
123 Mercury 0.01 0.00 0.00
124 Nickel °«61 1<45 °-57
125 Selenium 0.00 0.00 0.0
126 Silver 12.0 24.1 13.9
128 Zinc 0.18 0.44 0.38
Aluminum 3.40 12.0 0.48
Ammonia NA NA NA
Iron NA NA NA
Manganese 0.11 0.08 0.10
Phenols, Total NA NA NA
Oil & Grease NA NA NA
Total Suspended Solids 27.0 23.0 13.0
pH, Minijnum 2.0 2.2 2.1
pH, Maximum 2.6 2.5 2.5
NA-Not Analyzed
378
-------
Table V-119
POLLUTANT MASS LOADINGS IN THE
SILVER POWDER PRODUCTION
WASTE STREAMS (PLANT A)
rug/kg
POLLUTANTS DAYS
123
Flow (I/kg) 23.7 20.1 19.8
Temperature (Deg C) 14.0 15.0 14.0
11 1,1,1-Trichloroethane 0.00 0.00 0.00
13 1,1-Dichloroethane 0.00 0.00 0.00
29 1,1-Dichloroethylene 0.00 0.00 0.00
30 1,2-Trans-dichloroethylene 0.00 0.00 0.00
38 Ethylbenzene 0.00 0.00 0.00
44 Methylene chloride 0.002 0.002 0.002
55 Naphthalene 0.00 0.00 0.00
64 Pentachlorophenol NA NA NA
66 Bis(2-ethylhexyl) phthalate NA NA NA
70 Diethyl phthalate 0.00 0.00 0.00
85 Tetrachloroethylene 0.00 0.00 0.00
86 Toluene 0.00 0.00 0.00
87 Trichloroethylene 0.00 0.00 0.00
114 Antimony 0.00 0.00 0.00
115 Arsenic 0.00 0.00 0.00
118 Cadmium 0.00 0.14 0.00
119 Chranium, Total 16.6 30.6 11.5
Chranium, Hexavalent 0.00 0.00 0.00
120 Copper 103. 212. 86.6
121 Cyanide, Total NA NA NA
Cyanide, Amn. to Chlor. NA NA NA
122 Lead 3.80 5.64 0.00
123 Mercury 0.19 0.00 0.00
124 Nickel 14.5 29.2 11.3
125 Selenium 0.00 0.00 0.00
126 Silver 285. 485. 275.
128 Zinc 4.27 8.86 7.53
Aluminun 80.7 242. 9.51
Ammonia NA NA NA
Iron NA NA NA
Manganese 2.61 1.57 1.98
Phenols, Total NA NA NA
Oil & Grease NA NA NA
Total Suspended Solids 641. 463. 258.
pH, Minimum 2.0 2.2 2.1
pH, Maximum 2.6 2.5 2.5
NA-Not Analyzed
379
-------
Table V-120
POLLUTANT CONCENTRATIONS IN THE WASTE
STREAMS FROM SILVER PEROXIDE PRODUCTION
ELEMENT
mg/1
POLLUTANTS
Temperature (Deg C) NA
11 1,1,1-Trichloroethane
13 1,1-Didiloroethane 0-00
29 1,1-Dichloroethylene 0.00
30 1,2-JTrans-dichloroethylene 0.00
38 Ethylbenzene °«°°
44 Methylene chloride *
55 Naphthalene °-°°
64 Pentachlorophenol NA
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate 0.00
85 Tetrachloroethylene 0.00
86 Toluene O-00
8 7 Trichloroethylene 0.00
114 Antimony °-0°
115 Arsenic 5.91
118 Cadmium 0.00
119 Chrcmium, Total 0.09
Chromium, Hexavalent I
120 Copper 0.00
121 Cyanide, Total NA
Cyanide, Amn. to Chlor. NA
122 Lead 0.00
123 Mercury 0.04
124 Nickel 0.00
125 Selenium 4.80
126 Silver 0.77
128 Zinc 0.08
Aluminum 0.00
Ammonia NA
Iron NA
Manganese 0.00
Phenols, Total NA
Oil & Grease NA
Total Suspended Solids 31.0
pH, Minimum 11.0
pH, Maximum 12.5
I-Interference
NA-Not Analyzed
*-Less than 0.01
380
-------
Table V-121
POLLUTANT MASS LOADINGS IN THE WASTE
STREAMS FROM SILVER PEROXIDE PRODUCTION
ELEMENT
mg/kg
POLLUTANTS
FLOW (I/kg) 14'3
Temperature (Deg C) ^
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane o.uu
29 1,1-Dichloroethylene JJ-OJJ
30 1,2-Trans-dichloroethylene 0.00
38 Ethylbenzene °-°°
44 Methylene chloride "-JJ*
55 Naphthalene "*uu
64 Pentachlorophenol ^A
66 Bis(2-ethylhexyl) phthalate NA
70 Diethyl phthalate °-™
85 Tetrachloroethylene "•""
86 Toluene "•""
87 Trichloroethylene "•""
114 Antimony "'"u
115 Arsenic °?'
118 Cadmium ?•""
119 Ghronium, Total J--/:::'
Chranium, Hexavalent -1
120 Copper ^°°
121 Cyanide, Total ^
Cyanide, Arm. to Chlor. ^
122 Lead °'°°
123 Mercury "-J
124 Nickel "'"U
125 Selenium °°^
126 Silver x|^
128 Zinc J- 0
Aluminum '
Ammonia
Iron 0 00
Manganese •
Phenols, Total
Oil & Grease
Total Suspended Solids
pH,'Minimum
pH, Maximum
I-Interference
NA-Not Analyzed
*-Less than 0.01
381
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The priority, non-conventional, 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. The selected priority pollutants are presented
in numerical order and are followed by non-conventional 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 each subcategory. The rationale for that
final selection is included.
VERIFICATION PARAMETERS
Pollutant parameters selected for verification sampling and analysis
are listed in Table V-8 (Page 262 ) and the subcategory for each is
designated. 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(ll). 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-
Trichloroethane 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 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,
383
-------
the ambient water criterion is 15.7 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 factor 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.
1,l-Dichloroethane(13). 1,1-Dichloroethane, also called ethylidene
dichloride and ethylidene chloride is a colorless liquid manufactured
by reacting hydrogen chloride with vinyl chloride in 1,1-dichloro-
ethane solution in the presence of a catalyst. However, it is
reportedly not manufactured commercially in the U.S. 1,1-
dichloroethane boils at 57°C and has a vapor pressure of 182 mm Hg at
20°C. It is slightly soluble in water (5.5 g/1 at 20°C) and very
soluble in organic solvents.
1,1-Dichloroethane is used as an extractant for heat-sensitive
substances and as a solvent for rubber and silicone grease.
1,1-Dichloroethane is less toxic than its isomer (1,2-dichloroethane)
but its use as an anesthetic has been discontinued because of marked
excitation of the heart. It causes central nervous system depression
in humans. There are insufficient data to derive water quality
criteria for 1,1-dichloroethane.
Data on the behavior of 1,1-dichloroethane in POTW are not available.
Many of the organic priority pollutants have been investigated, at
least in laboratory scale studies, at concentrations higher than those
384
-------
expected to be contained by most municipal wastewaters. General
observations have been developed relating molecular structure to ease
of degradation for all of the organic priority pollutants. The
conclusion reached by study of the limted data is that biological
treatment produces only a moderate removal of 1,1-dichloroethane in
POTW by degradation.
The high vapor pressure of 1,1-dichloroethane is expected to result in
volatilization of some of the compound from aerobic processes in POTW.
Its water solubility will result in some of the 1,1-dichloroethane
which enters the POTW leaving in the effluent from 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.
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. Concentrations of chloroform estimated to
result in additional lifetime cancer risks at the levels of 10~7,
10-*, and 10-s were 0.000021 mg/1, 0.00021 mg/1, and 0.0021 mg/1,
respectively.
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.
385
-------
l,l-Dichloroethylene(29). 1,1-Dichloroethylene (1,1-DCE), also called
vinylidene chloride, is a clear colorless liquid manufactured by
dehydrochlorination of 1,1,2-trichloroethane. 1,1-DCE has the formula
CC12CH2. It has a boiling point of 320C, and a vapor pressure of 591
mm Hg at 25°C. 1,1-DCE is slightly soluble in water (2.5 mg/1) and is
soluble in many organic solvents. U.S. production is in the range of
a hundreds of thousands of tons annually.
1,1-DCE is used as a chemical intermediate and for copolymer coatings
or films. It may enter the wastewater of an industrial facility as
the result of decomposition of 1,1,1-trichlorpethylene used in
degreasing operations, or by migration from vinylidene chloride
copolymers exposed to the process water.
Human toxicity of 1,1-DCE has not been demonstrated, however it is a
suspected human carcinogen. Mammalian toxicity studies have focused
on the liver and kidney damage produced by 1,1-DCE. Various changes
occur in those organs in rats and mice ingesting 1,1-DCE.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to 1,1-dichloroethylene through
ingestion of water and contaminated aquatic organisms, the ambient
water concentration is zero. The concentration of 1,1-DCE estimated
to result in an additional lifetime cancer risk of 1 in 100,000 is
0.0013 mg/1.
Under laboratory conditions, dichloroethylenes have been shown to be
toxic to fish. The primary effect of acute toxicity of the
dichloroethylenes is depression of the central nervous system. The
octanol/water partition coefficient of 1,1-DCE indicates it should not
accumulate significantly in animals.
The behavior of 1,1-DCE in POTW has not been studied. However, its
very high vapor pressure is expected to result in release of
significant percentages of this material to the atmosphere in any
treatment involving aeration. Degradation of dichloroethylene in air
is reported to occur, with a half-life of 8 weeks.
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 wastewaters. 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 little
or no degradation of 1,1-dichloroethylene. No evidence is available
for drawing conclusions about the possible toxic or inhibitory effect
of 1,1-DCE on POTW operation. Because of water solubility, 1,1-DCE
which is not volatilized or degraded is expected to pass through POTW.
Very little 1,1-DCE is expected to be found in sludge from POTW
386
-------
1,2-trans-Dichloroethylene(30). 1,1-trans-Dichloroethylene (trans-
1,2-DCE) is a clear, colorless liquid with the formula CHC1CHC1.
Trans-1,2-DCE is produced in mixture with the cis-isomer by
chlorination of acetylene. The cis-isomer has distinctly different
physical properties. Industrially, the mixture is used rather than
the separate isomers. Trans-l,2-DCE has a boiling point of 48°C, and
a vapor pressure of 324 mm Hg at 25°C.
The principal use of 1,2-dichloroethylene (mixed isomers) is to
produce vinyl chloride. It is used as a lead scavenger in gasoline,
general solvent, and for synthesis of various other organic chemicals.
When it is used as a solvent trans.-1,2-DCE can enter wastewater
streams.
Although trans-1,2-DCE is thought to produce fatty degeneration of
mammalian liver, there are insufficient data on which to base any
ambient water criterion.
In the one reported toxicity test of trans-1,2-DCE on aquatic life,
the compound appeared to be about half as toxic as the other
dichloroethylene (1,1-DCE) on the priority pollutants list.
The behavior of trans-1,2-DCE in POTW has not been studied. However,
its high vapor pressure is expected to result in release of
significant percentage of this compound to the atmosphere in any
treatment involving aeration. Degradation of the dichloroethylenes in
air is reported to occur, with a half-life of 8 weeks.
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. General
observations relating molecular structure to ease of degradation have
been developed for all of these pollutants. The conclusion reached by
the study of the limited data is that biochemical oxidation produces
little or no degradation of 1,2-trans-dichloroethylene. No evidence
is available for drawing conclusions about the possible toxic or
inhibitory effect of 1,2-trans-dichloroethylene on POTW operation. It
is expected that its low molecular weight and degree of water
solubility will result in trans-1,2-DCE passing through a POTW to the
effluent if it is not degraded or volatilized. Very little trans-1,2-
DCE is expected to be found in sludge from POTW.
Ethylbenzene(38). Ethylbenzene is a colorless, flammable liquid
manufactured commercially from benzene and ethylene. Approximately
half of the benzene used in the U.S. goes into the manufacture of more
than three million tons of ethylbenzene annually. Ethylbenzene boils
at 136°C and has a vapor pressure of 7 mm Hg at 20°C. It is slightly
soluble in water (0.14 g/1 at 15°C) and is very soluble in organic
solvents.
387
-------
About 98 percent of the ethylbenzene produced in the U.S. goes into
the production of styrene, much of which is used in the plastics and
synthetic rubber industries. Ethylbenzene is a consitutent of xylene
mixtures used as diluents in the paint industry, agricultural
insecticide sprays, and gasoline blends.
Although humans are exposed to ethylbenzene from a variety of sources
in the environment, little information on effects of ethylbenzene in
man or animals is available. Inhalation can irritate eyes, affect the
respiratory tract, or cause vertigo. In laboratory animals
ethylbenzene exhibited low toxicity. There are no data available on
teratogenicity, mutagenicity, or carcinogenicity of ethylbenzene.
Criteria are based on data derived from inhalation exposure limits.
For the protection of human health from the toxic properties of
ethylbenzene ingested through water and contaminated aquatic
organisms, the ambient water quality criterion is 1.1 mg/1.
The behavior of ethylbenzene in POTW has not been studied in detail.
Laboratory scale studies of the biochemical oxidation of ethylbenzene
at concentrations greater than would normally be found in municipal
wastewaters have demonstrated varying degrees of degradation. In one
study with phenol-acclimated seed cultures 27 percent degradation was
observed in a half day at 250 mg/1 ethylbezene. Another study at
unspecified conditions showed 32, 38, and 45 percent degradation after
5, 10, and 20 days, respectively. Based on these results and general
observations relating molecular structure to ease of degradation, the
conclusion is reached that biological treatment produces only a
moderate removal of ethylbenzene in POTW by degradation.
Other studies suggest that most of the ethylbenzene entering a POTW is
removed from the aqueous stream to the sludge. The ethylbenzene
contained in the sludge removed from the POTW may volatilize.
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
388
-------
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 extermely 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 conduting and interpreting the 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 toxic properties of
methylene chloride ingested through water and contaminated aquatic
organisms, the ambient water criterion is 0.002 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
2000, 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.
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
389
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laboratory animals. No carcinogenicity 'studies are available which
can be used to demonstrate carcinogenic activity for naphthalene.
Naphthalene does bioconcentrate in aquatic organisms.
For the protection of human health from the toxic properties of
naphthalene ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be .143 mg/1.
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 .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 laboratory-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.
Pentachlorophenol(64). Pentachlorophenol (C«C15OH) is a white
crystalline solid produced commercially by chlorination of phenol or
polychlorophenols. U.S. annual production is in excess of 20,000
tons. Pentachlorophenol melts at 190°C and is slightly soluble in
water (14 mg/1). Pentachlorophenol is not detected by the 4-amino
antipyrene method.
Pentachlorophenol is a bactericide and fungacide and is used for
preservation of wood and wood products. It is competative with
creosote in that application. It is also used as a preservative in
glues, starches, and photographic papers. It is an effective algicide
and herbicide.
Although data are available on the human toxicity effects of penta-
chlorophenol, interpretation of data is frequently uncertain.
Occupational exposure observations must be examined carefully because
exposure to pentachlorophenol is frequently accompained by exposure to
other wood preservatives. Additionally, experimental results and
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occupational exposure observations must be examined carefully to make
sure that observed effects are produced by the pentachlorophenol
itself and not by the by-products which usually contaminate
pentachlorophenol.
Acute and chronic toxic effects of pentachlorophenol in humans are
similar; muscle weakness, headache, loss of appetite, abdominal pain,
weight loss, and irritation of skin, eyes, and respiratory tract.
Available literature indicates that pentachlorophenol does not
accumulate in body tissues to any significant extent. Studies on
laboratory animals of distribution of the compound in body tissues
showed the highest levels of pentachlorophenol in liver, kidney, and
intestine, while the lowest levels were in brain, fat, muscle, and
bone.
Toxic effects of pentachlorophenol in aquatic organisms are much
greater at pH of 6 where this weak acid is predominantly in the
undissociated form than at pH of 9 where the ionic form predominates.
Similar results were observed in mammals where oral lethal doses of
pentachlorophenol were lower when the compound was administered in
hydrocarbon solvents (un-ionized form) than when it was administered
as the sodium salt (ionized form) in water.
There appear to be no significant teratogenic, mutagenic, or
carcinogenic effects of pentachlorophenol.
For the protection of human health from the toxic properties of penta-
chlorophenol ingested through water and through contaminated aquatic
organisms, the ambient water quality criterion is determined to be
0.140 mg/1.
Only limited data are available for reaching conclusions about the
behavior of pentachlorophenol in POTW. Pentachlorophenol has been
found in the influent to POTW. In a study of one POTW the mean
removal was 59 percent over a 7 day period. Trickling filters removed
44 percent of the influent pentachlorophenol, suggesting that
biological degradation occurs. The same report compared removal of
pentachlorophenol of the same plant and two additional POTW on a later
date and obtained values of 4.4, 19.5 and 28.6 percent removal, the
last value being for the plant which was 59 percent removal in the
original study. Influent concentrations of pentachloropehnol ranged
from 0.0014 to 0-0046 mg/1. Other studies, includng the general
review of data relating molecular structure to biological oxidation,
indicate that pentachlorophenol is not removed by biological treatment
processes in POTW. Anaerobic digestion processes are inhibited by
0.4 mg/1 pentachlorophenol.
The low water solubility and low volatility of pentachlorophenol lead
to the expectation that most of the compund will remain in the sludge
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in a POTW. The effect on plants grown on land treated with
pentachlorophenol - containing sludge is unpredicatable. Laboratory
studies show that this compound affects crop germination at 5.4 mg/1.
However, photodecomposition of pentachlorophenol occurs in sunlight.
The effects of the various breakdown products which may remain in the
soil was not found in the literature.
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 C6H5OH.
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 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 3.4 mg/1.
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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.
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 terephathalic acids. The formula for all three acids
is C«H4(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,
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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. 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
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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. A chronic toxicity test with bis(2-ethylhexyl)
phthalate showed that significant reproductive impairment occurred at
3 mg/1 in the freshwater crustacean, Daphnia magna. In acute toxicity
studies, saltwater fish and organisms showed sensitivity differences
of up to eight-fold to butyl benzyl, diethyl, and dimethyl phthalates.
This suggests that each ester must be evaluated individually for toxic
effects.
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 all
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 their removal by biological
treatment in a POTW is expected to occur to a moderate degree. Using
these data and other observations relating molecular structure to ease
of biochemical degradation of other organic pollutants, the conclusion
was reached that butyl benzyl phthalate and dimethyl phthalate would
be removed in a POTW to a moderate degree by biological treatment. On
the same basis, it was concluded that di-n-octyl phthalate would be
removed to a slight degree or not at all.
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.
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 C6H4(COOC8H17)2. 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 OOP, in the plastics
industry where it is the most extensively used compound for the
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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 criterion is determined
to be 10 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 benzyl
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 expected to occur to a moderate degree.
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(COOC4H9)2 is the same as for its isomer, di-isobutyl
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phthalate. DBF 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 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 5
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.
Biological treatment in POTW is expected to remove di-n-butyl
phthalate to a moderate degree.
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 C6H4(COOCBH17)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 polyvinvl
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.
Diethyl phthalate (70). In addition to the general remarks and
discussion on phthalate esters, specific information on diethyl
phthalate is provided. Diethyl phthalate, or DEP, is a colorless
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liquid boiling at 296°C, and is insoluble in water. Its molecular
formula is C6H4(COOC2H5)2. Production of diethyl phthalate
constitutes about 1.5 percent of phthalate ester production in the
U.S.
Diethyl phthalate is approved for use in plastic food containers by
the U.S. FDA. In addition to its use as a polyvinylchloride (PVC)
plasticizer, DEP is used to plasticize cellulose nitrate for gun
powder, to dilute polysulfide dental impression materials, and as an
accelerator for dying triacetate fibers. An additional use which
would contribute to its wide distribution in the environment is as an
approved special denaturant for ethyl alcohol. The alcohol-containing
products for which DEP is an approved denaturant include a wide range
of personal care items such as bath preparations, bay rum, colognes,
hair preparations, face and hand creams, perfumes and toilet soaps.
Additionally, this denaturant is approved for use in biocides,
cleaning solutions, disinfectants, insecticides, fungicides, and room
deodorants which have ethyl alcohol as part of the formulation. It is
expected, therefore, that people and buildings would have some surface
loading of this priority pollutant which would find its way into raw
wastewaters.
For the protection of human health from the toxic properties of
diethyl phthalate ingested through water and through contaminated
aquatic organisms, the ambient water quality criterion is determined
to be 60 mg/1.
Although the behavior of diethylphthalate 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 79, 84, and 89 percent of theoretical was observed after 5, 5, and
20 days, respectively. Biological treatment in POTW is expected to
lead to a moderate degree of removal of diethylphthalate.
Dimethyl phthalate (71). In addition to the general remarks and dis-
cussion on phthalate esters, specific information on dimethyl
phthalate (DMP) is provided. DMP has the lowest molecular weight of
the phthalate esters - N.W. = 194 compared to M.W. of 391 for bis(2-
ethylhexyDphthalate. DMP has a boiling point of 282°C. It is a
colorless liquid, soluble in water to the extent of 5 mg/1. Its
molecular formula is C6H4(COOCH3)2.
Dimethyl phthalate production in the U.S. is just under one percent of
total phthalate ester production. DMP is used to some extent as a
plasticizer in cellulosics. However, its principle specific use is
for dispersion of polyvinylidene fluoride (PVDF). PVDF is resistant
to most chemicals and finds use as electrical insulation, chemical
process equipment (particularly pipe), and as a base for long-life
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finishes for exterior metal siding. Coil coating techniques are used
to apply PVDF dispersions to aluminum or galvanized steel siding.
For the protection of human health from the toxic properties of
dimethyl phthalate ingested through water and through contaminated
aquatic organisms, the ambient water quality criterion is determined
to be 160 mg/1.
Biological treatment in POTW is expected to provide a moderate degree
of removal of dimethyl 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 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
73
Benzo(a)anthrancene (1,2-benzanthracene1
m.p. 162°C
Benzo(a)pyrene (3,4-benzopyre
74 3,4-Benzofluoranthene
ne)
m.p. 176°C
75
76
m.p. 168QC
Benzo(k)fluoranthene (11,12-benzofluoranthene)
m.p. 217°C
Chrysene (1,2-benzphenanthrene)
77 Acenaphthylene
m.p. 255°C
m.p. 92<>C
78
Anthracene
m.p. 216 C
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79 Benzo(ghi)perylene (1,12-benzoperylene)
m.p. not reported
80
82
83
Fluorene (alpha-diphenylenemethane)
m.p. 116°C
81 Phenanthrene
m.p. 101°C
m.p. 101°C
Dibenzo(a,h)anthracene (1,2,5,6-dibenzoanthracene)
m.p. 269°C
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
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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 (GO.
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, 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 car-
cinogenic effects of exposure to polynuclear aromatic hydrocarbons
(PAH) through ingestion of water and contaminated aquatic organisms,
the ambient water concentration is zero. Concentrations of PAH
estimated to result in additional risk of 1 in 100,000 were derived by
the EPA and the Agency is considering setting criteria at an interim
target risk level in the range of 10~5, 10~«, or 10~7 with
corresponding criteria of 0.0000097 mg/1, 0.00000097 mg/1, and
0.000000097 mg/1, respectively.
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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 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.
Tetrachloroethylene(85). Tetrachloroethylene (CC12CC1Z), also called
perchloroethylene and PCE, is a colorless nonflammable liquid produced
mainly by two methods - chlorination and pyrolysis of ethane and
propane, and oxychlorination of dichloroethane. U.S. annual
production exceeds 300,000 tons. PCE boils at 121°C and has a vapor
pressure of 19 mm Hg at 20°C. It is insoluble in water but soluble in
organic solvents.
Approximately two-thirds of the U.S. production of PCE is used for dry
cleaning. Textile processing and metal degreasing, in equal amounts
consume about one-quarter of the U.S. production.
The principal toxic effect of PCE on humans is central nervous system
depression when the compound is inhaled. Headache, fatigue,
sleepiness, dizziness and sensations of intoxication are reported.
Severity of effects increases with vapor concentration. High
integrated exposure (concentration times duration) produces kidney and
liver damage. Very limited data on PCE ingested by laboratory animals
indicate liver damage occurs when PCE is administered by that route.
PCE tends to distribute to fat in mammalian bodies.
One report found in the literature suggests, but does not conclude,
that PCE is teratogenic. PCE has been demonstrated to be a liver
carcinogen in B6C3-F1 mice.
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For the maximum protection of human health from the potential
carcinogenic effects of exposure to tetrachloroethylene through
ingestion of water and contaminated aquatic organisms, the ambient
water concentration is zero. Concentrations of tetrachloroethylene
estimated to result in additional lifetime cancer risk levels of 10~7,
10~6, and 10~5 are 0.000020 mg/1, 0.00020 mg/1, and 0.0020 mg/1,
respectively.
No data were found regarding the behavior of PCE in POTW. Many of the
organic priority pollutants have been investigated, at least in
laboratory scale studies, at concentrations higher than those expected
to be contained by most municipal wastewaters. General observations
have been developed relating molecular structure to ease of
degradation for all of the organic priority pollutants. The
conclusions reached by the study of the limited data is that
biological treatment produces a moderate removal of PCE in POTW by
degradation. No information was found to indicate that PCE
accumulates in the sludge, but some PCE is expected to be adsorbed
onto settling particles. Some PCE is expected to be volatilized in
aerobic treatment processes and little, if any, is expected to pass
through into the effluent from the POTW.
Toluene(86). Toluene is a clear, colorless liquid with a benzene like
odor. It is a naturally occuring compound derived primarily from
petroleum or petrochemical processes. Some toluene is obtained from
the manufacture of metallurgical coke. Toluene is also referred to as
totuol, methylbenzene, methacide, and phenymethane. It is an aromatic
hydrocarbon with the formula C6H5CH3. It boils at 111°C and has a
vapor pressure of 30 mm Hg at room temperature. The water solubility
of toluene is 535 mg/1, and it is miscible with a variety of organic
solvents. Annual production of toluene in the U.S. is greater than 2
million metric tons. Approximately two-thirds of the toluene is
converted to benzene and the remaining 30 percent is divided
approximately equally into chemical manufacture, and use as a paint
solvent and aviation gasoline additive. An estimated 5,000 metric
tons is discharged to the environment annually as a constituent in
wastewater.
Most data on the effects of toluene in human and other mammals have
been based on inhalation exposure or dermal contact studies. There
appear to be no reports of oral administration of toluene to human
subjects. A long term toxicity study on female rats revealed no
adverse effects on growth, mortality, appearance and behavior, organ
to body weight ratios, blood-urea nitrogen levels, bone marrow counts,
peripheral blood counts, or morphology of major organs. The effects
of inhaled toluene on the central nervous system, both at high and - low
concentrations, have been studied in humans and animals. However,
ingested toluene is expected to be handled differently by the body
because it is absorbed more slowly and must first pass through the
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liver before reaching the nervous system. Toluene is extensively and
rapidly metabolized in the liver. One of the principal metabolic
products of toluene is benzoic acid, which itself seems to have little
potential to produce tissue injury.
Toluene does not appear to be teratogenic in laboratory animals or
man. Nor is there any conclusive evidence that toluene is mutagenic.
Toluene has not been demonstrated to be positive in any in vitro
mutagenicity or carcinogenicity bioassay system, nor to be
carcinogenic in animals or man.
Toluene has been found in fish caught in harbor waters in the vicinity
of petroleum and petrochemical plants. Bioconcentration studies have
not been conducted, but bioconcentration factors have been calculated
on the basis of the octanol-water partition coefficient.
For the protection of human health from the toxic properties of
toluene ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 12.4 mg/1.
Acute toxicity tests have been conducted with toluene and a variety of
freshwater fish and Daphnia magna. The latter appears to be
significantly more resistant than fish. No test results have been
reported for the chronic effects of toluene on freshwater fish or
invertebrate species.
No detailed study of toluene behavior in POTW is available. However,
the biochemical oxidation of many of the priority pollutants has been
investigated in laboratory scale studies at concentrations greater
than those expected to be contained by most municipal wastewaters. At
toluene concentrations ranging from 3 to 250 mg/1 biochemical
oxidation proceeded to fifty percent of theroetical or greater. The
time period varied from a few hours to 20 days depending on whether or
not the seed culture was acclimated. Phenol adapted acclimated seed
cultures gave the most rapid and extensive biochemical oxidation. The
conclusion reached by study of the limited data is that biological
treatment produces moderate removal of toluene in POTW. The
volatility and relatively low water solubility of toluene lead to the
expectation that aeration processes will remove significant quantities
of toluene from the POTW.
Trichloroethylene(87). Trichloroethylene (1,1,2-trichloroethylene or
TCE) is a clear colorless liquid boiling at 87°C. It has a vapor
pressure of 77 mm Hg at room temperature and is slightly soluble in
water (1 g/1). U.S. production is greater than 0.25 million metric
tons annually. It is produced from tetrachloroethane by treatment
with lime in the presence of water.
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TCE is used for vapor phase degreasing of metal parts, cleaning and
drying electronic components, as a solvent for paints, as a
refrigerant, for extraction of oils, fats, and waxes, and for dry
cleaning. Its widespread use and relatively high volatility result in
detectable levels in many parts of the environment.
Data on the effects produced by ingested TCE are limted. Most studies
have been directed at inhalation exposure. Nervous system disorders
and liver damage are frequent results of inhalation exposure. In the
short term exposures, TCE acts as a central nervous system depressant
- it was used as an anesthetic before its other long term effects were
defined.
TCE has been shown to induce transformation in a highly sensitive iri
vitro Fischer" rat embryo cell system (F1706) that is used for
identifying carcinogens. Severe and persintant toxicity to the liver
was recently demonstrated when TCE was shown to produce carcinoma of
the liver in mouse strain B6C3F1. One systematic study of TCE
exposure and the incidence of human cancer was based on 518 men
exposed to TCE. The authors of that study concluded that although the
cancer risk to man cannot be ruled out, exposure to low levels of TCE
probably does not present a very serious and general cancer hazard.
TCE is bioconcentrated in aquatic species, making the consumption of
such species by humans a significant source of TCE. For the
protection of human health from the potential-carcinogenic effects of
exposure to trichloroethylene through ingestion of water and
contaminated aquatic organisms, the ambient water concentration is
zero. Concentrations of trichloroethylene estimated to result in
additional lifetime cancer risk of 1 in 100,000 corresponds to an
ambient water concentration of 0.00021 mg/1.
Only a very limited amount of data on the effects of TCE on freshwater
aquatic life are available. One species of fish (fathead minnows)
showed a loss of equilibrium at concentrations below those resulting
in lethal effects.
The behavior of trichloroethylene in POTW has not been studied.
However, in laboratory scale studies of organic priority pollutants,
TCE was subjected to biochemical oxidation conditions. After 5, 10,
and 20 days no biochemical oxidation occurred. On the basis of this
study and general observations relating molecular structure to ease of
degradation, the conclusion is reached that TCE would undergo no
removal by biological treatment in a POTW. The volatility and
relatively low water solubility of TCE is expected to result in
volatilization of some of the TCE in aeration steps in a POTW.
Antimony(114). Antimony (chemical name - stibium, symbol Sb)
classified as a non-metal or metalloid, is a silvery white , brittle,
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crystalline solid. Antimony is found in small ore bodies throughout
the world. Principal ores are Qxides 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 non
- metal 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 epidemiolocy 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 appetitie,
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
organisms the ambient water criterion is determined to be 0.145 mg/1.
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
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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 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 of exposure to arsenic through ingestion of water
and contaminated aquatic organisms, the ambient water concentration is
zero. Concentrations of arsenic estimated to result in additional
lifetime cancer risk levels of 10-*, 10-«, and lO-« are 0.0000002
mg/1, 0.000002 mg/1, and 0.00002 mg/1, respectively.
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
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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.
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 allpwed 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).
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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 no adverse
effects from soils with levels up to 100 mg/kg cadmium, these
contaminated crops could have a significant impact on human health.
Chromium(119). Chromium is an elemental metal usually found as a
chromite (FeOCr203). 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 (Na2CrO4), 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
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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.
For the protection of human health from the toxic properties of
chromium (except hexavalent chromium) ingested through water and
contaminated aquatic organisms, the recommended water qualtiy
criterion is 0.050 mg/1.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to hexavalent chromium through
ingestion of water and contaminated aquatic organisms, the ambient
water concentration is zero.
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 56 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
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concentrations of total chromium of over 20,000 mg/kg (dry basis) 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 (CuzO), malechite [CuCOj»Cu(OH)2], azurite [2CuCO3»Cu(OH)2],
chalcopyrite (CuFeS?), 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 some common fish species.
In general the salmonoids are very sensitive and the sunfishes are
less sensitive to copper.
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The recommended criterion to protect saltwater aquatic life is
0.00097 mg/1 as a 24-hour average, and 0.018 mg/1 maximum
concentration.
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.
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).
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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.
Cyanide(121). Cyanides are among the most toxic of pollutants
commonly observed in industrial wastewaters. Introduction of cyanide
into industrial processes is usually by dissolution of potassium
cyanide (KCN) or sodium cyanide (NaCN) in process waters. However,
hydrogen cyanide (HCN) formed when the above salts are dissolved in
water, is probably the most acutely lethal compound.
The relationship of pH to hydrogen cyanide formation is very
important. As pH is lowered to below 7, more than 99 percent of the
cyanide is present as HCN and less than 1 percent as cyanide ions.
Thus, at neutral pH, that of most living organisms, the more toxic
form of cyanide prevails.
Cyanide ions combine with numerous heavy metal ions to form complexes.
The complexes are in equilibrium with HCN. Thus, the stability of the
metal-cyanide complex and the pH determine the concentration of HCN.
Stability of the metal-cyanide anion complexes is extremely variable.
Those formed with zinc, copper, and cadmium are not stable - they
rapidly dissociate, with production of HCN, in near neutral or acid
waters. Some of the complexes are extremely stable. Cobaltocyanide
is very resistant to acid distillation in the laboratory. Iron
cyanide complexes are also stable, but undergo photodecomposition to
give HCN upon exposure to sunlight. Synergistic effects have been
demonstrated for the metal cyanide complexes making zinc, copper, and
cadmium, cyanides more toxic than an equal concentration of sodium
cyanide.
The toxic mechanism of cyanide is essentially an inhibition of oxygen
metabolism, i.e., rendering the tissues incapable of exchanging
oxygen. The cyanogen compounds are true noncummulative protoplasmic
poisons. They arrest the activity of all forms of animal life.
Cyanide shows a very specific type of toxic action. It inhibits the
cytochrome oxidase system. This system is the one which facilitates
electron transfer from reduced metabolites to molecular oxygen. The
human body can convert cyanide to a non-toxic thiocyanate and
eliminate it. However, if the quantity of cyanide ingested is too
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great at one time, the inhibition of oxygen utilization proves fatal
before the detoxifying reaction reduces the cyanide concentration to a
safe level.
Cyanides are more toxic to fish than to lower forms of aquatic
organisms such as midge larvae, crustaceans, and mussels. Toxicity to
fish is a function of chemical form and concentration, and is
influenced by the rate of metabolism (temperature), the level of
dissolved oxygen, and pH. In laboratory studies free cyanide
concentrations ranging from 0.05 to 0.15 mg/1 have been proven to be
fatal to sensitive fish species including trout, bluegill, and fathead
minnows. Levels above 0.2 mg/1 are rapidly fatal to most fish
species. Long term sublethal concentrations of cyanide as low as
0.01 mg/1 have been shown to affect the ability of fish to function
normally, e.g., reproduce, grow, and swim.
For the protection of human health from the toxic properties of
cyanide ingested through water and through contaminated aquatic
organisms, the ambient water quality criterion is determined to be
0.200 mg/1.
Persistence of cyanide in water is highly variable and depends upon
the chemical form of cyanide in the water, the concentration of
cyanide, and the nature of other constituents. Cyanide may be
destroyed by strong oxidizing agents such as permanganate and
chlorine. Chlorine is commonly used to oxidize strong cyanide
solutions. Carbon dioxide and nitrogen are the products of complete
oxidation. But if the reaction is not complete, the very toxic
compound, cyanogen chloride, may remain in the treatment system and
subsequently be released to the environment. Partial chlorination may
occur as part of a POTto treatment, or during the disinfection
treatment of surface water for drinking water preparation.
Cyanides can interfere with treatment processes in POTW, or pass
through to ambient waters. At low concentrations and with acclimated
microflora, cyanide may be decomposed by microorganisms in anaerobic
and aerobic environments or waste treatment systems. However, data
indicate that much of the cyanide introduced passes through to the
POTW effluent. The mean pass-through of 14 biological plants was 71
percent. In a recent study of 41 POTW the effluent concentrations
ranged from 0.002 to 100 mg/1 (mean = 2.518, standard
deviation = 15.6). Cyanide also enhances the toxicity of metals
commonly found in POTW effluents, including the priority pollutants
cadmium, zinc, and copper.
Data for Grand Rapids, Michigan, showed a significant decline in
cyanide concentrations downstream from the POTW after pretreatment
regulations were put in force. Concentrations fell from 0.66 mg/1
before, to 0.01 mg/1 after pretreatment was required.
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Lead (122). Lead is a soft, malleable ductible, blueish-gray,
metallic element, usually obtained from the 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 lead 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 cocarcinogen in some species of experimental
animals. Lead is teratogenic in experimental animals. Mutangenicity
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.
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.
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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 insoluable 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 introduced 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.
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 100 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 0.0002 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
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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 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)9Se], 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 con-
centrations in the range of 0.0001 to 0.006 mg/1 although the most
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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 0.133 mg/1.
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 POTW. 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
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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 organic matter in
sludge. Soil treatments, such as liming reduce the solubility of
nickel. Toxicity of nickel to plants is enhanced in acidic soils.
Selenium(125). Selenium (chemical symbol Se) is a non-metallic
element existing in several allotropic forms. Gray selenium, which
has a metallic appearance, is the stable form at ordinary temperatures
and melts at 220°C. Selenium is a major component of 38 minerals and
a minor component of 37 others found in various parts of the world.
Most selenium is obtained as a by-product of precious metals recovery
from electrolytic copper refinery slimes. U.S. annual production at
one time reached one million pounds.
Principal uses of selenium are in semi-conductors, pigments,
decoloring of glass, zerography, and metallurgy. It also is used to
produce ruby glass used in signal lights. Several selenium compounds
are important oxidizing agents in the synthesis of organic chemicals
and drug products.
While results of some studies suggest that selenium may be an
essential element in human nutrition, the toxic effects of selenium in
humans are well established. Lassitude, loss of hair, discoloration
and loss of fingernails are symptoms of selenium poisoning. In a
fatal case, of ingestion of a larger dose of selenium acid, peripheral
vascular collapse, pulumonary edema, and coma occurred. Selenium
produces mutagenic and teratogenic effects, but it has not been
established as exhibiting carcinogenic activity.
For the protection of human health from the toxic properties of
selenium ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determind to be 0.010 mg/1.
Very few data are available regarding the behavior of selenium in
POTW. One EPA survey of 103 POTW revealed one POTW using biological
treatment and having selenium in the influent. Influent concentration
was 0.0025 mg/1, effluent concentration was 0.0016 mg/1 giving a
removal of 37 percent. It is not known to be inhibitory to POTW
processes. In another study, sludge from POTW in 16 cities was found
to contain from 1.8 to 8.7 mg/kg selenium, compared to 0.01 to 2 mg/kg
in untreated soil. These concentrations of selenium in sludge present
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a potential hazard for humans or other mammuals eating crops grown on
soil treated with selenium containing sludge.
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 Targe 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 0.010 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.
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.
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Zinc(128). 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, 5 mg/1 was adopted for the ambient water criterion.
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.
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.
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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 non-conventional 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
(AlaOj) is extracted from the bauxite and 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.
Aluminum is non-toxic and its salts are used as coagulants in water
treatment. Although some aluminum salts are soluble, alkaline
conditions cause precipitation of the aluminum as a hydroxide.
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Aluminum is commonly used in cooking utensils. There are no reported
adverse physiological effects on man from low concentrations of
aluminum in drinking water.
Aluminum does not have any adverse effects on POTW operation at any
concentrations normally encountered.
Ammonia. Ammonia (chemical formula NH3) is a non-conventional
pollutant. It is a colorless gas with a very pungent odor, detectable
at concentrations of 20 ppm in air by the nose, and is very soluble in
water (570 gm/1 at 25°C). Ammonia is produced industrially in very
large quantities (nearly 20 millions tons annually in the U.S.). It
is converted to ammonium compounds or shipped in the liquid form (it
liquifies at -33°C). Ammonia also results from natural processes.
Bacterial action on nitrates or nitrites, as well as dead plant and
animal tissue and animal wastes produces ammonia. Typical domestic
wastewaters contain 12 to 50 mg/1 ammonia.
The principal use of ammonia and its compounds is as fertilizer. High
amounts are introduced into soils and the water runoff from
agricultural land by this use. Smaller quantities of ammonia are used
as a refrigerant. Aqueous ammonia (2 to 5 percent solution) is widely
used as a household cleaner. Ammonium compounds find a variety of
uses in various industries.
Ammonia is toxic to humans by inhalation of the gas or ingestion of
aqueous solutions. The ionized form (NH4+) is less toxic than the
unionized form. Ingestion of as little as one ounce of household
ammonia has been reported as a fatal dose. Whether inhaled or
ingested, ammonia acts distructively on mucous membrane with resulting
loss of function. Aside from breaks in liquid ammonia refrigeration
equipment, industrial hazard from ammonia exists where solutions of
ammonium compounds may be accidently treated with a strong alkali,
releasing ammonia gas. As little as 150 ppm ammonia in air is
reported to cause laryngeal spasm, and inhalation of 5000 ppm in air
is considered sufficient to result in death.
The behavior of ammonia in POTW is well documented because it is a
natural component of domestic wastewaters. Only very high
concentrations of ammonia compounds could overload POTW. One study
has shown that concentrations of unionized ammonia greater than
90 mg/1 reduce gasification in anaerobic digesters and concentrations
of 140 mg/1 stop digestion competely. Corrosion of copper piping and
excessive consumption of chlorine also result from high ammonia
concentrations. Interference with aerobic nitrification processes can
occur when large concentrations of ammonia suppress dissolved oxygen.
Nitrites are then produced instead of nitrates. Elevated nitrite
concentrations in drinking water are known to cause infant
methemoglobinemia.
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Cobalt. Cobalt is a non-conventional pollutant. It is a brittle,
hard, magnetic, gray metal with a reddish tinge. Cobalt ores are
usually the sulfide or arsenide [smaltite-(Co,Ni)As2; cobaltite-CoAsS]
and are sparingly distributed in the earth's crust. Cobalt is usually
produced as a by-product of mining copper, nickel, arsenic, iron,
manganese, or silver. Because of the variety of ores and the very low
concentrations of cobalt, recovery of the metal is accomplished by
several different processes. Most consumption of cobalt is for
alloys. Over two-thirds of U.S. production goes to heat resistant,
magnetic, and wear resistant alloys. Chemicals and color pigments
make up most of the rest of consumption.
Cobalt and many of its alloys are not corrosion resistant, therefore
minor corrosion of any of the tool alloys or electrical resistance
alloys can contribute to its presence in raw wastewater from a variety
of manufacturing facilities. Additionally, the use of cobalt soaps as
dryers to accelerate curing of unsaturated oils used in coatings may
be a general source of small quantities of the metal. Several cobalt
pigments are used in paints to produce yellows or blues.
Cobalt is an essential nutrient for humans and other mammals, and is
present at a fairly constant level of about 1.2 mg in the adult human
body. Mammals tolerate low levels of ingested water-soluble cobalt
salts without any toxic symptoms; safe dosage levels in man have been
stated to be 2-7 mg/kg body weight per day. A goitrogenic effect in
humans is observed after the systemic administration of 3-4 mg cobalt
as cobaltous chloride daily for three weeks. Fatal heart disease
among heavy beer drinkers was attributed to the cardiotoxic action of
cobalt salts which were formerly used as additives to improve foaming.
The carcinogenicity of cobalt in rats has been verified, however,
there is no evidence for the involvement of dietary cobalt in
carcinogenisis in mammals.
There are no data available on the behavior of cobalt in POTW. There
are no data to lead to an expectation of adverse effects of cobalt on
POTW operation or the utility of sludge from POTW for crop
application. Cobalt which enters POTW is expected to pass through to
the effluent unless sufficient sulfide ion is present, or generated in
anaerobic processes in the POTW to cause precipitation of the very
insoluble cobalt sulfide.
Iron. Iron is a non-conventional polluant. It is an abundant metal
found at many places in the earth's crust. The most common iron ore
is hematite (Fez03) 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.
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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.
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 non-conventional 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 (Mn02) 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
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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 been reported in the
literature. A small outbreak of encephalitis - like disease, with
early symptoms of lethergy 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 non-conventional 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
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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 grom 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.
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 non-conventional 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.
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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.
2. Heavy Hydrocarbons, Fuels, and Tars - These include the crude
oils, diesel oils, #6 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
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recommended that public water supply sources be essentially free fro'm
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 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
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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.
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
chemcials required to remove pollutants and to measure their
effectiveness. Removal of pollutants, especially dissolved solids is
affected by the pH of the wastewater.
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
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industry categories. A neutral pH range (approximately 6-9) is
generally desired because either extreme beyond this 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."
REGULATION OF SPECIFIC POLLUTANTS
For all subcategories except for the lead subcategory, discussion of
individual pollutant parameters selected or not selected for
consideration for specific regulation are based on concentrations
obtained from sampling analysis of total raw wastewater streams for
each battery manufacturing element. Depending on the specific
element, only one or many manufacturing wastewater streams may be
included in the total raw wastewater stream. Section V addressed each
element, the samples collected, and analysis of these samples. Tables
from the section are referenced where appropriate within each
subcategory.
Cadmium Subcateqory
Pollutant Parameters Selected for Regulation. Based on verification
sampling results of the manufacturing elements and wastewater sources
listed in Figure V-2 (Page 193 ), and a careful examination of the
cadmium subcategory manufacturing processes and raw materials, twelve
pollutant parameters were selected to be considered for regulation in
effluent limitations and standards for this subcategory. The twelve
are: cadmium, chromium, cyanide, lead, mercury, nickel, silver,
zinc, cobalt, oil and grease, total suspended solids, and pH. These
pollutants were observed at significant levels in raw wastewater
produced in this subcategory and are amenable to control by identified
wastewater treatment and control practices.
Cadmium concentrations appeared in 29 of 31 raw wastewater streams in
the cadmium subcategory Since it is a cell reactant in cadmium anodes,
it is involved in almost every step of the manufacturing process. The
maximum cadmium concentration was 365 mg/1. Cadmium was present at
levels that can be reduced by specific treatment methods. Therefore
cadmium is considered for specific regulation.
Chromium concentrations appeared in 21 of 31 raw wastewater streams in
the subcategory. The maximum concentration was 1.52 mg/1. Chromium
is removed by specific treatment methods to levels less than some of
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the observed levels. Therefore chromium is considered for specific
regulation.
Cyanide was found in 23 of 27 raw wastewater streams in the cadmium
subcategory. The maximum concentration was 9.45 mg/1. Cyanide
concentrations can be lowered by available specific treatment methods,
and is therefore considered for regulation.
Lead concentrations appeared in 6 of 31 raw wastewater streams in the
cadmium subcategory with appreciable levels (greater than 0.1 mg/1)
observed from silver powder production. Since the maximum
concentration of 0.281 mg/1 can be reduced by specific treatment
methods, lead is considered for specific regulation.
Mercury concentrations appeared in 15 of 31 raw wastewater streams in
the cadmium subcategory. The maximum concentration was 0.032 mg/1.
This priority pollutant is not an identified raw material in this
subcategory. Mercury can be removed to lower concentrations by use of
specific treatment methods. Accordingly, mercury is considered for
specific regulation.
Nickel concentrations appeared in 30 of 31 raw wastewater streams in
the cadmium subcategory. Since it is a cathode reactant and an
electrode support material in cadmium anodes, nickel is involved in
almost every step of the manufacturing process. The maximum nickel
concentration in raw wastewater was 514 mg/1. Nickel can be removed
by specific treatment methods and therefore is considered for specific
regulation.
Silver concentrations appeared in 4 of 4 raw wastewater streams in the
cadmium subcategory. All quantifiable concentrations were from silver
powder production where the maximum concentration was 24.1 mg/1.
Silver can be removed by specific treatment methods and is therefore
considered for specific regulation in this subcategory.
Zinc concentrations appeared in 28 of 31 raw wastewater streams in the
cadmium subcategory. The maximum zinc concentration in raw wastewater
was 6,430 mg/1 - in the stream from cadmium powder production. Other
streams had concentrations of less than 13 mg/1. Zinc can be removed
by specific treatment methods to concentrations lower than those
measured in the raw wastewaters. Therefore zinc is considered for
specific regulation.
Cobalt concentrations appeared in the raw wastewater in 13 of 31
streams in the cadmium subcategory. Cobalt is added to some nickel
electrodes used in this subcategory. The maximum concentration was 5
mg/1. Because of its potentially toxic effect, and the fact that
cobalt can be removed by specific treatment methods, cobalt is
considered for specific regulation in this subcategory.
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Oil and grease, a conventional pollutant, appeared at concentrations
of up to 1960 mg/1 in raw wastewater streams from all process elements
in the cadrnlrum subcategory. This pollutant can be removed by
conventional ' treatment methods, and is therefore considered for
regulation. Because it is present at raw waste concentrations greater
than the 100 mg/1 level considered acceptable for introduction into a
POTW, it is considered for regulation for both indirect and direct
discharges.
Suspended solids concentrations appeared in 27 of 30 raw wastewater
streams from the cadmium subcategory analyzed for TSS. The maximum
concentration was 2687 mg/1. Some of the TSS is comprised of
hydroxides of cadmium, nickel or zinc. Because this conventional
pollutant contains quantities of toxic metals, TSS requires
consideration for regulation, both direct and indirect discharges from
this subcategory.
The pH of wastewater streams resulting from the manufacture of cadmium
anode batteries is observed to range from 1 to 14. Acid discharges
may be associated with electrodeposition, impregnation, and metal
recovery processes, and with the manufacture of cadmium powder.
Highly alkaline wastewaters result from electrolyte losses and from
rinses following precipitation of impregnated cadmium or nickel.
Since deleterious environmental effects may result from pH values
outside the range of 7.5 to 10.0, regulation of this parameter in the
cadmium subcategory effluents is clearly required. Further, pH must
be controlled for effective removal of other pollutants present in
these effluents.
Pollutant Parameters Not Selected for Specific Regulation. Four
pollutant parameters - methylene chloride, trichloroethylene, ammonia,
and total phenols - were included in verification sampling and
analysis, but were dropped from consideration for regulation in this
subcategory after careful examination of concentration levels and
manufacturing materials and processes.
Methylene chloride concentrations appeared in 6 of 30 raw wastewater
streams from the cadmium subcategory. All values were below the
quantifiable limit. Specific regulation of methylene chloride is not
considered further.
Trichloroethylene concentrations appeared in 12 of the 30 raw
wastewater streams from the cadmium subcategory. All values were
below the quantifiable limit, therefore, specific regulation of
trichloroethylene is not considered.
Ammonia concentrations appeared in 19 of 25 raw wastewater streams on
which analysis was performed for this pollutant parameter in the
cadmium subcategory. The maximum concentration was 86 mg/1. Other
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concentrations were significantly less, and were below the level
achievable with available specific treatment methods. Most
concentrations were in the range of ammonia concentrations found in
typical domestic wastewater. Specific regulation of ammonia is
therefore not considered.
"Total phenols" concentrations appeared in 24 of 27 raw wastewater
streams analyzed. The maximum concentration was 0.086 mg/1. Some of
the priority pollutant phenols as well as many phenols which are not
priority pollutants contribute to "total phenols." Because
concentrations found in this subcategory are below the levels for
which practical specific treatment methods exist, and because some
plant inlet water samples showed total phenols as high as 0.020 mg/1,
specific regulation of "total phenols" is not considered.
Calcium Subcategory
Parameters Selected for Specific Regulation. To be determined after
verification analysis completed.
Lead Subcategory
Parameters Selected for Specific Regulation. Analysis of pollutant
parameters in the lead subcategory included an evaluation of
concentration in total raw wastewater streams from five plants in the
subcategory (Table V-36 Page 292 ), an evaluation of concentrations in
samples of individual process element streams ( Table V-40 Page 298 ),
and an evaluation of the raw materials and the manufacturing processes
employed. This analysis led to the selection of thirteen pollutant
parameters considered for specific regulation. The parameters
selected are: antimony, cadmium, chromium, copper, lead, mercury,
nickel, silver, zinc, iron, oil and grease, total suspended solids and
pH. Each has been found in raw wastewater from plants in this
subcategory at levels that are amenable to treatment and monitoring.
Antimony concentrations appeared in 4 of 13 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 0.19 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, antimony is considered for specific
regulation in this subcategory.
Cadmium concentration appeared in 10 of 13 total raw wasterwater
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
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measured concentrations in raw wastewaters are above the concentration
level which can be achieve by specific treatment methods, cadmium is
considered for specific regulation in this subcategory.
Chromium concentrations appeared in 12 of 12 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 raw wastewater samples. Specific treatment
methods can reduce chromium below this level. Therefore, chromium is
considered for specific regulation.
Copper concentrations appeard in 12 of 12 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 9.85 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. All of the total raw
wastewater 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 five plants in the
lead subcategory. The maximum concentration was 45.9 mg/1 in the
total raw wastewater streams and as high as 6000 mg/1 in the pasting
raw wastewater samples. All concentrations 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 from the lead subcategory. Streams from only two plants
contained this pollutant. The maximum concentration was 0.065 mg/1
which was from the battery wash 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 a process addition, specific regulation of
mercury is considered in this subcategory.
Nickel concentrations appeared in 10 of 12 total raw wastewater
streams in the lead subcategory. The maximum concentration was 2.8
mg/1 which appeared in the battery wash 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 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.
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Silver concentrations appeared in 8 of 13 total raw wastewater streams
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 grid in this subcategory. Silver is considered for
specific regulation in this subcategory.
Zinc concentrations appeared in all total raw wastewater streams from
the five plants in the lead subcategory. The maximum concentration
was 6.8 mg/1 in the total raw wastewater streams and as high as
9.87 mg/1 in the battery repair 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 in this
subcategory.
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
460 mg/1 in the battery repair 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. The concentrations were greater than those
which can be achieved by specific treatment methods. Therefore, iron
is considered for specific regulation.
Oil and grease concentrations appeared in all raw wastewater streams
and samples of 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 streams at concentrations as high as
1300 mg/1 in total raw wastewater streams at plants within the lead
subcategory. 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
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and in process steps. The pH of these wastewater samples range from
12 down to 1.8. 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-ethylhexyl)phthalate, butyl benzyl phthalate, di-n-butyl
phthalate, di-n-octyl phthalate, anthracene, phenanthrene, pyrene,
arsenic, strontium, and "total phenols."
1,1,1-Trichloroethane concentrations appeared in all of the total raw
wastewater streams from plants in the lead subcategory. 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.
Chloroform concentrations appeared in 6 of 13 total raw wastewater
streams in the lead subcategory. The maximum concentration was 0-009
mg/1. 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 8 of 13 total raw
wastewater streams in the lead subcategory. 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 13 total raw wastewater
streams from the lead subcategory. 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
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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 streams concentrations
appeared in total raw wastewater streams from the lead subcategory.
Bis (2-ethylhexyl) phthalate concentrations appeared in all total raw
wastewater streams at concentrations up to 0.135 mg/1. The other four
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. Therefore, even though specific treatment
methods can achieve lower concentrations than some which were found,
specific regulation of these four phthalate esters in the lead
subcategory is not considered.
Three PAH - anthracene, phenanthrene, and pyrene concentrations
appeared in total raw wastewater streams analyzed for these priority
pollutant parameters. The maximum concentration was 0.03.2 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 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 4 of 12 total raw wastewater
streams from the lead subcategory. In the total raw wastewater
streams the maximum concentration was 0.12 mg/1 and as high as
0.13 mg/1 in a battery wash raw waster sample. Only two of the five
plants sampled had arsenic in the raw wastewater. Arsenic is an
additive of lead used in some battery plate grids. However,
concentration levels attainable by specific treatment methods are
several times 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. Streams from three of
the five plants sampled in the lead subcategory contained strontium.
The maximum concentration of 0.039 mg/1 which appeared in the battery
wash raw wastewater samples is lower than the level that can be
achieved by available specific treatment methods. Therefore,
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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.
Leclanche Subcateqory
Pollutant Parameters Selected for Specific Regulation. The analysis
of raw wastewater samples from the manufacturing elements (including
the screening sample) and wastewater sources listed in Figure V-19
(Page 211 ), and an evaluation of raw materials and manufacturing
processes employed led to the selection of thirteen pollutant
parameters for consideration for specific regulation. The parameters
selected are: arsenic, cadmium, chromium, copper, lead, mercury,
nickel, selenium, zinc, manganese, oil and grease, total suspended
solids and pH. Each has been found in raw wastewaters from plants in
this subcategory at levels that are amenable to treatment and
monitoring.
Arsenic concentrations appeared 3 of 13 raw wastewater streams in the
Leclanche subcategory. All concentrations appeared in ancillary
operations from one plant on three sampling days. The concentration
ranged from 0.07 mg/1 to 0.64 mg/1. Arsenic has been determined to
have carcinogenic properties, and specific treatment methods for
removal of arsenic at the observed concentrations are available.
Therefore, arsenic is considered for specific regulation.
Cadmium concentrations appeared in all 13 raw wastewater streams from
the Leclanche subcategory. The maximum concentration was 0.47 mg/1.
Cadmium is a toxic metal and can be removed by specific treatment
. methods to concentrations below those found in most of the raw
wastewater streams. Therefore, cadmium is considered for specific
regulation.
Total chromium concentrations appeared in 7 of 13 raw wastewater
streams from the Leclanche subcategory. The maximum concentration was
2.88 mg/1. Chromium is a toxic metal which can be removed by specific
treatment methods. Therefore, it is considered for specific
regulation.
439
-------
Copper concentrations appeared in all 13 raw wastewater streams from
the Leclanche subcategory at concentrations up to 3.22 mg/1. Copper
is not introduced as a raw material or as part of a process. However,
all concentrations are above the level which can be achieved by
specific treatment methods. Therefore, copper is considered for
specific regulation in this subcategory.
Lead concentrations appeared in 4 of 13 raw wastewater streams
sampled, and also from one analysis supplied by one plant in the
Leclanche subcategory. The concentrations ranged from 0.07 mg/1 to
0.94 mg/1 (verification sample) and the maximum concentration was
6.0 mg/1 (screening sample). All concentrations were greater than the
levels which can be obtained with specific treatment methods for lead
removal. Therefore, even though lead is not a raw material and is not
introducted by an identified process in this subcategory it is
considered for specific regulation.
Mercury concentrations appeared in 10 of 12 sampled raw wastewater
streams in the Leclanche subcategory and concentrations were also
reported from dcp information for three plants. The maximum
concentration was 6.0 mg/1 from the sampling data and 117 mg/1 from
dcp data. Mercury is a toxic metal used as a raw material in this
subcategory. It can be removed from wastewaters by specific treatment
methods at the concentrations found. Mercury is considered for
specific regulation.
Nickel concentrations appeared in all 13 sampled raw wastewater
streams in the Leclanche subcategory and, also one chemical analysis
was supplied by one plant. The maximum concentration was 10.1 mg/1.
Nickel is a toxic metal and can be removed by specific treatment
methods. Therefore, nickel is considered for specific regulation.
Selenium concentrations appeared in the same 3 out of 13 raw waste-
water streams in which arsenic was found in the Leclanche subcategory.
The concentration range was 0.07 mg/1 to 0.6 mg/1. Although selenium
is not a recognized component of any of the raw materials used in this
subcategory, it was reported as present in one plant's wastewater by
dcp information. Because of its toxic nature and the fact that
specific treatment methods can remove this pollutant parameter,
selenium is considered for specific regulation.
Zinc concentrations appeared in all raw wastewater streams analyzed
for zinc in the Leclanche subcategory, and also from two chemical
analyses supplied by two plants. The maximum concentration from
sampling was 2000 mg/1 (screening) and 1640 mg/1 from plant data.
Zinc is a major raw material for this subcategory and can be removed
by specific treatment methods. Therefore, this priority pollutant is
considered for specific regulation.
440
-------
Manganese concentrations appeared in all raw wastewater samples in the
Leclanche subcategory. The maximum concentration was 383 mg/1, and
six concentrations were 10 mg/1 or greater. Manganese dioxide is a
raw material for this subcategory and is generally regarded as
undesirable in water used for various processes as well as for
drinking water. Manganese can be removed by specific treatment
methods. Therefore, manganese is considered for specific regulation.
The oil and grease parameter concentrations appeared in all raw
wastewater streams, but the screening raw wastewater streams in the
Leclanche subcategory. The maximum concentration was 482 mg/1 and in
one other sample a concentration of 438 mg/1 was found. All other
concentrations were below 100 mg/1. Conventional methods can be used
to remove oil and grease, therefore, this parameter is considered for
specific regulation.
Suspended solids were present in process wastewater streams from the
Leclanche subcategory at concentrations as high as 14,200 mg/1.
Additional suspended solids will result from chemical treatment of
these waste streams to precipitate metallic pollutants. Although TSS
is a conventional pollutant, the TSS generated in this subcategory
consists of large proportions of priority pollutants. Specific
treatment methods remove TSS below the levels which were found in most
samples. Therefore specific regulation of TSS must be considered in
this subcategory.
The pH of wastewater streams from the Leclanche subcategory was
observed to range between 5.1 and 10.4. Treatment of these waste
streams for removal of toxic metals may require adjustment of the pH
outside of the range acceptable for discharge to surface waters - pH
7.5 to 10. Therefore, pH requires specific regulation in process
wastewater effluents from this subcategory.
Pollutant Parameters Not Selected for Specific Regulation.
Three pollutant parameters included in verification sampling and
analysis - diethyl phthalate, antimony, and total phenols were not
selected for specific regulation. These parameters were present
infrequently, or at low concentrations, in raw wastewaters and are not
directly attributable to processes or raw materials used in this
subcategory.
Diethyl phthalate concentrations appeared in all raw wastewaters
streams in the Leclanche subcategory, but the maximum concentration
was only 0.016 mg/1. This priority pollutant is not a known component
of any raw material or process used in this subcategory. Because of
the widespread use of diethyl phthalate as a plasticizer, the compound
is found in many components of plant equipment and piping as well as
various consumer products used by employees. These are not process
441
-------
specific sources. The concentrations are below the levels that
available specific treatment methods are expected to achieve.
Therefore, diethyl phthalate is not considered for specific
regulation.
Antimony concentrations appeared in only the screening raw wastewater
stream in the Leclanche subcategory. It is not used or introduced in
the raw materials of manufacturing process. Therefore, antimony is
not considered for specific regulation.
The parameter designated "total phenols" had concentrations appearing
in 11 of 11 raw wastewater streams in this subcategory. The maximum
concentration was 14.9 mg/1. All other values ranged from 0.009 to
0.253 mg/1. Phenols are not used in any process or as a raw material
in the Leclanche subcategory. However, the maximum value was from the
single sample from a wet pasting operation for which phenolic
compounds are commonly used as starch paste preservatives. This
operation has been discontinued since sampling the plant. Although
specific removal of phenols is possible, specific treatment is costly.
Many phenols are removed with oil and grease. Therefore, total
phenols is not considered for specific regulation.
Lithium Subcategory
Parameters Selected for Specific Regulation. To be determined after
verification analysis completed.
Magnesium Subcategory
Parameters Selected for Specific Regulation. To be determined after
verification analysis completed.
Zinc Subcategory
Parameters Selected for Regulation. Based on verification sampling
results and a careful examination of the zinc subcategory
manufacturing elements and wastewater sources listed in Figure V-25
(Page 217), manufacturing processes and raw materials, seventeen
pollutant parameters were selected for consideration for specific
regulation in effluent limitations and standards for this subcategory.
The seventeen are: arsenic, cadmium, total chromium, copper, total
cyanide, lead, mercury, nickel, selenium, silver, zinc, aluminum,
iron, manganese, oil and grease, total suspended solids, and pH.
These pollutants were found in raw wastewaters from this subcategory
at levels that are amenable to control by specific treatment methods.
Arsenic concentrations appeared in 26 of 59 raw wastewater streams
from the zinc subcategory. The maximum concentration was 5.9 mg/1.
Ten values were greater than 1 mg/1. Arsenic is not a raw material
442
-------
and is not associated with any process used in the subcategory. The
arsenic probably is a contaminant in one of the raw materials.
Specific treatment methods achieve lower concentrations than were
found in many samples/ therefore, arsenic is considered for specific
regulation.
Cadmium concentrations appeared in 50 of 70 raw wastewater streams
from the zinc subcategory. The maximum concentrations were 79.2 mg/1
from nickel impregnated cathodes, and 5.99 mg/1 from silver peroxide
raw wastewater streams. All other values were less than 0.2 mg/1.
Cadmium can be removed by specific treatment methods to concentrations
lower than those reported for many of the samples. Therefore, cadmium
is considered for specific regulation.
Total chromium concentrations appeared in 56 of 70 raw wastewater
streams from the zinc subcategory. Three samples from the cell wash
operation at one plant contained 253 to 318 mg/1 total chromium.
Other raw wastewater streams ranged from 73.1 mg/1 down to 0.002 mg/1.
Many of the observed concentrations are greater than the level that
can be achieved with specific treatment methods. Therefore, total
chromium is considered for specific regulation.
Copper concentrations appeared in 48 of 58 raw wastewater streams from
the zinc subcategory. Copper is used for electrode supports in cells.
It is also used as an electrical conductor in process equipment. The
maximum concentration was 10.5 mg/1. Copper can be removed by
specific treatment methods to levels lower than many of the observed
values. Therefore, copper is considered for specific regulation in
the zinc subcategory.
Total cyanide concentrations appeared in 28 of 38 raw wastewater
streams. The maximum concentrations were observed in the cell wash
stream from one plant where the range was 2.1 to 7.2 mg/1. Most raw
wastewater streams contained less than 0.1 mg/1. However, the
wastewater streams contain levels that can be treated by specific
methods to achieve lower concentrations. Therefore, cyanide is
considered for specific regulation.
Lead concentrations appeared in 21 of 68 raw wastewater streams in the
zinc subcategory. The maximum concentration was 0.82 mg/1. Although
lead is not a raw material and is not part of a process, it was
present in various raw wastewater streams at seven of the eight
sampled plants in this subcategory. Lead can be removed by specific
treatment methods to achieve lower concentrations than most of those
found. Therefore, lead is considered for specific regulation in the
zinc subcategory.
Mercury concentrations appeared in 45 of 57 raw wastewater samples
from the zinc subcategory. This priority pollutant is used to
443
-------
amalgamate zinc anodes and therefore is expected in raw wastewaters.
The maximum concentration was 30.78 mg/1. Specific treatment methods
can achieve mercury concentrations lower than most of the reported raw
wastewater values. Therefore, mercury is considered for specific
regulation in this subcategory.
Nickel concentrations appeared in 46 of 70 raw wastewater streams from
the zinc subcategory. Nickel is the primary raw material for
impregnated nickel cathodes in this subcategory, but it also appeared
in various raw wastewater streams from all plants sampled. The
maximum concentrations were 514 mg/1 from the nickel cathode streams
and 24.4 mg/1 from cell wash streams. Nickel is considered for
regulation in the zinc subcategory.
Selenium concentrations appeared in 12 of 39 raw wastewater streams
from the zinc subcategory. The measured concentrations ranged from
0.046 to 4.8 mg/1. Most concentrations are above the level which can
be achieved by specific treatment methods. Selenium is not a raw
material nor is it a process material in this subcategory. Its
presence is probably associated with the use of silver or other raw
material with a high selenium content. This priority pollutant is
considered for specific regulation in the zinc subcategory.
Silver concentrations appeared in 42 of 60 raw wastewater streams in
the zinc subcategory. Silver is the raw material for silver oxide
cathodes used in some of the batteries in this subcategory. The
maximum concentration was 71 mg/1. Silver can be removed by specific
treatment methods to give concentrations lower than many of the
reported values. Silver is considered for specific regulation in the
zinc subcategory.
Zinc, is a principal raw material in the zinc subcategory. Zinc
concentrations appeared in 67 of 69 raw wastewater streams. The two
streams showing zero concentrations of zinc were from two streams for
silver cathodes. Nearly half of the samples contained more than 10
mg/1 zinc, and the maximum concentration was 1,100 mg/1. All of those
concentrations are greater than those that can be achieved by specific
treatment methods. Therefore, zinc is considered for specific
regulation in this subcategory.
Aluminum concentrations appeared in 15 of 38 raw wastewater streams in
the zinc subcategory. The maximum concentration was 106 mg/1 from
reject cell wastewater samples. Aluminum can be removed by specific
treatment methods to levels less than those found in several of the
samples. Therefore, aluminum is considered for specific regulation.
Iron concentrations appeared in two of two raw wastewater streams
sampled. The maximum concentration was 0.57 mg/1. This concentration
is treatable and iron is therefore considered for regulation.
444
-------
Manganese concentrations appeared in 47 of 60 raw wastewater streams
from the zinc subcategory. The maximum concentration was 69.6 mg/1.
Manganese dioxide is a raw material for plants that make alkaline
manganese cells in this subcategory. Some of the concentrations are
above the level which can be achieved by specific treatment methods.
Therefore, manganese is considered for specific regulation.
Phenols (total) concentrations appeared in 30 of 43 raw wastewater
streams from the zinc subcategory. The maximum value was 0.12 mg/1 in
one raw wastewater stream. Several element streams and total plant
raw wastewater streams contain treatable wastewaters, however, the
concentrations detected are not environmentally significant, and only
some of the concentrations detected are treatable. Therefore, total
phenols is not considered for specific regulation.
Oil and grease concentrations appeared in 42 of 43 raw wastewater
streams in the zinc subcategory. The maximum concentration was 205
mg/1, and half the samples contained more than 10 mg/1. Oil and
grease can enter the raw wastewater from cell washing operations and
from production machinery. Many oil and grease concentrations
reported in this subcategory can be reduced by specific treatment
methods. Some of the concentrations found are greater than are
acceptable by POTW. Therefore, oil and grease are considered for
specific regulation in this subcategory.
Suspended solids concentrations appeared in 66 of 68 raw wastewater
samples in the zinc subcategory. The maximum concentration of total
suspended solids (TSS) was 2,800 mg/1. About half the sample
contained greater than 50 mg/1 TSS. TSS consists of a variety of
metal powders and oxides from raw materials and processes. In
addition, TSS is generated by chemical precipitation methods used to
remove some other pollutants. Specific treatment methods remove TSS
to levels below those found in many samples. Therefore, TSS is
considered for specific regulation in the zinc subcategory.
The pH of 43 raw wastewater samples in the zinc subcategory ranged
from 1.0 to 13.5. Alkaline values predominated because the
electrolytes in the cells in this subcategory are alkaline. Treatment
of raw wastewaters for removal of other pollutant parameters can
result in pH values outside the acceptable 7.5 to 10.0 range.
Specific treatment methods can readily bring pH values within the
prescribed limits. Therefore, pH is considered for specific
regulation in the zinc subcategory.
Parameters Not Selected for Specific Regulation. Sixteen pollutant
parameters which were evaluated in verification analysis were dropped
from further consideration for specific regulation in the zinc
subcategory. These parameters were found to be present in raw
wastewaters infrequently, at levels considered to be not
445
-------
environmentally significant, or at concentrations below those usually
achieved by specific treatment methods. The sixteen were: 1,1,1-
trichloroethane, 1,1-dichloroethane, 1,1-dichloroethylene, 1,2-trans-
dichloroethylene, ethylbenzene, methylene chloride, naphthalene,
pentachlorophenol, bis(2-ethylhexyl) phthalate, diethyl phthalate,
tetrachloroethylene, toluene, trichloroethylene, antimony, ammonia,
and total phenols.
1,1,1-trichloroethane concentrations appeared in 22 of 57 raw
wastewater streams analyzed for this priority pollutant parameter in
the zinc subcategory. The maximum concentration was 0.025 mg/1. All
but one other concentration were less than the quantifiable limit.
Available specific treatment methods are not expected to remove 1,1,1-
trichloroethane present in wastewater at this concentration.
Therefore, this priority pollutant is not considered for specific
regulation in this subcategory.
1,1-Dichloroethane concentrations appeared in 12 of 34 raw wastewater
streams analyzed for this priority pollutant in the zinc subcategory.
The maximum concentration was 0.03 mg/1. All other concentrations
were less than the quantifiable limit. Available specific treatment
methods are not expected to remove 1,1-dichloroethane present in
wastewaters at this concentration. Therefore, this priority pollutant
is not considered for specific regulation in this subcategory.
1,1-Dichloroethylene concentrations appeared in 12 of 36 raw
wastewater streams analyzed for this priority pollutant in the zinc
subcategory. All concentrations were less than the quantifiable
limit. Therefore, 1,1-dichloroethylene is not considered for specific
regulation in this subcategory.
1,2-Trans-dichloroethylene concentrations appeared in only 4 of 36 raw
wastewater streams in the zinc subcategory. All concentrations were
less than the quantifiable limit. Therefore, 1,2-trans-
dichloroethylene is not considered for regulation in this subcategory.
Ethylbenzene was detected in only 2 of 32 raw wastewater samples in
the zinc subcategory. The concentrations were below the quantifiable
limit. Therefore, ethyl benzene is not considered for specific
regulation in this subcategory.
Methylene chloride concentrations appeared in 18 of 67 raw wastewater
streams in the zinc subcategory. The maximum concentration was 0.023
mg/1. All other concentrations were below the quantifiable limit.
Available specific treatment methods are not expected to remove
methylene chloride present in wastewater at the maximum concentration
found. Therefore, methylene chloride is not considered for specific
regulation in this subcategory.
446
-------
Naphthalene concentrations appeared in 16 of 37 raw wastewater streams
in the zinc subcategory. The maximum concentration was 0.02 mg/1.
All concentrations were less than the quantifiable limit. Available
treatment methods are not expected to remove napthalene present in the
wastewater at the maximum concentration found. Therefore, naphthalene
is not considered for specific regulation in this subcategory.
Pentachlorophenol concentrations appeared in 1 of 14 raw wastewater
streams in the zinc subcategory. The concentration was 0.042 mg/1.
Available specific treatment methods are considered capable of
achieving lower concentrations of this priority pollutant than the
observed value. However, because pentachlorophenol was detected only
once,
this priority pollutant is not considered
for specific regulation in this subcategory.
Bis(2-ethylhexyl) phthalate concentrations appeared in all 21 raw
wastewater streams analyzed for this priority pollutant. The maximum
concentration was 0.161 mg/1. Available specific treatment methods
are considered capable of achieving lower concentrations of this
priority pollutant than many of those reported. This priority
pollutant is not a raw material or process chemical and is found
distributed widely in industrial environments as a plasticizer.
Therefore, bis(2-ethylhexyl) phthalate
is not considered for specific regulation in this subcategory.
Diethyl phthalate concentrations appeared in 14 of 37 raw wastewater
streams in the zinc subcategory. All concentrations were less than
the quantifiable limit. Therefore, diethyl phthalate is not
considered for specific regulation in this subcategory.
Tetrachloroethylene concentrations appeared in 5 of 38 raw wastewater
streams in the zinc subcategory. All of the concentrations were less
than the quantifiable limit. Therefore, tetrachloroethylene is not
considered for specific regulation in this subcategory.
Toluene concentrations appeared in 10 of 67 raw wastewater streams in
the zinc subcategory. All concentrations were less than the
quantifiable limit. Therefore, toluene is not considered for specific
regulation in this subcategory.
Trichloroethylene was found in 17 of 51 raw wastewater samples in the
zinc subcategory. The only value greater than the quantifiable limit
was 0.012 mg/1. Available specific treatment methods are not expected
to remove trichloroethylene present in raw wastewaters at the maximum
concentration found. Therefore, trichloroethylene is not considered
for regulation in this subcategory.
447
-------
Antimony concentrations did not appear in any of the 56 raw wastewater
streams from the zinc subcategory. Antimony was included in
verification sampling for this subcategory on the basis of dcp reports
that antimony was present in the raw wastewaters. Antimony is not
considered for specific regulation in this subcategory.
Ammonia concentrations appeared in 31 of 31 raw wastewater streams
analyzed for this pollutant in the zinc subcategory. Maximum
concentrations for each element stream ranged from 0.84 to 120 mg/1.
The maximum concentration in total plant raw wastewater streams was
8.0 mg/1. Available specific treatment methods are not expected to
remove ammonia present in total raw wastewaters at the maximum level
found. Therefore, ammonia is not considered for specific regulation
in this subcategory.
Summary
Tables VI-1, VI-3, VI-6, and VI-7 (Pages 449-476) present the
selection of priority pollutant parameters for consideration for
specific regulation for the cadmium, lead, leclanche and zinc
subcategories, respectively. The selection is based on all sampling
results. The "Not Detected" column includes pollutants which were not
detected and not selected during screening analysis of total plant raw
wastewater, and those that were selected at screening, but not
detected during verification analysis of process raw wastewater
streams within the subcategories. "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 each subcategory. For screening samples, "Environmentally
Insignificant" includes those samples which were detected at higher
concentrations than the raw wastewater in the influent and effluent
and not selected for verification. For verification analysis,
"Environmentally Insignificant" includes parameters found in only one
plant, present only below an environmentally significant level, or
those that cannot be attributed to the point source category because
they are generally found in plant equipment. "Not Treatable" means
that concentrations were lower than the level achievable with the
specific treatment methods considered in Section VII. Table VI-8
(Page 477) summarizes the selection of non-conventional and
conventional pollutant parameters for consideration for specific
regulation by subcategory.
448
-------
TABLE VI-1
PRIORITY POLLUTANT DISPOSITION
Cadmium Subcategory
001
002
003
004
005
006
007
008
009
010
Oil
012
013
014
015
016
017
018
019
020
021
022
023
024
025
026
027
028
029
030
POLLUTANT
Acenaphthene
Acrolein
Aery lonit rile
Benzene
Benzidine
Carbon tetrachloride
(tetrachloromethane)
Chlorobenzene
1, 2, 4-tri Chlorobenzene
Hexachlorobenzene
1,2-dichloroethane
1,1,1-trichlorethane
Hexachloroethane
1,1-dichloroethane
1,1,2-trichloroethane
1,1,2,2-tetrachloroethane
Chloroethane
Bis (chloromethyl) ether
Bis (2-chloroethyl) ether
2-chloroethyl vinyl ether
(mixed)
2-chloronaphthalene
2,4,6-trichlorophenol
Parachlorometa cresol
Chloroform (trichloro-
methane)
2-chlorophenol
1,2-di Chlorobenzene
1,3-di Chlorobenzene
1,4-di Chlorobenzene
3,3-dichlorobenzidine
1,1-dichloroethylene
1,2-trans-dichloroethylene
033
1,2-dichloropropylene
( 1 ,3-di chl oropropene )
NOT
DETECTED
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
I
X
X
NOT
QUANTIFIABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
-------
TABLE VI-1 Continued
034 2,4-dimethylphenol X
035 2,4-dinitrotoluene X
036 2,6-dinitrotoluene X
037 1,2-diphenylhydrazine X
038 Ethyl benzene X
039 Fluoranthene X
040 4-chlorophenyl phenyl ether x
041 4-brompphenyl phenyl ether X
042 Bis(2-chloroisopropyl) ether x
043 Bis(2-chloroethoxy) methane x
044 Methylene chloride
(dichloromethane)
045 Methyl chloride X
(dichloromethane)
046 Methyl bromide X
(bromomethane)
047 Bromoform (tribromo- X
methane)
048 Di chlorobromomethane
049 Trichlorofluoromethane x
050 Dichlorodifluoromethane x
^ 051 Chlorodibromomethane x
o 052 Hexachlorobutadiene x
053 Hexachloromyclopenta- x
diene
054 Isophorone x
055 Naphthalene x
056 Nitrobenzene X
057 2-nitrophenol x
058 4-nitrophenol x
059 2,4-dinitrophenol x
060 4,6-dinitro-o-cresol x
061 N-nitrosodimethylamine x
062 N-nitrosodiphenylamine x
063 N-nitrosodi-n-propylamine x
064 Pentachlorophenol x
065 Phenol x
066 Bis(2-ethylhexyl)phthalate
067 Butyl benzyl phthalate x
068 Di-N-Butyl Phthalate x
069 Di-n-octyl phthalate x
070 Diethyl Phthalate x
071 Dimethyl phthalate x
072 1,2-benzanthracene x
-------
TABLE VI-1 Continued
(benzo(a)anthracene)
073 Benzo(a)pyrene (3,4-benzo- X
pyrene)
074 3,4-Benzofluoranthene X
(benzo(b)fluoranthene)
075 11,12-benzofluoranthene X
(benzo(b)fluoranthene)
076 Chrysene X
077 Acenaphthylene X
078 Anthracene X
079 1,12-benzoperylene x
(benzo(ghiJperylene)
080 Fluorene X
081 Phenanthrene x
082 1,2,5,6-dibenzanthracene X
(dibenzo(.h)anthracene)
083 Indeno(l,2,3-cd) pyrene X
(2,3-o-pheynylene pyrene)
084 Pyrene X
085 Tetrachloroethylene x
086 Toluene
087 Trlchloroethylene
088 Vinyl chloride (chloroethylene) x
089 Aldrln X
090 Dieldrin X
091 Chlordane (technical mixture x
and metabolites)
092 4,4-DDT X
093 4,4-DDE (p,p-DDX) x
094 4,4-DDD (p,p-TDE) x
095 Alpha-endosulfan x
096 Beta-endosulfan x
097 Endosulfan sulfate x
098 Endrln X
099 Endrln aldehyde x
100 Heptachlor x
101 Heptachlor epoxide x
(BHC-hexach1orocyc1o-
hexane)
102 Alpha-BHC X
103 Beta-BHC X
104 Gamma-BHC (llndane) X
105 Delta-BHC (PCB-poly- x
chlorinated biphenyls)
-------
TABLE VI-1 Continued
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
(Arochlor
(Arochlor
(Arochlor
(Arochlor
(Arochlor
(Arochlor
(Arochlor
1242)
1254)
1221)
1232)
1248)
1260)
1016)
(NOT ANALYZED)
Cyanide, Total
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8-t«
•trachlorc
1-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X 1 /
-------
TABLE VI-2
PRIORITY POLLUTANT DISPOSITION
Calcium Subcategory
in
co
POLLUTANT
001 Acenap'hthene
002 Acroleln
003 Acrylon1tr1le
004 Benzene
005 Benzidine
006 Carbon tetrachlorlde
(tetrachl oromethane)
007 Chi orobenzene
008 1,2,4-trichlorobenzene
009 Hexachl orobenzene
010 1,2-dichloroethane
Oil 1,1,1-trlchlorethane
012 Hexachl oroethane
013 1,1-dichl oroethane
014 1,1,2-trichl oroethane
015 1,1, 2, 2-tetrachl oroethane
016 Chi oroethane
017 Bis (chloromethyl) ether
018 Bis (2~chloroethy1) ether
019 2-chloroethyl vinyl ether
(mixed)
020 2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlorometa cresol
023 Chloroform (trlchloro-
methane)
024 2-chlorophenol
025 1,2-dlchl orobenzene
026 1,3-dichl orobenzene
027 1 ,4-di chl orobenzene
028 3.3-dichlorobenzidine
029 1,1-dichloroethylene
030 1,2-trans-dlchloroethylene
NOT
DETECTED
NOT
QUANTIFICABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
l.Z-dicnloropropylene
(l»3-d1chloropropene)
-------
TABLE VI-2 Continued
034 2,4-dimethyiphenol
035 2,4-dinitrotoluene
036 2,6-d1nitrotoluene
037 1,2-diphenylhydrazine
038 Ethyl benzene
039 Fluoranthene
040 4-chlorophenyl phenyl ether
041 4-bromophenyl phenyl ether
042 B1s(2-chloroisopropyl) etht
043 B1s(2-chloroethoxy) methant
044 Methylene chloride
(dichloromethane)
045 Methyl chloride
(dichloromethane)
046 Methyl bromide
(bromomethane)
047 Bromoform (tribromo-
methane)
048 Dichlorobromomethane
049 Trichlorofluoromethane
050 Dichlorodifluoromethane
051 Chiorodibromomethane
052 Hexachlorobutadiene
053 Hexachloromyclopenta-
diene
054 Isophorone
055 Naphthalene
056 Nitrobenzene
057 2-nitrophenol
058 4-nitrophenol
059 2.4-dinitrophenol
060 4,6-dinitro-o-cresol
061 N-nitrosodimethylamine
062 N-nitrosodlphenylamine
063 N-nitrosod1-n-propylamine
064 Pentachlorophenol
065 Phenol
066 Bis(2-ethylhexyl)phthalate
067 Butyl benzyl phthalate
068 Di-N-Butyl Phthalate
069 Di-n-octyl phthalate
070 Oiethyl Phthalate
071 Dimethyl phthalate
072 1,2-benzanthracene
-------
TABLE VI-2 Continued
(benzo(a)anthracene)
073 Benzo(a)pyrene (3,4-benzo-
pyrene)
074 3,4-Benzofluoranthene
(benzo(b)fluoranthene)
075 11,12-benzofluoranthene
(benzq(b)fluoranthene)
076 Chrysene
077 Acenaphthylene
078 Anthracene
079 1,12-benzoperylene
(benzo(ghi)perylene)
080 Fluorene
081 Phenanthrene
082 1,2,5,6-dlbenzanthracene
(dibenzo(,h)anthracene)
083 Indeno(l,2,3-cd) pyrene
(2,3-o-pheynylene pyrene)
084 Pyrene
085 Tet rachloroethy1ene
086 Toluene
087 Trlchl oroethy 1 ene
088 Vinyl chloride (chloroethylene)
089 Aldrln
090 Oleldrln
091 Chlordane (technical mixture
and metabolites)
092 4,4-DOT
093 4.4-DDE (p.p-DDX)
094 4,4-DDD (p,p-TDE)
095 Alpha-endosulfan
096 Beta-endosulfan
097 Endosulfan sulfate
098 Endrln
099 Endrln aldehyde
100 Heptachlor
101 Heptachlor epoxlde
(BHC-hexachlprocyclo-
hexane)
185 6lE5!iSHcc
104 Gamna-BHC (llndane)
105 Delta-BHC (PCB-poly-
chlorlnated blphenyls)
-------
TABLE VI-2 Continued
106 PCB-1242 (Arochlor 1242)
107 PCB-1254 (Arochlor 1254)
108 PCB-1221 (Arochlor 1221)
109 PCB-1232 (Arochlor 1232)
110 PCB-1248 (Arochlor 1248)
111 PCB-1260 (Arochlor 1260)
112 PCB-1016" (Arochlor 1016)
113 Toxaphene
114 Antimony
115 Arsenic
116 Asbestos
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
121 Cyanide, Total
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
^ 127 Thallium
en
128 Z1nc
129 2r ANALYZED)
-------
TABLE VI- 3
PRIORITY POLLUTANT DISPOSITION
Lead Subcategory
01
POLLUTANT
001 Acenaphthene
002 Acrolein
003 Acrylonitrile
004 Benzene
005 Benzidine
006 Carbon tetrachloride
(t et rac h1orometh ane)
007 Chlorobenzene
008 1,2,4-trichlorobenzene
009 Hexachlorobenzene
010 1,2-dichloroethane
Oil 1,1,1-trichlorethane
012 Hexachloroethane
013 1,1-dichloroethane
014 1,1,2-trichloroethane
015 1,1,2,2-tetrachloroethane
016 Chloroethane
017 Bis (chloromethyl) ether
018 Bis (2-chloroethyl) ether
019 2-chloroethyl vinyl ether
(mixed)
020 2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlorometa cresol
023 Chloroform (trichloro-
methane)
024 2-chlorophenol
025 1,2-dichlorobenzene
026 1,3-dichlorobenzene
027 1,4-di chlorobenzene
028 3,3-dichlorobenzidine
029 1,1-dichloroethylene
030 1,2-trans-dichloroethylene
IB* frfcfflgRWSPSJe
033 1.2-dichloropropylene
(1,3-di chloropropene)
NOT
DETECTED
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
NOT
QUANTIFIABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
X
X
X
X
X
X
X
X
-------
TABLE VI-3 Continued
034 2,4-dimethylphenol J
035 2,4-dinitrotoluene
036 2,6-dlnltrotoluene X
037 1,2-diphenylhydrazine X
038 Ethyl benzene J
039 Fluoranthene x
040 4-chlorophenyl phenyl ether X
041 4-bromophenyl phenyl ether X
042 Bis(2-chloroisopropyl) ether X
043 Bis(2-chloroethoxy) methane X
044 Methylene chloride X
(dichloromethane)
045 Methyl chloride X
(dichloromethane) ..
046 Methyl bromide
(bromomethane) x
047 Bromoform (tribromo-
methane) X
048 Dichlorobromomethane x
049 Trichlorofluoromethane x
050 Dichlorodifluoromethane x
051 Chiorodibromomethane x
052 Hexachlorobutadiene x
053 Hexachloromyclopenta-
diene x
054 Isophorone
055 Naphthalene x
056 Nitrobenzene x
057 2-nitrophenol x
058 4-nitrophenol x
059 2,4-dinitrophenol x
060 4,6-dinitro-o-cresol x
061 N-nitrosodimethylamine
062 N-n1trosodiphenylamine
063 N-nitrosodi-n-propylamine
064 Pentachlorophenol x
065 Phenol X
066 Bis(2-ethylhexyl)phthalate x
067 Butyl benzyl phthalate x
068 Di-N-Butyl Phthalate x
069 Di-n-octyl phthalate
070 Diethyl Phthalate *
071 Dimethyl phthalate *
072 1,2-benzanthracene A
-------
TABLE VI-3 Continued
(benzo(a)anthracene)
073 Benzo(a)pyrene (3,4-benzo- x
pyrene)
074 3,4-Benzofluoranthene x
(benzo(b)fluoranthene)
075 11,12-benzofluoranthene x
(benzq(b)f1uoranthene)
076 Chrysene x
077 Acenaphthylene x
078 Anthracene
079 1,12-benzoperylene X
(benzo(ghi)perylene)
080 Fluorene X
081 Phenanthrene
082 1,2,5,6-dibenzanthracene X
(dibenzo(,h)anthracene)
083 Indeno(l,2,3-cd) pyrene X
(2,3-o-pheynylene pyrene)
084 Pyrene X
085 Tetrachloroethylene X
086 Toluene
^ 087 Trichloroethylene X
S 088 Vinyl chloride (chloroethylene) X
089 Aldrin X
090 Dleldrin X
091 Chlordane (technical mixture X
and metabolites)
092 4,4-DDT X
093 4,4-DDE (p,p-DDX) X
094 4,4-DDD (p,p-TDE) X
095 Alpha-endosulfan X
096 Beta-endosulfan X
097 Endosulfan sulfate X
098 Endrin X
099 Endrin aldehyde X
100 Heptachlor X
101 Heptachlor epoxide X
(BHC-hexachlorocyclo-
hexane)
102 Alpha-BHC X
103 Beta-BHC X
104 Gamma-BHC (lindane) X
105 Delta-BHC (PCB-poly- x
chlorinated biphenyls)
-------
TABLE VI-3 Continued
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
(Arochlor
(Arochlor
(Arochlor
(Arochlor
(Arochlor
(Arochlor
(Arochlor
1242)
1254)
1221)
1232)
1248)
1260)
1016)
Cyanide, Total
Lead
Mercury
Nickel
Selenium
Silver
Thallium
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
128 Zinc
129 2,3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDD) (NOT ANALYZED)
-------
TABLE VI-4
PRIORITY POLLUTANT DISPOSITION
Leclanche Subcategory
POLLUTANT
001 Acenaphth,ene
002 Acrolein
003 Aerylonitrile
004 Benzene
005 Benzidlne
006 Carbon tetrachloride
(tetrachloromethane)
007 Chlorobenzene
008 1,2,4-triChlorobenzene
009 Hexachlorobenzene
010 1,2-dichloroethane
Oil 1,1,1-trichlorethane
012 Hexachloroethane
013 1,1-dichloroethane
014 1,1,2-trichloroethane
015 1,1,2,2-tetrachloroethane
016 Chioroethane
017 Bis (chloromethyl) ether
018 Bis (2-chloroethyl) ether
019 2-chloroethyl vinyl ether
(mixed)
020 2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlorometa cresol
023 Chloroform (trichloro-
me thane)
024 2-chlorophenol
025 1,2-diChlorobenzene
026 1,3-diChlorobenzene
027 1,4-dichlorobenzene
028 3,3-dichlorobenzidine
029 1,1-dichloroethylene
030 1,2-trans-dichToroethylene
031 2,4-dichlorophenol
832 1,2-djchloropropane
33 1.2-dichloropropylene
(1,3-dichloropropene)
NOT
DETECTED
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
NOT
QUANTIFICABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
-------
TABLE VI-4 Continued
034 2,4-dlmethylphenol x
035 2,4-dinitrotoluene x
036 2,6-dinitrotoluene x
037 1,2-dlphenylhydrazine x
038 Ethyl benzene x
039 Fluoranthene x
040 4-chlorophenyl phenyl ether x
041 4-bromophenyl phenyl ether x
042 Bis(2-chloroisopropyl) ether x
043 Bis(2-chloroethoxy) methane x
044 Methylene chloride
(dichloromethane) x
045 Methyl chloride
(dichloromethane) x
046 Methyl bromide
(bromomethane) x
047 Bromoform (tribromo-
methane) x
048 Dichlorobromomethane x
049 Trichlorofluoromethane x
en 050 Dichlorodifluoromethane x
1X1 051 Chlorodi bromomethane x
052 Hexachlorobutadiene x
053 Hexachloromyclopenta-
diene x
054 Isophorone x
055 naphthalene x
056 Nitrobenzene x
057 2-nitrophenol x
058 4-nitrophenol x
059 2,4-dinitrophenol x
060 4,6-dinitro-o-cresol x
061 N-nitrosodimethylamine x
062 N-nitrosodiphenylamine x
063 N-nitrosodi-n-propylamine x
064 Pentachlorophenol x
065 Phenol
066 Bis(2-ethylhexyl)phthalate x
067 Butyl benzyl phthalate x
068 Di-N-Butyl Phthalate x
069 Di-n-octyl phthalate x
070 Diethyl Phthalate
071 Dimethyl phthalate x
07 2 1,2-benzanthracene
-------
TABLE VI-4 Continued
(benzo(a)anthracene) x
073 Benzo(a)pyrene (3,4-benzo-
pyrene) x
074 3,4-Benzofluoranthene
• (benzo(b)fluoranthene) x
075 11,12-benzofluoranthene
(benzo(b)fluoranthene) x
076 Chrysene ' x
077 Acenaphthylene x
078 Anthracene x
079 1,12-benzoperylene
(benzo(ghi)perylene) x
080 Fluorene x
081 Phenanthrene x
082 1,2,5,6-dibenzanthracene
(dibenzo(,h)anthracene) x
083 Indeno(l,2,3-cd) pyrene
(2,3-o-pheynylene pyrene) x
084 Pyrene x
085 Tetrachloroethylene x
086 Toluene
087 Trichloroethylene x
088 Vinyl chloride (chloroethylene) x
089 Aldrin x
090 Dieldrin x
091 Chlordane (technical mixture
and metabolites) x
092 4,4-DDT x
093 4,4-DDE (p,p-DDX) x
094 4,4-DDD (p,p-TDE) x
095 Alpha-endosulfan x
096 Beta-endosulfan x
097 Endosulfan sulfate x
098 Endrin x
099 Endrin aldehyde x
100 Heptachlor x
101 Heptachlor epoxide
(BHC-hexachlorocyclo- x
hexane)
102 Alpha-BHC x
103 Beta-BHC x
104 Gamma-BHC (lindane) x
105 Delta-BHC (PCB-poly-
chlorinated biphenyls) x
-------
TABLE VI-4 Continued
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Toxaphene,
Antimony
Arsenic
Asbestos
Beryllium
Cadmi urn
Chromium
Copper
Cyanide, Total
Lead
Mercury
Nickel
Selenium
Silver
Thallium
X
X
X
X
X
X
X
X
128 Zinc
129 2,3,7,8-tetrachloro-
dibenzo-D-dioxin (TCDD) (NOT ANALYZED)
x
X
X
X
X
X
-------
TABLE VI-5
PRIORITY POLLUTANT DISPOSITION
Lithium Subcateyory
en
001
002
003
004
005
006
007
008
009
010
Oil
012
013
014
015
016
017
018
019
020
021
022
023
024
025
026
027
028
029
030
POLLUTANT
Acenap'hthene
Acrolein
Aery Ion it rile
Benzene
Benzidine
Carbon tetrachloride
(tetrachl oromethane)
Chlorobenzene
1,2,4-trichlorobenzene
Hexachlorobenzene
1,2-dichloroethane
1,1,1-trichlorethane
Hexachloroethane
1,1-dichloroethane
1.1,2-trichloroethane
1,1,2,2-tetrachloroethane
Chloroethane
Bis (chloromethyl) ether
Bis (2-chloroethyl) ether
2-chloroethyl vinyl ether
(mixed)
2-chloronaphthalene
2,4,6-trichlorophenol
Parachlorometa cresol
Chloroform (trichloro-
methane)
2-chlorophenol
1,2-di Chlorobenzene
1.3-di Chlorobenzene
1,4-di Chlorobenzene
3,3-dichlorobenzidine
1,1-dichloroethylene
1,2-trans-dichloroethylene
NOT
DETECTED
NOT
QUANTIFICABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
033
1.2-dichloropropylene
(1,3-dichloropropene)
-------
TABLE VI-5 Continued
034 2,4-dimethylphenol
035 2,4-dinitrotoluene
036 2,6-dinitrotoluene
037 1,2-diphenylhydrazlne
038 Ethylbenzene
039 Fluoranthene
040 4-chlorophenyl phenyl ether
041 4-broniophenyl phenyl ether
042 Bis(2-chloroisopropyl) ethc
043 Bis(2-chloroethoxy) methane
044 Methylene chloride
(dichloromethane)
045 Methyl chloride
(dichloromethane)
046 Methyl bromide
(bromomethane)
047 Bromoform (tribromo-
methane)
048 Dichlorobromomethane
049 Trichlorofluoromethane
050 Dichlorodifluoromethane
051 Chiorodibromomethane
052 Hexachlorobutadiene
053 Hexachloromyclopenta-
diene
054 Isophorone
055 Naphthalene
056 Nitrobenzene
057 2-nitrophenol
058 4-nitrophenol
059 2,4-dinitrophenol
060 4,6-dinitro-o-cresol
061 N-nitrosodimethyl amine
062 N-nitrosodiphenylamine
063 N-nitrosodi-n-propylamine
064 Pentachlorophenol
065 Phenol
066 Bis(2-ethylhexyl)phthalate
067 Butyl benzyl phthalate
068 Oi-N-Butyl Phthalate
069 01-n-octyl phthalate
070 Dlethyl Phthalate
071 Dimethyl phthalate
07 2 1,2-benzanthracene
-------
TABLE VI-5 Cont-inued
(benzo(a)anthracene)
073 Benzo(a)pyrene (3,4-benzo-
pyrene)
074 3,4-Benzofluoranthene
(benzo(b)fluoranthene)
075 11.12-benzofluoranthene
(benzq(b)fluoranthene)
076 Chrysene
077 Acenaphthylene
078 Anthracene
079 1,12-benzoperylene
(benzo(ghl)perylene)
080 Fluorene
081 Phenanthrene
082 1,2,5,6-dlbenzanthracene
(dibenzo(,h)anthracene)
083 Indeno(l,2,3-cd) pyrene
(2,3-o-pheynylene pyrene)
084 Pyrene
085 Tet rachloroethylene
086 Toluene
087 Trichloroethylene
088 Vinyl chloride (chloroethylene)
089 Aldrin
090 Dleldrln
091 Chlordane (technical mixture
and metabolites)
092 4,4-DDT
093 4,4-DDE (p,p-DDX)
094 4,4-ODD (p.p-TDE)
095 Alpha-endosulfan
096 Beta-endosulfan
097 Endosulfan sulfate
098 Endrln
099 Endrln aldehyde
100 Heptachlor
101 Heptachlor epoxlde
(BHC-hexach1orocyc1o-
hexane)
102 Alpha-BHC
103 Beta-BHC
104 Gamma-BHC (llndane)
105 Delta-BHC (PCB-poly-
chlorlnated blphenyls)
-------
TABLE VI-5 Continued
00
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232
PCB-1248 (Arochlor 1248
PCB-1260 (Arochlor 1260
PCB-1016" (Arochlor 1016)
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide, Total
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8-tetrachloro-
d1benzo-p-d1ox1n (TCDD) (NOT ANALYZED)
-------
TABLE VI-6
PRIORITY POLLUTANT DISPOSITION
Magnesium Subcategory
10
001
002
003
004
005
006
007
008
009
010
Oil
012
013
014
015
016
017
018
019
020
021
022
023
024
025
026
027
028
029
030
POLLUTANT
Acenap'hthene
Acrolein
Acrylonitrlle
Benzene
Benzidine
Carbon tetrachloride
(tetrachl oromethane)
Chi orobenzene
1, 2, 4-trichl orobenzene
Hexachl orobenzene
1,2-dichloroethane
1.1,1-trlchlorethane
Hexachl oroethane
1,1-dichl oroethane
1,1,2-trichloroethane
1,1, 2, 2-tetrachl oroethane
Chi oroethane
Bis (chloromethyl) ether
Bis (2-chloroethyl) ether
2-chloroethyl vinyl ether
(mixed)
2-chloronaphthalene
2,4,6-trichlorophenol
Parachlorometa cresol
Chloroform (trlchloro-
methane)
2-chlorophenol
1.2-dichl orobenzene
1,3-dichl orobenzene
1,4-dichl orobenzene
3,3-dichlorobenzidine
1,1-dlchloroethylene
1,2-trans-dichloroethylene
NOT
DETECTED
NOT
QUANTIFICABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
033
,2-dichloropropylene
(1,3-dlchloropropene)
-------
TABLE VI-6 Continued
034 2,4-dimethylphenol
035 2,4-dinltrotoluene
036 2,6-d1nitrotoluene
037 1.2-dlphenylhydrazlne
038 Ethyl benzene
039 Fluoranthene
040 4-chlorophenyl phenyl ether
041 4-brombphenyl phenyl ether
042 Bis(2-chloroisopropyl) eth<
043 B1s(2-chloroethoxy) metham
044 Methylene chloride
(dichloromethane)
045 Methyl chloride
(dichloromethane)
046 Methyl bromide
(bromomethane)
047 Bromoform (tribromo-
methane)
048 Dichlorobromomethane
049 Trlchlorofluoromethane
.p. 050 Dlchlorodlfluoromethane
5 051 Chiorodibromomethane
052 Hexachlorobutadiene
053 Hexachloromyclopenta-
diene
054 Isophorone
055 Naphthalene
056 Nitrobenzene
057 2-nitrophenol
058 4-nitrophenol
059 2,4-dinitrophenol
060 4,6-din1tro-o-cresol
061 N-hitrosodimethylamlne
062 N-nltrosodiphenylamine
063 N-n1trosod1-n-propylamine
064 Pentachlorophenol
065 Phenol
066 B1s(2-ethy1hexy1)phtha1 ate
067 Butyl benzyl phthalate
068 Di-N-Butyl Phthalate
069 Dl-n-octyl phthalate
070 D1ethyl Phthalate
071 Dimethyl phthalate
07 2 1,2-benzanthracene
-------
TABLE VI-6 Continued
(benzo(a)anthracene)
073 Benzo(a)pyrene (3,4-benzo-
pyrene)
074 3,4-Benzofluoranthene :
(benzo(b)fluoranthene)
075 11,12-benzof1uoranthene
(benza(b)f1uoranthene)
076 Chrysene
077 Acenaphthylene
078 Anthracene
079 1,12-benzoperylene
(benzo(ghi)perylene)
080 Fluorene
081 Pfcenanthrene
082 1,2,5,6-dibenzanthracene
(dibenzo(,h)anthracene)
083 Indeno(l,2,3-cd) pyrene
(2,3-o-pheynylene pyrene)
084 Pyrene
085 Tet rachloroethy 1ene
086 Toluene
087 Tr1chloroethy1ene
088 Vinyl chloride (chloroethy1ene)
089 Aldrin
090 Dieldrin
091 Chlordane (technical mixture
and metabolites)
092 4,4-DDT
093 4,4-DDE (p.p-DDX)
094 4.4-DDD (p.p-TDE)
095 Alpha-endosulfan
096 Beta-endosulfan
097 Endosulfan sulfate
098 Endrin
099 Endrin aldehyde
100 Heptachlor
101 Heptachlor epoxide
(BHC-hexach)procyc1o-
hexane) :
102 Alpha-BHC
103 Beta-BHC
104 Gamma-BHC (lindane)
105 Delta-BHC (PCB-poly-
chlorlnated biphenyls)
-------
TABLE VI-6 Continued
ro
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 Arochlor 1232)
PCB-1248 Arochlor 1248)
PCB-1260 Arochlor 1260)
PCB-1016" (Arochlor 1016)
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide, Total
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2.3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDD) (NOT ANALYZED)
-------
TABLE VI-7
PRIORITY POLLUTANT DISPOSITION
Zinc Subcategory
CO
POLLUTANT
001 Acenapht,hene
002 Acrolein
003 Acrylonitrile
004 Benzene
005 Benzidine
006 Carbon tetrachloride
(tetrachloromethane)
007 Chlorobenzene
008 1,2,4-trlChlorobenzene
009 Hexachlorobenzene
010 1,2-dichloroethane
Oil 1,1,1-trichlorethane
012 Hexachloroethane
013 1,1-dichloroethane
014 1,1,2-trichloroethane
015 1,1,2,2-tetrachloroethane
016 Chloroethane
017 Bis (chloromethyl) ether
018 Bis (2-chloroethyl) ether
019 2-chloroethyl vinyl ether
(mixed)
020 2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlorometa cresol
023 Chloroform (trichloro-
methane)
024 2-chlorophenol
025 1,2-diChlorobenzene
026 1,3-dichlorobenzene
027 1,4-diChlorobenzene
028 3,3-dichlorobenzidine
029 1,1-dichloroethylene
030 1,2-trans-dichloroethylene
031 2,4-dichlorophenol
n?? 1,2-dichloropropane
033 1.2-dichloropropylene
(1,3-d i ch1oropropene)
NOT
DETECTED
x
x
X
X
X
X
X
X
NOT
QUANTIFICABLE
ENVIRONMENTALLY
INSIGNIFICANT
NOT
TREATABLE
REGULATION
CONSIDERED
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE VI-7 Continued
034 2,4-dimethylphenol x
035 2,4-dinitrotoluene x
036 2,6-dinitrotoluene x
037 1,2-diphenylhydrazine x
038 Ethyl benzene x
039 Fluoranthene x
040 4-chlorophenyl phenyl ether x
041 4-bromophenyl phenyl ether x
042 Bis(2-cnloroisopropyl) ether x
043 Bis(2-chloroethoxy) methane x
044 Methylene chloride
(dichloromethane) x
045 Methyl chloride
(dichloromethane) x
046 Methyl bromide
(bromomethane) x
047 Bromoform (tribromo-
methane) x
048 Dichlorobromomethane x
049 Trichlorofluoromethane x
050 Dichlorodifluoromethane x
051 Chiorodibromomethane x
052 Hexachlorobutadiene x
053 Hexachloromyclopenta-
diene x
054 Isophorone x
055 Naphthalene x
056 Nitrobenzene x
057 2-nitrophenol x
058 4-nitrophenol x
059 2,4-dinitrophenol x
060 4,6-dinitro-o-cresol x
061 N-nitrosodimethylamine x
062 N-nitrosodiphenylamine x
063 N-nitrosodi-n-propylamine • x
064 Pentachlorophenol x
065 Phenol x
066 Bis(2-ethylhexyl)phthalate x
067 Butyl benzyl phthalate x
068 Di-N-Butyl Phthalate x
069 Di-n-octyl phthalate x
070 Diethyl Phthalate x
071 Dimethyl phthalate x
072 1,2-benzanthracene
-------
TABLE VI-7 Continued
(benzo(a)anthracene) x
073 Benzo(a)pyrene (3,4-benzo-
pyrene) x
074 3,4-Benzofluoranthene
(benzo(b)fluoranthene) x
075 11,12-benzofluoranthene
(benzo(b)fluoranthene) x
076 Chrysene x
077 Acenaphthylene x
078 Anthracene x
079 1,12-benzoperylene
(benzo(ghi)perylene) x
080 Fluorene x
081 Phenanthrene x
082 1,2,5,6-dibenzanthracene
(dibenzo(,h)anthracene) x
083 Indeno(l,2,3-cd) pyrene
(2,3-o-pheynylene pyrene) x
084 Pyrene x
085 Tetrachloroethylene x
086 Toluene x
087 Trichloroethylene x
088 Vinyl chloride (chloroethylene) x
089 Aldrin x
090 Dieldrin x
091 Chlordane (technical mixture
and metabolites) x
092 4,4-DDT x
093 4,4-DDE (p,p-DDX) x
094 4,4-DDD (p,p-TDE) x
095 Alpha-endosulfan x
096 Beta-endosulfan x
097 Endosulfan sulfate x
098 Endrin x
099 Endrin aldehyde x
100 Heptachlor x
101 Heptachlor epoxide
(BHC-hexachlorocyclo- x
hexane)
102 Alpha-BHC x
103 Beta-BHC . x
104 Gamma-BHC (lindane) x
105 Delta-BHC (PCB-poly-
chlorinated biphenyls) x
-------
TABLE VI-'7 Continued
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-12601 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium
Copper
Cyanide, Total
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8-tetrachloro-
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
dibenzo-p-dioxin (TCDD) (NOT ANALYZED)
-------
TABLE VI-8
Other Pollutants Considered for Regulation
Subcategory
Cadmium
Aluminum
Cobalt x
Iron
Manganese
Oil & Grease x
TSS x
pH x
Lead
x
x
x
Leclanche
x
x
x
x
Zinc
x
x
x
x
477
-------
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 battery manufacturing industrial point source
category. Included are discussions of individual end-of-pipe
treatment technologies and in-plant technologies.
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
battery manufacturing facilities. Each description includes a
functional description and discussions 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 wastewater streams characteristically contain
significant levels of toxic inorganics. Cadmium, chromium, lead,
mercury, nickel, silver and zinc are found in battery manufacturing
wastewater streams at substantial concentrations. These 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 end-of-pipe technologies.
MAJOR TECHNOLOGIES
In Sections IX and X, the rationale for selecting treatment systems is
discussed. The individual technologies used in the system are
described here. The major end-of-pipe technologies are: chemical
479
-------
precipitation of dissolved metals, chemical reduction of hexavalent
chromium, cyanide precipitation, granular bed filtration, pressure
filtration, settling of suspended solids, and skimming of oil. 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.
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 and
fluorides as calcium fluoride.
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 insoluble 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 colloidal in
nature, coagulating agents may also be added to facilitate 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 - precipitation
of the unwanted metals and removal of the precipitate. Some small
amount of metal will remain dissolved in the wastewater after complete
precipitation. The amount of residual dissolved metal depends on the
480
-------
treatment chemicals used and related factors. The effectiveness of
this method of removing any specific metal depends on the fraction of
the specific metal in the raw waste (and hence in the precipitate) and
the effectiveness of suspended solids removal.
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 aluminum, antimony, arsenic,
beryllium, cadmium, chromium, cobalt, copper, iron, lead, manganese,
mercury, molybdenum, tin and zinc. 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 most important factors affecting precipitation
effectiveness are:
1. Maintenance of an 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.
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 571) and by
plotting effluent zinc concentrations against pH as shown in Figure
VII-2 (Page 572). It is partially illustrated by data obtained from 3
consecutive days of sampling at one metal processing plant as
displayed in Table VII-1.
481
-------
TABLE VII-1
pH CONTROL EFFECT ON METALS REMOVAL
Day 1 Day 2 Day 3
In Out 111 Out In Out
pH Range 2.4-3.4 8.5-8.7 1.0-3.0 5.0-6.0 2.0-5.0 6.5-8.1
(mg/1)
TSS 39 8 16 19 16 7
Copper 312 0.22 120 5.12 107 0.66
Zinc 250 0.31 32.5 25.0 43.8 0.66
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
and intermediate values were were achieved on the third day when pH
values were less than desirable but in between the first and second
days.
Sodium hydroxide is used by one facility 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 6,000 gal/hr.
TABLE VII-2
Effectiveness of Sodium Hydroxide for Metals Removal
Day 1 Day 2 Day 3
In Out In Out In Out
pH Range 2.1-2.9 9.0-9.3 2.0-2.4 8.7-9.1 2.0-2.4 8.6-9.1
(mg/1)
Cr
Cu
Fe
0.097
0.063
9.24
0.0
0.018
0.76
0.057
0.078
15.5
0.005
0.014
0.92
0.068
0-053
9.41
0.005
0.019
0.95
482
-------
Pb 1.0 0.11 1.36 0.13 1.45 0.11
Mn 0.11 0.06 0.12 0.044 0.11 0.044
Ni 0.077 0.011 0.036 0.009 0.069 0.011
Zn .054 0.0 0.12 0.0 0.19 0.037
TSS 13 11 11
These data indicate that the system was operated efficiently. Ef-
fluent pH was controlled within the range of 8.6-9.3, and, while raw
waste loadings were not unusually high, most toxic metals were removed
to very low concentrations.
Lime and sodium hydroxide 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 VI1-3 shows sampling data from this
system, which uses lime and sodium hydroxide for pH adjustment,
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 5,000 gal/hr.
483
-------
TABLE VII-3
Effectiveness of Lime and Sodium Hydroxide for Metals Removal
Day 1 Day 2 Day 3
In Out In Out .In Out
pH Range 9.2-9.6 8.3-9.8 9.2 7.6-8.1 9.6 7.8-8.2
(mg/1)
Al
Cu
Fe
Mn
Ni
Se
Ti
Zn
TSS
37.3
0.65
137
175
6.86
28.6
143
18.5
4390
0.35
0-003
0.49
0.12
0.0
0.0
0.0
0.027
9
38.1
0-63
110
205
5.84
30.2
125
16.2
3595
0.35
0.003
0.57
0.012
0.0
0.0
0.0
0.044
13
29.9
0.72
208
245
5.63
27.4
115
17.0
2805
0.35
0.003
0.58
0.12
0.0
0.0
0.0
0.01
13
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 suf-
ficient 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. 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.
484
-------
TABLE VI1-4
THEORETICAL SOLUBILITIES OF HYDROXIDES AND SULFIDES
OF SELECTED METALS IN PURE WATER
Solubility of metal ion, mg/1
Metal
Cadmium
Chromium (Cr+++)
Cobalt (Co++)
Copper (Cu++)
Iron (Fe++)
Lead (Pb++)
Manganese (Mn++)
Mercury (Hg++)
Nickel (Ni++)
Silver (Ag+)
Tin (Sn++)
Zinc (Zn++)
As
9
Hydroxide
2.3 x 10-5
8.4 x 10~4
2.2 x 10-»
2.2 x ID-2
8.9 x 10~»
2.1
1.2
3.9 x 10-*
x 10~3
13.3
1.1 x 10-*
1.1
As Carbonate
1.0 x
*
7.0 x
3.9 x
1.9 x 10-»
2.1 x
7.0 x
io-»
10~3
10-2
10-1
10-*
As sulfide
6.7 x 10-»°
No precipitate
1.0 x 10-«
5.8 x 10-»«
3.4 x 10-s
3.8 x 10-»
2.1 x 10-3
9.0 x 10-20
6.9 x 10-»
7.4 x 10-12
3.8 x 10-«
2.3 x 10~7
TABLE VI1-5
SAMPLING DATA FROM SULFIDE
PRECIPITATION-SEDIMENTATION SYSTEMS
Treatment
PH
(mg/1)
Cr+6
Cr
Cu
Fe
Ni
Zn
Lime, FeS, Poly-
electrolyte,
Settle, Filter
In
Out
5.0-6.8 8-9
25.6
32.3
0.52
39.5
<0.014
<0.04
0.10
<0.07
Lime, FeS, Poly-
electrolyte,
Settle, Filter
In
7.7
Out
7.38
0.022 <0.020
2.4 <0.1
108 0.6
0.68 <0.1
33.9 <0.1
NaOH, Ferric
Chloride, Na2S
Clarify (1 stage)
In
11.45
18.35
0.029
0.060
Out
<.005
<.005
0.003
0.009
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.
485
-------
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 shown for the metals listed in
Table VI1-13. 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 hy-
droxides, 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 VI1-6 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.
TABLE VI1-6
SULFIDE PRECIPITATION-SEDIMENTATION PERFORMANCE
Parameter Treated Effluent
(mg/1)
Cd 0.01
CrT 0.05
Cu 0.05
Pb 0.01
Hg 0.03
Ni 0.05
Ag 0.05
Zn 0.01
486
-------
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.
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-12 (Page 582) explain this phenomenon.
Advantages and Limitations. Chemical precipitation has proven 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 mixed wastewaters and treatment chemicals, or
because of the potentially hazardous situation involved with the
storage and handling of those chemicals. Lime is usually added as a
slurry when used in hydroxide precipitation. The slurry must be kept
well mixed and the addition lines periodically checked to prevent
blocking of the lines, which may result from a buildup of solids.
Also, hydroxide precipitation usually makes recovery of the
precipitated metals difficult, because of the heterogeneous nature of
most hydroxide 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 prevent the generation of toxic hydrogen
sulfide gas. For this reason, ventilation of the treatment tanks may
be a necessary precaution in most installations. The use of ferrous
sulfide reduces or virtually eliminates 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 post 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 with hydroxide
precipitants, and disposal of metallic sulfide sludges may pose
487
-------
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.
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 coil coating category. As noted
earlier, sedimentation to remove precipitates is discussed separately.
Use iji Battery Manufacturing Plants. Chemical precipitation is used
at 76 battery manufacturing. 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.
488
-------
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 S02 + 3 H20 3 H2S03
3 H2SO, + 2H2Cr04 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-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
VI1-30 (Page 600) 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 usually used
to treat electroplating rinse waters, but may also be used in battery
manufacturing plants. A study of an operational waste treatment
facility chemically reducing hexavalent chromium 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.
489
-------
Advantages and Limitations. The major advantage of chemical reduction
to destroy 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 which is a function of 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. There may, however, be small amounts of sludge collected
due to minor shifts in the solubility of the contaminants. This
sludge can be processed by the main sludge treatment equipment.
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 and noncontact
cooling.
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 and
ferricyanide complexes.
490
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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 is very dependent on
pH. At pH's of 8 and 10 the residual cyanide concentrations measured
are twice those 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%) 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 VI1-7 presents data from three coil coating plants.
TABLE VI1-7
CONCENTRATION OF TOTAL CYANIDE
(mg/1)
Plant Method In Out
1057 FeS04 2.57
2.42
3.28
33056 FeS04 0.14
0.16
12052 ZnS04 0.46
0.12
Mean 0.07
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.
491
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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.
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 bouyancy 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
492
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filtration efficiency. The biflow design is an attempt to overcome
this problem.
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 VI1-14 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.
Auxiliary 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 carryover basis
from turbidity monitoring of the outlet stream. All of these schemes
have been used successfully.
493
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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 as follows;
Slow Sand
Rapid Sand
High Rate Mixed Media
2.04 - 5.30 1/sq m-hr
40.74 - 51.48 1/sq m-hr
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 VI1-8 below.
Table VII-8
Plant ID
06097
13924
18538
30172
36048
mean
Multimedia Filter Performance
TSS Effluent Concentration, mg/1
0.
1.
3.
1.
1.
2.
2.
0,
8,
o,
0
4,
1,
61
0.
2.
2.
7.
2.
0,
2,
0,
0,
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
Advantages and Limitations. The principal advantages of granular bed
filtration are its 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.
494
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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.
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.
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 VI1-15 (Page 585) 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 is mounted a filter made of cloth or a synthetic
fiber. 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
495
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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 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 avail-
able.
For larger operations, the relatively high space requirements, as
compared to those of a centrifuge, could be prohibitive in some
situations.
496
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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 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.
Demonstrat ion Status. Pressure filtration is a commonly used
technology in a great many commercial applications. Pressure
filtration is used in six battery manufacturing plants.
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 effected by reducing the velocity of the
feed stream in a large volume tank or lagoon so that gravitational
settling can occur. Figure VI1-13 (Page 583) 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
497
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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
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.
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.
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 retention time, particle size and density, and the
surface area of the basin.
The data displayed in Table VI1-9 indicate suspended solids removal
efficiencies in settling systems.
498
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TABLE VI1-9
PERFORMANCE OF SAMPLED SETTLING SYSTEMS
PLANT ID
01057
09025
11058
12075
19019
33617
40063
44062
46050
SETTLING
DEVICE
SUSPENDED SOLIDS CONCENTRATION (mg/1)
Day 1 Day 2 Day 3
In
Out In
Out In
Out
Lagoon 54
Clarifier 1100
Settling
Ponds
Clarifier 451
Settling 284
Pond
Settling 170
Tank
Clarifier &
Lagoon
Clarifier 4390
Clarifier 182
Settling 295
Tank
6
9
17
6
9
13
10
56
1900
242
50
1662
3595
118
42
6
12
10
1
16
12
14
10
50
1620
502
1298
2805
174
153
5
5
14
13
23
8
The mean effluent TSS concentration obtained by the plants shown in
Table VI1-9 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 plate, 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.
499
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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 by 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.
Skimming
Pollutants with a specific gravity less than water will often float
unassisted to the surface of the wastewater. Skimming 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
500
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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
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. Using an API
separator system in conjunction with a drum type skimmer would be a
very effective method of removing floating contaminants from non-
emulsified oily waste streams. Sampling data shown below illustrate
the capabilities of the technology with both extremely high and
moderate oil influent levels.
501
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Table VII-10
SKIMMING PERFORMANCE
Oil & Grease
mg/1
Plant Skimmer Type Ir\ Out
06058 API 224,669 17.9
06058 Belt 19.4 8.3
Based on data from installations in a variety of manufacturing plants,
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 the copper and copper alloy industry 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 due to leaching from plastic
lines and other materials.
A study of priority organic compounds commonly found in copper and
copper alloy 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 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 organic compounds present in
the raw waste. The API oil-water separation system and the thermal
emulsion breaker performed notably in this regard, as shown in the
following table (all values in mg/1).
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TABLE VII-11
TRACE ORGANIC REMOVAL BY SKIMMING
Eff.
API (06058)
Inf.
Oil & Grease 225,000
Chloroform .023
Methylene Chloride .013
Naphthalene 2.31
N-nitrosodiphenylamine 59.0
Bis-2-ethylhexylphthalate 11.0
Diethyl phthalate
Butylbenzylphthalate .005
Di-n-octyl phthalate .019
Anthracene - phenanthrene 16.4
Toluene .02
14.6
.007
.012
.004
.182
.027
—
2,590
0
0
1.83
-
1.55
.017
.002
.002
.014
.012
TEB (04086)
Inf. Eff.
10.3
0
0
.003
.018
.005
.002
144
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. Therefore,
skimming alone may not remove all the pollutants capable of being
removed by air flotation or other more sophisticated technologies.
Operational Factors. Reliability: Because of its simplicity,
skimming is a very reliable technique.
Maintainability: The skimming mechanism requires
lubrication, adjustment, and replacement of worn parts.
periodic
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.
503
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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 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 skimming are installed and
operating properly where appropriate.
L&S Performance
Sampling data was analyzed from fifty-five industrial plants which use
chemical precipitation as a waste treatment technology. These plants
include the electroplating, mechanical products, metal finishing, coil
coating, pprcelain enameling, battery manufacturing, copper forming
and aluminum forming categories. All of the plants employ pH
adjustment and hydroxide precipitation using lime or caustic, followed
by settling (tank, lagoon or clarifier) for solids removal. Most also
add a coagulant or flocculant prior to solids removal. No sample
analyses were included where effluent TSS levels exceeded 50 mg/1 or
where the effluent pH fell below 7.0. This was done to exclude any
data which represented clearly inadequate operation of the treatment
system. These data are derived from a variety of industrial
manufacturing operations which have wastewater relatively similar to
battery manufacturing wastewaters. Plots were made of the available
data for eight metal pollutants showing effluent concentration vs. raw
waste concentration (Figures VII-3 - VII-11) (Pages 573-581) for each
parameter. Table VI1-12 summarizes data shown in Figures VII-3
through VII-11, tabulating for each pollutant of interest the number
of data points and average of observed values. Generally accepted
design values (GADV) for these metals are also shown in Table VI1-12.
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TABLE VI1-12
Hydroxide Precipitation - Settling (L&S) Performance
Specific No. data Observed
metal points Average GADV
Cd 38 0.013 0.02
Cr 64 0.47 0.2
Cu 74 0.61 0.2
Pb 85 0.034 0.02
Ni 61 0.84 0.2
Zn 69 0.40 0.5
Fe 88 0.57 0.3
Mn 20 0.11 0.3
P 44 4.08
A number of other pollutant parameters were considered with regard to
the performance of hydroxide precipitation-settling treatment systems
in removing them from industrial wastewater. Sampling data for most
of these parameters is scarce, so published sources were consulted for
the determination of average and 24-hour maximum concentrations.
Sources consulted include text books, periodicals and EPA publications
as listed in Section XV as well as applicable sampling data.
The available data indicate that the concentrations shown in Table
VII-13 are reliably attainable with hydroxide precipitation and
settling. The precipitation of silver appears to be accomplished by
alkaline chloride precipitation and adequate chloride ions must be
available for this reaction to occur.
TABLE VII-13
Hydroxide Precipitation-Settling (L&S) Performance
ADDITIONAL PARAMETERS
Parameter Average 24-Hour Maximum
(mg/1)
Sb 0.05 0.50
As 0.05 0.50
Be 0.3 1.0
Hg 0.03 0.10
Se 0.01 0.10
Ag 0.10 0.30
Al 0.2 0.55
Co 0.07 0.50
F 15 30
Ti 0.01 0.10
505
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LS&F Performance
Tables VI1-6 and VI1-7 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 pressure filtration, while Plant B uses a rapid
sand filter.
Raw waste data was collected only occasionally at each facility and
the raw waste 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.
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TABLE VI1-14
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-Treated 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
1.65
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
Mean + 2
std. dev,
0.10
0.03
0.48
0.35
0.06 +0.10
0.016 +0.010
0-20 +0.14
0.23 +0.34
0.49 +0.18
0.26
0.04
0.48
0.91
0.85
507
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TABLE VII-15
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant B
Parameters
No Pts.
Range mq/1
For 1979-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
For 1978-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
144
143
143
131
144
0.0
0.0
0.0
0.0
0.0
- 0.40
- 0.22
- 1.49
- 0.66
- 2.40
- 1.00
0.70
0.23
1.03
0.24
1.76
Total 1974-1979-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
1288
1290
1287
1273
1287
0.0
0.0
0.0
0.0
0.0
- 0.56
- 0.23
- 1.88
- 0.66
- 3.15
Raw Waste
Cr
Cu
Ni
Zn
Fe
TSS
3
3
3
2
3
2
177
-446
Mean +_
std. dev.
0.068 +0.075
0.024 +0.021
0.219 +0.234
0.054 +0.064
0.303 +0.398
Mean + 2
std. dev.
0.22
0.07
0.69
0.18
1.10
0.059 +0.088
0.017 +0.020
0.147 +0.142
0.037 +0.034
0.200 +0.223
0.038 +0.055
0.011 +0.016
0.184 +0.211
0.035 +0.045
0.402 +0.509
2.80
0.09
1.61
2.35
3.13
- 9.15
- 0.27
- 4.89
- 3.39
-35.9
5.90
0.17
3.33
22.4
0.24
0.06
0.43
0.11
0.47
0.15
0.04
0.60
0.13
1.42
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 waste of both
plants is high. This results in coprecipitation of toxic metals with
iron, a process sometimes called ferrite precipitation. Ferrite
precipitation using high-calcium lime for pH control yields the
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results shown above. Plant operating personnel indicate that this
chemical treatment combination (sometimes with polymer assisted
coagulation) generally produces better and more consistant metals
removal than other combinations of sacrificial metal ions and alkalis.
Analysis of. Treatment System Effectiveness
Data were presented in Tables VI1-14 and VI1-15 showing the
effectiveness of L&S and LS&F technologies when applied to battery
manufacturing or essentially similar wastewaters. An analysis of
these data has been made to develop one-day-maximum and 30-day-average
values for use in establishing effluent limitations and standards.
Several approaches were investigated and considered. These approaches
are briefly discussed and the average (mean), 30-day average, and
maximum (1-day) values are tabulated for L&S and LS&F technologies.
L&S technology data are presented in Figures VI1-3 through VII-11
(Page 573-581) and are summarized in Table VII-12. The data summary
shows observed average values. To develop the required regulatory
base concentrations from these data, variability factors were
transferred from electroplating pretreatment (Electroplating
Pretreatment Development Document, 440/1-79/003, page 397). and
applied to the observed average values. One-day-maximum and 30-day-
average values were calculated and are presented in Table VI1-16.
For the pollutants for which no observed one-day variability factor
values are available the average variability factor from
electroplating one-day values (i.e. 3.18) was used to calculate one-
day maximum regulatory values from average (mean) values presented in
Tables VII-12 and VII-13. Likewise, the average variability factor
from electroplating 30-day-average variability factors (i.e. 1.3) was
used to calculate 30-day average regulatory values. These calculated
one-day maximums and 30-day averages, to be used for regulations, are
presented in Table VII-16.
Table - A
Variability Factors of Lime and Settle (L&S) Technology
Metal one-day maximum 30 day average
electro- electro-
plating plating
Cd 2.9 1.3
Cr 3.9 1.4
Cu 3.2 1.3
Pb 2.9 1.3
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Ni 2.9 1.3
Zn 3.0 1.3
Fe 3.81 1.3
Mean 3.18 1.3
LS&F technology data are presented in Tables VII-14 and VII-15. 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 occured during the data 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 pollutant. Fifty-one data days 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 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 were eliminated by both procedures. Since
common engineering practice (mean plus 3 sigma) and logic (treated
waste should be less than raw waste) seem to coincide, the data base
with the 51 spurious data days eliminated will be the basis for all
further analysis. Range, mean, standard deviation and mean plus two
standard deviations are shown in Tables VII-14 and VII-15 for Cr, Cu,
Ni, Zn and Fe.
The Plant B data was separated into 1979, 1978, and total data base
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.
Selecting the greatest mean and greatest mean plus two standard
deviations draws values from four of the five data bases. These
values are displayed in the first two columns of Table VII-B and
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TABLE VI1-16
Summary of Treatment Effectiveness
Pollutant
Parameter
114 Sb
115 As
117 Be
118 Cd
119 Cr
120 Cu
121 CN
122 Pb
123 Hg
124 Ni
125 Se
126 Ag
128 Zn
Al
Co
F
Fe
Mn
P
Ti
O&G
TSS
L&S
Technology
System
One Thirty
Mean
0.05
0.05
0.3
0.02
0.47
0.61
0.07
0.034
0.03
0.84
0.01
0.1
0.5
0.2
0.07
15
0.57
0.11
4.08
0.01
10.1
Day
Max.
0.16
0.16
0.96
0.06
1.83
1.95
0.22
0.10
0.10
1.44
0.03
0.32
1.5
0.64
0.22
47.7
2.17
0.35
13.0
0.03
20.0
35.0
Day
Avg.
0.07
0.07
0.39
0.03
0.66
0.79
0.09
0.05
0.04
1.09
0.01
0.13
0.65
0.26
0.09
19.5
0.65
0.14
5.30
0.01
10.0
25.0
Mean
0.033
0.033
0.20
0.014
0.07
0.41
0.047
0.034
0.02
0.22
0.007
0.007
0.23
0.14
0.047
10.0
0.49
0.079
2.78
0.007
2.6
LS&F Sulfide
Technology Precipitation
System Filtration
One Thirty One Thirty
Day
Max.
0.11
0.11
0.63
0.044
0.27
1.31
0.15
0.10
0.063
0.64
0.021
0.21
0.69
0.42
0.147
31.5
1.87
0.23
8.57
0.021
10.0
15.0
Day
Avg. Mean
0.043
0.043
0.26
0.018 0.01
0.10 0.05
0.53 0.05
0.06
0.044 0.01
0.026 0.03
0.29 0.05
0.009
0.087 0.05
0.30 0.01
0.18
0.061
13.0
0.64
0.095
3.54
0.009
10.0
10.0
Day Day
Max. Avg.
0.032 0.013
0.16 0.065
0.16 0.065
0.032 0.013
0.095 0.039
0.16 0.065
0.16 0.065
0.032 0.013
-------
represent one approach to analysis of the LS&F data to obtain average
(mean) and one-day maximum values for regulatory purposes.
The other candidates for regulatory values are presented in Table VII-
B and were derived by multiplying the mean by the appropriate
variability factor from electroplating (Table A). These values are
the ones used for one-day maximum and 30-day average regulatory
numbers.
Composite
Mean
Table - B
Analysis of Plant A and Plant B data
Composite Composite
Mean X Mean X
Plant B One Day 30 day
Mean* Electpltg. Electpltg.
2 siqma Var.Fact. Var.Fact.
Cr 0.068
Cu 0.02
Ni 0.22
Zn 0.23
Fe 0.49
0.26
0.07
0.69
0.91
1.42
0.27
0.077
0.64
0.69
1.87
0.095
0.026
0.286
0.299
0.637
Concentration values for regulatory use are displayed in Table VII-16.
Mean values for L&S were taken from Tables VI1-12, VI1-13, and the
discussions following Tables VII-9, and VII-10. Thirty-day average
and one-day maximum values for L&S were derived from means and
variability factors as discussed earlier under L&S.
Copper levels achieved at Plants A and B are lower than believed to be
generally achievable because of the high iron content of the raw
wastewaters. Therefore, the mean concentration value achieved is not
used; LS&F mean used is derived from the L&S technology.
The mean concentration of lead is not reduced from the L&S
because of the relatively high solubility of lead carbonate.
value
L&S cyanide mean levels shown in Table VI1-7 are ratioed to one day
maximum and 30 day average 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 filter performance for removing TSS as shown in Table VI1-8 yields
a mean effluent concentration of 2.61 mg/1 and calculates to a 30 day
average of 5.58 mg/1; a one day maximum of 8.23. These calculated
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values more than amply support the classic values of 10 and 15,
respectively, which are used for LS&F.
Mean values for LS&F for pollutants not already discussed are derived
by reducing the L&S mean by one-third. The one-third reduction was
established after examining the percent reduction in concentrations
going from L&S to LS&F data for Cr, Ni, Zn, and TSS. The reductions
were 85 percent, 74 percent, 54 percent, and 74 percent, respectively.
The 33 percent reduction is conservative when compared to the smallest
reduction for metals removals of more than 50 percent in going from
L&S to LS&F.
The one-day maximum and 30-day average values for LS&F for pollutants
for which data were not available were derived by multiplying the
means by the average one-day and 30-day variability factors. Although
iron was reduced in some LS&F operations, some facilities using that
treatment introduce iron compounds to aid settling. Therefore, the
value for iron at LS&F was held at the L&S level so as to not unduly
penalize the operations which use the relatively less objectionable
iron compounds to enhance removals of toxic metals.
MINOR TECHNOLOGIES
Several other treatment technologies were considered for possible
application in BPT or BAT. These technologies are presented here with
a full discussion for most of them. A few are described only briefly
because of limited technical development.
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, 500-1500 m2/sq m resulting from a large
number of internal pores. Pore sizes generally range from 10-100
angstroms in radius.
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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 and, because of this selectivity, is particularly effective
in removing organic compounds from aqueous solution.
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 VI1-26. 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. Removal levels
found at three manufacturing facilities are:
Table VII-17
ACTIVATED CARBON PERFORMANCE (MERCURY)
Mercury levels - mg/1
Plant In Out
A 28.0 0.9
B 0.36 0.015
C 0.008 0.0005
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
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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
VI1-18 (Page 601) summarizes the treatability effectiveness for most
of the organic priority pollutants by activated carbon as compiled by
EPA. Table VI1-19 (Page 602) 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 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 usage 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 the removing and some times recovering, of
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.
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Centrifuqation
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 VI1-17 (Page 587).
There are three common types of centrifuges: the disc, basket, and
conveyor type. All three operate by removing solids under the
influence of centrifugal force. The fundamental difference between
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, they are moved by a
screw to the end of the machine, at which point whey 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 20-35 percent.
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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.
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.
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
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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 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 re-
placeable 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
10-15 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
prefilters may be necessary when raw waste oil concentrations are
high.
Operational Factors. Reliability: Coalescing is inherently highly
reliable since there 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 not
in use at any battery manufacturing facilities.
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 + 2H20
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 VI1-27.
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 tank 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 treatment, the supernatant is
discharged and the sludges are collected for removal and ultimate
disposal.
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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.
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 VI1-28.
Application and Performance. Ozonation has been applied commercially
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 to cyanate and to oxidize
phenols and dyes to a variety of colorless nontoxic products.
Oxidation of cyanide to cyanate is illustrated below:
CN- + 03 = CNO- + 02
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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, and 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.
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 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
521
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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 VI1-29 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.
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 - 54°C (120 - 130°F) and the pH is adjusted to 10.5 -
11.8. Formalin (37 percent formaldehyde) is added while the tank is
vigorously agitated. After 2-5 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 filled. A settling
tank or a filter is needed to concentrate the precipitate.
Application and Performance. The hydrogen peroxide oxidation process
is applicable to cyanidebearing 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.
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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.
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 VI1-20 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 subse-
quently released to the atmosphere. Thus, evaporation occurs by
humidification of the air stream, similar to a drying process. Equip-
ment 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.
Another form of atmospheric evaporator also works on the air humidi-
fication 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 vacuum 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
523
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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. Another means
of increasing energy efficiency is vapor recompression (thermal or
mechanical), which enables heat to be transferred from the condensing
water vapor to the evaporating wastewater. Vacuum evaporation
equipment may be classified as submerged tube or climbing film
evaporation units.
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. Waste water 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 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. Waste water 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.
524
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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 heating could be inexpensively and effectively
applied to evaporation units. 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 distillable 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 handling corrosive liquids.
Maintainability: Operating parameters can be automatically
controlled. Pretreatment may be required, as well as periodic
cleaning of the system. Regular replacement of seals, especially in a
corrosive environment, may be necessary.
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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. One battery plant has recently reported
showing the use of evaporation.
Flotation
Flotation is the process of causing particles such as metal hydroxides
or oil to float to the surface of a tank where they 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-24 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.
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.
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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 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 waste water
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. Auxilliary 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 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.
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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 cor-
rosion or breakage and may require periodic replacement.
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.
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 VI1-18 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.
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Advantages and Limitations. The principal advantage of a gravity
sludge thickening process is that it facilitates further sludge
dewatering. Other advantages are high reliability and minimum
maintenance requirements.
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.
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 operation, 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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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 be-
cause the exchange occurs on the surface of the resin, and the ex-
changing ion must undergo a phase transfer from solution phase to
solid phase. Thus, ionic contaminants in a waste stream can be ex-
changed for the harmless ions of the resin.
Although the precise technique may vary slightly according to the ap-
plication 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 re-
generation of the resin, which now holds those impurities retained
from the waste stream. An ion exchange unit with in-place regen-
eration is shown in Figure VII-21 (Page 591). 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.
C) Cyclic Regeneration: In this process, the regeneration of the
spent resins takes place within the ion exchange unit itself in
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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 proven 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 utilize 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 solu-
tions. 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. 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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Table VII-20
Parameter
Ion Exchange Performance
Plant A
Plant B
All Values mg/1
Al
Cd
Cr+3
Cr+6
Cu
CN
Au
Fe
Pb
Mn
Ni
Ag
S04
Sn
Zn
Prior To
Purifi-
cation
5.6
5.7
3.1
7.1
4.5
9.8
7.4
4.4
6.2
1.5
1.7
14.8
After
Purifi-
cation
0.20
0.00
0.01
0.01
0.09
0.04
0.01
0.00
0.00
0.00
0.00
0.40
Prior To
Purifi-
cation
43.0
3.40
2.30
1.70
1.60
9.10
210.00
1.10
After
Purifi-
cation
0.10
0.09
0.10
0.01
0.01
0.01
2.00
0.10
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 waste water 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
preferentially 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.
532
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Solid Waste Aspects: Few, if any, solids accumulate within the ion
exchangers, and those which do appear are removed by the regeneration
process. Proper prior treatment and planning can eliminate solid
buildup problems altogether. The brine resulting from regeneration of
the ion exchange resin most usually must 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 compartmented 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.
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.
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 non-gelatinous, 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.
533
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They have also been used for heavy 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 the following table, 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 below unless lower
levels are present in the influent stream.
Table VII-21
MEMBRANE FILTRATION SYSTEM EFFLUENT
Specific
Metal
Al
Cr,
Cr
Cu
Fe
Pb
CN
Ni
Zn
TSS
(+6)
(T)
Manufacturers
Guarantee
0.5
0.02
0.03
Plant 19066
In Out
Plant 31022
In Out
0,
0,
0.46
4.13
18.8
288
0.01
0.018
0.043
0.3
0.05
0.02
0,
0,
0.652 0.01
<0.005 <0.005
9.56 0.017
2.09 0.046
632 0.1
5.25
98.4
8.00
21.1
0.288
<0.005
194
5.00
13.0
<0.005
0.057
0.222
0.263
0.01
<0.005
0.352
0.051
8.0
Predicted
Performance
0.05
0.20
0.30
0.05
0.02
0.40
0.10
10.0
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, 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
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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 6-24 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.
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 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.
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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.
The following table contains performance figures obtained from pilot
plant studies. Peat adsorption was preceded by pH adjustment for
precipitation and by clarification.
Table VII-22
PEAT ADSOPRTION PERFORMANCE
Pollutant In. 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
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 disposing 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.
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.
536
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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.
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 permeate 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 VI1-22
depicts a reverse osmosis system.
As illustrated in Figure VII-23, 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.
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 - 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.
537
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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
facilities.
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 advantage
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.
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 due to
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
538
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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 solutions.
It has been shown that RO 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 and 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 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 limitation 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 available
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. Down time for
539
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flushing or cleaning is on the order of 2 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 waste water applications in a variety of industries.
In addition to these, there are thirty to forty 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 success in commercial
applications. Reverse osmosis is used at one battery plant to treat
process wastewater for reuse as boiler feedwater.
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 VI1-19 shows the
construction of a drying bed.
Drying beds are usually divided into sectional areas approximately 7.5
meters (25 ft) wide x 30 to 60 meters (100 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
540
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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.
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
541
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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.
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 weight materials
pass through the membrane under the applied pressure of 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 VI1-25 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 are 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.
542
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The following test data indicate ultrafiltration performance (note
that UF is not intended to remove dissolved solids):
Table VII-23
ULTRAFILTRATION PERFORMANCE
Parameter Feed (mq/1) Permeate (mq/1)
Oil (freon extractable) 1230 4
COD 8920 148
TSS 1380 13
Total Solids 2900 296
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.
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.
543
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Op
ul
erational 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.
Maintainabi1ity; A limited amount of regular maintenance is required
for the pumping system. In addition, membranes must be periodically
changed. Maintenance associated with membrane plugging can be reduced
by selection of a membrane with optimum physical characteristics and
sufficient velocity of the waste stream. It is often necessary to
occasionally 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.
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-16.
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.
544
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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
waste water 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, 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 two battery manufacturing
plants for sludge dewatering.
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IN-PROCESS POLLUTION CONTROL TECHNIQUES
Introduction
In general, the most cost-effective pollution reduction techniques
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 presenting the pollutants to
treatment in smaller, more concentrated waste streams from which they
can be more completely removed, or by eliminating pollutants which are
not readily removed or which interfere with the treatment of other
pollutants. They also frequently yield economic benefits both 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 VII-24 shows, some in-process control measures have been
implemented by many battery manufacturing facilities. The wide range
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 control at these
facilities.
While many in-process pollution control techniques are of general
significance, specific applications of these techniques vary among
different battery manufacturing subcategories. In addition, some 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 waste segregation,
water recycle and reuse, water use reduction, process 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, waste segregation is frequently a prerequisite for the
extensive practice of wastewater recycle or reuse.
Waste Segregation - The segregation of wastewater streams is a key
element in effective pollution control. Separation of non-contact
cooling water from process wastewater prevents dilution of the process
wastes and maintains the purity of the non-contact stream for
subsequent reuse or discharge. Similarly, the segregation of process
waste streams differing significantly in their chemical
characteristics can increase effectiveness and reduce treatment costs.
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Segregation of specific process wastewater streams is common in
battery manufacturing plants.
Mixing process wastewater with non-contact cooling water generally has
an adverse effect on both performance and treatment costs. The
resultant waste stream is usually too contaminated for continued reuse
in non-contact cooling, or for discharge without treatment. The
increased volume of wastewater increases the size and cost of
treatment facilities and lowers removal effectiveness. Thus a plant
which segregates non-contact cooling water and other nonprocess waters
from process wastewater can generally achieve a lower mass discharge
of pollutants while incurring lower treatment costs.
Battery manufacturing facilities commonly produce multiple process
wastewater streams having significantly different chemical
characteristics; some are high in toxic metals; some may contain
primarily suspended solids; and others may be quite dilute.
Wastewater from a specific process or operation usually contains only
a few of the many pollutants generated at a particular site.
Segregation of these individual process waste streams may allow
reductions in treatment costs and pollutant discharges.
The segregation of dilute process waste streams from those bearing
high pollutant loads often allows further process use of the dilute
streams; they may be recycled to the process from which they were
discharged; or they may be suitable for use in another process.
Sometimes, the dilute process waste streams are suitable for
incorporation into the product.
Segregation of waste streams containing high levels of suspended
solids allows separate treatment of these streams in relatively
inexpensive settling systems. 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 these waste streams may yield an
additional economic benefit to the plant by allowing increased
recovery of process materials. Because the solids borne by wastewater
from a specific process operation are primarily composed of materials
used in that operation, sludges resulting from separate settling of
these streams may frequently be reclaimed for use in the process with
little or no processing. This technique presently is used to recover
materials used in processing pasted, electrodeposited and impregnated
electrodes at battery manufacturing plants.
Wastewater Recycle and Reuse - The recycle or reuse of process
wastewater is effective in the reduction of both pollutant discharges
and treatment costs. The term recycle is used to designate the return
of process wastewater to the process or processes from which it
originated while reuse refers to the use of wastewater from one
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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 water, and wastewater from
equipment and area cleaning. Numerous other process wastewater
streams from battery manufacturing activities may also be recycled or
reused.
Both recycle and reuse are frequently possible without treatment of
the wastewater; process pollutants present in the wastewater stream
are often 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 complications and
expense; treatment requirements are likely to be least for recycle;
and piping to remote locations in the plant is not generally required.
Common points of wastewater recycle in present practice incude air
pollution control scrubbers, and equipment and area wash water. In
addition, recycle of wastewater is observed in some product rinsing
operations and in contact cooling.
The rate of water use in wet 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 characteristically very dilute
and high in volume. These streams may usually be recycled extensively
without treatment with no deleterious effect on scrubber performance.
Limited treatment such as neutralization where acid fumes are scrubbed
can significantly 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 sub-
categories 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 is characteristically very
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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 ultimately
limited by the concentrations of materials rinsed off the product in
the rinsewater. Wastewater from contact cooling operations also may
contain low concentrations of pollutants which do not interfere with
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 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 level of contaminants in
these high volume waste streams is sometimes low enough to allow
recycle to the process. With minimal treatment, a high degree of
recycle of wastewater from contact cooling streams may require pro-
visions for neutralization or removal of heat.
The extent of recycle possible in most process water uses is
ultimately limited by the increasing concentrations of dissolved
solids in the water. The build-up of dissolved salts generally
necessitates some small discharge or "blowdown" from the process to
treatment. In some cases, the rate of addition of dissolved salts may
be sufficiently low to be balanced by removal of dissolved solids in
water entrained in settled solids. In these cases complete recycle
with no discharge can be achieved. In other instances, the
contaminants which buildup in the recycle loop may be compatible with
another process operation, and the blowdown may be reused in another
process. One example of this is observed in lead subcategory
scrubber, 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 discharged from a
facility or specific process operation may be reduced simply by
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 numerous opportunities for water use
reductions. Additional reductions in process water use and discharge
may be achieved by modifications to process techniques and equipment.
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Many production units in battery manufacturing facilities were
observed to operate intermittently or at highly variable production
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 involves the human factor and
has been found to be somewhat unreliable in practice; production per-
sonnel may fail to turn off manual valves when production units are
shut down and have been observed 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 manufacturing
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 site where the daily average production
normalized discharge flow 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 at this
site at relatively little cost.
Additional flow reductions may be achieved by the implementation of
more effective water use in some process operations. These measures
generally require the purchase or modification of some process
equipment and involve larger capital investment than the simple flow
control measures discussed above. The most significant areas for
improvement in water use effectiveness are in rinsing operations and
in equipment and area clean-up. Under some circumstances, process
water use in removing excess materials from electrode stock and in
washing batteries may be eliminated without any significant change in
the manufacturing process or the final product.
Rinsing is a common operation in the manufacture of batteries, and a
major source of wastewater discharge at most plants. Efficient
rinsing implies the removal of the greatest mass of material in the
smallest 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 long product
residence times and high mixing rates in rinses). Rinsing efficiency
is also increased by the use of multi-stage and countercurrent rinses.
Multi-stage rinses reduce the total rinse water requirements by
allowing the removal of most of the contaminants in more concentrated
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waste streams with only the final stage rinse diluted to the levels
required for final product purity. In a counter-current 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.
Equipment and area clean-up practices observed at battery manu-
facturing facilities vary widely. While some facilities employ
completely dry clean-up techniques others use water with varying
degrees of efficiency. The practice of "hosing down" equipment and
production areas generally represents a very inefficient use of water,
especially when hoses are left running during periods when they are
not used. Alternative techniques which use water more efficiently
include floor wash machines and bucket and sponge or bucket and mop
techniques as observed at some facilities.
A major factor necessitating battery washing in many cases is
electrolyte spillage on the battery case during filling. This
spillage and subsequent wash requirements are maximized when batteries
are filled by immersion or by "overfill and withdraw." 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 discharge may
be achieved by the substitution of dry air pollution control devices
such as baghouses for wet scrubbers where the emissions requiring
control are amenable to these techniques.
Process Modification - There are numerous process alternatives for the
manufacture of batteries in most of the battery manufacturing
subcategories, and the alternatives frequently differ significantly in
the quantity and quality of wastewater produced. Most process
modifications which may be considered as techniques for reducing
pollutant discharge are specific to individual subcategories and are
discussed in subsequent sections. In general, process modifications
considered deal with changes in electrolyte addition techniques as
discussed previously and changes in electrode formation processes. In
addition, changes in amalgamation procedures and improvements in
process control to reduce rework requirements are viable techniques to
reduce wastewater discharge at some sites.
One process modification applicable to several subcategories is the
substitution of alternative formulations for cell wash materials
containing chromate and cyanide. This substitution will eliminate
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these pollutants from process wastewater at the plants which presently
use them.
Plant Maintenance and Good Housekeeping - Housekeeping practices are
particularly significant for pollution control at battery
manufacturing facilities. Large quantities of toxic materials used as
active materials in battery electrodes are handled and may be spilled
in production areas. The use of water in cleaning up these materials
may contribute significantly to wastewater discharges at some
facilities.
Maintenance practices are important in eliminating unnecessary spills
and leaks and in reducing contamination of non-contact cooling water.
Examples of the impact of faulty maintenance were observed in the
contamination of non-contact cooling water in a leaking ball mill
cooling jacket at one lead subcategory facility and in the use of
excess water in hosing down asmalfunctioning amalgamation blender. In
both cases, the volume of wastewater requiring treatment and losses of
process materials were increased resulting in increased treatment and
manufacturing process costs as well as increased pollutant discharges.
Good housekeeping encompasses a variety of plant design and operating
practices which are important for efficient plant operation and worker
hygiene and safety as well as for water pollution control. These
include:
Floor maintenance and treatment in areas where pollutant
materials are handled to minimize cracks and pores in which
spilled materials may lodge. This reduces the volume of
water required to clean up spills and increases the
efficiency of dry cleanup techniques.
Preventing drips and spills and collecting those which cannot
be avoided, especially in electrolyte addition areas.
Isolating the materials rather than letting them run over
equipment and floor surfaces can greatly reduce wash-down
requirements and also allow the collected materials to be
returned for process use instead of being discharged to waste
treatment.
Reduction in spillage during bulk handling by provision for
dust control and for rapid dry clean-up of spilled materials.
Cadmium Subcategory
Cadmium subcategory manufacturing involves a wide variety of process
water uses in active material preparation, electrode processing and
rinses, cell washing, equipment and area washing, and air pollution
control. Consequently, many different in-process control techniques
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are applicable. These include waste segregation, material recovery,
process water recycle and reuse, water use control (reduction), and
process modification possibilities.
Waste Segregation - The segregation of wastewater streams from
individual process operations is presently practiced by some
manufacturers in this subcategory. Segregation of specific waste
streams is useful in allowing recycle and reuse and in making the
recovery of some process materials feasible. Waste streams segregated
for these purposes include wet air pollution control scrubber
discharges which are segregated for recycle, formation process
solutions which are segregated for reuse in formation or in other
process operations, and waste streams from impregnation,
electrodeposition and wet plate cleaning or brushing which are
segregated to allow material recovery. Segregation of process wastes
is not practiced for end-of-pipe treatment in this subcategory because
all process waste streams are amenable to treatment by the same
technologies. The segregation of noncontact cooling and heating water
from process wastewater is essential for effective removal of process
pollutants in end-of-pipe treatment, and it is presently practiced at
most plants in the subcategory. Many plants recirculate noncontact
cooling water through cooling towers.
Material Recovery - Cadmium or nickel hydroxide particles, formed
during impregnation or electrodeposition do not adhere to the
electrode structure and are removed in rinse or process discharges.
If the discharges from cathode and anode processes are segregated,
these particles may be recovered by settling to yield separate sludges
rich in cadmium or nickel. The metal values may be recovered from
these sludges. This practice, presently employed in the subcategory,
yields an economic return from recovered cadmium and nickel; reduces
the waste loads flowing to treatment; and reduces the quantities of
toxic metal sludge requiring disposal.
Wastewater Recycle and Reuse - Process wastewater streams produced in
this subcategory which are presently recycled or suitable for recycle
include wet scrubber discharges, wastewater from cleaning impregnated
electrodes or electrode stock and process solutions used in material
deposition and electrode formation. Recycle of these waste streams is
presently practiced and yields large reductions in process wastewater
flow.
Air pollution control scrubbers are employed to control emissions of
acid fumes and toxic metals (cadmium and nickel) from process
solutions used in electrodeposition, impregnation, active material
preparation and material recovery operations. Recycle of water used
in these scrubbers is common but not universal. Of six wet scrubbers
reported in use at plants in this subcategory, five employ extensive
recycle of the scrubber water. Discharge flow rates from recirculated
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scrubber systems were as low as 1.1 1/hr, while the non-recirculated
scrubber had a discharge of 9538 1/hr. In many cases, caustic
solutions are used in the scrubbers and recirculated until neutralized
by the collected acid fumes. This practice results in the
presentation to treatment of a concentrated small volume discharge
from which pollutants may be effectively removed.
Wet cleaning of impregnated electrodes or electrode stock results in
large volumes of wastewater bearing high concentrations of particulate
nickel or cadmium hydroxide. This wastewater may be treated by
settling and recycled for continued use in the cleaning operation.
Since the primary contaminant in this waste stream is suspended
solids, a very high degree of recycle after settling is practical.
Recycle of this wastewater stream following settling to remove
suspended solids is practiced at one facility with wastewater dis-
charged only once per month. The volume of wastewater from this
process after recycle is only 4.8 I/kg. This may be compared to a
discharge volume of 108 I/kg observed at another facility which does
not recycle electrode cleaning wastewater.
Water used in washing process equipment and production floor areas in
this subcategory also becomes contaminated primarily with suspended
solids. The wastewater may be treated by settling and recycled for
further use in floor and equipment wash operations. Recycle of these
waste streams will allow effective maintenance of equipment and floor
areas with little or no process wastewater discharge.
Process solutions used in material deposition and electrode formation
are extensively reused at most plants and represent a minimal
contribution to the total wastewater flow. Reuse of these process
solutions significantly reduces pollutant loads discharged to waste
treatment and also yields economic benefits in reduced consumption of
process chemicals.
Water Use Control and Reduction - Large volumes of process water are
used in rinsing at cadmium subcategory plants. On site observations
at several facilities, and analysis of flow rate information from
other sites indicate that effective control of water use in these
operations is not achieved, and that substantial reductions from
present discharge rates may be attained by instituting effective water
use control. The lack of effective water use control in these
operations is demonstrated by the wide range of flow rates among
facilities and on different days at individual facilities. Practices
contributing to excessive water use and discharge in rinsing were
observed during sampling visits at four cadmium subcategory plants.
At one plant, for example, measured rinse flow was observed to be
about 25 percent greater than the values reported in the dcp, and
production was about 50 percent less than that reported. The
wastewater discharge per unit of production was approximately three
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times the value indicated by dcp information. At this site rinsing
was practiced on a batch basis, and the rinse cycle included an
overflow period after the rinse tank was filled with water. The
length of this overflow period was observed to vary arbitrarily and
was frequently lengthened considerably when the water was left running
through coffee breaks and meals. Similar rinse flow variability was
observed at other plants.
Flows reported in dcp's for wastewater discharge from process rinses
associated with anode and nickel cathode electrodeposition and
impregnation are attainable by implementation of rinse flow control at
all sites. This can be achieved through the use of automatic shut-
off s which will close water supply valves when the process line is not
running and adjustment of rinse flows when production rates vary.
Further reductions may be achieved by application of multi-stage
countercurrent rinse techniques. While multi-stage rinses are common
in the subcategory, countercurrent rinsing is practiced only sometimes
and is not accompanied by effective water use control. Implementation
of countercurrent rinses in this subcategory will differ since rinsing
equipment and techniques are observed to vary.
Another technique used to reduce process flow rates is the use of dry
air pollution control equipment such as bag houses. Two facilities
reported using bag houses to control dust emissions caused by
processing dry materials.
Wastes from electrolyte preparation and addition to cells result from
equipment washing and from drips and spills of electrolyte.
Collection of electrolyte drips in filling operations and reusing this
material in filling cells can aid in eliminating this waste stream.
Wastewater from washing electrolyte preparation and addition equipment
is reported by only a few plants. Other facilities evidently use dry
equipment maintenance procedures or recycle equipment wash water.
Floor cleaning at cadmium subcategory plants may also be accomplished
with or without the use of process water, and where water is used the
efficiency of use varies. Efficient use of floor wash water may
substantially reduce wastewater discharge at some plants as indicated
by the comparison of reported normalized discharge flows for this
activity which range from 0.25 to 33.4 liters per kilogram of finished
cells produced. Dry floor clean-up is a viable option in this
subcategory since most of the materials requiring removal from pro-
duction floor areas are dry solids. Seven active plants in the
subcategory reported no process wastewater from washing floors and
apparently employ dry floor cleaning techniques. Only two plants
reported wastewater discharge from floor cleaning.
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Process Modification - Numerous manufacturing processes for the pro-
duction of cadmium subcategory batteries are observed. They vary
widely in the volume and characteristics of process wastewater
produced. Many of the process variations, however, correspond to
variations in battery performance characteristics and therefore may
not be suitable for use as bases for pollutant discharge reductions
throughout the subcategory. For example, the manufacture of pasted
and pocket plate powder electrodes is observed to yield significantly
lower wastewater discharges than the production of sintered,
impregnated electrodes, but the current and power densities attained
in pocket plate electrodes are lower than those in sintered,
impregnated electrodes. Since the products of these two process
alternatives are not completely equivalent, process modification by
substitution of one for the other may not be a viable basis for
effluent limitations. There are however, some observed or potential
process modifications which can result in reduced pollutant discharges
without significantly affecting product characteristics. These
include modifications in electrode formation practices, and
improvements in process control on active material preparation
operations.
In-case formation appears to be feasible without any apparent impact
on battery performance characteristics. This practice which
eliminates wastewater discharge from spent formation solutions and
from post formation rinses could be applied to reduce pollutant
discharges.
In the production of cadmium powder for use in battery manufacturing,
the product is rinsed after precipitation. Improved process control
of the precipitation step and of rinsing would reduce the volume of
wastewater from this operation by approximately 40 percent.
Calcium Subcateqory
Process water use in this subcategory is very limited. Consequently,
the opportunities for in-process controls significantly reducing water
use or wastewater discharge are correspondingly limited. Water used
in the disposal of calcium scrap may be reduced by limiting the amount
of scrap produced and by limiting the amount of water used per unit
weight of scrap disposed. Alternatively, this waste source may be
eliminated altogether by allowing the calcium to react with
atmospheric moisture and disposing of the resultant calcium hydroxide
as a solid waste.
Lead Subcategory
Process water uses in lead subcategory plants include contact cooling,
electrode rinsing, battery washing, equipment and area washing, and
air pollution control scrubbers. Wastewater discharges from these
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sources may be reduced or eliminated by application of a variety of
in-process control techniques. Most of the identified applicable in-
process controls are presently in use at one or more plants in the
subcategory. Some, such as pasting area wash down recirculation,
scrubber discharge recycle, use of dry air pollution control
techniques, and elimination of contact cooling water discharges, are
extensively practiced.
Waste Segregation - The segregation of wastewater streams from
different process operations is a vital part of effective pollution
control at lead subcategory plants. Wastewater from pasting area and
equipment wash-down is commonly segregated from other process waste
streams because it carries extremely high concentrations of
recoverable suspended leady oxide particles. Scrubber discharges and
battery rinse water are segregated to allow recycle or reuse. In
addition acid used in forming batteries is kept separate from process
wastewater at essentially all sites so that it can be reused in
formation. Battery wash water may also be segregated when it contains
detergents or significant quantities of oil and grease.
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.
Wastewater Recycle and Reuse - Process wastewater streams which are
presently recycled or reused in this subcategory include pasting area
wash-down, scrubber wastewater, battery rinse water and contact
cooling water. In addition, some plants in the subcategory return
treated effluent water for reuse in the manufacturing process. While
the extent of recycle and reuse varies from plant to plant, numerous
examples in present practice show that these techniques can be highly
effective in reducing wastewater volume and pollutant discharges.
Equipment and floor wash water 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 from the
recirculated wash-down stream may be used in the paste mixing
operation and ultimately be evaporated from the plates in drying and
curing. Some water is also entrained with the solids settled from the
wastewater. As a result, this operation often has a net negative
water balance and requires the introduction of fresh make-up or of
wastewater from another process which is suitable for reuse in this
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way. Fifty-five plants in the subcategory reported the reuse of past-
ing area wastewater.
Wet scrubbers are used for the control of sulfuric acid fumes and mist
resulting from electrolyte preparation and battery formation
processes. Significant recycle of these scrubber streams is possible
before acid concentrations become high enough to impair fume scrubbing
efficiency. If no reagents are added the concentrated scrubber
discharge after recycle is suitable for use in electrolyte
formulation. Alternatively, caustic solutions may be used in the
scrubber allowing a still higher degree of recycle, and reducing the
volume of discharge to very low values.
Rinsing of batteries is performed primarily to remove sulfuric acid
spilled on the outside of the battery case. If the acid results from
overfilling the battery or dumping electrolyte from the battery, or if
it has previously been used in formation it will contain lead as well.
The wastewater from rinsing the batteries will consequently contain
acid, lead, and other contaminants from process conveyors, racks or
floors over which the acidic rinse water is permitted to run. Failure
to segregate the battery rinse water from battery wash water in which
detergent formulations are used may also result in the presence of
detergents in this waste stream.
The rinse water characteristically becomes only slightly contaminated
in a single use and it may be recycled for use in rinsing several
times before acidity becomes too high for effective rinsing. When the
acidity becomes too high for further use in rinsing, the rinse water
may be reused in pasting area washdown or in electrolyte preparation.
Use in acid cutting for electrolyte, however, requires that levels of
contaminants, especially iron, be generally low. This may be achieved
by care in rinsing to prevent contact of the corrosive rinse water
with exposed iron and steel surfaces or contaminated floor areas.
Alternatively, the spent rinse water may be treated to remove iron
prior to use in acid cutting. Nineteen plants reported the reuse of
rinse water. Five of these plants treat process wastewater before
reusing in the rinse operations. Typically treatment involves pH
adjustment and settling to remove particulates before the wastewater
is reused for rinsing purposes.
Contact cooling water used in battery formation may be recirculated
extensively as described for battery rinse water. In this case, the
rate of acid build-up in the recycled stream should be quite low, but
the water may require cooling in a cooling tower for continued use. A
small bleed from the recycle loop is sufficient to control the levels
of acid and lead in the water, and the bleed stream may be reused in
acid cutting, pasting area washdown or paste preparation. Caustic may
be added to the recycled water to maintain an alkaline or neutral pH
and prevent corrosion or safety hazards.
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Iron accumulating in the contact cooling water as a result of the
contact of acid water with production racks or conveyors may be an
obstacle to reuse of the bleed stream. This problem may be resolved
either by treatment to remove the iron by chemical precipitation or by
the prevention of contamination through the use of epoxy coatings on
racks or conveyors and control of contact cooling water flow patterns.
Wastewater from vacuum pump seals and ejectors used in dehydrating
formed plates for use in dehydrated 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.
Discharges from steam curing processes and wastewater from general
floor area and equipment washdown can be retained for reuse in acid
cutting operations, along with bleed streams from recirculation
systems used for wet scrubbers, contact cooling, or battery rinsing.
Process Modification - While there are numerous process alternatives
for many operations in the manufacture of batteries in the lead
subcategory, the alternatives which are most significant in their
impact on wastewater discharge are in the processes for formation of
the battery electrodes. In addition, differences in plate curing
techniques also influence process wastewater discharge to some extent,
as does the addition of a rinse prior to battery washing.
The greatest differences in wastewater discharge in this subcategory
result from the difference between dehydrated plate battery
manufacture and wet or damp battery manufacture. This difference in
formation procedures also results in significant differences in
product characteristics as discussed in Section V.
The major water uses in the formation and dehydration of electrodes
for dehydrated plate batteries are in rinsing and dehydrating the
formed plates. Thorough rinsing is required to remove residual
sulfuric acid from the formed plates and 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 water seals or vacuum pumps used for the same purpose.
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 plates was observed, and
approximately 50 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 introduction of inert or reducing atmospheres
into the drying ovens.
559
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Several distinct formation procedures are employed in the production
of wet and damp batteries resulting in significant variations in
wastewater discharge flow rate. In addition to the differences
between wet and damp 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 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 on 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 used in acid cutting and therefore the potential
amount of process wastewater which may be used in battery acid
cutting.
The formation of assembled batteries 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.
The formation process generates heat which must be removed from the
batteries being formed if an acceptable product quality is to be
achieved. The rate at which this heat is generated depends upon the
rate at which formation proceeds. When batteries are formed rapidly
as is common in present practice, heat generation is so rapid that the
batteries must be cooled using fine sprays of water on the battery
cases. This contact cooling water constitutes a significant source of
wastewater discharge at many plants. When batteries are formed more
slowly the heat may be dissipated to the atmosphere without the use of
contact cooling water and this source of wastewater discharge is
eliminated. In addition, formation at a lower rate reduces gassing
during formation and consequently reduces acid mist and fumes
associated with this process, limiting the need for scrubbers and the
560
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extent of acid contamination of battery cases and formation areas and
equipment.
Battery formation at a lower rate without the use of contact cooling
water is practiced by a significant number of manufacturers and was
observed in visits to lead subcategory plants. While batteries formed
at high rates are frequently placed on conveyors during charging,
batteries subjected to low rate formation are often stacked on
stationary racks for the formation period which may last up to seven
days. Low rate formation requires somewhat more floor area and more
charging harnesses than high rate formation to allow for the larger
inventory of batteries being formed simultaneously, but eliminates the
need for piping and spray nozzles for contact cooling. Battery
handling requirements and electric power consumption are substantially
identical for high and low rate formation.
Most electrodes used in this subcategory are produced by application
of a leady oxide paste to a supporting grid and subsequently curing
the pasted electrode. In the curing process, the free lead content of
the plates is reduced by oxidation and sulfation resulting in improved
paste adhesion and mechanical strength of the electrodes. At most
plants, curing is accomplished over several days in curing rooms
providing controlled temperature and humidity. No process water is
used, and no wastewater results. A few facilities achieve faster
plate curing by the use of steam. In this process steam condenses on
the electrodes producing a small volume of 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.
Possible areas of reuse include acid cutting and paste formulation.
Washing batteries with detergent formulations generates process
wastewater which, unlike most lead subcategory waste streams, may not
be suitable for reuse in electrolyte preparation or paste formulation.
This is due to the presence of detergents and oils and greases removed
by detergent action. The provision of a rinse prior to detergent
washing allows removal of most of the lead and sulfuric acid from the
battery case in a stream which is suitable for reuse in the process.
This reduces the loads of these pollutants which must be removed in
treatment, and reduces the volume of water needed for detergent
washing (due to the reduced amounts of contaminants to be removed from
the battery). The volume of wastewater to be treated and discharged
is also reduced.
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
561
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addition, effective plant maintenance and housekeeping practices may
reduce or eliminate some process wastewater sources. ,planl
maintenance practices such as epoxy coating of racks and equipment
which contact process wastewater and 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 facilities 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 clean-up
techniques.
Control of lead dust within the plant also represents a significant
water use at some facilities 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 clean-up techniques can reduce or
eliminate the volume of discharge from this source. Examples of water
efficient clean up techniques include floor wash machines and bucket
and mop floor washing.
Equipment maintenance may also contribute significantly to wastewater
discharge reduction. At one facility 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 due to the corrosive action 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.
Leclanche Subcategory
Process water use and wastewater discharge in this subcategory are
limited. Many facilities presently report no discharge of process
wastewater and most others discharge only limited volumes of
wastewater from one or two sources. All of the existing discharges
may be eliminated by the implementation of effective in-process
control measures, especially wastewater recycle and reuse.
Waste Segregation - At most plants in this subcategory, waste
segregation is not required except for the segregation of process
wastewater from other waters. Only one or two battery manufacturing
562
-------
waste sources are typically encountered in this subcategory, and the
characteristics of the resultant waste streams are generally similar.
One exception to this observation occurs where paste separators are
employed or pasted paper separators are produced. In this case,
segregation of wastewater from the paste preparation and handling
operations from other process waste streams is important for effective
treatment as well as wastewater recycle and reuse.
Wastewater Recycle and Reuse - Essentially all of the process
wastewater discharge streams reported in this subcateogry result from
washing production equipment, fixtures, and utensils. While the
specific recycle and reuse techniques differ, waste streams from both
paste preparation and application and from other equipment clean-up
may be completely recycled and reused eliminating process wastewater
discharged from these sources. Process water used to supply heat for
setting paste separators in some cells is also amenable to extensive
recycle.
Equipment used in the preparation and application of paste to cells
containing paste separators or to paper for use as cell separator
material, is generally washed down with water periodically as a part
of normal maintenance. The resultant wastewater, generally containing
paste, ammonium chloride, zinc and mercury, may be retained and reused
in subsequent equipment washing. The build up of contaminants in the
wash water can be controlled by using a portion of the wash stream in
paste preparation. The contaminants which are normal constituents of
the paste are thereby included in the product and discharge of process
wastewater pollutants from this operation is eliminated. This recycle
and reuse practice is demonstrated at plants which report no process
wastewater discharge from paste preparation and application.
Water used in washing equipment and utensils for most other production
operations serves primarily to remove insoluble materials such as
carbon and manganese dioxide particles. Wastewater from these washing
operations can be retained, treated by settling to remove the solids,
and reused in further equipment washing. The buildup of dissolved
materials in this stream may be controlled by using some of the wash
water in electrolyte or cathode formulation. Since the primary source
of dissolved salts in the wash water is electrolyte incorporated in
cell cathodes or handled in the process equipment, the contaminants in
the wash water after settling are normal electrolyte constituents, and
no deleterious effect on cell performance will result from this
practice.
Water is used to supply heat for setting paste separators by one
manufacturer. As a result of contact with machinery used to convey
the cells, and occasional spillage from cells, this water becomes
moderately contaminated with oil and grease, paste, manganese dioxide
particulates, zinc, ammonium chloride and mercury. These
563
-------
contaminants, however, do not interfere with the use of this water for
heat transfer to the outside of assembled cells. Wastewater discharge
from this operation results from manufacturing conveniences,
maintenance of the equipment, and from dragout of water on the cells
and conveyors. Discharge from each of these process sources may be
eliminated by recycle and reuse of the water.
The paste processing steps in making mercury containing separator
paper generates a wastewater discharge when the paste mixing equipment
is washed. The flow from the wash operation is minimal and can be
eliminated either by dry maintenance of the equipment or recycle of
the wash water for inclusion in the paste.
Water Use Control and Reduction - Water use in equipment and floor
cleaning at some sites in this subcategory may be substantially
reduced by the implementation of water use controls or eliminated
entirely by the substitution of dry equipment clean-up procedures.
Most plants in the subcategory presently employ dry equipment and
floor cleaning techniques and discharge no process wastewater. Dry
air pollution control devices also serve to reduce water use in this
subcategory.
Reduction in water use in cleaning electrolyte handling and delivery
equipment and cathode blending equipment may be possible by more
effective control of flow rates at several sites in the subcategory.
These reductions would decrease the cost of treating wastewater for
recycle or of contract removal of the wastes. The potential for such
reductions is indicated by the broad range in water use for this
purpose within the subcategory. Normalized discharge flows ranging
from 0.01 I/kg of cells produced to 6.37 I/kg of cells produced were
reported by plants that discharge from this operation. Some of this
variation, however, is attributable to variations in the type of cells
produced and the nature of the production equipment requiring
cleaning. As noted in the previous discussion, this water may be
recycled, eliminating all wastewater discharge to the environment from
this source. Use of dry maintenance techniques will also serve to
eliminate equipment cleaning wastewater discharge. The majority of
plants do not report any wastewater discharge from equipment
maintenance indicating that these techniques are widely applied in
this subcategory.
Water is used in a washing machine at one facility to clean fixtures
used to transport cell cathodes to the assembly. Since the machine is
often used with only a partial load, wastewater discharge from this
process may be reduced by scheduling washing cycles so that a complete
load is washed each time. This may require a somewhat increased
inventory of the fixtures but will reduce waste treatment costs as
well as pollutant discharge.
564
-------
A majority of manufacturers reported no wastewater discharged from
floor wash procedures and it is concluded that dry maintenance tech-
niques are widely applied in the subcategory although not specifically
identified by most facilities. Some of these dry techniques include
either sweeping or vacuuming floor areas and using desiccant materials
in instances of spillage.
Process Modification - Variations in manufacturing processes and
products in this subcategory are observed to correspond to variations
in process water use and wastewater discharge. Significant
differences in wastewater discharge are observed between plants
producing cells with paste separators and pasted paper separators.
Among plants producing cells with paste separators differences in
wastewater discharge result from differences in assembly technique and
in the paste formulation employed. Relatively high water use and
wastewater discharge are also associated with the manufacture of
foliar batteries. While cells using pasted paper and paste separators
serve the same applications and are directly competitive, the foliar
batteries are designed for a unique application.
The manufacture of cells using heat-set paste separators is observed
to produce a wastewater discharge from the paste setting operation.
This source of discharge may be eliminated by substitution of a paste
formulation which sets at a lower temperature or by use of pasted
paper separators. Industry personnel report that production of paste
separator cells is significantly less costly than the manufacture of
cells with pasted paper separators.
Plant Maintenance and Good Housekeeping - Dry clean-up of production
areas is practiced at essentially all sites in this subcategory. In
addition, most facilities employ dry cleaning techniques in
maintaining process equipment. These practices contribute to the low
wastewater discharge rates typical of this subcategory.
Lithium Subcateqory
Process water use and wastewater discharges in the lithium subcategory
are limited. The cell anode material reacts vigorously with water
necessitating the use of non-aqueous electrolytes and dry processes
for most manufacturing operations. Correspondingly, opportunities for
in-process control are also limited.
Thermal batteries similar to those produced in the calcium subcategory
are manufactured in this subcategory including the production of heat
generation component material. As discussed for the calcium
subcategory, this waste stream may be recycled after settling
eliminating this source of wastewater discharge.
565
-------
At some plants in this subcategory, wet scrubbers are used to control
emissions from sulfur dioxide and thionyl chloride depolarizer
materials. Extensive recycle of the scrubber discharge streams is
possible, reducing the volume of wastewater discharge to minimal
values.
Magnesium Subcateqory
Half of the plants in this subcategory report zero discharge of
magnesium battery manufacturing process wastewater. The remaining
facilities report process wastewater discharges from eight process
operations to which a variety of in-process control techniques may be
applied.
At one plant which produces magnesium anode thermal batteries, process
wastewater discharges result from wet scrubbers on dehumidification
equipment used to control conditions in process areas and from the
production of heating component material. These waste streams may be
extensively recycled significantly reducing or eliminating wastewater
discharges from these sources.
Significant wastewater discharge from floor washing operations is also
reported in this subcategory and may be reduced by the use of water-
efficient or dry floor cleaning techniques. Alternatively, the floor
wash water may be treated and recycled.
Zinc Subcateqorv
Manufacturing operations in the zinc subcategory involve a wide
variety of process water uses and wastewater discharge sources.
Wastewater discharges result from active material preparation,
electrode processing and associated rinses, cell washing, and
equipment and area cleaning. A variety of techniques may be applied
within the process to reduce the volume of wastewater or mass of
pollutants discharged.
Waste Segregation - The segregation of individual process waste
streams which differ markedly in character is an important factor in
effective water pollution control. The segregation of non-contact
cooling and heating water from process wastes is essential for
effective removal of process pollutants in end-of-pipe treatment.
Waste segregation is presently practiced at most plants in the
subcategory, many of which recirculate non-contact cooling water
through cooling towers.
Many cell cleaning or electrode preparation operations involve the use
of organic reagents such as methanol, methylene chloride, and
hydrazine which ultimately leave the process in organic laden was*"
streams. The segregation of the organic laden waste streams
566
-------
waste stteams bearing predominantly toxic metals and suspended solids
is necessary if these pollutants are to be removed effectively and
without incurring excessive costs.
The volume of the organic laden waste streams is quite small at most
sites and contract removal to a central location is generally less
costly and is predominant in present practice. Efficient segregation
therefore also contributes to minimizing the cost of contract
disposal.
Silver oxides are used as the depolarizer in some of the cells
manufactured in this subcategory and silver is present at particularly
high concentrations in wastewater streams from some active material
and cathode preparation operations. The segregation of these waste
streams may allow economic recovery of the silver for use on site or
return to a refinery.
Amalgamation of zinc anodes consumes large quantities of mercury, part
of which enters process wastewater. Specific process waste streams
contain substantial concentrations of mercury and segregation and
separate treatment of these streams can reduce the total amount of
mercury released to the environment.
Wastewater Recycle and Reuse - Process operations in this subcategory
produce waste streams which may be recycled for use in the same
operation or reused at some other point in the process. Waste streams
which may be recycled or reused in this subcategory include a variety
of process solutions, cell wash and rinse wastewater, electrolyte
dripped in battery filling, equipment and area wash water, and
wastewater from rinsing amalgamated zinc powder. While most of these
streams may be recycled without treatment, a few, notably the floor
and equipment wash wastewater, may require treatment before being
recycled.
The opportunity for wastewater recycle and reuse in this subcategory
is in general minimal because plants in the subcategory do not employ
wet scrubbers and the electrolyte content of many zinc subcategory
cells is low. Process solutions in this subcategory are commonly
reused extensively until either depleted or heavily contaminated, and
consequently represent a minimal contribution to the total wastewater
flow. Reuse of process solutions significantly reduces pollutant
loads discharged to waste treatment, and also yields economic benefits
in reduced consumption of process chemicals.
At several facilities it was observed that the addition of electrolyte
to assembled cells resulted in small volumes of dripped or spilled
electrolyte which was collected and discarded. With care in
maintaining the cleanliness of the drip collection vessels, this
567
-------
electrolyte can be returned for addition to cells eliminating this
source of highly concentrated wastes.
For cell washing the observation was made that water use was governed
by the need to ensure adequate contact of the wash solution and rinse
water with the complete cell surface. Recycle of cell wash water and
isolations is therefore feasible. Cell wash operations in which recycle is
practiced have substantially lower discharge volumes than similar cell
washes without recycle.
Water is frequently used to wash production equipment, especially
equipment used in mixing slurries for the preparation of pasted
electrodes and for the amalgamation of zinc powder. The usual purpose
of this equipment wash water is to remove solids from the equipment.
Because the concentrations of dissolved materials in the equipment
wash water are generally moderate, the wastewater from equipment
washing can be recycled for further use with any minor treatment.
This practice is employed so effectively at one plant that water from
equipment washing is discharged only once every six months.
Water used in washing production floor areas also serves primarily to
remove solid materials. Wastewater from this operation may be
recycled generally if suspended solids removal is provided; where
mercury is used in the production areas being cleaned, the wastewater
must be treated by a technique which is effective in removing mercury.
Wastewater from rinsing wet amalgamated zinc powder contains zinc,
mercury, and soluble materials used in the amalgamation process.
Countercurrent rinsing, if applied to these rinse steps, will result
in smaller volume discharge which contain relatively high
concentrations of mercury and zinc. These contaminants may readily be
reduced to levels acceptable for reuse of the water in washing floors.
Water Use Control and Reduction - The degree of control of process
water use is observed to vary significantly among zinc subcategory
plants. Production normalized process water use and wastewater
discharge in specific process operations are observed to vary by as
much as a factor of twenty between different plants, and by factors of
six or more from day to day at a single plant. The most significant
area where wastewater discharge may be reduced through more effective
flow control and efficient water use is in rinsing active materials,
electrodes and finished cells. These reductions may often be achieved
by very simple actions such as turning off rinse water flows when
production stops, by adjusting rinse flow rates to correspond to
varying levels of production activity, and by the modification of
rinsing techniques to provide multistage Countercurrent rinses.
Other techniques which reduce process flows include the replacement of
wet processes with processes that do not use water. For example,
568
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floor maintenance can be performed by using dry sweeping or vacuuming
techniques. In instances of spillage, desiccant material can be
applied with subsequent dry floor cleaning. Since most plants report
no wastewater from cleaning, these dry techniques are apparently
widely applied in the subcategory although not specifically identified
by most facilities. Only a few facilities discharge significant
volumes of floor wash water due to such practices as hosing down floor
areas.
Material recovery may also significantly reduce pollutant loadings.
Zinc cell manufacturers practice material recovery for silver and
mercury from both process wastewater and reject cells.
Process Modification - Manufacturing processes in this subcategory are
widely varied often corresponding to differences in product types,
physical configuration and performance characteristics. A significant
number of manufacturing operations are governed by military
specifications. Some of the observed variations, however, do not
correspond to discernible differences in the end product, and reflect
only differences in plant practices.
Zinc powder for use in anodes is amalgamated by three techniques;
"wet" amalgamation in which the zinc powder and mercury are mixed in
an aqueous solution and subsequently rinsed, drained off and
discharged; "gelled" amalgamation in which the zinc and mercury are
moistened with a small volume of electrolyte and mixed with binders to
produce an amalgamated anode gel; and "dry" amalgamation in which
mercury and zinc are mixed without the introduction of any aqueous
phase. Since amalgamated material produced by all three techniques is
used on a competitive basis in many cell types, the substitution of a
dry amalgamation technique for wet amalgamation may be considered a
viable in-process control technique for the reduction of process
wastewater discharges in this subcategory.
Silver peroxide is presently produced by several chemical processes at
facilities in this subcategory, and different wastewater discharge
volumes are observed to result. Substantially less wastewater per
unit of product is discharged from one process and the process
solutions are completely recycled.
Cell wash procedures and materials are highly variable in this
subcategory/ and the resultant normalized discharge volumes vary over
nearly three orders of magnitude, from 0-09 to 34.1 I/kg of cells
produced. At some sites, organic solvents are used to remove oils and
greases from cell cases eliminating most water use- At others cells
are simply rinsed with water without the use of any chemicals in the
cell wash.
569
-------
Cell wash formulations used sometimes contain toxic pollutants,
especially chromium and cyanide, not otherwise encountered in battery
manufacturing wastewater. Cells are successfully washed at many
facilities using formulations which do not contain cyanide or
chromate. Therefore substitution of an alternative chemical in the
cell wash is a practical method for eliminating these pollutants from
wastewater discharges in this subcategory.
Plant Maintenance and Good Housekeeping - As in subcategories
previously—discussedT" plant maintenance and housekeeping practices
play a vital role in water pollution control. Because large
quantities of mercury are used in this subcategory, good housekeeping
practices to control losses of the toxic metal are of particular
importance for both water pollution control and industrial hygiene.
These include the maintenance of floors in process areas where mercury
is used, to eliminate cracks and pits in which mercury could be
trapped necessitating excessive water use in cleaning. Most plant
maintenance and housekeeping practices applicable in this subcategory
are similar to those previously discussed for other subcategories.
570
-------
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571
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0
•
€
1
1
-1
«
0
.0
,
«
1
-
1.
Lead Raw Waste Concentration (mg/1)
(Number of observations =85)
FIGURE VII-7
HYDROXIDE PRECIPITATION & SEDIMENTATION EFFECTIVENESS
LEAD
-------
Ul
~J
00
1 n
p-j
X
c>
e
ration
D
mt
Jj « • J.
C
>j
£-•
(U
0)
C
e
3
©
3
(
>
©
9
9
0.1
1.0 10 100
Manganese Raw Waste Concentration (rog/1)
,1000
(Number of observations =20)
FIGURE VII-8
HYDROXIDE PRECIPITATION & SEDIMENTATION EFFECTIVENESS
3ANESE
-------
Ul
«J
VO
J.U . U
.^
\
£
c
o
2 i n
M X . \>
4J
C
C
o
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(a)
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'•l
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!»'
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'
(
«?
•
['*
"
t
0.1
1.0 10.0 100.0
Nickel Raw Waste Concentration (mg/1)
dOOO.O
(Number of observations = 61)
FIGURE VI1-9
HYDROXIDF PRECIPITATION & SEDIMENTATION EFFECTIVENESS
NICKEL
-------
Ul
03
O
Phosphorus Treated Effluent concentration (mg/1) ,_
3 h-> 0 C
• • • •
-. o o -
®
*
&
w
(ft
(*
<•)
(•
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\
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£
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W
C-)
).0
,
Pi
-1
1
1
-•
00
Zinc Paw Waste Concentration (mg/1)
(Number of observations = 69)
FIGURE VII-11
HYDROXIDE PRECIPITAITON & SEDIMENTATION EFFECTIVENESS
ZINC
-------
Soda ash and
caustic soda
8.0
10.5
FIGURE VII-12
LEAD SOLUBILITY IN THREE ALKALIES
582
-------
Sedimentation Basin
Inlet Zone,
Inlet Liquid
Settled Particles Collected
And Periodically Removed
Baffles To Maintain
"Quiescent Conditions
* «
5?
• . *. •*"~v-f».«^i *. r. //•'•*'t
^fe^S^Ai
\f
Outlet Zone
Outlet Liquid
Belt-Type Solids Collection Mechanism
Circular Clarifier
Inlet Liquid
Circular Baffle
Annular Overflow Weir
Outlet Liquid
Settling Zone*
Revolving Collection
Mechanism
Sen! ing Particles
Settled Particles "T Collected And Periodically Removed
I Sludge Drawoff
FIGURE VII-13
REPRESENTATIVE TYPES OF SEDIMENTATION
583
-------
INFLUENT
ALUM
Z
«
u 3
WATER LEVEL>
STORED
BACKWASH
WATER
FILTER
COMPARTMENT\ MEDIA
>£•/• COLLECTION CHAMBER
POLYMER
FILTER—
—BACK W ASH-^L 3
FILTER U T
COAL I
SAND
THREE WAY VALVE
SUMP
n
DRAIN
FIGURE VII-14
GRANULAR BED FILTRATION
584
-------
PERFORATED
BACKING PLATE
FABRIC
FILTER MEDIUM
SOLID
RECTANGULAR
END PLATE
INLET
SLUDGE
FABRIC
FILTER MEDIUM
ENTRAPPED SOLIDS
PLATES AND FRAMES ARE PRESSED
TOGETHER DURING FILTRATION
CYCLE
RECTANGULAR
METAL PLATE
FILTERED LIQUID OUTLET
RECTANGULAR FRAME
FIGURE VII-15
PRESSURE FILTRATION
585
-------
FABRIC OR WIRE
FILTER MEDIA
STRETCHED OVER
REVOLVING DRUM
DIRECTION OF ROTATION
ROLLER
SOLIDS SCRAPED
OFF FILTER MEDIA
SOLIDS COLLECTION
HOPPER
INLET LIQUID
TO BE
FILTERED
TROUGH
FILTERED LIQUID
FIGURE VII-16
VACUUM FILTRATION
586
-------
CONVEYOR DRIVE ._ DRYING
LIQUID
OUTLET
CYCLOOEAR
SLUDGE
DISCHARGE
SLUDGE
INLET
REGULATING .„„_. , __
CONVEYOR BOWL ,R|NG IMPELLER
FIGURE VII-17
CENTRIFUGATION
587
-------
CONDUIT
TO MOTOR
INFLUENT
CONDUIT TO
OVERLOAD
ALARM
EFFLUENT PIPE
EFFLUENT CHANNEL
PLAN
INFLUENT
CENTER COLUMN
CENTER CAGE
WEIR
STILTS
CENTER SCRAPER
SQUEEGEE
SLUDGE PIPE
FIGURE VII-18
GRAVITY THICKENING
588
-------
c
A
if
U
IT
H
h
1 l
][
II
1 !!
SPLASH BOX
JL, P
n *
— *w L '
II
II
II
ll
1
V
i.
9 *
< 'i
j 1 1
S " il
o - !
U 0 |l
jzjj
H 0. M
> ° II
J t II
• * ll
41,
._ .
I1
"I
1
1
1
1
1
ll
• 1
j| ,6-IN. FLANGEDll
E SHEAR GATE, ~\
GbJ
1 !! LJU.' :
I?
II
1 (
J 1
1 1
1 1
M
ll
1 1 I
«l
1
ll
I
Ij
i
,1
ll t
1 1
n
-ill
A
J
PLAN
FINE SAND
COARSE-SAND
FINE GRAVEL
MEDIUM GRAVEL
'2-IN. PLANK
WALK
PIPE COLUMN FOR
GLASS-OVER
3 TO • IN. COARSE GRAVEL
3-IN. MEDIUM GRAVEL
•-IN. UNDERDRAIN LAID
WITH OPEN JOINTS
SECTION A-A
FIGURE VI1-19
SLUDGE DRYING BED
589
-------
EXHAUST
HATER VAPOR
PACKED TOKER
EVAPORATOR
CONCENTRATE
Ol
10
O
CONOENSATC
MASTEHATER
CONCENTRATE-*
ATMOSPHERIC EVAPORATOR
STEAM
CONDENSATE
STEAN
**^*fmmm
HASTE
HATCH
FEED
EVAPORATOR-
STEAM -
STEAM
CONOENSATE
HASTEHATER-
HOT VAPOR
VAPOR-LIQUID
MIXTURE
CONDENSER
\ MIXTURE -^ror
«„_._„_
SEPARATOR
HATER VAPOR
LIQUID RETURN
frr
COOLING
HATER
J.
.COMPENSATE
VACUUM PUMP
••-CONCENTRATE
CLIMBING FILM EVAPORATOR
VAPOR
STEAN
CONDENSATE
CONCENTRATE
CONDENSER
COOLING
HATER
CONDENSATE
kTE
CONDENSATC
VACUUM PUMP
»• EXHAUST
ACCUMULATOR
CONDEHSATE
»- FOR
REUSE
CONCENTRATE FOR REUSE
SUBHCP.CCD tUtX. EVAPORATOR
DOMBLE-RFrECT EVAPORATOR
FIGURE VI1-20
TYPES OP EVAPORATION EQUZPFENT
-------
WASTE WATER CONTAINING
DISSOLVED METALS
OH OTHER IONS
OIVERTER VALVE
REOENERANT TO MCU9E,
TREATMENT. ON DISPOSAL.
MEaENCRANT'
SOLUTION
METAL-FREE WATER
FOR REUSE OR DISCHARGE
FIGURE VII-21
ION EXCHANGE WITH REGENERATION
591
-------
MACROMOLECULeS
AND
SOLIDS
MOST ^
>* •••..••
450 PS I
MEMBRANE
WATER
MEMBRANE CROSS SECTION.
IN TUBULAR, HOLLOW FIBER.
OR SPIRAL-WOUND CONFIGURATION
PERMEATE (WATER)
' -C ••" •i'/-/.-'-f ••
3« • J« •« *0 * . ' • d •' O. -rt. •
FEED
•"- I -••••-" IP *.•• . -j
-------
SB*
O> IMM4 MCMSNAMI
SPIRAL MEMBRANf MOOULf
fomm Support Tubi
•nth Mwnbr«n»
Product Wrar FkrmMtt Fto
Wrar
b.:;;U':^s) v
"¥ '"'""
•rin*
Product wMiV
TUBULAR REVERSE OSMOSIS MODULE
CONCENTRATE
SNAP RING OUTLET
OPEN ENDS
or mm
tTRMCSCAL
tfOVt
END PLATE
POROUS
BACK-UP DISC
SNAP RING
FIBER
SHELL
FEED
DISTRIBUTOR TUBE
END PLATE
HOLLOW FIMR MODULE
FIGURE VII-23
REVERSE OSMOSIS MEMBRANE CONFIGURATIONS
593
-------
OILY WATER
INFLUENT
WATER
DISCHARGE
OVERFLOW
SHUTOFF
VALVE
EXCESS
AIR OUT
LEVEL
CONTROLLER
TO SLUDGE
TANK >—
FIGURE VII-24
DISSOLVED AIR FLOTATION
594
-------
ULTRAFILTRATION
MACROMOLECULES
P-10-50 PSI %
MEMBRANE
*
WATER SALTS
•MEMBRANE
PERMEATE
*.! t* • • :• • > •/, • *** t • •
o*' 'V'' -o': o • :• v o. - o. :oTr
FEED* • * O.•*..•*. * O *• CONCENTRATE
- - i 4 ~. *. •• t -. . • . .i /
O OIL PARTICLES -DISSOLVED SALTS AND LOW-
MOLECULAR-WEIGHT ORGANICS
FIGURE VII-25
SIMPLIFIED ULTRAFILTRATION FLOW SCHEMATIC
595
-------
WASTE WATER
INFLUENT
DISTRIBUTOR
WASH WATER
BACKWASH
BACKWASH
REPLACEMENT CARBON
SURFACE WASH
MANIFOLD
CARBON REMOVAL PORT
TREATED WATER
SUPPORT PLATE
FIGURE VI1-26
ACTIVATED CARBON ADSORPTION COLUMN
596
-------
RAW WASTE
*»H,
CONTROLLER
'CAUSTIC
SODA
in
VO
CONTROLLER
TREATED
WASTE
REACTION TANK
FIGURE V-27
TREATMENT OF CYANIDE WASTE BY ALKALINE CHLORINATION
-------
CONTROLS
OZONE
GENERATOR
£,fl
|—t DRV AIR 1—I D U
plAJ H N~—
i 1 II II • —
RAW WASTE •
OZONE
REACTION
TANK
TREATED
WASTE
FIGURE VII-28
TYPICAL OZONE PLANT FOR WASTE TREATMENT
598
-------
MIXER
0
r
S'
sc
ST
WASTEWATER I.
FEED 1
TANK
j
1 1
.1
mil
HIT
RST oil
FACE 311
>
3 11
M
:OND §
AGE 3
>
3
•IIRD oil
FACE j|
>
HD
PUMP
TREATED WATER
n
jf
w
I
a
Ll
'
c
3
Ti
C
n
'
CAS
• — — TEMPERATURE
CONTROL
— — PH MONITORING
TEMPERATURE
CONTROL
— — PH MONITORING
— — TEMPERATURE
CONTROL
— — PH MONITORING
OZONE
OZONE
GENERATOR
FIGURE VI1-29
UV/OZO NATION
599
-------
Sill fllHIC Sill I III!
AOII1 mOXlOE
I IMI oil CAMS I 1C
J ,
Jx J
ni CONIHOLI
"D-—.
HAW WAS1 t
(MtXAVALL NT CIHIOMIIIM)
ON
O
O
D
OtD
(IHt> COHlNOtl IN
i
__ I |i*M r.ONl HOI I f M
(irllVAl FNT CHROMIUM)
— •-~-''-"'""""*— *"•"
O
1
3 r
(
lit AC I ION TANK
PRECIPITATION TANK
roc* A** IF it'n
IIOMHtM IIYnHOXini)
FIGURE VII-30
MEXAVALENT CHROMIUM REDUCTION WITH SULFUR DIOXIDE
-------
TABLE VII-18
TREATABILITY RATING OF PRIORITY POLLUTANTS
UTILIZING CARBON ADSORPTION
Priority Pollutant 'Itenioval Ratino
1 . acenaphthene
2. acrelein
3. acrV'Sr.itrile
4. benzene
5. benzidine
i. carbon tetrachloride
(tetracMrraa* thane)
7. chloroter.zene
8. 1,2.4-trictiIorober.zene
9. hexarhjorobenrene
10. l,2-£ichlorc«thane
11. I,l,!-tr>chl3roethane
12. henicMorwthane
13. l,l-dichloro*thane
14. 1,1,2-trichlorcethane
15. l,1.2,r-tetrachloro«thane
16. chJoroethane
17. bisiCRlCTOi^ethylJether
18. bisC-cMoroethyliether
19. 2-crJoroethyl vinyl ether
(mixed)
20. 2-cf.loronaphthalene
21. 2,4,6-trichiorophenol
22. parachl 3ron*ta cresol
23. chloroform (triehlorcnethane)
24. 2-ehlorcohenol
25. 1.2-dichlorober.zene
26. l,3-dichlo;3ber.zene
27. l,4-<)ichlorobenzene
26. 3, 3'-<3iehlorriienz:dine
29. l,:-dicr.:oro*ihylene
30. 1,2-trans-dichleroethylene
31. 2.4-3icMorophenol
32. 1,2-dichloroprceane
1^ 1 ?_4; «K* n..j-*v»w» -J ...M
jj» *• <~cj CTIJ vro^*ropyuerie
( 1 , 3 . -^ i chl oropropene )
34. 2.4-tfiaethylphenol
35. 2,4-dinitrotoljene
»< ^ f j .'.J.-....1 ...
37. l,I-diphenvlh.i.-iiine
38. ethyl benzene
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bronophenyl pfienyl ether
42. bis!2-chloroisoDropyl;tther
43. bis(2-chrt.hoxv)inethane
44. methylene chloride
(di chl orome thane )
45. aiethyi chloride 'chlororaethane)
46. methyl brocade (broncne thane)
47. broRoforffi (tribrorcne thane)
46. dichJorobrononethane
H
L
L
H
H
M
H
H
H
M
n
H
M
H
H
L
_
H
L
H
H
H
L
H
H
H
H
B
L
L
H
H
N
B
H
g
H
H
H
H
R
H
N
L
L
L
H
H
Priority
49.
SO.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
86.
81.
82.
83.
84.
85.
86.
87.
88.
106.
107.
106.
109.
110.
111.
112.
trichJoroflucram? thane
dichJ wodi f 1 jcram? thane
chl orocJ j br cno^? thane
he xac*' J orot/u t ad i »ne
isoptorone
naphtha lene
nitrobenzene
2-nitrof**nol
4-nitrophenol
2.4-dir.it.ropher»ol
4 , t-di.-u lrc>-o-cTesol
N-n j t rosod L.-S6- thy I ar.i ne
N-n i t rasod : ?*••«?••.•: ar.i ne
N-nitrcsodi-n-prcoyJsmine
pentactslorop.'-ienol
phenol
bis{2-ethylhexyl Jphthalate
butyl benzyl ph thai ate
di-n-butyl pr.t.-,a:ate
di-n-octyl phthalate
diethyl phthalate
dL-nethyl pftthalate
1.2-t«nzanthracene (benzo
(aianthracene)
benzol a )p>-rene (3,«-benzo-
pyrene)
3, 4-benzof 1 joranthene
(benzo(b) f 1 jsrant-hene )
11 . 12-bs»zof 1 uorar.thene
(berzo(k )f ] joranthene )
ehrysane
acenaphthylene
anthracene
1.12-ber.roperylene (benzo
fljorene
phenanthrene
1, 1, S, i— Ji^ri.ioUn »C*ne
(u^benzo (a,h) anthracene)
indeno (l,2,J-cd) ?>rene
(2. 3-o-phenylene pyrene)
pyrene
tetrachloroethy 1 ene
toluene
trichloroethylene
vinyl chloride
(chloroethylene)
KB-1242 (Arochlor 1242)
PCS-1254 (Arochlor 1254)
KE-1221 {Arochlor 1221)
PCB-1332 (Arocrlor 1232)
PCE-1248 (Arachlor 1248)
PCE-1260 (Arocrilcr 1260)
KB-1016 (Arochlot :016)
H
L
n
H
H
H
H
H
B
H
H
N
H
M
H
•1
H
H
H
H
H
H
H
H
H
B
H
B
B
H
H
H
n
H
-
K
H
L
L
H
H
H
H
H
K
H
MOTE: Explanation of Removal RAtings
Category H (high removal)
adsorbs at levels > 100 mg/g carbon at C, • 10 mj/l
adsorbe at levels "> IOC mg/g carbon at CJ < 1.0 ng/1
Category M federate renoval)
adsorbs
adsorbs
at levels > 100 mg/g carbon at Cf •
at levels 7 100 ng/g carbon at Cj <
• 10 ng/1
l.Omg/1
Category L (low removal)
adsorbs at levels < IOC -ng/g carbon at Cf » 10 ng/1
adsorbs at levels < 10 ag/g carbon at Cf < 1.0 mg/1
Cf • final concentrations of priority pollutant at equilibria
60-1
-------
TABLE VII-19
CLASSES OF ORGANIC COMPOUNDS ADSORBED ON CARBON
Organic Chemical Class
\romatic 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 Aromatic Acids
*High Molecular Weight Aliphatic Amines
and Aromatic Amines
*High Molecular Weight Ketones, Esters,
Ethers & Alcohols
Surfactants
Soluble Organic Dyes
Examples of Chemical Class
benzene, toluene, xylene
naphthalene, anthracene
biphenyls
chlorobenzene, polychlorinated
biphenyls, aldrin, endrin,
toxaphene, DDT
phenol, cresol, reso'rcenol
and polyphenyls
trichlorophenol, pentachloro-
phenol
gasoline, kerosine
carbon tetrachloride,
perchloroethylene
tar acids, benzoic acid
aniline, toluene diamine
hydroguinone, polyethylene
glycol
alkyl benzene sulfonates
melkylene blue, Indigo carmine
* High Molecular Weight includes compounds in the broad range of from
4 to 20 carbon atoms
602
-------
WASTEWATER RECYCLE AND REUSE i
TABLE Vn-11
CONTIJOL TBCliNOl.nr.IKS HJ USE AT DATTKRY MAHIIKACTUKE PIANTS
WATER USE KEOUCTION
CUMU1NKD MUm-
THEATED DRY MR STAGE DRY
POUUTION COUNTER- PLAQUE
PROCESS MODIFICATION
TOHMATION
BATTERY CONTACT IN CASE
WASH COOLING (EXCEPT DRY AMAL-
NASIIiiPASTE PROCESS SCRUBBER PLAQUE STREAMS
EPA IDt FORMULATION SOLUTION RINSES WASTE SCRUBBING IN-PROCESS
Cadnium Subcategory
X X
X
X
x
X X
X X
Calcium Subcategory
o\ kea<* Subcategocy
0 XXX
<-» a a x
a xxx
• x x
x
• XX
x x
x
x
• XX
X
X
X X
• X • X X
X
X X
X
*
• X X
X
• a • x
• X X
CONTROL CURRENT SCRUB ELIMI- ELIMI- LEAD SUB- GAMATION
TECHNOLOGY RINSE TECHNIQUE NATION NATION CATEGORY PROCESS
X
X
xxx 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
MATERIAL
RECOVERY
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE VB-24 (CONT'D.)
EQUIPMENT
WASHfcPASTE
EPA 101 FORMULATION,
Lead Subcategory Con't
X
X
•
X
«
X
X
X
X
X
•
X
•
X
X
X
X
•
•
X
X
•
WASTEWATER RECYCLE AND REUSE
PROCESS SCRUBBER PLAQUE
SOLUTION RINSES WASTE SCRUBBING
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
XXX
X
X
X X
X.
X X
WATER USE REDUCTION PROCESS MODIFICATION
COMBINED MULTI- FORMATION
TREATED DRY AIR STAGE DRY BATTERY CONTACT IN CASE
WASTE POLLUTION COUNTER- PLAQUE WASH COOLING (EXCEPT DRY AMAL-
STREAMS CONTROL CURRENT SCRUB ELIMI- ELIMI- LEAD SUB- GAMATION
IN-PROCESS TECHNOLOGY RINSE TECHNIQUE NATION NATION CATEGORY PROCESS
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
MATERIAL
RECOVERY
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 VH-Z-i (CONT'D.)
PROCeSS CONTROL TECHNOLOGIES IN USB AT BATTERY MANUFACTURE PLANTS
WASTEHATER RECYCLE AND REUSE
COMBINED
TREATED
EQUIPMENT WASTE
HASH6PASTE PROCESS SCRUBBER PLAQUE STREAMS
EPA ID| FORMULATION SOLUTION RINSES WASTE SCRUBBING IN-PROCESS
Lead Subcategory Con't
X
X
X
X
X X
X
X
X X
X
X X
X XX
• XI
• X X
X
X X
• XX
X X
• X X
• X X
X
• X X
X X
X X
X
X
• X • X
X
X
X
WATER USE REDUCTION PROCESS MODIFICATION
MULTI- FORMATION
DRY AIR STAGE DRY BATTERY CONTACT IN CASE
POLLUTION COUNTER- PLAQUE WASH COOLING (EXCEPT DRY AMAL-
CONTHOL CURRENT SCRUB ELIMI- ELIMI- LEAD SUB- GAMATION
TECHNOLOGY RINSE TECHNIQUE NATION NATION CATEGORY PROCESS
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
MATERIAL
RECOVERY
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE VH-M (COHT'D.)
PROCESS CONTROL TECHNOLOGIES IN USE AT BATTERY MANUFACTURE PLANTS
WASTBiATER RECYCLE AND REUSE
COMBINED
TREATED
EQUIPMENT WASTE
WASH&PASTE PROCESS SCRUBBER PLAQUE STUEAMS
EPA IDt PORMULA'CIOM SOLUTION RINSES WASTE SCRUBBING IN-PHOCESS
WATER USE REDUCTION
MULTI-
DRY AIR STAGE DRY
POLUmON COUWTER- PLAQUE
CONTROL CURKEWT SCKUB
TECHHOLOGY RINSE TECHNIQUE
PROCESS MODIFICATION
FORMATION
BATTERY CONTACT IN CASE
WASH COOLING (EXCEPT DRY AMAL-
ELIHI- ELIMI- LEAD SUB- GAMATION MATERIAL
NATION NATION CATEGORY PROCESS RECOVERY
Leclanche Subcategoty
X
X
Lithium SuboategotV
X
X
Magnesium Subcategory
Zinc Subcategory
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
NOTE: Each line represents one plant.
i/ Recycle or reuse following treatment
indicated by 8
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SECTION VIII
COST OF WASTEWATER CONTROL AND TREATMENT
This section presents estimates of the cost of implementation of
wastewater treatment and control options for each of the subcategories
included in the battery manufacturing category. These cost estimates,
together with the pollutant reduction performance estimates for each
treatment and control option presented in Sections IX, X, XI, and XII
provide a basis for evaluation of the options presented and
identification of the best practicable control technology currently
available (BPT), best available technology economically achievable
(BAT), best demonstrated technology (BDT), and the best alternative
for pretreatment. The cost estimates also provide the basis for the
determination of the probable economic impact of regulation at
different pollutant discharge levels on the battery manufacturing
category. In addition, this section addresses non-water quality
environmental impacts of wastewater treatment and* control alternatives
including air pollution, noise pollution, solid wastes, and energy
requirements.
To arrive at the cost estimate presented in this section, specific
wastewater treatment technologies and in-process control techniques
from among those discussed in Section VII were selected and combined
in wastewater treatment and control systems appropriate for each
subcategory. As described in more detail below, investment and annual
costs for each system were estimated based on wastewater flows and raw
waste characteristics for each subcategory as presented in Section V.
Cost estimates are also presented for individual treatment
technologies included in the waste treatment systems.
COST ESTIMATION METHODOLOGY
Cost estimation is accomplished with the aid of a computer program
which accepts inputs specifying the treatment system to be estimated,
chemical characteristics of the raw waste streams treated, flow rates
and operating schedules. The program accesses models for specific
treatment components which relate component investment and operating
costs, materials and energy requirements, and effluent stream
characteristics to influent flow rates and stream characteristics.
Component models are exercised sequentially as the components are
encountered in the system to determine chemical characteristics and
flow rates at each point. Component investment and annual costs are
also determined and used in the computation of total system costs.
Mass balance calculations are used to determine the characteristics of
combined streams resulting from mixing two or more streams and to
determine the volume of sludges or liquid wastes resulting from
treatment operations such as sedimentation, filtration, flotation, and
oil separation.
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Cost estimates are broken down into several distinct elements in
addition to total investment and annual costs: operation and
maintenance costs, energy costs, depreciation, and annual costs of
capital. The cost estimation program incorporates provisions for
adjustment of all costs to a common dollar base on the basis of
economic indices appropriate to capital equipment and operating
supplies. Labor and electrical power costs are input variables
appropriate to the dollar base year for cost estimates. These cost
breakdown and adjustment factors as well as other aspects of the cost
estimation process are discussed in greater detail in the following
paragraphs.
Cost Estimation Input Data
The waste treatment system descriptions input to the computer cost
estimation program include both a specification of the waste treatment
components included and a definition of their interconnections. For
some components such as holding tanks, retention times or other
operating parameters are also specified in the input, while for
others, such as reagent mix tanks and clarifiers, these parameters are
specified within the program based on prevailing design practice in
industrial waste treatment. The waste treatment system descriptions
may include multiple raw waste stream inputs and multiple treatment
trains. For example, treatment for lead-acid battery manufacturing
wastes includes segregation of wastewater from grid pasting operations
and separate settling and recycle of these wastes in addition to
chemical treatment of the remaining process wastewater.
The specific treatment systems selected for cost estimation for each
subcategory were based on an examination of raw waste characteristics
and consideration of manufacturing processes as presented in Section
V, and an evaluation of available treatment technologies discussed in
Section VII. The rationale for selection of these systems is
presented in Section IX where pollution removal effectiveness is also
addressed.
The input data set also includes chemical characteristics for each raw
waste stream specified as input to the treatment systems for which
costs are to be estimated. These characteristics are derived from the
raw waste sampling data presented in Section V. The pollutant
parameters which are presently accepted as input by the cost
estimation program are shown in Table VIII-1 (Page 677). The values
of these parameters are used in determining materials consumption,
sludge volumes, treatment component sizes and effluent
characteristics. The list of input parameters is expanded
periodically as additional pollutants are found to be significant in
waste streams from industries under study and as additional treatment
technology cost and performance data become available. For the
battery manufacturing category, individual subcategories commonly
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encompass a number of widely varying waste streams which are present
to varying degrees at different facilities. The raw waste
characteristics shown as input to waste treatment represent a mix of
these streams including all significant pollutants generated in the
subcategory and will not in general correspond precisely to process
wastewater at any existing facility. The process by which these raw
wastes were defined is explained in Section IX.
The final input data set comprises raw waste flow rates for each input
stream for one or more plants in each subcategory addressed. Three
cases corresponding to high, low and typical flows encountered at
existing facilities were used for each battery manufacturing
subcategory to represent the range of treatment costs which would be
incurred in the implementation of each control and treatment option
offered. In addition, data corresponding to the flow rates reported
by each plant in the category were input to the computer to provide
cost estimates for use in economic impact analysis.
System Cost Computation
A simplified flow chart for the estimation of wastewater treatment and
control costs from the input data described above is presented in
Figure VIII-1 (Page 677). In the computation, raw waste
characteristics and flow rates for the first case are used as input to
the model for the first treatment technology specified in the system
definition. This model is used to determine the size and cost of the
component, materials and energy consumed in its operation, and the
volume and characteristics of the stream(s) discharged from it. These
stream characteristics are then used as input to the next component(s)
encountered in the system definition. This procedure is continued
until the complete system costs and the volume and characteristics of
the final effluent stream(s) and sludge or concentrated oil wastes
have been determined. In addition to treatment components, the system
may include mixers in which two streams are combined, and splitters in
which part of a stream is directed to another destination. These
elements are handled by mass balance calculations and allow cost
estimation for specific treatment of segregated process wastes such as
oxidation of cyanide bearing wastes prior to combination with other
process wastes for further treatment, and representation of partial
recycle of wastewater.
As an example of this computation process, the sequence of
calculations involved in the development of cost estimates for the
simple treatment system shown in Figure VIII-2 {Page 678) may be
described. Initially, input specifications for the treatment system
are read to set up the sequence of computations. The subroutine
addressing chemical precipitation and clarification is then accessed.
The sizes of the mixing tank and clarification basin are calculated
based on the raw waste flow rate to provide 45 minute retention in the
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mix tank and 4 hour retention with 33.3 gph/ft2 surface loading in the
clarifier. Based on these sizes, investment and annual costs for
labor, supplies and for the mixing tank and clarifier including
mixers, clarifier rakes and other directly related equipment are
determined. Fixed investment costs are then added to account for
sludge pumps, controls and reagent feed systems.
Based on the input raw waste concentrations and flow rates, the
reagent additions (lime, alum, and polyelectrolyte) are calculated to
provide fixed concentrations of alum and polyelectrolyte and 10
percent excess lime over that required for stoichiometric reaction
with the acidity and metals present in the waste stream. Costs are
calculated for these materials, and the suspended solids and flow
leaving the mixing tank and entering the clarifier are increased to
reflect the lime solids added and precipitates formed. These modified
stream characteristics are then used with performance algorithms for
the clarifier (as discussed in Section VII) to determine
concentrations of each pollutant in the clarifier effluent stream. By
mass balance, the amount of each pollutant in the clarifier sludge may
be determined. The volume of the sludge stream is determined by the
concentration of TSS which is fixed at 4-5 percent based on general
operating experience, and concentrations of other pollutants in the
sludge stream are determined from their masses and the volume of the
stream.
The subroutine describing vacuum filtration is then called, and the
mass of suspended solids in the clarifier sludge stream is used to
determine the size and investment cost of the vacuum filtration unit.
Operating hours for the filter are calculated from the flow rate and
TSS concentration and determine manhours required for operation.
Maintenance labor requirements are added as a fixed additional cost.
The sludge flow rate and TSS content are then used to determine costs
of materials and supplies for vacuum filter operation including iron
and alum added as filter aids, and the electrical power costs for
operation. Finally, the vacuum filter performance algorithms are used
to determine the volume and characteristics of the vacuum filter
sludge and filtrate, and the costs of contract disposal of the sludge
are calculated. The recycle of vacuum filter filtrate to the chemical
precipitation-clarification system is not reflected in the
calculations due to the difficulty of iterative solution of such loops
and the general observation that the contributions of such streams to
the total flow and pollutant levels are in practice, negligibly small.
Allowance for such minor contributions is made in the 20 percent
excess capacity provided in most components.
The costs determined for all components of the system are summed and
subsidiary costs are added to provide output specifying total
investment and annual costs for the system and annual costs for
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capital, depreciation, operation and maintenance, and energy. Costs
for specific system components and the characteristics of all streams
in the system may also be specified as output from the program.
In-Process Technologies
Costs calculated by the computer estimation procedure are highly
dependent upon discharge flows produced by plants in the industry. As
is described elsewhere in this document, the use of in-process
technology to achieve flow reduction is highly cost effective.
Reliance on the computer estimation procedure without attention to in-
process technologies results in an overstatement of the cost required
to achieve various levels of environmental improvement. For the
cadmium, lead, Leclanche, and zinc subcategories there was sufficient
data available from both visits and (dcp's) to estimate costs of
treatment which include in-process control. Since each plant has a
different process flow diagram, these calculations require extensive
hand calculations to provide the relevant instrumentation, holding
tanks, and process equipment appropriate to individual plants. Flows
resulting from in-plant technology were then used as input to the
computer. In the presentation of subcategory costs, costs are
selected to provide a minimum cost (other than zero), where
appropriate a median cost, and a maximum cost as realized in the
subcategory. The flow rate associated with the cost is the flow to
end-of-pipe treatment for the plant associated with the cost. In
certain cases part of this flow may be recycled to the process.
Treatment Component Models
The cost estimation program presently incorporates subroutines
providing cost and performance calculations for the treatment
technologies identified in Table VIII-2 (Page 678). These subroutines
have been developed over a period of years from the best available
information including on-site observations of treatment system
performance, costs, and construction practices at a large number of
industrial facilities, published data, and information obtained from
suppliers of wastewater treatment equipment. The subroutines are
modified and new subroutines added as additional data allow
improvements in treating technologies presently available, and as
additional treatment technologies are required for the industrial
wastewater streams under study. Specific discussion of each of the
treatment component models used in costing wastewater treatment and
control systems for the battery manufacturing category is presented
later in this section.
In general terms, cost estimation is provided by mathematical
relationships in each subroutine approximating observed correlations
between component costs and the most significant operational
parameters such as water flow rate, retention times, and pollutant
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concentrations. In general, flow rate is the primary determinant of
investment costs and of most annual costs with the exception of
materials costs. In some cases, however, as discussed for the vacuum
filter, pollutant concentrations may also significantly influence
costs.
Cost Factors and Adjustments
As previously indicated, costs are adjusted to a common dollar base
and are generally influenced by a number of factors including: Cost of
Labor, Cost of Energy, Capital Recovery Costs and Debt-Equity Ratio.
These cost adjustment and factors are discussed below.
Dollar Base - A dollar base of January 1978 was used for all costs.
Investment Cost Adjustment - Investment costs were adjusted to the
aforementioned dollar base by use of the Sewage Treatment Plant
Construction Cost Index. This cost is published monthly by the EPA
Division of Facilities Construction and Operation. The national
average of the Construction Cost Index for January 1978 was 288.0.
Supply Cost Adjustment - Supply costs such as chemicals were related
to the dollar base by the Wholesale Price Index. This figure was
obtained from the U.S. Department of Labor, Bureau of Labor
Statistics, "Monthly Labor Review". For January 1978 the "Industrial
Commodities" Wholesale Price Index was 201.6. Process supply and
replacement costs were included in the estimate of the total process
operating and maintenance cost.
Cost of_ Labor - To relate the operating and maintenance labor costs,
the hourly wage rate for non-supervisory workers in water, stream, and
sanitary systems was used from the U.S. Department of Labor, Bureau of
Labor Statistics Monthly publication, "Employment and Earnings". For
January 1978, this wage rate was $6.00 per hour. This wage rate was
then applied to estimates of operation and maintenance man-hours
within each process to obtain process direct labor charges. To
account for indirect labor charges, 10 percent of the direct labor
costs was added to the direct labor charge to yield estimated total
labor costs. Such items as Social Security, employer contributions to
pension or retirement funds, and employer-paid premiums to various
forms of insurance programs were considered indirect labor costs.
Cost of. Energy - Energy requirements were calculated directly within
each process. Estimated costs were then determined by applying an
electrical rate of 3.3 cents per kilowatt hour.
The electrical charge for January 1978 was corroborated through
consultation with the Energy Consulting Services Department of the
Connecticut Light and Power Company. This electrical charge was
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determined by assuming that any electrical needs of a waste treatment
facility or in-process technology would be satisfied by an existing
electrical distribution system; i.e., no new meter would be required.
This eliminated the formation of any new demand load base for the
electrical charge.
Capital Recovery Costs - Capital recovery costs were divided into
straight line ten-year depreciation and cost of capital at a ten
percent annual interest rate for a period of ten years. The ten year
depreciation period was consistent with the faster write-off
(financial life) allowed for these facilities even though the
equipment life is in the range of 20 to 25 years. The annual cost of
capital was calculated by using the capital recovery factor approach.
The capital recovery factor (CRF) is normally used in industry to help
allocate the initial investment and the interest to the total
operating cost of the facility. It is equal to:
CRF = i + (l+i)N-l
where i is the annual interest rate and N is the number of years over
which the capital is to be recovered. The annual capital recovery was
obtained by multiplying the initial investment by the capital recovery
factor. The annual depreciation of the capital investment was
calculated by dividing the initial investment by the depreciation
period N, which was assumed to be ten years. The annual cost of
capital was then equal to the annual capital recovery minus the
depreciation.
Debt-Equity Ratio - Limitations on new borrowings assume that debt may
not exceed a set percentage of the shareholders equity. This defines
the breakdown of the capital investment between debt and equity
charges. However, due to the lack of information about the financial
status of various plants, it was not feasible to estimate typical
shareholders equity to obtain debt financing limitations. For these
reasons, no attempt was made to break down the capital cost into debt
and equity charges. Rather, the annual cost of capital was calculated
via the procedure outlined in the Capital Recovery Costs section
above.
Subsidiary Costs
The waste treatment and control system costs presented in Tables VIII-
20 through VII1-43 (Pages 696 -719) for end-of-pipe and in-process
waste water control and treatment systems include subsidiary costs
associated with system construction and operation. These subsidiary
costs include:
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administration and laboratory facilities
garage and shop facilities
line segregation
yardwork
land
engineering
legal, fiscal, and administrative
interest during construction
Administrative and laboratory facility investment is the cost of
constructing space for administration, laboratory, and service
functions for the wastewater treatment system. For these cost
computations, it was assumed that there was already an existing
building and space for administration, laboratory, and service
functions. Therefore, there was no investment cost for this item.
For laboratory operations, an analytical fee of $90 (January 1978
dollars) was charged for each wastewater sample, regardless of whether
the laboratory work was done on or off site. This analytical fee is
typical of the charges experienced by EPA contractors during the past
several years of sampling programs. The frequency of wastewater
sampling is a function of wastewater discharge flow and is presented
in Table VIII-3 (Page 679). This frequency was suggested by the Water
Compliance Division of the USEPA.
For industrial waste treatment facilities being costed, no garage and
shop investment cost was included. This cost item was assumed to be
part of the normal plant costs and was not allocated to the wastewater
treatment system.
Line segregation investment costs account for plant modifications to
segregate wastes. The investment costs for line segregation included
placing a trench in the existing plant floor and installing the lines
in this trench. The same trench was used for all pipes and a gravity
feed to the treatment system was assumed. The pipe was assumed to run
from the center of the floor to a corner. A rate of 2.04 liters per
hour of wastewater discharge per square meter of area (0.05 gallons
per hour per square foot) was used to determine floor and trench
dimensions from wastewater flow rates for use in this cost estimation
process.
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The yardwork investment cost item includes the cost of general site
clearing, intercomponent piping, valves, overhead and underground
electrical wiring, cable, lighting, control structures, manholes,
tunnels, conduits, and general site items outside the structural
confines of particular individual plant components. This cost is
typically 9 to 18 percent of the installed components investment
costs. For these cost estimates, an average of 14 percent was
utilized. Annual yardwork operation and maintenance costs are
considered a part of normal plant maintenance and were not included in
these cost estimates.
No new land purchases were required. It was assumed that the land
required for the end-of-pipe treatment system was already available at
the plant.
Engineering costs include both basic and special services. Basic
services include preliminary design reports, detailed design, and
certain office and field engineering services during construction of
projects. Special services include improvement studies, resident
engineering, soils investigations, land surveys, operation and
maintenance manuals, and other miscellaneous services. Engineering
cost is a function of process installed and yardwork investment costs
and ranges between 5.7 and 14 percent depending on the total of these
costs.
Legal, fiscal and administrative costs relate to planning and
construction of waste water treatment facilities and include such
items as preparation of legal documents, preparation of construction
contracts, acquisition to land, etc. These costs are a function of
process installed, yardwork, engineering, and land investment costs
ranging between 1 and 3 percent of the total of these costs.
Interest cost during construction is the interest cost accrued on
funds from the time payment is made to the contractor to the end of
the construction period. The total of all other project investment
costs (process installed; yardwork; land; engineering; and legal,
fiscal/ and administrative) and the applied interest affect this cost.
An interest rate of 10 percent was used to determine the interest cost
for these estimates. In general, interest cost during construction
varies between 3 and 10 percent of total system costs depending on the
total costs.
COST ESTIMATES FOR INDIVIDUAL TREATMENT TECHNOLOGIES
Table VII1-4 (Page 680 ) lists those technologies which are
incorporated in the wastewater treatment and control options offered
for the battery manufacturing category and for which cost estimates
have been developed. These treatment technologies have been selected
from among the larger set of available alternatives discussed in
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Section VII on the basis of an evaluation of raw waste
characteristics, typical plant characteristics (e.g. location,
production schedules, product mix, and land availability), and present
treatment practices within the subcategories addressed. Specific
rationale for selection is 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.
Investment - Investment is the capital expenditure required to bring
the technology into operation. If the installation is a package
contract, the investment is the purchase price of the installed
equipment. Otherwise, it includes the equipment cost, cost of
freight, insurance and taxes, and installation costs.
Total Annual Cost - Total annual cost is the sum of annual costs for
depreciation, capital, operation and maintenance (less energy), and
energy (as a separate function).
Depreciation - Depreciation is an allowance, based on tax
regulations, for the recovery of fixed capital from an investment
to be considered as a non-cash annual expense. It may be regarded
as the decline in value of a capital asset due to wearout and
obsolescence.
Capital - The annual cost of capital is the cost, to the plant, of
obtaining capital expressed as an interest rate. It is equal to
the capital recovery cost (as previously discussed on cost
factors) less depreciation.
Operation and Maintenance - Operation and maintenance cost is the
annual cost of running the wastewater treatment equipment. It
includes labor and materials such as waste treatment chemicals.
As presented on the tables, operation and maintenance cost does
not include energy (power or fuel) costs because these costs are
shown separately.
Energy - The annual cost of energy is shown separately, although
it is commonly included as part of operation and maintenance cost.
Energy cost has been shown separately because of its importance to
the nation's economy and natural resources.
Lime Precipitation and Clarification
This technology removes dissolved pollutants by the formation of
precipitates by reaction with added lime and subsequent removal,of the
precipitated solids by gravity settling in a clarifier. Several
distinct operating modes and construction techniques are costed to
provide least cost treatment over a broad range of flow rates.
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Because of their interrelationships and integration in common
equipment in some installation, both the chemical addition and solids
removal equipment are addressed in a single subroutine.
Investment Cost - Investment costs are determined for this technology
for continuous treatment systems and for batch treatment. The least
cost system is selected for each application. Continuous treatment
systems include controls, reagent feed equipment, a mix tank for
reagent feed addition and a clarification basin with associated sludge
rakes and pumps. Batch treatment includes only reaction-settling
tanks and sludge pumps.
Controls and reagent feed equipment: costs for continuous treatment
systems include a fixed charge of $9075 covering an immersion pH probe
and transmitter, pH monitor, controller, lime slurry pump, 1 hp mixer,
and transfer pump. In addition, an agitated storage tank sufficient
to hold one days operating requirements of a 30 percent lime slurry is
included. Costs for this tank are estimated based on the holding tank
costs discussed later in this section and shown in Figure VIII-17
(Page 659 ). Lime feed to the slurry tank is assumed to be manual.
Hydrated lime is used and no equipment for lime slaking or handling is
included in these cost estimates. At facilities with high lime
consumption mechanical lime feed may be used resulting in higher
investment costs, but reduced manpower requirements in comparison to
manual addition.
Mix Tank: Continuous systems also include an agitated tank providing
45 minutes detention for reagent addition and formation of
precipitates.
Clarifier: The clarifier size is calculated based on a hydraulic
loading of 33.3 gph/ft2 and a retention time of 4 hours with a 20
percent allowance for excess flow capacity. Costs include both the
settling basin or tank and sludge collection mechanism. Investment
costs as a function of flow rate are shown in Figure VII1-3 (Page
645). The type of construction used is selected internally in the
cost estimation program to provide least cost.
Sludge Pumps: A cost of $3202 is included in the total capital cost
estimates regardless of whether steel or concrete construction is
used. This cost covers the expense for two centrifugal sludge pumps.
To calculate the total capital cost for continuous lime precipitation
and clarification, the costs estimated for the controls and reagent
feed system, mix tank, clarifier and sludge pump must be summed.
For batch treatment, dual above-ground cylindrical carbon steel tanks
sized for 8 hour retention and 20 percent excess capacity are used.
If the batch flow rate exceeds 5204 gph, then costs for fabrication
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are included. The capital cost for the batch system (not including
the sludge pump costs) is shown in Figure VIII-4 (Page 646 ). To
complete the capital cost estimation for batch treatment, a fixed
$3,202 cost is included for sludge pumps as discussed above.
Operation £ Maintenance Costs
The operation and maintenance costs for the Chemical Precipitation-
Clarification routine include:
1) Cost of chemicals added (lime, alum, and polyelectrolyte)
2) Labor (operation and maintenance)
3) Energy
Each of these contributing factors is discussed below.
CHEMICAL COST
Lime, alum and polyelectrolyte are added for metals and solids
removal. The amount of lime required is based on equivalent amounts
of various pollutant parameters present in the stream entering the
clarifier unit. The methods used in determining the lime requirements
are shown in Table VII1-5 (Page 681 ). Alum and polyelectrolyte
additions are calculated to provide a fixed concentration of 200 mg/1
of alum and 1 mg/1 of polyelectrolyte.
LABOR
Figure VII1-5 (Page 647 ) presents the manhour requirements for the
continuous clarifier system. For the batch system, maintenance labor
is assumed negligible and operation labor is calculated from:
(man-hours for operation) * 390 + (0.975) x (Ibs. lime added per day)
ENERGY
The energy costs are calculated from the clarifier and sludge pump
horsepower requirements.
Continuous Mode
The clarifier horsepower requirement is assumed constant over the
hours of operation of the treatment system at a level of 0.0000265
horsepower per 1 gph of flow influent to the clarifier. The sludge
pumps are assumed operational for 5 minutes of each operational hour
at a level of 0.00212 horsepower per 1 gph of sludge stream flow.
Batch Mode
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The clarifier horsepower requirement is assumed to occur for 7.5
minutes per operation hour at the following levels:
influent flow < 1042 gph; 0.0048 hp/gph
influent flow > 1042 gph; 0.0096 hp/gph
The power required for the sludge pumps in the batch system is the
same as that required for the sludge pumps in the continuous system.
Given the above requirements, operation and maintenance costs are
calculated based on the following:
$6.00 per man-hour + 10 percent indirect labor charge
$41.26/ton of lime
$44.91 ton of alum
$3.59/lb of polyelectrolyte
$0.032/kilowatt-hour of required electricity
Sulfide Precipitation - Clarification
This technology removes dissolved pollutants by the formation of
precipitates by reaction with sodium sulfide, sodium bisulfide, or
ferrous sulfide and lime, and subsequent removal of the precipitates
by settling. As discussed for lime precipitation and clarification,
the addition of chemicals, formation of precipitates, and removal of
the precipitated solids from the wastewater stream are addressed
together in cost estimation because of their interrelationships and
commonality of equipment under some circumstances.
Investment Cost. Capital cost estimation procedures for sulfide
precipitation and clarification are identical to those for lime
precipitation and clarification. Continuous treatment systems using
concrete and steel construction and batch treatment systems are costed
to provide a least cost system for each flow range and set of raw
waste characteristics. Cost factors are also the same as for lime
precipitation and clarification.
Operation and Maintenance Costs. Costs estimated for the operation
and maintenance of a sulfide precipitation and clarification system
are also identical to those for lime precipitation and clarification
except for the cost of treatment chemicals. Lime is added prior to
sulfide precipitation to achieve an alkaline pH of approximately 8.5-9
and will lead to the precipitation of some pollutants as hydroxides or
calcium salts. Lime consumption based on both neutralization and
formation of precipitates is calculated to provide a 10 percent excess
over stochiometric requirements. Sulfide costs are based on the
addition of ferrous sulfate and sodium bisulfide (NaHS) to form a 10
percent excess of ferrous sulfide over stoichiometric requirements for
precipitation. Reagent additions are calculated as shown in Table
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VIII-6 (Page 682 ). Addition of alum and polyelectrolyte is identical
to that shown for lime precipitation and clarification as are labor
and energy rates.
The following rates are used in determining operating and maintenance
costs for this technology.
$6.00 per man-hour + 10 percent indirect labor charge
$44.91/ton of alum
$3.59/lb of polyelectrolyte
$41.26/ton of lime
$0.27/lb of sodium bisulfide
$143.74/ton of ferrous sulfate
$0.032/kilowatt-hour of electricity
Multi-Media Filtration
This technology provides removal of suspended solids by filtration
through a bed of particles of several distinct size ranges. As a
polishing treatment after chemical precipitation and clarfication
processes, multi-media filtration provides improved removal of
precipitates and thereby improved removal of the original dissolved
pollutants.
Capital Cost. The size of the multi-media filtration unit is based on
20 percent excess flow capacity and a hydraulic loading of 0.5
ft2/gpm. The capital cost, presented in Figure VIII-6 (Page 648) as a
function of flow rate, includes a backwash mechanism, pumps, controls,
media and installation.
Operation And Maintenance. The costs shown in Figure VIII-6 (Page
648) for annual costs includes contributions of materials, electricity
and labor. These curves result from correlations made with data
obtained from a major manufacturer. Energy costs are estimated to be
3 percent of total O&M.
Membrane Filtration
Membrane filtration includes addition of sodium hydroxide to form
metal precipitates and removal of the resultant solids on a membrane
filter. As a polishing treatment, it minimizes solubility of metal
and provides highly effective removal of precipitated hydroxides and
sulfides.
Capital Cost. Based on manufacturer's data, a factor of $52.6 per 1
gph flow rate to the membrane filter is used to estimate capital cost.
Capital cost includes installation.
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Operation and Maintenance Cost. The operation and maintenance costs
for membrane filtration include:
1) Labor
2) Sodium Hydroxide Added
3) Energy
Each of these contributing factors are discussed below.
LABOR
2 man-hours per day of operation are included.
SODIUM HYDROXIDE ADDITION
Sodium hydroxide is added to precipitate metals as hydroxides or to
insure a pH favorable to sulfide precipitation. The amount of sodium
hydroxide required is based on equivalent amounts of various pollutant
parameters present in the stream entering the membrane filter. The
method used to determine the sodium hydroxide demand is shown below:
POLLUTANT ANaOH
Chromium, Total 0.000508
Copper - 0.000279
Acidity £1.000175
Iron, DIS 0.000474
Zinc 0.000268
Cadmium 0.000158
Cobalt 0.000301
Manganese 0.000322
Aluminum 0.000076
(Sodium Hydroxide Per Pollutant, Ib/day) = ANaOH x Flow Rate
(GPH) x Pollutant Concentration (mg/1)
ENERGY
The horsepower required is as follows:
two 1/2 horsepower mixers operating 34 minutes per operational
hour
two one horsepower pumps operating 37 minutes per operational hour
one 20 horsepower pump operating 45 minutes per operational hour
Given the above requirements, operation and maintenance costs are
calculated based on the following:
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$6.00 per man-hour + 10 percent indirect labor charge
$0.11 per pound of sodium hydroxide required
$0.032 per kilowatt-hour of energy required
calculated costs in the battery industry as a
function of flow rate for membrane filtration
are presented in Figure VI1-7.
Reverse Osmosis
This technology achieves the concentration of 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. A number
of different membrane types and constructions are available which are
optimized for different wastewater characteristics (especially pH and
temperature). Two variations, one suited specifically to recovery of
nickel plating solutions, and the other of more general applicability
are addressed in cost and performance models.
Capital Cost. Investment cost data from several manufacturers of RO
equipment is summarized in the cost curve shown in Figure VIII-8 (Page
650). The cost shown include a prefilter, chemical feed system, scale
inhibitor tank, high pressure pump, and permeators. Installation is
also included. Two different systems, one using cellulose acetate
membranes and suitable for nickel plating bath recovery, and one using
polyamide membranes which are tolerant of a wider pH and temperature
range are addressed. The polyamide resin systems are applicable to
treatment of battery manufacturing wastewaters.
Operation and Maintenance Cost. Contributions to operation and
maintenance costs include:
LABOR
The annual labor requirement is shown in Figure VIII-9 (Page 651 ).
Labor cost is calculated using a $6.00 per hour labor rate plus a 10
percent indirect labor charge.
MATERIALS
The annual cost of materials used in operation and maintenance of the
reverse osmosis unit is shown in Figure VIII-10 (Page 652). The major
component of the materials cost is the cost of replacement of
permeator modules which are assumed to have a 1.5 year service life
based on manufacturers' data.
POWER
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The horsepower requirements for reverse osmosis unit is shown in
Figure VIII-11 (Page 653 ). This requirement is assumed to be constant
over the operating hours of the system being estimated. The energy
cost is determined using a charge of $0.032 per kilowatt-hour.
Vacuum Filtration
Vacuum filtration is widely used to reduce the water content of high
solids streams. In the battery manufacturing industry, this
technology is applied to dewatering sludge from clarifiers, membrane
filters and other waste treatment units.
Capital Cost. The vacuum filter is sized based on a typical loading
of 14.6 kilograms of influent solids per hour per square meter of
filter area (3 lbs/ftz-hr). The curves of cost versus flow rate at
TSS concentrations of 3 percent and 5 percent are shown in Figure
VIII-12 (Page 654). The capital cost obtained from this curve
includes installation costs.
Operation and Maintenance Cost
LABOR
The vacuum filtration subroutine may be run for off-site sludge
disposal or for on-site sludge incineration. For on-site sludge
incineration, conveyor transport is assumed, and operating man-hours
are reduced from those for off-site disposal. The required operating
hours per year varies with both flow rate and the total suspended
solids concentration both flow rate and the total suspended solids
concentration in the influent stream. Figure VII1-13 (Page 655 ) shows
the variance of operating hours with flow rate and TSS concentration.
Maintenance labor for either sludge disposal mode is fixed at 24
manhours per year.
MATERIALS
The cost of materials and supplies needed for operation and
maintenance includes belts, oil, grease, seals, and chemicals required
to raise the total suspended solids to the vacuum filter. The amount
of chemicals required (iron and alum) is based on raising the TSS
concentration to the filter by 1 mg/1. Costs of materials required as
a function of flow rate and unaltered TSS concentrations is presented
in Figure VIII-14 (Page 656 ).
ENERGY
Electrical costs needed to supply power for pumps and controls is
presented in Figure VIII-15 (Page 657 ). As the required horsepower of
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the pumps is dependent on the influent TSS level, the costs are
presented as a function of flow rate and TSS level.
Holding Tanks
Tanks serving a variety of purposes in wastewater treatment and
control systems are fundamentally similar in design and construction
and in cost. They may include equalization tanks, solution holding
tanks, slurry or sludge holding tanks, mixing tanks, and settling
tanks from which sludge is intermittently removed manually or by
sludge pumps. Tanks for all of these purposes are addressed in a
single cost estimation subroutine with additional costs for auxilliary
equipment such as sludge pumps added as appropriate.
Capital Costs. Costs are estimated for either steel or concrete
tanks. Tank construction may be specified as input data, or
determined on a least cost basis. Retention time is specified as
input data and, together with stream flow rate, determines tank size.
Capital costs for tanks sized for 20 percent excess capacity are shown
as functions of volume in Figure VIII-16 (Page 658).
Operation ;»nd Maintenance Costs. For all holding tanks except sludge
holding tanks, operation and maintenance costs are minimal in
comparison to other system O&M costs. Therefore only energy costs for
pump and mixer operation are determined. These energy costs are
presented in Figure VIII-17 (Page 659 ).
For sludge holding tanks, additional operation and maintenance labor
requirements are reflected in increased O&M costs. The required
manhours used in cost estimation are presented in Figure VII1-18 (Page
660 ). Labor costs are determined using a labor rate of $6.00 per
manhour plus 10 percent indirect labor charge.
Where tanks are used for settling as in lime precipitation and
clarification batch treatment, additional operation and maintenance
costs are calculated as discussed specifically for each technology.
p_H Adjustment
The adjustment of pH values is a necessary precursor to a number of
treatment operations and is frequently required to return waste
streams to a pH value suitable for discharge following metals
precipitation. This is typically accomplished by metering an alkaline
or acid reagent into a mix tank under automatic feedback control.
Figure VII1-19 (Page 661 ) presents capital costs for pH adjustment as
a function of the flow rate going into the units. The cost
calculations are based on steel or concrete tanks with a 15 minute
retention time and an excess capacity of 20 percent. Tank
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construction is selected on a least cost basis. Costs include a pH
probe and control system, reagent mix tanks, a mixer in the pH
adjustment tank, and system installation.
Operation and Maintenance Costs
LABOR
The required man-hours as a function of flow rate is presented in
Figure VIII-20 (Page 662.). The cost of labor may be calculated using
a labor rate of $6.00 per hour plus a 10 percent indirect labor
charge.
MATERIALS
Sodium hydroxide or sulfuric acid are added according to the stream
pH, and acidity or alkalinity. The amount of lime or acid required
may be calculated by the procedure shown in Table VIII-7 (Page 683 )•
The cost of lime or acid added may be determined using the rates of
$0.11 per pound of sodium hydroxide and $70.0 per ton of sulfuric
acid.
ENERGY
Power, required for a mixer, is based on a representative installation
with 1-turnover per minute. The daily horsepower requirement is 3 hp
per 10,000 gph flow rate. The energy cost may be calculated using the
rates of .8 kilowatts per horsepower and $.032 per kilowatt-hour.
Contract Removal
Sludge, waste oils, and in some cases concentrated waste solutions
frequently result from wastewater treatment processes. These may be
disposed of on-site by incineration, landfill or reclamation, but are
most often removed on a contract basis for off-site disposal. System
cost estimate presented in this report are based on contract removal
of sludges and waste oils. In addition, where only small volumes of
concentrated wastewater are produced, contract-removal for off-site
treatment may represent the most cost-effective approach to water
pollution abatement. Estimates of solution contract haul costs are
also provided by this subroutine and may be selected in place of on-
site treatment on a least-cost basis.
Capital Costs - Capital investment for contract removal is zero.
Operating Costs - Annual costs are estimated for contract removal of
total waste streams or sludge and oil streams as specified in input
data. Sludge and oil removal costs are further divided into wet and
dry haulage depending upon whether or not upstream sludge dewatering
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is provided. The use of wet haulage or of sludge dewatering and dry
haulage is based on least cost as determined by annualized system
costs over a ten year period. Wet haulage costs are always used in
batch treatment systems and when the volume of the sludge stream is
less than 100 gallons per day. Both wet sludge haulage and total
waste haulage differ in cost depending on the chemical composition of
the water removed. Wastes are classified as cyanide bearing,
hexavalent chromium bearing, or oily and assigned different haulage
costs as shown below.
Waste Composition
>.05 mg/1 CN-
>.l mg/1 Cr+6
Oil Se grease >
All others
TSS
Haulage Cost
$0.45/gallon
$0.20/gallon
$0.12/gallon
$0.16/gallon
Dry sludge haul costs are estimated at $0.12/gallon and 40 percent dry
solids in the sludge.
Carbon Adsorption
This technology removes organic and inorganic pollutants and suspended
solids by pore adsorption, surface reactions, physical filtering by
carbon grains, and in some cases as part of a biological treatment
system. It typically follows other types of treatment as a means of
polishing effluent. A variety of carbon adsorption systems exist:
upflow, downflow, packed bed, expanded bed, regenerative and
throwaway. Regeneration of carbon requires an expensive furnace and
fuel. As a general criteria, it is not economically feasible to
install a thermal regeneration system unless carbon usage is above
1000 Ibs per day.
Capital Costs
Capital costs estimated for carbon adsorption systems applied to
battery manufacturing wastewater are provided in Figure VII1-21 (Page
663) and assume a packed bed throwaway system. All equipment costs
are based on the EPA Technology Transfer Process Design Manual Carbon
Adsorption and include a contactor system, a pump station, and initial
carbon. Costs for carbon adsorption are highly variable and it is
usually cost effective to pretreat waste before using carbon. The
high cost of removing a small amount of a given priority pollutant
results from the requirement that the system must be sized and
operated to remove all organics present which are more easily removed
than the species of interest. Accuracy of model predictions depends
upon the estimate of other organics present. Removal efficiencies
depend upon the type of carbon used and a mixture of carbon types may
be cost beneficial. Where regenerative systems are considered, it is
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important to distinguish between removals achieved using regenerated
carbon and fresh carbon which are vastly different. Equipment sizing
is based on dynamic (as opposed to carbon isotherm) studies.
Operation and Maintenance Costs
The chief operation and maintenance costs are labor, replacement
carbon, and electricity for the pump station. Annual costs determined
for battery manufacturing applications are shown in Figure VI11-21
(Page 663). Carbon usage selected to provide 99 percent removal of
each organic priority pollutant is determined from a reciprocal carbon
efficiency of an appropriate mix of carbons (bituminous and lignite)
estimated at 0.2 ft3 of fresh unregenerated (virgin) carbon per pound
of organics provided by the influent. Carbon is costed at $1.19/lb
and electricity at $0.033/kw hr.
Chromium Reduction
This technology provides chemical reduction of hexavalent chromium
under acid conditions to allow subsequent removal of the trivalent
form by precipitation as the hydroxide. Treatment may be provided in
either continuous or batch mode, and cost estimates are developed for
both. Operating mode for system cost estimates is selected on a least
cost basis.
Capital Cost. Cost estimates include all required equipment for
performing this treatment technology including reagent feed, reaction
tanks, mixers and controls. Different reagents are provided for batch
and continuous treatment resulting in different system design
considerations as discussed below.
For both continuous and batch treatment, sulfuric acid is added for pH
control. A 90-day supply is stored in the 25 percent aqueous form in
an above-ground, covered concrete tank, 0.305 m(l ft) thick.
For continuous chromium reduction the single chromium reduction tank
is sized as an above-ground cylindrical concrete tank with a 0.305 m
(1 ft) wall thickness, a 54 minute retention time, and an excess
capacity factor of 1.2. Sulfur dioxide is added to convert the
influent hexavalent chromium to the trivalent form.
The control system for continuous chromium reduction consists of:
1 immersion pH probe and transmitter
1 immersion ORP probe and transmitter
1 pH and ORP monitor
2 slow process controllers
1 sulfonator and associated pressure regulator
1 sulfuric acid pump
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1 transfer pump for sulfur dioxide ejector
2 maintenance kits for electrodes, and miscellaneous
electrical equipment and piping
For batch chromium reduction, the dual chromium reduction tanks are
sized as above-ground cylindrical concrete tanks, 0.305 m (1 ft)
thick, with a 4 hour retention time, an excess capacity factor of 0.2.
Sodium bisulfite is added to reduce the hexavalent chromium.
A completely manual system is provided for batch operation.
Subsidiary equipment includes:
1 sodium bisulfite mixing and feed tank
1 metal stand and agitator collector
1 sodium bisulfite mixer with disconnects
1 sulfuric acid pump
1 sulfuric acid mixer with disconnects
2 immersion pH probes
1 pH monitor, and miscellaneous piping
Capital costs for batch and continuous treatment systems are presented
in Figure VIII-22 (Page 664').
Operation and Maintenance. Costs for operating and maintaining
chromium reduction systems include labor, chemical addition, and
energy requirements. These factors are determined as follows:
Labor
The labor requirements are plotted in Figure VIII-23 (Page 665).
Maintenance of the batch system is assumed negligible and so it is not
shown.
Chemical Addition
For the continuous system, sulfur dioxide is added according to the
following:
(Ibs S02/day) = (15.43) (flow to unit-MGD) Cr+6 mg/1)
In the batch mode, sodium bisulfite is added in place of sulfur
dioxide according to the following:
(Ibs NaHS03/day) = (20.06) (flow to unit-MGD) (Cr+6 mg/1)
Energy
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Two horsepower is required for chemical mixing. The mixers are
assumed to operate continuously over the operation time of the
treatment system.
Given the above requirements, operation and maintenance costs are
calculated based on the following:
$6.00 per manhour +10 percent indirect labor charge
$380/ton of sulfur dioxide
$20/ton of sodium bisulfite
$0.032/kilowatt hour of required electricity
In Process Treatment and Control Components
A wide variety of in-process controls have been identified for
application to battery manufacturing wastewaters, and many of these
require in process treatment or changes in manufacturing facilities
and capital equipment for which additional costs must be estimated.
For most of these, especially recirculation and reuse of specific
process streams, the required equipment and resultant costs are
identical to end-of-pipe components discussed above. In particular,
cost estimates (Figures VIII-24 and VIII-25 (Pages 666-667) for the
recirculation of rinsewater, scrubber water, seal or ejector water,
and area wash water except for amalgamation areas are based on holding
tank costs with sizing assumptions discussed for each system
addressed, and additional costs for line segregation to cover piping
changes (Figure VIII-26 (Page 668)). The recirculation of
amalgamation area wash water requires the removal of mercury for which
costs are estimated based on the sulfide precipitation and
clarification system previously discussed. Costs for recirculation of
lead-acid battery wash waters are presented in Figure VII1-27 (Page
669).
In process control techniques for which specific costs must be
estimated include the use of slow-rate charging for lead-acid
batteries, and the implementation of countercurrent rinses in a
variety of process operations.
The use of slow charging rates for lead acid batteries eliminates the
use of contact cooling water, reduces the need for wet scrubbers and
battery rinsing, and is compatible with single fill operation. Its
implementation requires the provision of additional floor area and
charging racks to accommodate a larger inventory of batteries on-
charge simultaneously. Instantaneous power demand, and therefore the
size of required rectification and control equipment are unchanged.
Capital Cost. Required capital expenditures are estimated based on
erection of a building to provide 0.8 square feet of floor area per
pound of batteries produced per hour to allow for an increase in the
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time on-charge of 6 days. This area is based on a typical density of
approximately 50 Ibs per square foot for the batteries themselves and
a 40 percent packing density in the charging area and six high
stacking of the batteries.
Building costs are shown as a function of lead used in Figure VIII-28
(Page 670 ). Twenty percent is included in these costs to allow for
installation of charging racks and necessary services. Annual costs
of capital for the building are estimated based on a 25 year capital
recovery rather than the 10 year period used for waste treatment
equipment. This is consistent with normal accounting practices.
Operation and Maintenance. Required handling of batteries and
electric power requirements are not affected by this process change.
Further, batteries on slow-rate charge require minimal attention.
Therefore, no operating and maintenance costs are calculated for this
in process control technique.
Countercurrent rinsing requires additional rinse tanks or spray
equipment and plumbing as compared to single stage rinses, and
extension of materials handling equipment or provision of additional
manpower for rinse operation.
Summary of. Treatment and Control Component Costs. Costs for each of
the treatment and control components discussed above as applied to
process wastewater streams within the battery manufacturing category
are presented in Tables VIII-8 through VIII-19 (Pages 684-695). Three
levels of cost are provided for each technology representative of
typical, low, and high raw waste flow rates encountered within the
category.
TREATMENT SYSTEM COST ESTIMATES
Estimates of the total cost of wastewater treatment and control
systems for battery manufacturing process wastewater are made by
incorporating the treatment and control components discussed above.
Cost estimates representing three different flow rates corresponding
to median (typical), low and high flow rates in the subcategory
addressed are presented for each system in order to provide an
indication of the range of costs to be incurred in implementing each
level of treatment. Since some plants in each subcategory report zero
wastewater discharge, and will therefore incur zero treatment and
control costs, low flow rates used in cost estimation represent low
flow values at plants reporting wastewater and are not true minima for
the subcategory. All available flow data from industry data
collection portfolios were used in defining median, maximum and
minimum raw waste flows, and flow breakdowns where streams are
segregated for treatment, for use in these cost estimates. Raw waste
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characteristics were determined based on sampling data as discussed in
Section V.
The system costs presented include component costs as discussed above
and subsidiary costs including engineering, line segregation,
administration, and interest expense during construction. In each
case, it is assumed that none of the specified treatment and control
measures are in place so that the presented costs represent total
costs for the systems.
BPT System Cost Estimates
Cadmium-Subcateqory - The BPT treatment system for this subcategory,
shown in Figure IX-1 (Page 738 ), consists of lime precipitation and
clarification of all process wastewater for the removal of nickel,
cadmium and other toxic metals, and includes a vacuum filter for
dewatering the clarifier sludge. Rationale for selection of this
system is presented in Section IX.
Assumptions used in sizing system components are those discussed for
the individual treatment components. Estimates of costs for
implementation of BPT treatment and control for this subcategory are
presented in Table VII1-20 (Page 696').
Data from dcps and visits were evaluated to determine what kinds of
in-process treatment existed for wastewater conservation and what
kinds of loadings had been achieved or were achievable. These
technologies include control of water fluctuations by adequate
instrumentation, reuse of water in another process, countercurrent
rinsing and in-line treatment followed by water reuse. A summary of
investment and annual costs for in-process control technologies as
identified in Sections IX and X are provided in Figures VII1-29 and
VIII-30 (Pages 671-672) for all treatment levels for all eight plants
considered. BPT in-process costs reflect additional controls required
for water use reduction at high flow plants.
Calcium Subcateqory - The BPT treatment system, shown in Figure IX-2
(Page 739), consists of the treatment of two streams. The first waste
stream is settled to remove asbestos, barium chromate and suspended
zirconium powder, reduced to insure that no slightly soluble barium
chromate provides hexavalent chrome, and then merged with the second
stream. The combined stream, treated with lime to remove various
dissolved metals is settled and skimmed in the same clarification
system to remove residual oil and grease, and discharged. Resultant
cost estimates are provided in Table VIII-21 (Page 697).
Lead Subcateqorv - The BPT treatment and control system for the lead
subcategory is shown in Figure IX-3 (Page 740). It includes
segregation of process wastewater resulting from paste application,
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multi-stage settling of this waste stream, and subsequent reuse of
both the water and the settled solids in the pasting operation. For
the balance of the process wastewater, lime precipitation and
clarification is provided for the removal of lead and other metals.
Vacuum filtration for dewatering clarifier sludge is included.
Each of the settling tanks used for pasting wastewater recirculation
is sized to provide one hour of retention. Assumptions used in
costing other system components are those presented in the individual
technology discussions. System cost estimates include an allowance
for segregating paste application wastewater as described under "Line
Segregation". Resultant cost estimates are presented in Table VIII-22
(Page 698 ). In-process investment and annual costs are provided in
Figures VIII-31 and VIII-32 (Pages 673 and 674 ).
Leclanche Subcateqory - BPT for this subcategory achieves zero
discharge of process wastewater pollutants by the application of in-
process control techniques. No costs are incurred in achieving BPT at
most plants in the subcategory because no process wastewater is
presently produced. Cost estimates for the remaining facilities
reflect holding tanks, pumps, piping, and treatment facilities needed
to achieve recycle of process wastewater from paste setting and from
equipment and tool washing operations. Paste setting wastewater is
treated by sulfide precipitation (using ferrous sulfide) prior to
recycle, and equipment wash wastewater is treated in settling tanks.
In some cases, where the reported volume of process wastewater was
small, estimated costs reflect contract removal of the wastes rather
than treatment and recycle. Resultant cost estimates are summarized
in Table VIII-23 (Page 699 ).
Lithium Subcategory - BPT treatment for this subcategory Figure IX-4
(Page 741 ) includes grouping wastes into three possible streams. The
first stream resulting from the cathode system of the cell may contain
thionyl chloride and sulfur dioxide. It is aerated to reduce oxygen
demand neutralized to form harmless products, settled and discharged.
The second stream associated with heat paper manufacture is settled to
remove asbestos, barium chromate, and zirconium powder suspension and
reduced to insure that any chromate is in the trivalent state. This
stream is merged with remaining wastes which are treated by lime and
settled in a clarifier containing a skimmer for removal of residual
oil and grease. Resultant metallic sludges are passed to a vacuum
filter and the treated water is discharged. Typical costs for the
system are provided by Table VII1-24 (Page 700 ). Rationale for
selection of the BPT system as well as the basis for determination of
flow rates and raw waste characteristics are discussed in Section IX.
Magnesium Subcategory - The BPT treatment for this subcategory
presented in Figure IX-5 (Page 742) includes grouping wastes into four
possible streams. Wastes from etching glass beads used as battery
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separators are treated with lime to precipitate calcium fluoride,
aerated to remove ammonia, and then blended with other waste streams
for further treatment. Water containing silver chloride and photo
development chemicals is also aerated with the preceding waste to
reduce oxygen demand before being joined with other waste streams.
Water associated with heat paper manufacture is settled to remove
asbestos, barium chromate and zirconium and reduced to insure any
chromate remaining is in the trivalent state before joining with other
waste streams. Miscellaneous wastes are blended with wastes resulting
from the above treatment and treated with lime and settled to remove
trivalent chromium, metals, and suspended solids. The clarifier may
incorporate oil skimming for the removal of residual oils. All
precipitates are dewatered by vacuum filtration. Representative
treatment costs are presented in Table VIII-25 (Page 701 ). Rationale
for selection of the BPT system as well as the basis for the
determination of flow rates and raw waste characteristics are
discussed in Section IX.
Zinc Subcategory - The BPT wastewater treatment and control system for
this subcategory includes sulfide precipitation, clarification, and
filtration as shown in Figure IX-6 (Page 743). In-process controls
included in BPT are limited to water use controls widely demonstrated
in present practice, and the use of water-efficient techniques for
general plant floor cleaning. Data from DCPs and plant visits were
evaluated to determine the effects of in-process technology on
individual process loadings. Adequate instrumentation to control
water use fluctuations was included in BPT costs. Holding tanks,
water reuse, countercurrent rinsing, and in lime treatment followed by
reuse are all successfully practiced and were costed for various
treatment levels. For BAT-2 in-line sulfide precipitation and
settling for wet amalgamation and treatment of process solutions and
rinses by reverse osmosis for reuse in divalent silver production were
costed. A summary of investment and annual costs are provided in
Figures VII1-33 and VII1-34 (Pages 675 and 676) respectively for the
thirteen plants considered.
BPT cost estimates are presented in Table VII1-26.
The assumptions in costing end-of-pipe treatment components are those
discussed for the individual technologies. Wastewater flow rates
represented in Table VII1-26 span the range encountered in data
collection portfolios from plants in this subcategory (except for zero
discharge facilities). Raw waste characteristics used in cost
estimation correspond to a representative mix of waste streams derived
from plant visit data. Rationale for selection of the BPT system is
discussed in Section IX.
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BAT Treatment System Cost Estimates
Cadmium Subcateqory - Costs are provided for three alternative levels
of treatment and control considered appropriate for BAT.
BAT Option 1
As shown in Figure X-l (Page 766), end-of-pipe treatment includes
sulfide precipitation and clarification. A vacuum filter is provided
for dewatering clarifier sludge. In addition, a number of in-process
control techniques are included to limit the volume of process
wastewater and pollutant loads to treatment. These include
recirculation of wet scrubber solutions, control of rinse flow rates,
and use of dry brushing for removal of excess material from
impregnated anodes and cathodes.
Costs for recirculation of scrubber solutions are based on the
provision of tanks providing 2 hours retention of the scrubber
discharge. No costs are determined for control of rinse flow rates
since this can be accomplished with minimum manpower and manual flow
control values which are present on most units or available at low
cost. Similarly, no costs were estimated for the use of dry brushing
processes since these are observed to be used in existing facilities
on a competitive basis with wet brushing techniques. Cost estimates
also include costs for the segregation of two scrubber discharge
streams. Assumptions in costing end-of-pipe treatment components are
those discussed for the individual technologies. Resultant cost
estimates are presented in Table VIII-27 (Page 703). In-process costs
are presented in Figures VII1-29 and VII1-30 (Pages 671 and 672).
BAT Option 2
End-of-pipe treatment provided for cadmium subcategory wastes at BAT
Option 2 is identical to that provided at BAT Option 1. In-process
control techniques include those recommended for BAT Option 1 plus the
use of multistage countercurrent rinses after electrode deposition
impregnation and formation, and the reuse of final product wash water
after cadmium powder precipitation.
Cost estimation for multistage countercurrent rinses are based on
present rinse flow and production rates and considerations previously
discussed for this in-process technique. Costs for reuse of final
product wash water after cadmium powder precipitation are based on
provision of a tank for retention of final wash water from one batch
of product for use in early rinses of the next batch. Table X-2 (Page
767) shows total BAT Option 2 system cost estimates. In-process costs
are presented in Figures VII1-29 and VII1-30 (Pages 671 and 672 ).
Resultant cost estimates are in Table VIII-28 (Page 704).
634
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BAT Option 3
End of pipe treatment for BAT Option 3 includes concentration of
process wastewater using reverse osmosis prior to treatment identical
to that provided at BAT Option 2. Permeate from the reverse osmosis
unit is reused in the process. As shown in Figure X-3 (Page 768•)/
wastewater is treated by neutralization and filtration prior to
reverse osmosis to protect the permeators. In process control
techniques at BAT Option 3 include formation of electrodes in the
battery case without subsequent rinsing, and improved process control
on cadmium powder precipitation to eliminate the need for rework of
this product in addition to the in-process controls discussed as BAT
Option 2.
No costs are estimated for the additional BAT Option 3 in-process
control techniques. Total system costs are presented in Table VII1-29
(Page 70b).
BAT Option 4
Costs for BAT Option 4 presented in Figure X-4 (Page 769 ) have not
been evaluated and will be included in the proposed development
document.
Calcium Subcategory - Costs are provided for two alternative levels of
treatment and control considered appropriate for BAT.
BAT Option 1
At BAT Option 1, end-of-pipe treatment is identical to that provided
for BPT except the discharge from the BPT system is passed through a
multi-media filter prior to discharge. This filter is intended to act
as on polishing unit on the treated waste stream. The filter backwash
is returned to the treatment system. A schematic of the system is
provided in Figure X-5 (Page 770). Representative costs for this
level of treatment are provided by Table VII1-30 (Page 706 ).
BAT Option 2
This level of treatment is similar to BAT Option 1 except that waste
stream 1 from heat paper production is recycled back to the process.
A schematic of the system is provided in Figure X-6 (Page 771).
Representative summary costs for this level of treatment are provided
by Table VIII-31 (Page 707 ).
Lead Subcateqory - Costs are provided for four alternative levels of
treatment and control considered appropriate for BAT.
BAT Option 1
635
-------
As BAT Option 1, end-of-pipe treatment is identical to that provided
for BPT, but additional in-process control techniques significantly
reduce the volume of wastewater which is treated and discharged. In
process controls included in BAT Option 1 include:
elimination of wastewater discharges from formation of
formation of wet and damp batteries.
elimination of wastewater discharges from battery rinses
reduction of wastewater discharges from battery wash
reduction of wastewater discharge from formation and
dehydration of plates for dehydrated batteries.
recirculation of paste preparation and application wastewater
as specified for BPT
Cost estimates for in process controls include paste recirculation
costs included at BPT, costs for additional plant floor space to allow
low rate charging of batteries, and tanks for retention of 2 hours
flow from wet scrubbers on formation operations to allow
recirculation and eventual use of the scrubber bleed in acid cutting.
Recirculation tanks providing one hour retention to allow reuse of
battery rinse water and eventual use of the discharge in acid cutting,
tanks providing for retention and reuse of wastewater from vacuum
ejectors or vacuum pump seals, and countercurrent rinses for dry
charged electrodes are also included in cost estimates. Additional
in-process control techniques applicable as BAT Option 1 for which no
specific costs are estimated or which are alternatives to the control
techniques chosen as a basis for cost estimates, are discussed in
Sections vn and X. A schematic of the system is provided in Figure
X-7 (Page 772). Total costs for implementation of this level of
control and treatment are presented in Table VII1-32 (Page 708 >.
BAT Option 2
This level of treatment and control involves replacement of lime
precipitation as included in BAT Level 1 with sulfide precipitation
and clarification as shown in Figure X-8 (Page 773). In-process
control techniques are identical to those included at BAT Option 1.
Assumptions in costing the end-of-pipe treatment components are those
discussed for the individual technologies. In-process control costs
are determined as for BAT Option 1. Total system costs are presented
in Table VII1-33 (Page 709).
BAT Option 3
636
-------
As shown in Figure X-9 (Page 774), the end-of-pipe treatment system
provided for this level of treatment and control is equivalent to that
provided for BAT Option 2 plus the provision of membrane filtration to
polish the effluent from sulfide precipitationclarification treatment.
In-process controls as specified for BAT Option 2 are augmented to
provide for the use of recirculated treated process wastewater in
rinsing open formation cathodes.
Cost estimates for this additional in-process control technique are
based on the calculation of line segregation costs as previously
presented to provide an estimate of typical costs of return piping
from waste treatment to positive plate rinsing. Total system costs
are presented in Table VIII-34 (Page 710 )•
BAT Option 4
In-process control techniques included at BAT Option 4 are identical
to those at BAT Option 3 but, as shown in Figure X-10 (Page 775), end
of pipe treatment is significantly changed. Process wastewater is
concentrated by reverse osmosis to reduce its volume prior to
treatment in the BAT Option 3 system. Permeate from the RO unit is
returned for process use, especially in dehydrated plate anode rinsing
where high quality water is required. Prior to reverse osmosis
treatment, the waste stream is pH adjusted and filtered to protect the
permeation modules.
Assumptions in costing end-of-pipe treatment components are those
presented in individual technology discussions. In-process control
costs are identical to those estimated for BAT Option 3. Total system
costs are presented in Table VIII-35 (Page 711 ).
Leclanche Subcategory - Only one option is considered for BAT for this
subcategory. This option is identical to BPT and achieves zero
discharge of process wastewater pollutants by the application of in-
pcess control technology. Cost estimates for the implementation of
this technology at Leclanche subcategory plants are presented in Table
VIII-3.3.
Lithium Subcateqorv - Cost estimates are provided for three al-
ternative levels of treatment and control presented for evaluation as
BAT.
BAT Option 1
This level of treatment is similar to that prescribed for BPT except
that discharge from settling is passed through a multimedia polishing
filter. The schematic for this system is provided in Figure X-ll
(Page 775). The filter backwash is returned to waste treatment.
Costs are provided in Table VIII-36 (Page 712 )•
637
-------
BAT Option 2
At this level of treatment and control (Figure X-12 (Page 77 7)) / BAT
Level 1 treatment is supplemented by 100 percent recycle of the heat
paper waste stream and chemical reduction is consequently eliminated.
Costs are provided in Table VIII-37 (Page 713).
BAT Option 3
At this level of treatment and control (Figure X-13 (Page 773)),
treatment identical to BAT Option 2 is provided, all of the wastewater
from S02 or thionyl chloride handling is recycled for process use
after treatment. Costs are identical to those for BAT Option 2 as
shown in Table VIII-37.
Magnesium Subcateoorv - Cost estimates are provided for three
alternative levels of treatment and control presented for evaluation
as BAT.
BAT Option 1
This level of treatment is similar to that prescribed for BPT except
that effluent from the BPT system is passed through a polishing
filter. The schematic for this system is provided in Figure X-14
(Page 779 ). Costs are provided in Table VIII-38 (Page 714 ).
BAT Option 2
At this level of treatment (Figure X-15 (Page 780)) and control the
treatment of BAT Option 1 is supplemented by recycle of 100 percent of
the heat paper waste stream to the process, and chrome reduction is
eliminated. Costs are provided in Table VIII-39 (Page 715 ).
BAT Option 3
This level of treatment is similar to that prescribed for BAT Option 2
except that photographic chemicals associated with the silver chloride
stream are separated from the effluent by a carbon adsorption system
prior to further treatment. A schematic is provided by Figure X-16
(Page 781 ) and costs are presented in Table VIII-40 (Page 716 J.
zinc Subcateoorv - Cost estimates are provided for three alternative
levels of treatment and control presented for evaluation as BAT.
BAT Option 1
This level of treatment and control combines end-of-pipe treatment as
specified for BPT with additional in-process control techniques to
reduce wastewater flow rates and pollutant loads discharged to
638
-------
treatment. In process controls include countercurrent rinsing of
amalgamated zinc, treatment and reuse of amalgamation area clean up,
reductions in rinse flow rates by using multi-stage and countercurrent
rinses on a variety of process operations, and use of dry clean-up
techniques for general plant floor areas. The schematic for the
system is shown in Figure X-17 (Page 782).
Cost estimates include provision of eight tanks, associated pumps and
piping to provide retention of rinse waters from wet amalgamation
operations allowing countercurrent rinsing in which water is used in
an earlier rinse stage on each batch of amalgam produced, and water
from only the first rinse is discharged to treatment. Treatment and
recycle costs for amalgamation area wash water are based on batch
treatment using ferrous sulfide and are discussed under sulfide
precipitation-clarification. Cost estimates are also provided for
countercurrent rinses as described in the general discussion of that
technology. No costs are estimated for dry clean up of general plant
floor areas. Total system costs are presented in Table VII1-41 (Page
717 ).
BAT Option 2
At this level of treatment and control, end-of-pipe treatment is
improved by replacement of the multimedia filter used for polishing
clarified effluent in BPT and BAT Option 1 with a membrane filter as
shown in Figure X-18 (Page 783). In process controls in addition to
those provided in BAT Option 1 are also included. Specifically, reuse
of treated wastewater for amalgamation equipment wash on wet
amalgamation operations, elimination of equipment and area wash waters
from other amalgamation processes, and selection of cell wash
formulations to eliminate chromium and cyanide from process effluents
are included.
Costs for reuse of treated wastewater for amalgamation equipment wash
are estimated based on provision of pumps and piping as discussed for
line segregation costs. No costs are estimated for elimination of
amalgamation wastewater (from other than wet amalgamation operations)
or for cell wash formulation substitution since these are observed in
present practice on a competitive basis. Assumptions in costing end-
of-pipe treatment components are discussed in general discussion for
each of the individual technologies involved. Total system costs are
presented in Table VIII-42 (Page 718 )•
BAT Option 3
This level of treatment and control provides for concentration of
process wastewater by reverse osmosis prior to treatment equivalent to
thin provided at BAT Option 1. As shown in Figure X-19 (Page 784 )
wastewater is treated by pH adjustment and filtration prior to RO.
639
-------
Permeate is recycled for use in the process. Additional in-process
controls are also provided to eliminate all wastewater from
amalgamation by substitution of a dry amalgamation process for wet
amalgamation where it is practiced.
Since dry and wet amalgamation are observed to be competitive
processes in the subcategory at present, no costs for process
substitution are estimated. Assumptions in costing end-of-pipe
components have been discussed in earlier sections. Total system cost
estimates are presented in Table VIII-43 (Page 719).
System Cost Estimates - (New Sources)
The suggested treatment alternatives for NSPS Levels 1 through 3 are
identical to the treatment alternatives for existing sources BAT
Levels 1 through 3. These costs were presented in Tables VII1-20
through VIII-43 (Pages 696—719).
Pretreatment System Cost Estimates
Three alternative levels of pretreatment presented for consideration
are identical to BPT and BAT Options 1 and 2 respectively. Cost
estimates for these levels of treatment and control have been
presented on the preceding pages. Rationale for selection of these
pretreatment technologies are discussed in Section XII.
Use of. Cost Estimation Results
Cost estimates presented in the tables in this section are
representative of costs typically incurred in implementing treatment
and control equivalent to the specified levels. They will not, in
general, correspond precisely to cost experience at any individual
plant. Specific plant conditions such as age, location, plant layout,
or present production and treatment practices may yield costs which
are either higher or lower than the presented costs. Because the
costs shown are total system costs and do not assume any treatment in
place, it is probable that most plants will require smaller
expenditures to reach the specified levels of control from their
present status.
The actual costs of installing and operating a BPT system at a
particular plant may be substantially lower than the tabulated values.
Reductions in investment and operating costs are possible in several
areas. Design and installation costs may be reduced by using plant
workers. Equipment costs may be reduced by using or modifying
existing equipment instead of purchasing all new equipment.
Application of an excess capacity factor, which increases the size of
most equipment foundation costs could be reduced if an existing
concrete pad or floor can be utilized. Equipment size requirements
640
-------
may be reduced by the ease of treatment (for example, shorter
retention time) of particular waste streams. Substantial reduction in
both investment and operating cost may be achieved if a plant reduces
its water use rate below that assumed in costing.
ENERGY AND NON-WATER QUALITY ASPECTS
Energy and non-water quality aspects of the wastewater treatment
technologies described in Section VII are summarized in Tables VII1-44
and VIII-45 (Pages 720 and 721 ). Energy requirements are listed, the
impact on environmental air and noise pollution is noted, and solid
waste generation characteristics are summarized. The treatment
processes are divided into two groups, wastewater treatment processes
on Table VII1-44 and sludge and solids handling processes on Table
VIII-45.
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. Electrical power and fuel requirements (coal, oil, or
gas) are listed in units of kilowatt hours per ton of dry solids for
sludge and solids handling. Specific energy uses are noted in the
"Remarks" column.
Energy requirements are generally low, although evaporation can be an
exception if no waste heat is available at the plant. Thus, if
evaporation is used to avoid discharge of pollutants, the influent
water rate should be minimized. For example, an upstream reverse
osmosis, ion exchange, or ultrafiltration unit can drastically reduce
the flow rate of wastewater to an evaporation device.
Non-Water Quality Aspects
It is important to consider the impact of each treatment process on
air, noise, and radiation pollution of the environment to preclude the
development of a more adverse environmental impact.
In general, 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 bag houses, scrubbers or stack gas precipitators as well as
proper incinerator operation and maintenance. Due to their high
content of volatile heavy metals, (eg. cadmium and mercury) sludges
from battery manufacturing wastewater treatment are not amenable to
incineration except in retorts for metals recovery. None of the
wastewater treatment processes causes objectionable noise and none of
641
-------
the treatment processes has any potential for radioactive radiation
hazards.
The solid waste impact of each wastewater treatment process is
indicated in two columns on Table VIII-4.1 and VIII-4.2. The first
column shows whether effluent solids are to be expected and, if so,
the solids content in qualitative terms. The second column lists
typical values of percent solids of sludge or residue.
The processes for treating the wastewaters from this category produce
considerable volumes of sludges. In order to ensure long-term
protection of the environment from harmful sludge constituents,
special consideration of disposal sites should be made by RCRA and
municipal authorities where applicable.
642
-------
FIGURE VIII-1
SIMPLIFIED LOGIC DIAGRAM
SYSTEM COST ESTIMATION PROGRAM
NON-RECYCLE
SYSTEMS
INPUT
A) RAW WASTE DESCRIPTION
B SYSTEM DESCRIPTION
C 'DECISION" PARAMETERS
D) COST FACTORS
PROCESS CALCULATIONS
A) PERFORMANCE - POLLUTANT
PARAMETER EFFECTS
B) EQUIPMENT SIZE
C) PROCESS COST
(RECYCLE SYSTEMS)
CONVERGENCE
A) POLLUTANT PARAMETER
TOLERANCE CHECK
(NOT WITHIN
TOLERANCE LIMITS)
(WITHIN TOLERANCE LIMITS)
COST CALCULATIONS
A) SUM INDIVIDUAL PROCESS
E) ADD SUBSIDIARY COSTS
C) ADJUST TO DESIRED DOLLAR
B^SE
OUTPUT
A) STREAM DESCRIPTIONS -
COMPLETE SYSTEM
B) INDIVIDUAL PROCESS SIZE
AND COSTS
C) OVERALL SYSTEM INVESTMENT
' AND ANNUAL COSTS
643
-------
Raw Waste
Flow
TSS
Pb
Zn
Acidity
Lime Flocculant
I
Chemical
Addition
Mixing
Clarifier
Effluent
Filtrate
Vacuum
Filter
Sludge Contractor Removed
FIGURE VIII-2
SIMPLE WASTJE TREATMENT SYSTEM
644
-------
10
100
10
100 10"
Flow Rate (1/hr)
FIGURE VII1-3
10"
ODenotes flow limits observed for
this treatment for the lead
subcategory
PREDICTED LIME PRECIPITATION/CLARIFICATION COSTS
CONTINUOUS
-------
en
in6
10 in'J
*
,-j
I
tfl
«
r-H
O
0
!«in4
o
o
in'
,
e-
~
" -
n
^^
, ^
^.
4
100 10
I'low Kdte ( I/hi )
FIGURE VII1-4
oUenotes Mow limit CO) observed Cor
this tredtmtMit in the battery
industry (non-leadsubcateqory).
Individual plants may differ because
of vjiiation in operating hours.
All coinputei selected treatment was
batch.
i'i
-------
800
700-
£ eoof-
2 500
o
.c
400
u
O
* 300
*x/
£ 200-
D1
t)
a 100
50 100 150 200 250
Flow Rate (1/hr)
300
350
400
FIGURE VIII-5
CHEMICAL PRECIPITATION/CLARIFICATION COSTS
647
-------
«
10
c
-------
10
10
100
Flow Rate (1/hr)
FIGURE VIII-7
10
10
o Denotes flow limits for this treatment
in the battery category.
MEMBRANE FILTRATION COSTS
-------
10'
o>
c
nj i
O 10
I
01
O
Q
o> w
01 O
O O
clO
e
4J
in
0)
10
3.785
i\
^
X
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VIII-8
REVERSE OSMOSIS INVESTMENT COSTS
-------
104
u
(0
0)
>i
^103
0
JC.
at
4-1
c
-------
tn
ro
in0
Material And Supply Costs (Dollars - Jan, 78)
1— • »— • HI
O O O
ui «k i_n
/
/
,
^
^
/
!/
{
/
/
/
f
/
f
1
H
/
V
j
/
t
—f
r
r
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VI11-10
RRVFRSE OSMOSIS MATERIAL COSTS
-------
10
-. 100
cu
DC
•o
o>
CT
Oi «
CO
01
o
D*
10
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
37U500
FIGURE VIII-H
REVERSE OSMOSIS POWER REQUIREMENTS
-------
in
10
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VIII-12
VACUUM FILTRATION INVESTMENT COSTS
-------
o>
en
01
100
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VII1-13
VACUUM FILTRATION f.ADOR REQUIREMENTS
-------
en
Cfl
10
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VIII-14
VACUUM FILTRATION MATRRIAL COSTS
-------
10'
co
c
n)
i 10
CO
O
Q
in
*J
ui
Sio4
o
o>
i-H
u
^
10
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VIII-15
VACUUM FILTRATION ELECTRIAL COSTS
-------
8S9
Investment Costs (Dollars - Jan, 78)
h- )_• »— *-
O 0 O C
^o ui ^
^x
x
<^
/
'
X"
^
^x*
_^~
^^
/
'
'
X
X
^x
^
^
x^
x
X
X
^
^x*'
^x^
•^
x*^^
x^
X
X*
X"
xX^
/
X"
X*
X
E
2 120 1200 12000 120000 1200000
Volume (liters)
r>x-»c-»- /I 1 QT X W.-.1 l.m.-. / 1 j *.n^r. \ " • J Jfl"
FIGURE VIII-16
Retention Time = 12 Hours
HOLDING TANK INVESTMENT COSTS
-------
105
699
ral Costs (Dollars - Jan, 78)
-* •- .
=> 0
UJ ^
Electric
i- i
0 '
H- 0
X
„
X"
x1
X
X
i^M
x*"
^M
t
^
• 1
«
.,.-— ^
x^
=-^
x
*^
X*
^
X*
ri
x
?*
^X"
, ^^
x
.X"
jr
/
68 1680 16,800 168,000 1,680,000
Volume (liters)
Retention Time =
>
r
^
?
'
j
1
16,800,000
7 Days
FIGURE VIII-17
HOLDING TANK ELECTRICAL COSTS
-------
i-
O
hours/year
VJ
en O
en -Q
o
-------
10'
CD
1^
C
10
•->
ars
o
Q
(/)
-P
w
o
U
-U
c
<0
4J
en
(U
>
c
•-
o
100
10
100 10
Flow Rate (1/hr)
FIGURE VIII-19
NEUTRALIZATION INVESTMENT COSTS
10"
10-
o Denotes flow limit (^0) observed for
this treatment in the non-lead
subcategories of the battery industry.
Individual plants may differ because of
variation in operating costs.
-------
CT>
ro
10
M
CO
01
>. 10'
in
I*
D
O
x:
M
O
A
(0
vJ
•a
a>
M
g. 10
ai
ac.
X"
1.785
X"
X
z:
z:
x
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VIII-20
NKUTRALIZATION LABOR REQUIREMENTS
-------
en
CO
10
oo
I
in
10'
o
Q
U
O
0
10J
10
100
Flow Rate (1/hr)
1000
FIGURE VIII-21
CARBON ADSORPTION COSTS
-------
CM
01
CO
C
at
1-3
in
u
o
Q
4J
V)
O
u
V)
IV
t>
C
3.785
37.85
378.5 3785
Flow Rate (1/hr)
37850
378500
FIGURE VIII-22
CHEMICAL REDUCTION OF CHROMIUM
INVESTMENT COSTS
-------
hours/year
99
Labor
m
3
C
C
en
n"
no
10
3.
Min
imu
n C
lor
it
i
1U
5us Prc
• >
ces
/
s ^
/
la
/
X
ir
,
X
t
'
^
e
/
-
i
'
'
a
t
t
nee
— —f-
jf
jf
X
/
X
/
X
/
I/
x
/
r
^
I
/
•*
><
e
V. j^
^ >r
^ X
L/
— ?
^X"^
xrJ^
f
>
> >
/
x
X
C
x
0°
^
-7^-
s
f
f - •"
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r'
r>^'
\vv -P"
o^ix^r i
k^T
v\
—X
1
>-
-ce
V
r
^
i
^
L^
*
>»
^
785 37.85 378.5 3785 37850 378
Flow Rate (1/hr)
FIGURE VIII-23
Batch maintenance equals 0 hours
ANNUAL LABOR FOR CHEMICAL REDUCTION OF CHROMIUM
-------
10'
X
c
-------
CT>
10
co a
r- 10*
c
m
i
«J
i-i
•-H
o
Q
4J
W ?
0103
100
1
/
J
f
f
'
/
/
A
'
/
f
*
/
,
/
J
J
J
r
/
/
/
/
s
'
/
— /* — !
X
^
Ob 106 107 10
Battery Production (pounds/year)
FIGURE VIII-25
LABOR FOR COUNTERCURRENT RINSES DEHYDRATED BATTERIES
-------
00
100
Total Lead Used In Batteries (kg/hr)
FIGURE VIII-26
IN-PROCESS PIPING AND SEGREGATION COSTS FOR THE LEAD SUBCATEGORY
-------
J.U
00 -»
•*• io3
C
1
in
CPi •"•
(f> <-t
vo o
Q
8 100
u
10
X'
X
1
s
X
r~
X
X
^
/
?
+
*
\
]
J
^
X
10
X
X
x-
X
X
X
^
'
^
,
X
.
1
^\
-
-------
10'
c
id
I
in
o
Q
SlO4
o
o
10-
>
10 100 1000 10000
Total Lead Used In Wet or Damp Batteries (kg/hr)
FIGURE VII1-28
IN-PROCESS COSTING FOR SLOW CHARGING BATTERIES LEAD SUBCATEGORY
-------
x
Jan
ars
Costs (Do
*-
o
•*>•
x
x
nvestmen
•X
XA
x^
3
X
10 15 20 30 40 50 60 70 80 85
Cumulative Percentage Of Plants
90
95
98
BPT
BAT 1
BAT 2 and BAT 3
Median
$ 5910
$10700
$16800
Average N
$ 8250 3
$13400 8
$21300 8
FIGURE VIII-29
IN-PROCESS INVESTMENT COSTS CADMIUM SUBCATEGORY
671
-------
10
- 1C
OB
C
<9
-i
Tx*
X
ID
3
100
10 15 20 30 40 50 60 70 ^ I 90
Cumulative Percentage Of Plants
9
9"
Median Average N
O BPT $ 1990 S 2510 3
A BAT 1 $ 2630 $ 3250 8
• BAT 2 and BAT 3 $ 3980 $ 5050 8
FIGURE VIII-30
IN-PROCESS ANNUAL COSTS CADMIUM SUBCATEGOR*
672
-------
1 vestment Costs (Dollars - .Ian, 78)
£ (^ ^ <-
0 0 o 0
..° Ul ^ 01
y
^
f
/
/
/
T
/
/
f
/
/
/
/
/
/
S
^
^"
1
I
^~
5 10 15 20 30 40 50 60 70 30 B5 90 95 98
Cumulative Percentage Of Plants
Median S 99,000
Average $129.600
N ' 124
FIGURE VIII-31
IN-PROCESS COSTS LEAD SUBCATE30RY
673
-------
S ic4
c
13
-3
1
M
b
H
I
V)
4J
n
O
U
*f*
it
*10>
100
^/
••*'
/
/
/
/
/
/
/
/
>
/
/
/
/
/
/
/
/
^
/
/
f
S
_^~
X"
1
^^^
> 10 15 20 30 40 50 60 70 80 65 90 95 9
Cumulative Percentage Of Plants
Median S18700
Average $27100
N 124
FIGURE VIII-32
IN-PROCESS COSTS LEAD SUBCATEGORY
674
-------
10 20 30 40 50 60 70 80 90 95
Cumulative Percentage Of Plants
98
Median Average N
BPT $ 1900 $ 4870 8
BAT 1 $18000 $21500 13
BAT 2 and BAT 3 $21COO $22100 13
FIGURE VII1-33
IN-PROCESS INVESTMENT COSTS ZINC SUBCATEGORY
675
-------
12
o
o
o
X
«
<0
o
Q
W
o
u
C
c
10 20 30 40 50 60 70 80 90
Cumulative Percentage Of Plants
95
98
BPT
BAT 1
BAT 2 AND BAT 3
Median
$ 400
$3700
$4500
Average N
$ 1600 8
$ 4500 13
$ 4700 13
FIGURE VIII-34
IN-PROCESS ANNUAL COSTS ZINC SUBCATEGORY
676
-------
TABLE VIII-1
COST PROGRAM POLLUTANT PARAMETERS
Parameter, Units
Flow, MGD
pH,. pH units
Turbidity, Jackson Units
Temperature, degree C
Dissolved Oxygen, mg/1
Residual Chlorine, mg/1
Acidity, mg/1 CaCO..
Alkalinity, mg/1 CaCO.,
Ammonia, mg/1 J
Biochemical Oxygen Demand mg/1
Color, Chloroplatinate units
Sulfide, mg/1
Cyanides, mg/1
Kjeldahl Nitrogen, mg/1
Phenols, mg/1
Conductance, micromhos/cm
Total Solids, mg/1
Total Suspended Solids, mg/1
Settleable Solids, mg/1
Aluminum, mg/1
Barium, mg/1
Cadmium, mg/1
Calcium, mg/1
Chromium, Total, mg/1
Copper, mg/1
Fluoride, mg/1
Iron, Total, mg/1
Lead, mg/1
Magnesium, mg/1
Molybdenum, mg/1
Total Volatile Solids, mg/1
Parameter, Units
Oil, Grease, mg/1
Hardness, mg/1 CaCO,
Chemical Oxygen Demand, mg/1
Algicides, mg/1
Total Phosphates, mg/1
Polychlorobiphenyls, mg/1
Potassium, mg/1
Silica, mg/1
Sodium, mg/1
Sulfate, mg/1
Sulfite, mg/1
Titanium, mg/1
Zinc, mg/1
Arsenic, mg/1
Boron, mg/1
Iron, Dissolved, mg/1
Mercury, mg/1
Nickel, mg/1
Nitrate, mg/1
Selenium, mg/1
Silver, mg/1
Strontium, mg/1
Surfactants, mg/1
Beryllium, mg/1
Plasticizers, mg/1
Antimony, mg/1
Bromide, mg/1
Cobalt, mg/1
Thallium, mg/1
Tin, mg/1
Chromium, Hexavalent, mg/1
677
-------
TABLE VII1-2
TREATMENT TECHNOLOGY SUBROUTINES
Treatment Process Subroutines Presently Available
Spray/Fog Rinse
Countercurrent Rinse
Vacuum Filtration
Gravity Thickening
Sludge Drying Beds
Holding Tanks
Centrifugation
Equalization
Contractor Removal
Reverse Osmosis
Chemical Reduction of Chrom.
Chemical Oxidation of Cyanide
Neutralization
Clarification (Settling Tank/Tube Settler)
API Oil Skimming
Emulsion Breaking (Chem/Thermal)
Membrane Filtration
Filtration (Diatoraaceous Earth)
Ion Exchange - w/?lant Regeneration
Ion Exchange - Service Regeneration
Flash Evaporation
Climbing Film Evaporation
Atmospheric Evaporation
Cyclic Ion Exchange
Posu Aeration
Sludge Pumping
Copper Cementation
Sanitary Sewer Discharge Fee
Ultrafiltration
Submerged Tube Evaporation
Flotation/Separation
Wiped Film Evaporation
Trickling Filter
Activated Carbon Adsorption
Nickel Filter
Sulfide Precipitation
Sand Filter
Pressure Filter
Multimedia Granular Filter
Sump
Cooling Tower
Ozonation
Activated Sludge
Coalescing Oil Separator
rfen Contact Cooling Basin
Raw Wastewater Pumping
Preliminary Treatment
Preliminary Sedimentation
Aerator - Final Settler
Chlorination
Flotation Thickening
Multiple Hearth Incineration
Aerobic Digestion
Lime Precipitation (metals)
Treatment Process Subroutines Currently Being Developed
Peroxide Oxidation
Air Stripping (Ammonia Removal)
Arsenic Removal
Fluoride Removal (Lime Addition)
678
-------
TABLE VIII-3
WASTE WATER SAMPLING FREQUENCY
Waste Water Discharge
(liters Per day) Sampling Frequency
0 - 37,850 once per month
37,850 - 189,250 twice per month
189,250 - 378,500 once per week
378,500 - 946,250 twice per week
946,250+ thrice per week
679
-------
TABLE
VIII-2.4
VIII-2.5
VIII-2.6
VIII-2.7
VIII-2.8
VIII-2.9
VIII-2.10
VIII-2.11
VIII-2.12
VIII-2.13
VIII-2.14
VIII-2.15
TABLE VII1-4
INDEX TO TECHNOLOGY COST TABLES
WASTE TREATMENT TECHNOLOGY
Hydroxide Precipitation And Settling
Sulfide Precipitation And Settling; Batch Treatment
Sulfide Precipitation And Settling; Continuous Treatment
Multimedia Filtration
Membrane Filtration
Reverse Osmosis
Vacuum Filtration
Holding And Settling Tanks
pH Adjustment
Aeration
Carbon Adsorption
Chrome Reduction
680
-------
TABLE VIII-5
Lime Additions for Lime Precipitation
Stream Parameter Lime Addition
kg/kg (Ibs/lb)
Acidity (as CaCCO 0.81
Aluminum 4.53
Antimony 1.75
Arsenic 2.84
Cadmium 2.73
Chromium 2.35
Cobalt 1.38
Copper 1.28
Iron (Dissolved) 2.19
Lead 0.205
Magnesium 3.50
Manganese 1.48
Mercury 0.42
Nickel 1.45
Selenium 3.23
Silver 0.39
Zinc 1.25
681
-------
TABLE VIII-6
Reagent Additions for Sulfide Precipitation
Stream Parameter
(Hexavalent)
(Trivalent)
Cadmium
Calcium
Chromium
Chromium
Cobalt
Copper
Lead
Mercury
Nickel
Silver
Tin
Zinc
Sodium Bisulfide Requirement
Ferrous Sulfate Requirement
Lime Requirement
Ferrous Sulfide Requirement
kg/kg (Ibs/lb)
0.86
2.41
1.86
2.28
1.64
1.52
0.47
0.24
1.65
0.45
0.81
1.48
0.65 x Ferrous Fulfide Requirement
1.5 x Ferrous Sulfide Requirement
0.49 x FeSO.dbs) + 3.96 x NaHS(lbs!
+ 2.19 x Ibs of Dissolved Iron
682
-------
TABLE VIII-7
NEUTRALIZATION CHEMICALS REQUIRED
Chemical Condition A
"mL " '"'" ~ "'""" -T- nil. ........ . ©
Lime pH less than 6.5 .00014
Sulfuric Acid pH greater than 8.5 .00016
(Chemical demand, Ibs/day) = Ao x Flow Rate (GPH) x Acidity
(Alkalinity, mgCaCC>3/l)
683
-------
TABLE VIII-8
WATER TREAT>
-------
TABLE VIII-9
WATER TREATMENT COMPONENT COSTS
Process: SULFIDE PRECIPITATION AMD SETTLING
Least cost:
system flew rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating i Maintenance
costs (excluding energy!
Er.erqv costs
BATCH
234
27:
82^
.031
BATCH
95
600
61(11
383
610
2438
6529
13800
1949
3106
3351
10:
Total annual costs:
S 1430
5 3484
S 8513
685
-------
TABLE VI11-10
WATER TREATMENT COMPONENT COSTS
Process: SULFIDE PRECIPITATION' AND SETTLING
Least cost
Systen flew rate: 1/hr
gal/day
Ir.vest.Tent:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Enersv costs
CONTINUOUS
5677
24000
26820
1683
2682
6615
4.88
CONTINUOUS CCNTrrUCUS
10740 15240
45400 122000
32300 3903C
2027 2i^9
3230 3903
9780 20231
8.84 22.36
Total annual costs:
$ 10980
$15050
S2671C
686
-------
TABLE VIII-11
WATER TREATMENT COMPONENT COSTS
Process:
MULTIMEDIA FILTRATION
Least cost:
System flew rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciacion
Operating « Maintenance
costs (excluding energy)
Energy coses
CONTINUOUS
4
8
261
16
26
6065
284
CONTINUOUS
5195
10980
21470
1247
2147
6065
284
CONTINUOUS
17348
110000
44800
2S11
443C
6065
284
Total annual costs:
S 6291
S 9843
687
-------
TABLE VII1-12
WATER TREATMENT COMPONENT COSTS
Process:
MEMBRANE FILTRATION
Least cost:
yszaTi flew rate; 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating i Maintenance
costs (excluding energy)
Enercy costs
CONTINUOUS
26
112
367
23
37
3128
1650
CONTINUOUS
38C
2412
5280
321
527
3300
2610
CONTINUOUS
1223
7755
16970
1C65
1597
3406
2694
Total annual coses:
3 4838
S 6769
3862
688
-------
TABLE VIII-13
WATER TREATMENT COMPONENT COSTS
Process;
REVERSE OSMOSIS
Least cost:
System flow race: 1/hr
gal/day
InvestTient:
Annua costs:
Depreciation
Operating v '•'.-'. i.--V:-2'V.viC'2
•nscs (>*
-------
TABLE VIII-14
WATER TREATMENT COMPONENT COSTS
Process: VACUUM FILTRATION
Least cost:
System flow rate: l./nr
gal/day
Investment:
Annual costs:
Capital coses
Depreciation
Operating i Maintenance
costs (excluding energy)
Energy costs
CONTIGUOUS CONTINUOUS
25 168
106 210
25220 25220
1582 15S2
2522 2522
3990 5179
0 0
CONTINUOUS
326
1377
25220
1532
2522
5940
0
Total ar.rual costs:
5 8094
S 9233
S 10C4Q
690
-------
TABLE VIII-15
TREATMENT COMPONENT COSTS
Process: HOLDING AND SETTLING TANKS
Least cost
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital ccs-s
Depreciation
Operating & Maintenance
costs (excluding energy)
Enerov costs
CONTINUOUS
4
8
700
44
70
0
50
CONTINUOUS CONTINUOUS
151 3406
640 7200
1130 3592
74 225
113 359
0 0
107 75
Total annual costs:
S 164
$ 300
$ 560
691
-------
TABLE VIII-16
WATER TREATMENT COMPONENT COSTS
Process:
pK ADJUSTMENT
Least exist:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital cests
Depreciation
Operating & Maintenance
costs (excluding energy)
Enerov costs
CONTINUOUS
4
8
106
7
11
11
.008
CONTINUOUS
261
552
891
56
39
120
0.536
CONTINUOUS
526?
33400
4144
26C
414
1190
34
Total annual costs:
S 29
265
139$
692
-------
TABLE VII1-17
WATER TREATMENT COMPONENT COSTS
Process: AERATION
Least cost
System flew rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Er.ercv cos ts
CONTINUOUS
53
223
800
50
30
0
101
CONTINUOUS
466
984
1191
75
119
0
52
Total aanual costs: S 231 $ 245
693
-------
TABLE VIII-18
WATER TREATMENT COMPONENT COSTS
Process:
CARBON ADSORPTION
Least cost:
System flow rate: l./hr
gal/day
Annual costs:
Capital coses
Decree! acion
Operating & Maintenance
costs (excluding energy)
Snercy costs
45
192
14630
913
1463
491
0.88
466
984
26190
1643
2613
1767
4.49
Total annual costs:
$ 2873
$ 5033
694
-------
TABLE VII1-19
TREATMENT COMPONENT COSTS
Process:
Least cost:
System flow rate: l./hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Enersv costs
CHSOME REDUCTION
BATCH
26
56
7853
423
785
108
SATCH
61
129
3355
335
16
103
BATCH
3406
7200
19970
1997
391
103
Total annual costs:
S 1393
1479
$ 4244
695
-------
TABLE VII1-20
WATER EFFLUENT TREATMENT COSTS
CADMIUM SUBCATEGORY
Treatment level: 3PT
Least cost:
Systen flow rate: 1/hr
gal/day
Ir.ves tr".ent:
.-r.r.ual costs:
Capital costs
Depreciation
Operating i Maintenance
costs (excluding energy}
Er.erry costs
Total annual costs:
Ien~3 cer couna
Batch
202.7
860.8
14070
883
1407
3074
2.5
Batch
1576.8
9996
27880
1749
2788
7739
40
Batch
12167
51424
1C18CO
6390
101SO
9545
200
S 5367
ZI.o
S 12320
12.3
S 2632C
5.26
696
-------
TABLE VIII-21
WATER EFFLUENT TREATMENT COSTS
CALCIUM SUBCATEGORY
Treatment level:
Least cost:
System £lcw rate: l./hr
gal/day
Investment:
Annual cos~s:
Capital ccsts
Depreciation
Operating a Mainzsnar.ee
costs (excluding energy)
Energy costs
B?T
Total annual coses:
Cents cec sound
BATCH
25.5
56
23434
1470
2343
1963
161
BATCH
60.7
128
25520
1601
2551
1951
155
$ 5938
36.38
$ 6258 s
20.86
697
-------
TABLE VIII-22
WATER EFFLUENT TREATMENT COSTS
LEAD SUBCATEGORY
Treatment level:
Least cost:
5yste:n flew rate: 1/hr
gal/day
Inves treat:
Annual costs:
Capital ccsts
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
Cents oer oound
BPT
Batch Batch
3.8 3634
8 23040
24801 87235
1556 5473
2480 8723
1942 9835
0 92
Batch
6624
420CO
313493
21367
2C665
9846
548
3 5972 $ 2413C
1.07 0.215
$ 52^30
0.635
698
-------
TABLE VIII-23
WATER EFFLUENT TREATMENT COSTS
LECLANCKE SUBCATEGORY
Treatment level:
Least cost:
BPT
System flew rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating i Maintenance
•costs (excluding energy)
Energy costs
local anr.uai costs:
cents oer cocna
BATCH
.484
1
120
8
1 2
181
0
BATCH
143.8
608
1906
119
191
3502
25
BATCH
306.5
12S6
17283
ICC A
1728
10278
187
J 201
S 3837
S 13277
6.7
.011
.153
699
-------
TABLE VII1-24
WATER EFFLUENT TREATMENT COSTS
LITHIUM SU3CATEGORY
Treatment level:
Least cost:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating i Maintenance
costs (excluding energy)
Enersv costs
3PT
Total annual costs:
Cents oer pound
BATCH BATCH
3.79 151
8 320
4015 5698
252 358
401 570
1096 1300
100 216
BATCH
145.7
308
28601
1795
2S6G
2C51
156
$ 1850 $2443
5.99
$6801
22.37
700
-------
TABLE VIII-25
WATER EFF1UES7 TREATMENT COSTS
MAGNESIuM SUSCAIECCRY
Treatment level:
Least cost:
SPT
flow rate: l.'>.ir
gal/day
Annual costs:
Capital coses
Depreciation
Operating i Maintenance
costs (excluding energy)
Energv costs
Total an.njjal costs
Cents oer ocund
BATCH
54.5
230.4
2C9C8
1312
2091
4529
202
S 3134
12.33
SATCK
666
1408
28272
1774
2827
2482
108
S 7191
11.22
BATCH
5224
11040
85196
5346
S520
7563
275
- ,:8ri.
109.02
701
-------
TABLE VIII-26
WATER EFFLUENT TREATMENT COSTS
ZINC SU3CATEGORY
Treatment le«/.;l: BPT
Least cost:
System flow rate: 1/hr
gal/day
Invest: neat:
Annual cos:-.s:
C^Ual costs
Depreciation
Ope racing .; Maintenance
costs {.f
-------
TABLE VIH-27
WATSR EFFLUENT TREATMENT COSTS
CADMIUM SUBCATECOP.Y
Treatment level:
Least cost:
BAT-1
System £l
-------
TABLE VII1-28
WATER EFFLUENT T5ZATMENT COSTS
CADMIUM SU3CATEGORY
Treatment level: 8AT-2
Least: cost:
System flew rate: 1/hr
gal/day
Investment:
Annual ccsts:
Capital ccsts
Depreciation
Operating i Maintenance
costs (excluding energy)
Eneray costs
Total annual costs:
Cents 09 r cound
BATCH
98.3
416
22690
1422
2269
3642
25.1
:7358
BATCH BATCH
481.9 5385.7
3055 11384
50070 121850
3142 76^6
5007 12185
9988 12230
347 897
$18483 $32950
29.4
18.5
704
-------
TABLE VIII-29
WATER EFFLUENT TREATMENT COSTS
CADMIUM SUBCATEGORY
Treatment level: BAT-3
Least cost:
Syster. flew rate: 1/hr
gal/day
Investment:
Annual costs:
~-2o[-:al costs
Depreciation
•Operating * Maincenance
i:;>3b3 {.^x.rl.iding energy)
Enerr-- cosb3
BATCH
53.2
224
38320
2405
3831
10873
863
BATCH
419.8
2664
95580
3997
9558
13120
1407
BATCH
4272
9024
165500
1C290
16550
15770
1648
117970
S30CSO
$44353
Cents aer pound
71.9
30.1
8.37
705
-------
TABLE VII1-30
WATER EFFLUENT TREATMENT COSTS
CALCIUM SUBCATEGORY
Treatment level: BAT'l
Least cost-.
System 'low ?a.t«: l/'hr
gal/day
Investment:
Annual costs:
Capital cost.?
Depreci-i'cio--i
Operating « M-aLTia-Tance
costs (excluding energy)
Energy coses
Total annual costs:
Cents per pound
BATCH
26.5
56
24721
1551
2472
8028
445
BATCH
60.7
128
27627
1723
2763
8016
439
; 12500
77.62
S 12950 $
43.17
706
-------
TABLE VIII-31
WATER EFFLUENT TREATMENT COSTS
CALCIUM SU3CATSGORY
Treatment level: BAT-2
Least cost:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Tctal annual costs:
Cents oer sound
BATCH
26.5
56
4412
277
441
1048
106
BATCH
60.7
128
4751
300
47S
1109
102
S1922
11.94
S 1990
6.63
707
-------
TABLE VIII-32
WATER EFFLUENT TREATMENT COSTS
LEAD SI'S CATEGORY
Treafcnent level: 3AT-1
Least cost:
System flow rate: l/lir
gal/day
Investment:
Ar.ruaJ. cos':^:
r.^oitai costs
Depreciation
Operating i Maintenance
costs {5,
-------
TABLE VIII-33
WATER EFFLUENT TREATTCNT COSTS
LEAD SUBCATEGORY
Treatment level: BAT-2
Least cost:
System flow rate: 1,/hr
gal/day
Annual costs:
Capital COSLS
Depreciation
Operating * Maintenance
cost.-; (excluding energy)
Energy costs
Total annual costs;
.er.ts oer ocunc
Continuous
2097
4432
11560
811
462
1397
152
Batch
8733
55370
78280
4342
7828
25842
495
Batch
3558
19140
491300
32715
21763
6949
490
12822
$ 385C7
S 61920
C.513
709
-------
TABLE VIII-34
WATER EFFLUENT TREATMENT COSTS
LEAD SUBCATECCRY
Trsatrent level
Least cost:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital ccsts
Depreciation
Operating i Maintenance
ccsts (excluding energy)
Enernv costs
Total annual costs:
lents oer ccunc
CONTINUOUS
2082
4400
11560
811
462
1397
152
CONTINUOUS
26.5
168
80950
4425
7238
8007
2126
BATCH
3250
14160
565900
394SO
29490
9464
2108
5 2S22
S 21SCC
S 76COO
0.513
.771
.124
710
-------
TABLE VIII-35
WATER EFFLUENT TREATMENT COSTS
LEAD SUBCATEGORY
Treatment level;
Least cost
3AT-4
Svste.T. flew rate: i/hr
gal/day
Invest-iient:
Annual costs:
Capital costs
Depreciation
Cperating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
oer rcur.a
CONTINUOUS
2082
4400
11560
811
Continuous BATCH
25.4 1692
107 7152
94019 650000
5825 44830
«62 9116 33477
10128
0
19430 26100
47C 2715
i 11401
S 34852 S10710C
2.07
1 31
.175
711
-------
TABLE VII1-36
WATER EFFLUENT TREATMENT COSTS
LITHIUM SUBCATEGORY
Treatment level: BAT-1
Least cost:
Systam flew rata: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating s Maintenance
costs (excluding energy)
Enersv costs
Total annual costs:
Cents oer sound
BATCH
3.79
8
4015
252
401
1096
100
*• * C 5 A
3-S30
5.99
BATCH BATCH
151 145.7
320 308
5698 32157
358 2018
570 3215
1300 8115
216 440
$2443 S 13790
45.97
712
-------
TABLE VIII-37
WATER EFFLUENT TREATMENT COSTS
LITHIUM SU3CATEGCRY
a IT>. i
Treatment level: OA~ *
Least cost:
Systsm flow rate: 1/hr
gal/day
Investnient:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
_ocai 5~-r.ua— c
Cents cer ocund
BATCH
3.79
3
4015
252
401
1096
100
BATCH
151
320
5698
358
570
1300
216
BATCH
145.7
308
18652
1170
1865
806S
387
5 1850
S 2443
S 11491
5.99
33.30
713
-------
TABLE VIII-38
WATER EFFLUENT TREATMENT COSTS
MAGNESIUM SUBCATEGORY
Treatment level:
Least cost:
System flow rate: 1/b.r
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating i Maintenance
costs (excluding energy)
Energy costs
BAT-1
BATCH BATCH.
54.5 666
BATCH
5224
* i C4Q
22S4Q 37371
115729
1436
2289
10594
84
2345
3737
8553
392
262
115
14086
559
Tocal annual costs:
Cents oer ccund
5 148C6
22.27
$ 150
23.44
S 33451
167.41
714
-------
TABLE VII1-39
WATER EFFLUENT TREATMENT COSTS
MAGNESIUM SUBCATEGORY
Treatment level;
Least cost:
BAT-2
System flow rste: lA
gal/day
Investment:
Depreciation
Operating a Maintenance
costs (excluding energy]
Energy costs
Total annual costs:
Cents cer ocund
BATCH
54.5
23C.4
22890
1436
2239
10594
486
BATCH
666
14 OS
37371
2345
3737
8553
392
BATCH
5224
11C4Q
58591
3676
3S59
11075
378
3 14306
22.27
S 15027
23.44
3 20990
104.95
715
-------
TABLE VIII-40
WATER EFFLUENT TREATMENT COSTS
MAGNESIUM SUBCATECORY
Treatment laveI:
Least cost;
SAT- 3
System flo* rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
Cents oec oound
BATCH
54.5
230.4
43457
2727
4346
11078
386
BATCH
666
1408
61907
3884
6191
11076
453
BATCH
5224
11C40
73784
4630
7378
1C284
345
3 18537
27.38
$ 21604
108.02
S 22637
35.32
716
-------
TABLE VIII-41
WATER EFFLUENT TREATMENT COSTS
ZINC SUBCATEGCRY
Treatment level:
Least cost:
BAT-1
System flow rate: 1/hr
gal/cay
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual coses:
Cents oer oocna
BATCH
227.1
1200
15846
994
1535
9122
288
BATCH
30.7
130
34638
2173
3464 .
9875
338
BATCH
447.4
1391
72570
4553
7257
11253
539
3 11989
0.25
5 159CO
3.18
602
1.30
717
-------
TABLE VIII-42
WATER EFFLUENT TREATMENT COSTS
ZINC SUBCATEGORY
System flew rat
Treatment level: BAT-2
Least cost:
1/hr
gal/day
Investment:
Annual CASKS:
"ioical :?:>scs
Depreciation
Operating & Maintenance
costs (excluding energy)
Enercy costs
Total annual costs:
Cents oer
BATCH
224.8
949
20593
1242
2060
6358
1744
BATCH CONTIGUOUS .
382.9 447.4
3400 1891
42279 81843
2652 5136
4228 RiP.A
8221 innrn
2690 107=
S 11450
$17791 $25370
0.239
.116
1.4
718
-------
TABLE VIII-43
WATER EFFLUENT TREATMENT COSTS
ZINC SUBCATEGORY
Treatment level:
Least cost:
BAT-3
Systsm flow rate: 1/hr
gal/day
Investment:
Annual ccsts:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy ccsts
Total annual costs:
Cents oer oound
BATCH
70.3
446
20343
1275
2035
1232
358
CONTINUOUS
110.5
700
45930
2882
4593
16740
1067
CONTINUOUS
1227.5
7783
112400
7054
11240
20610
1964
; 49CO
S 25280
$ 4C880
.0463
.661
719
-------
MIMAIIIN
TABLE VI I I -4 4
ASI1JT.; (» HA.VIT MATCH THHMMITW
INJ
O
tiiutus
Oicmicdl kiMiict ion
!ikininiiK|
Clur if ifdlloii
I'lotdtion
Clu-niicjl
OxKl.itioii fly Oilorine
Oxiiljtion By t>/one
Oi«.fliical H"ecl|t|tdt ion
StxtiiiMMitdt l*m
IH*|> lied
l«xi L'xdidncjt;
Msuipt i MKI Ml MIS
Kwer Y\i<;\
kwli
1000 liters
1.0
0.01-.1
O.I-J.2 --
1.0
0. J
O.'j-VO
1.02
O.l-i.2
0.10
0.5
0.1
•2.5
J.O
1.25-J.O
1.25-J.O
0.2-0.0
2.0
HiLiqy
Minii.j
Sk IIIWI.T lit ive
Uluil>je Pol lec-
tor Di ive
Kccirculdt ion
l\iii|i, C°4«t>iebsor,
Skim
Ml X 11*1
Mixiitj
(^/»IH: (it-fierdtion
Klncitilut ion
Simile O>llu< tot
l>i i i-e
Ik-jcl, IlickwdSll
|MII( fti
Ilin^t, LVd|»rdte
t ion
tVdiAMdte Wdler
Ilioli I're&tiiiie
nnif )
Miijii I'li-bbuie
\\u
II i. lli 1'iebi.ine
IM,,,.
H._-jrt il lei . l\un>
Kfjonei dl ion.
'•"'"i;
M»MATMI OIAI.ITV
Air N>ise
KJ! Union ll>l lul Um
ln»«t-l l!Kr«ct
H>ne Nune
Nunc Nune
lijne time
Nune Nune
M M le N >nc
Hune Nune
None N nie
Ume. Possible Hone
II..S tvolut ion
H»ie Nune
M.ine M»t
Hxif M.t
Oijci-'t loiulile
Nune M.mc
NiMie N^me
IMI'ACT
Solid
Waste
Nx»-
Conivntrated
Omirntrdtcd
OxKvntrated
xw
M.">*H;
t^jricentrdted
Cuncvntraled
Concvntrated
*„*
Njne/Hsute Cjrlxm
CoiiLViit idled/
Dilute
Concentrate
Dl lute
C'muvnlrale
Dilute
(\>ntt:ntrale
C»in.vntrdted
Mine
Sol id Haste
Concent i at ion
» Ihy Solids
5-50 (oil)
1-10
J-5
1-10
1-J
Variable
N/A
40
SO- 100
1-40
1-40
1 40
1-J
• 10" UTU/IOOO liters
-------
TABLE VIII-45
NUMATLK OIM.1TV *SfU~K, Of SUAiGL AND SOI.IUR
rwctss
Sludcjo
Iliickciiiny
Mressure
ft Iti at ion
Sand Bed
Oryimj
Vacuum
Kilter
Cent rifuyat ion
UimUill
togooniiKj
BWIIGY KUJUIMJItNIS
RKA.-I Kiel tlicrijy
kwti hull Ifcc
ton dry solids ton dry solids
2V-9JO SkiiuMM,
Sluiltjtf Kak«-
Uiive
21 lli^li Pressure
I\U{X>
35 Hei««dl
U)lll|IllOMl
16.7- Vacuum Kun>.
66. B liotdiioii
0.2- Nutation
9B.5
20-9UO Haul, Lanti-
fil! 1-10
Mile Tri|>
36 Meiioval
MM4A'n:i< cini-ii'y WPACT
Air Noise- Solid
K>llulion Killution Woste
liiftact Infvicl
MJIK.- Noric Concentrated
None Uane Dewatercd
None M.xie Cuwalercd
None Nut Dewatered
Objectionable
NJI* Nut Uewalered
t»)ject ioridhle
None Njne Lewatered
None None Oewatered
Sol id Waste
Concentration
% Dry Sol ids
4-27
25-50
15-40
20-40
15-50
N/A
3-5
-------
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
[Introductory Note - This section presents the strategy and technical
methodology for BPT. Further discussion and the development of
regulatory values will be included at proposal]
This section describes the best practicable control technology cur-
rently available (BPT) for each subcategory within the battery man-
ufacturing category. BPT reflects existing treatment and control
practices at battery manufacturing plants of various sizes, ages/ and
manufacturing processes. Particular consideration is given to the
treatment in-place at plants within each subcategory.
The factors considered in defining BPT include the total cost of
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 best existing practices at plants of various
ages, sizes, processes or other common characteristics. Where
existing practice is uniformaly 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, indeed, transferrable and a reasonable prediction that
it will be capable of achieving the prescribed effluent limits. (See
Tanner's Council of America V. Train Supra). BPT focuses on end-of-
pipe treatment rather than process changes or internal controls,
except where such are common industry practices.
TECHNICAL APPROACH TO BPT
The category was studied and previous effluent guideline development
work was examined to identify the processes used, wastewater
generated, and treatment practices employed by battery manufacturing
operations. After preliminary subcategorization and additional
information collection using both dcp forms and specific plant
sampling and analysis, the total information about the category was
examined. On the basis of that examination, the subcategorization was
revised as described in Section IV to reflect anode material and
electrolyte. Discrete process elements shown in Table IV-1 (Page 90 )
were identified to serve as the basis for effluent limitations and
standards. The collectedsinformation was then examined to determine
what constituted an appropriate BPT. Some of the salient
considerations are:
723
-------
o Each subcategory encompasses a number of different process
operations (elements) which can generate wastewater. These may be
combined in many different ways in battery manufacturing
facilities.
o Wastewater streams from different operations within each
subcategory are often treated in combined systems, and are usually
similar in treatment requirements.
o The most significant pollutants in process wastewater from
different subcategories are generally different. Combined
treatment or discharge of wastewater from different subcategories
occurs quite infrequently.
o Most wastewater streams generated in this category are
characterized by high levels of toxic metals (including cadmium,
mercury, and lead).
o Treatment practices vary among different subcategories. Observed
practices include: chemical precipitation of metals as hydroxide,
carbonate, and sulfides; amalgamation; sedimentation; filtration;
ion exchange; and carbon adsorption.
Some of the factors outlined above which must be considered in
establishing effluent limitations based on BPT have already been
addressed by this document. The age of equipment and facilities
involved and the processes employed were taken into account in
subcategorization and are discussed fully in Section IV. Nonwater
quality impacts and energy requirements are considered in Section
VIII.
The battery manufacturing category comprises seven subcategories each
of which includes a number of different process operations which
generate wastewater. Based on the considerations presented above, a
general approach to BPT was defined in which all process waste streams
within a subcategory are subjected to treatment in a single (common)
treatment system. Since the different waste streams do not differ
significantly in treatability, the treatment technology performance or
attainable effluent concentrations from treatment do not depend on the
relative contribution of each wastewater source. This fact allows the
development of uniform effluent limitations applicable to all of the
manufacturing process variations encountered in each subcategory.
This is accomplished by the strategy of providing mass discharge
allowances for each process element within the subcategory based on
the pollutant concentrations attainable from the combined subcategory
treatment system and wastewater flow allowances for each individual
process element.
724
-------
BPT for all subcategories must provide for removal of metals and
suspended solids. This requires chemical precipitation and sedi-
mentation (and, in some cases, polishing filtration). However,
optimum conditions and treatment chemicals differ for wastewater
streams from different subcategories. A reasonable degree of in
process water flow control is also found in BPT for all subcategories.
This is defined by the median flow observed in present practice for
each process element. Consequently, it was determined that a
different BPT is appropriate to each subcategory.
Finally, treatment was determined to be uniformaly inadequate in some
subcategories. As a result, BPT is based on transfer of technologies
in some cases, although the transfer may only involve proper
maintenance and operation of technologies presently in place within
the subcategory.
Specific factors must be considered and unique technical approaches
must be defined for each subcategory. These are addressed together
with the identified BPT for each subcategory in the ensuing sections.
Specific Regulation of_ Priority Pollutants
Final selection of priority pollutants will be based on raw wastewater
concentration levels and technical judgement factors covered in
Section X. Limitations will be based on treatment levels covered in
Section-VII and median flows for each process element presented in
Section V.
CADMIUM SUBCATEGORY
In defining BPT for the cadmium subcategory the information collected
to characterize process wastewater and present treatment practices was
carefully reviewed. The results of this review indicated that
treatment technologies presently applied at many plants in the sub-
category are suitable for consideration as BPT. However, many
existing treatment facilities are observed to be inadequately de-
signed, maintained, and operated. Few in-process control techniques
are widely applied in this subcategory. Consequently, BPT consists
primarily of end-of-pipe treatment.
Wastewater generated by plants in the cadmium subcategory contains
significant quantities of cadmium, nickel, silver, and suspended
solids. Cadmium is discharged from anode processing operations
whereas nickel, nickel and cadmium, or silver may be used in cathode
manufacture. As shown in Section V, essentially all streams contain
toxic metals, and none are observed to contain pollutants requiring
separate treatment except for silver powder production which will be
regulated the same as silver powder production in the zinc
subcategory.
725
-------
The pollutant concentrations discharged from these treatment systems
are observed to vary widely and to frequently exceed those listed in
Table VII-11 as attainable by application of chemical precipitation
and sedimentation technology. On-site observations at plants in this
subcategory indicate that this may be attributed to variable and
generally poor control over treatment conditions, especially for
suspended solids removal. Often "settling" is observed to be
performed in sumps or holding tanks with limited retention times,
sporadic removal of suspended solids, and little or no flow control or
use of settlig aids. Control of treatment pH is also frequently
questionable.
On the basis of the foregoing discussion, the approach to BPT for this
subcategory is to provide a single combined treatment system for all
process wastewater streams generated (except silver cathodes) within
this subcategory. No waste segregation or preliminary treatment of
individual waste streams is required, and BPT is limited to treatment
technologies presently practiced at a number of plants in the subcate-
gory.
BPT includes some water conservation measures presently demonstrated
by most plants practicing each process operation.
In-process control technologies considered to constitute BPT include:
Recycle or reuse of process solutions used for material
deposition and electrode formation.
Segregation of non-contact cooling and heating water from
process wastewater streams.
Control of electrolyte drips and spills and elimination or
recycle of electrolyte equipment wash.
Use of dry or water efficient floor cleaning procedures.
Dry clean-up of equipment and floor areas in pasted, pocket
or pressed powder cadmium anode production or recycle of
equipment and floor wash water.
Identification of BPT
End-of-pipe treatment included in BPT for the cadmium subcategory is
presented in Figure IX-1 (Page 733). The treatment system consists
of pH adjustment followed by settling. Lime, sodium hydroxide, or
acid is used to adjust the pH to a level that permits adequate
precipitation. The optimum pH for precipitation of metals from
cadmium subcategory waste streams is typically about 9.3; however,
higher values may prove to be appropriate for some waste streams in
726
-------
this subcategory due to the presence of high concentrations of cadmium
and nickel. If proper pH control is practiced, the settling of both
metal precipitates and suspended solids will be enhanced. Treatment
system performance for some wastewater streams in this subcategory may
be significantly enhanced by the addition of iron salts as an aid to
the removal of metals, particularly nickel. Where required for
acceptable effluent performance, this technique is included in BPT.
An effective settling device for use in the BPT system is a clarifier;
however similar results can be accomplished by using other settling
devices or filtration. In some cases, provision of an oil skimmer may
also be required to achieve acceptable effluent quality.
The effectiveness of end-of-pipe technology for the removal of
wastewater pollutants is enhanced by the application of water flow
controls within the process to limit the volume of wastewater re-
quiring treatment and the pollutants requiring removal. Those con-
trols which are included in BPT are generally applied in the sub-
category at the present time, and do not require any significant
modification of the manufacturing process or process equipment for
their implementation.
CALCIUM SUBCATEGORY
A careful review of collected information characterizing process
wastewater and present treatment practices in the calcium subcategory
indicates that treatment and control practices are universally
inadequate insofar as they do not provide for the reduction of
hexavalent chromium or the precipitation of toxic metals prior to
discharge. However, there are at present no plants which directly
discharge process wastewater from this subcatgory.
The construction of calcium anode thermal cells generates two distinct
wastewater streams which differ in their treatment requirements.
The presence of hexavalent chromium, asbestos, and significant
quantities of suspended solids in the heat paper production waste
stream makes separate treatment of this waste prior to mixing with the
wastewater from cell leak testing highly desirable. No in-process
control technologies are reported to be employed at these facilities.
On the basis of the foregoing discussion, the approach to BPT for this
subcategory is to first provide for segregation of the heat paper
process wastewater for reduction of hexavalent chromium, and
subsequently to provide combined treatment of both waste streams for
the removal of metals. Because most of the pollutants present in the
heat paper process wastes (including the hexavalent chromium) are
present in the form of particiilate solids, removal of these materials
by settling prior to the reduction of hexavalent chromium is appro-
priate. Because the existing technology within the subcategory is
727
-------
inadequate, BPT is based
industrial categories.
Identification of BPT
on the transfer of technology from other
A schematic diagram of the end-of-pipe treatment included in BPT for
the calcium subcategory is presented in Figure IX-2 (Page 739 ). The
wastewater from heat paper production is first settled to remove
undissolved constituents including zirconium metal, asbestos, and
barium chromate. After settling, chemical reduction is provided to
convert the remaining hexavalent chromium in the waste stream to the
trivalent form which may be effectively removed by precipitation as
the hydroxide.
Following reduction of the chromium, the wastewater is combined with
wastewater from cell leak testing. The combined stream is treated
with lime to precipitate metals and enhance the removal of suspended
solids, and is then clarified by settling. Either a clarifier or
settling tank may be used, or clarification may be achieved by
alternative techniques such as filtration.
The sludge which accumulates during settling must be removed to ensure
continued effective operation of the settling device. A vacuum filter
is provided 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 by chemical
precipitation and settling.
No in-process control techniques beyond reasonable control of process
water use as presently practiced in the subcategory are included in
BPT.
LEAD SUBCATEGORY
The identification of BPT for the lead subcategory is based on a
careful review of collected information characterizing process
wastewater, present treatment practices, and present manufacturing
practice. On the basis of this review, it has been concluded that the
removal of metals is the primary requirement in treating lead
subcategory process wastewater. This may be achieved by chemical
precipitation and sedimentation technologies similar to those
presently employed at some lead subcategory plants. Unfortunately,
these existing treatment facilities in the subcategory were found to
be improperly designed, maintained, or operated. In this subcategory,
some in-process control techniques which significantly reduce
pollutant discharge are commonly practiced and are consequently
included in BPT.
728
-------
Wastewater from plants in the lead subcategory is characterized by
significant concentrations of both lead and suspended solids in
addition to smaller concentrations of other metals and oil and grease.
The most frequently reported end-of-pipe treatment systems in this
subcategory involve pH adjustment and removal of solids. In addition
to end-of-pipe treatment, in-process controls contribute significantly
to pollutant discharge reduction at many facilities. The recycle of
wastewater from pasting operations is particularly effective.
The approach to BPT for the lead subcategory incorporates in-process
and end-of-pipe technology. Wastewaters from pasting operations, and
spent formation acid are collected separately for reuse (and treatment
where required for recycle). The remaining process waste streams are
combined for end-of-pipe treatment by chemical precipitation and
sedimentation technology. Because this technology is ineffectivly
practiced within the lead subcategory at this time, transfer of the
technology of proper maintenance and operation from other industrial
categories is required.
Identification of BPT
Treatment included in BPT for the lead subcategory is shown in Figure
IX-3 (Page 740 ). The system includes:
1) Collection and reuse of spent formation acid.
2) Elimination of process wastewater discharge from paste
preparation and application by collection, settling, and
reuse.
3) Treatment of all other process wastewater by chemical
precipitation and sedimentation.
The reuse of formation acid, which is common practice among the lead
subcategory plants, is conducted by limiting spillage and implementing
effective acid collection techniques during postformation 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.
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 sold to a smelter for recovery of lead. After settling, the
wastewater can be either used in paste formulation or pasting area
floor and equipment wash-down.
729
-------
In the end-of-pipe treatment system for the lead subcategory, caustic,
sodium carbonate, or lime is added to a pH of 8.8-9.3 to precipitate
lead and any other heavy metals that may be present. In some cases,
the addition of sodium carbonate may be required to assist the
effective precipitation of lead. A clarifier is the recommended
settling device. However, comparable effluent concentrations can be
achieved in tanks or lagoons, or by filtration. The resulting sludge
should be sent to metal recovery or to a secure landfill.
LECLANCHE SUBCATEGORY
To define BPT for the Leclanche subcategory, the information collected
to characterize manufacturing practices, wastewater sources and
present treatment and control practices was carefully reviewed. The
results of this review indicated that zero discharge is common
practice within the subcategory at the present time, and that
discharges which presently occur may be eliminated without significant
process change by techniques commonly used within the subcategory.
Consequently, BPT for this subcategory is to eliminate process
wastewater discharge by implementation of in-process treatment and
controls.
Process wastewater is generated infrequently at plants in this
subcategory, and where it is generated, it is sometimes reused or
collected for contract disposal. The wastewater is characterized by
significant levels of mercury and zinc as well as TSS, manganese, and
oil and grease.
Most plants in the subcategory employ manufacturing processes which
generate no process wastewater. At these sites, equipment and
production area maintenance are accomplished by dry techniques. Some
facilities generate wastewater by washing production equipment and
floor areas.
Production equipment which is washed is usually the equipment used to
prepare and handle paste separator materials or electrolyte.
Contaminants in the resulting waste streams are normal constituents of
the paste or electrolyte.
Water is used in some plants to clean the cathode- and anode-making
equipment. The resultant wastewater contains electrode materials in
the form of suspended solids and may contain oil and grease derived
from process machinery lubricants.
Wastewater from paste setting comes from a hot water bath in which the
water contacts only the outside of product cells. The water is
contaminated only as a result of process malfunctions. Discharge, as
described in Section V, is observed to be a matter of operating
convenience rather than technical necessity.
730
-------
On the basis of the foregoing discussion, the approach to BPT for this
subcategory is to eliminate sources of process wastewater by
implementing alternative operating and maintenance procedures, or by
recycling process wastewater. Recycling will generally involve the
segregation of process wastewater from individual operations and may
require treatment to provide acceptable quality for reuse.
Lithium Subcateqory
The identification of BPT for the lithium subcategory is based on a
careful review of the information collected to characterize process
wastewater and present treatment practices. Individual process waste
streams generated in this subcategory may require different treatments
and therefore must be segregated for separate treatment prior to or in
place of combined waste treatment. Present treatment practices within
the subcategory are uniformly inadequate. Consequently, BPT for this
subcategory does not provide for combined treatment of all wastewater
streams and is based on transfer of technology from other industrial
categories.
Wastewater sources identified in the dcp's and follow-up surveys for
this subcategory include depolarizer preparation, lithium scrap
disposal, heat paper production, cell wash, cell leak testing, and
employee clean-up. The characteristics of wastewater from some of
these process operations are distinctly different because of the raw
materials used. In this subcategory several battery types are
manufactured, and the several different wastewater streams are not all
associated with one battery type.
The approach to BPT for this subcategory is to provide separate
treatments for wastewaters from heat paper manufacture elements, and
wastewaters from the production of cells with thionyl chloride and
sulfur dioxide depolarizers. The heat paper manufacturing wastewater
requires treatment as described for the calcium subcategory for the
removal of TSS and reduction of hexavalent chromium. The wastewaters
from thionyl chloride and sulfur dioxide depolarizer handling are
treated to neutralize acidity, reduce the oxygen demand, and remove
TSS. Where they are present together, these individual wastewater
streams can be combined with all other wastewaters after the
prescribed preliminary treatment. Treatment of combined wastewaters
includes chemical precipitation (lime) followed by settling and
skimming. Sludge is dried on a vacuum filter and contractor hauled to
a secure landfill.
Identification of_ BPT
End-of-pipe treatment identified as BPT for the lithium subcategory is
presented in Figure IX-4 (Page 741 ). There are three distinct treat-
ment systems for BPT to treat three separate groupings of wastewater
731
-------
streams generated by this subcategory. Most lithium cell manu-
facturers do not conduct processes which produce waste streams
assigned to all three groups.
The treatment of heat paper waste as shown in Figure IX-4 has
previously been described in the calcium subcategory. Metals
precipitation treatment is provided in combination with other waste
streams as discussed below.
The waste streams associated with the second grouping result from (1)
lead iodide depolarizer production, (2) iron disulfide depolarizer
production, (3) lithium scrap disposal, (4) cell wash operations, and
(5) cell leak testing. The pollutants in this grouping include lead,
iron, lithium, oil and grease, and suspended solids. Once these waste
streams are combined with the partially treated wastewater from heat
paper production, trivalent chromium will become an additional
pollutant with various trace contaminants from the heat paper process.
The first step in treatment of the combined waste streams is chemical
precipitation using lime followed by settling to remove solids. Other
reagents including sodium hydroxide, sodium carbonate, or sodium
sulfide may be used to achieve similar results if optimum pH
conditions are maintained. The recommended settling device is a
clarifier with an oil skimming unit for removal of any oil and grease
which may be present in the waste stream.
The settled solids are removed from the clarifier, and dewatered in a
vacuum filtration unit. The sludge filter cake is disposed of by
contractor hauling to secure landfill. Oil and grease removed by the
skimming mechanism on the clarifier is contractor hauled. The liquid
filtrate from the vacuum filter is recycled back to the treatment
system to undergo further treatment.
The third grouping involves waste streams from manufacturing both
sulfur dioxide and thionyl chloride depolarizer materials. Initially
the wastewater is aerated. This step will reduce the oxygen demand of
the wastewater. Sulfuric acid will be formed by oxidation of
sulfurous acid. When thionyl chloride is used in the production
process, hydrochloric acid will be formed in addition to the sulfuric
acid. In either case, the low pH wastewater is neutralized using
sodium hydroxide prior to discharge. If lime is used to neutralize
the waste stream, precipitates of calcium sulfate and calcium oxide
may be present.
Because of the possibility of the formation of precipitates, the
neutralized waste stream is passed through a clarifier prior to
discharge. The clarifier will also remove any miscellaneous suspended
solids contained in the waste streams. Settled solids removed from
the clarifier will be removed by contractor hauling to secure
landfill.
732
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MAGNESIUM SUBCATEGORY
To define BPT for the magnesium subcategory, the information collected
to characterize process wastewater and present treatment practices was
carefully reviewed. Wastewater from different process elements within
the subcategory differed substantially in treatment requirements.
Present treatment practices within the subcategory are uniformly in-
adequate. Consequently BPT provides separate treatment for segregated
waste streams and is based in part on technology transferred from
other subcategories.
The processes generating wastewater in this subcategory include
depolarizer production, separator processing, heat paper production,
and ancillary operations such as cell washing and process area
maintenance. The raw materials used in the subcategory process
operations vary greatly, which results in distinct waste streams
requiring different specific treatments. In this subcategory several
battery types are manufactured, and the several different wastewater
streams are not all associated with one battery type.
Only two depolarizer manufacturing processes presently conducted in
the subcategory discharge wastewater. One facility manufactures cells
under dry conditions with vanadium pentoxide as the depolarizer.
Wastewater is generated from fume scrubbers associated with the
dehumidifier system. The pollutants in the scrubber wastewater may
include vanadium pentoxide and lithium chloride. Silver chloride
depolarizer material is presently produced using three separate
techniques. Two of these techniques generate process wastewater.
One facility makes separators by a process which generates wastewater.
Silica glass beads are chemically etched in an ammonium fluoride
solution. The resulting wastewater from the etching operation
contains both ammonium fluoride and silica particulates.
Pollutant loadings from ancillary operations may include oil and
grease, carbon, miscellaneous suspended solids, and various metals
found in trace quantities.
The approach to BPT for this subcategory is to provide separate
treatment of wastewater streams from some process operations for
specific pollutants followed by combined treatment of all wastewater
from this subcategory at a given facility for the removal of metals
and suspended solids. The wastewater from heat paper production, as
described for the calcium subcategory must be initially treated to
remove TSS and reduce hexavalent chromium. Wastewater bearing
ammonium fluoride require initial treatment for fluoride removal and
subsequent aeration together with wastewaters bearing organics from
silver chloride cathode surface treatment processes. Because present
treatment practice in the subcategory is limited and inadequate,
733
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technology transferred from other industrial categories constitutes
BPT for these wastes.
Identification of BPT
The end-of-pipe treatment included in BPT for the magnesium
subcategory is presented in Figure IX-5 (Page 742 ). Four separate
treatment schemes have been developed to handle wastewater from
specific process operations. Three of these systems are used to treat
wastewater from three separate process operations whereas the fourth
removes pollutants from the combined wastewater from a variety of
ancillary operations and certain depolarizer preparation processes.
The fourth system can be tied to any of the other three systems if any
of those systems are required by a given manufacturing facility.
The first system treats wastewater from separator preparation which
contains ammonium fluoride and silica particulates. The removal of
these pollutants is accomplished in a multi-stage treatment process.
In the first treatment operation, fluoride ion is removed from the
wastewater by chemical precipitation using lime followed by
clarification using settling. The optimum pH for precipitation of the
fluoride is 12. The fluoride dissolved in the wastewater will
precipitate from solution as calcium fluoride. The ammonia will
remain in solution and is subsequently treated by aeration to strip
the ammonia into the air. The calcium fluoride precipitate and silica
particulates settle out of the wastewater in a clarifier or settling
tank. The settled sludge is removed from the clarifier as required,
and dewatered in a vacuum filtration unit. The resulting sludge
filter cake is contractor hauled to secure landfill.
The second treatment system handles wastewater from the depolarizer
preparation process which subjects the silver chloride to an organic
photographic developer solution. The resulting product is silver
chloride with a metallic silver coating. The processed material is
subsequently rinsed and the rinse wastewater is combined with the
spent photo developer wastewater stream for treatment. Both of these
wastewater streams have similar pollutant parameters. The approach
for treating both of these waste streams is to discharge the
concentrated organic bath to a holding tank and slowly bleed the tank
contents into the rinse wastewater. This practice equalizes the
pollutant loads and wastewater concentrations flowing to treatment.
It thereby allows effective treatment system operation. In order to
reduce the oxygen demand presented by these organic-laden waste
streams, the wastewater is aerated. The wastewater generated from
heat paper production is treated by the third system which is
identical to the treatment described for this waste stream in the
calcium subcategory.
734
-------
All other wastewater streams are treated as combined wastewaters by
adjusting the pH to precipitate metals, settling in a clarifier
(equipped with an oil skimmer if necessary), and drying the sludge on
a vacuum filter. Where segregated wastewaters are treated in the same
manufacturing facility, some of the treatment steps can be carried out
in the same equipment for more than one stream.
ZINC SUBCATEGORY
A careful review of the information collected to characterize process
wastewater and present treatment practices in the zinc subcategory
indicates that all of the individual process element waste streams
produced can be effectively treated by the same technologies.
Appropriate treatment technologies are presently practiced within the
subcategory, but they are not found to be properly operated and
maintained at the present time. Few plants in the subcategory
practice in-process water use controls.
Wastewater from plants in the zinc subcategory is predominantly
alkaline as a result of contamination with alkaline electrolytes used
in the cells and in electrode processing. The primary pollutants
resulting from anode manufacturing processes are zinc and mercury.
Pollutants resulting from cathode processes presently used to produce
zinc subcategory cells include silver, nickel, manganese, and mercury.
In addition, oil and grease and suspended solids are frequently
present at substantial concentrations.
Sulfide precipitation, when properly implemented, provides effective
removal of most metals including mercury, silver, and zinc. But
sulfide precipitation systems observed in this subcategory were not
efficiently operated. Amalgamation removes only mercury and, in fact,
increases aluminum or zinc concentrations in the wastewater. Mercury
removal by amalgamation is observed to be less effective than that
achieved by other techniques. Ion exchange and carbon adsorption are
both capable of removing a variety of dissolved metals to very low
concentrations depending upon the amount of resin or carbon and
contact time provided. Mercury effluent concentrations from carbon
adsorption units in this subcategory are highly variable. Adjustment
of pH and solids removal also provides removal of toxic metals,
although effluent levels attainable by this technique are not as low
as those reached by sulfide precipitation.
On the basis of these considerations, the approach to BPT for this
subcategory is to provide combined treatment for all process
wastewater for the removal of metals and TSS. Chemical precipitation-
sedimentation-filtration technology presently employed within the
subcategory is appropriate as a basis for BPT. However, because of
the limitations observed in the present implementation of these
technologies within the subcategory, present practice is deemed
735
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uniformly inadequate, and transfer of proper operation and maintenance
from other industrial categories is required. BPT includes only water
conservation measures presently demonstrated by most plants practicing
each process operation within the subcategory. These may be
implemented without any significant change to process equipment or
practices.
Identification of. BPT
End-of-pipe treatment included in BPT for the zinc subcategory is
presented in Figure IX-6 (Page 743). The treatment system consists of
pH adjustment, sulfide precipitation, and solids removal by settling
in a clarifier and polishing filtration. Lime, sodium hydroxide or
sulfuric acid is used to adjust the pH to a level that permits
adequate precipitation.
Sulfide precipitation is used based on the fact that mercury sulfide
is twelve orders of magnitude less soluble than mercury hydroxide, and
lower effluent mercury concentrations are achieved by sulfide
precipitation. The reagent used may be either sodium sulfide or iron
disulfide. If iron disulfide is used, the iron precipitates as iron
hydroxide and is removed with the mercury sulfide. The concentration
of iron resulting from the use of iron disulfide in sulfide
precipitation will not exceed acceptable levels if proper pH control
and solids removal are practiced. After treatment with sulfide, other
settling devices or filtration could be used as alternatives to the
clarifier.
The final filter is a polishing step for the clarifier effluent.
Alternatively, a second clarification stage may be used or, for some
plants, the polishing step may prove unnecessary to achieve acceptable
treatment levels. The polishing filter which will generally be of
mixed media or granular bed construction operated by either pressure
or gravity flow.
In addition to end-of-pipe technology for the removal of wastewater
pollutants, BPT includes the application of controls within the
process to limit the volume of wastewater requiring treatment. Those
controls which are included in BPT are generally applied in the
subcategory at the present time, and do not require any significant
modification of the manufacturing process, process equipment or
product for their implementation. They are discussed in detail in
Section VII.
In-process control technologies considered to constitute BPT include:
Recycle or reuse of process solutions used for material
deposition, electrode formation, and cell washing.
736
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Segregation of non-contact cooling and heating water from
process wastewater streams.
Control of electrolyte drips and spills and elimination or
recycle of electrolyte equipment wash.
Elimination of equipment wash water discharge by reuse or
substitution of dry cleaning techniques.
Control of process water use in rinsing to correspond to
production requirements.
As discussed in Section VII, a large number of in-process control
techniques could be used in addition to the water use controls
specifically identified as BPT. Many of these, including multistage
and countercurrent rinses, are presently practiced at plants in this
subcategory.
737
-------
All Wastewater
pH
Adjustment
Filtrate
Sedimentation
^Sludge
Vacuua
Filter
Discharge
Sludge Hauled
to
00
In-Process Technology:
Recycle or reuse of process solutions
Segregation of non-contact cooling water from process water
Control electrolyte drips and spills
Use dry methods to clean floors
Use dry method to clean equipment
FIGURE IX-1
CADMIUM SUBCATEGORY
BPT TREATMENT
-------
Heat Paper
Production Wastewater
Cell Testing
Wastevater
t
Sludge Hauled
Settle
Hexavalent
Chromium
Reduction
co
vo
Filtrate
Chemical
Precipitation
(Lime)
Sludge
Vacuum
Filter
Sedimentation
Sludge Hauled
Discharge
FIGURE IX-2
CALCIUM SUBCATEGORY
BPT TREATMENT
-------
Paste Fotwulation
And Application
Are* Washdoim Water
Multistage
Settling
Recycle or
Reuse
Solids Ib Paste Formulation
Other Waste
Wastewater
pH Adjustment
Sedimentation
Filtrate
Vacua*
Filter
Discharge
Sludge Hauled
In-Process Technology.' Spent for not ion acid is reused
Pasting operation w*stewaters are recycled or reused
FIGURE IX-3
LEAD SUBCATEGORY
BPT TREATMENT
-------
Heat Paper Production
WdStewater
II
Other Waste
WdStewater
12
Tttlonyl Chloride
Sulfur Dioilde Uastewater
13
Sludge Hauled
Alternate
Filtrate
Chemical
Precipitation
Settle
-+- Sludge HauUd
Discharge
Plltrat
Sludge
VACUUM
Filter
Sludge
Sludge Hauled oiecharge
FIGURE IX-4
LITHIUM SUBCATEGORV
BPT TREATMENT
-------
Separator Process
Wastexater
flltrrte
INJ
Silver Chloride Cathode
Surface Treatment!
Ua&tcMaler
Baths Klnses
Chemical
Precipitation
of fluoride
(line To pH 12)
Filtrate
Filtrate
Sludye
Hauled
Sludge Hauled
Sludge
Discharge
Filtrate
FIGURE IX-5
MAGNESIUM SIIBCATBGOUY
BPT TREATMENT
-------
Backwash
All Wastewater After
In-Process Mater
Reduction
-P.
CO
pH Adjustment
Filtrate
I
Sulfide
Precipitation
And
Sedimentation
Filtration
Discharge
Sludge
Vacuum
Filter
Sludge
'Hauled
In-Process Technology: Ruuse of process solutions
in rroce« *t Segregation of non-contact cooling water
Segregation of organic-bearing cell cleaning waste water
.Control electrolyte drips and spills
Eliminate equipment wash water discharge
Flow controls for rinse waters
FIGURE IX-6
ZINC SUBCATEGORY
BPT TREATMENT
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
[Introductory Note - This section presents the strategy and technical
methodology for BAT. Further discussion and the development of
regulatory values will be included at proposal]
The factors considered in assessing the best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the processes employed, process changes, nonwater
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 uniformly
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.
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 and evaluate the available possibilities to ensure that the
most effective and beneficial technologies were used as the basis for
BAT. 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 are available and applicable to the battery
manufacturing subcategories, and to suggest technology trains which
would make substantial progress toward prevention of environmental
pollution above and beyond progress to be achieved by BPT.
In general, three levels of BAT were evaluated for each subcategory.
The BAT options considered build on BPT (as described in Section IX),
generally providing improved in-process control and end-of-pipe
treatment. For two subcategories, BAT options provide for zero
discharge of process wastewater pollutants from all process elements.
Other subcategory BAT options provide reduced pollutant discharge by
reducing both the volume of process wastewater and the concentrations
of pollutants, and may include the elimination of wastewater discharge
from specific process elements.
745
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In-Process Control Technology
In-process control technologies included in BAT options were selected
based on existing practice within each subcategory or within the
battery manufacturing category. Most of the BAT options presented
emphasize control of water use and in-process controls contributing to
effective water use. These include wastewater segregation,
countercurrent rinses, wastewater recycle and reuse, and flow rate
controls, in addition to process modifications which are specific to
each subcategory. In-process controls which are common to several
subcategories are described briefly below. More complete discussions
of each have been provided in Section VII.
Waste Segregation - The separation of wastewater streams of distinctly
different characteristics is necessary to achieve effective wastewater
treatment, recycle or reuse. The segregation of process wastewater
from non-contact cooling water is assumed in all BAT options for all
subcategories and is essential for the achievement of BAT performance
levels. In addition, segregation of specific process wastewater
streams to allow recycle or reuse is specified for most subcategories.
In some cases, specific wastewater streams are also segregated for
separate treatment. Some degree of wastewater segregation is
presently practiced by most battery manufacturing plants.
Countercurrent Rinses - Countercurrent rinses, while not common
practice in the battery manufacturing category, are encountered at a
number of plants in several subcategories.
Wastewater Recycle and Reuse - The recycle of process wastewater to
the manufacturing process is an effective means of reducing the volume
of process wastewater discharge. Processes in which wastewater
recycle is common include wet air pollution control scrubbers and
processes where water is used for the physical removal of solid
materials (as in lead subcategory electrode pasting for example).
Flow Rate Control - The means of achieving flow rate control include
manual valves, automatic shut-off valves, and proportional valves
controlled by conductivity, pH, or liquid level sensors.
End-Of-Pipe Treatment Technology
End-of-pipe treatment is provided for the removal of toxic metals by
chemical precipitation and of suspended solids (including metal
precipitates) by sedimentation and filtration. Different BAT options
for each subcategory provide different chemical precipitation or
solids removal techniques. For several subcategories, one BAT option
uses reverse osmosis technology to significantly reduce the volume of
process wastewater which must be treated to remove metals and TSS
before discharge.
746
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Specific technologies and approaches to BAT are unique to each
subcategory and are considered in the following discussions.
CADMIUM SUBCATEGORY
Four technology options are presented for consideration as BAT for the
cadmium subcategory. The first three build upon BPT and represent
incremental improvements in pollutant discharge reduction from that
technology level. The fourth, based on a system recently implemented
at one cadmium subcategory plant, provides zero discharge of process
wastewater pollutants.
BAT Option One
The end-of-pipe treatment system selected for BAT-1 is diagrammed in
Figure X-l (Page 766 ). This system is very similar to that described
as BPT, with the addition of sulfide precipitation to improve the
removal of dissolved heavy metals. The wastewater is first treated
with lime, sodium hydroxide or sulfuric acid to adjust the pH to
approximately 10.0. Addition of sodium sulfide or iron sulfide then
follows for the precipitation of heavy metals. A clarifier is used to
remove suspended solids by settling. Sludge from the clarifier is
processed through a vacuum filter. The dewatered sludge is disposed
of by a licensed contractor and the vacuum filtrate is returned to the
chemical precipitation tank.
Adjustment of the pH to <10 ensures that effective precipitation will
be achieved with minimum excess sulfide addition and minimizes the
release of hydrogen sulfide. Sulfide precipitation is used because of
the significantly lower solubility of metallic sulfides as compared
with metallic hydroxides. At the same time, any metal which does not
readily precipitate as a sulfide will precipitate as the hydroxide
because of the alkaline pH.
In-process controls included in BAT option 1 include:
Control of rinse flow rates to correspond with production
requirements.
Recirculation of wastewater from wet air scrubber.
Use of dry cleaning techniques to remove excess deposited
material from impregnated electrodes; or recirculation of
water used in wet cleaning.
Reduction of water use in cell washing.
Countercurrent rinsing of silver powder produced for use in
battery manufacturing.
747
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Control of. Rinse Flow Rates - The control of rinse flow is important
in many process elements within the cadmium subcategory. Flows equal
to or less than those reported in dcp's for wastewater discharged from
process rinses associated with anode electrodeposition, anode
impregnation, nickel cathode electrodeposition and nickel cathode
impregnation are attainable by implementation of rinse flow control at
all sites. This can be achieved through the use of automatic shut-off
valves which close water supply lines when the process is not running,
and manual adjustment of rinse flow rates when production rates vary.
Recirculation of_ Wet Scrubber Wastewater - Wet scrubbers are used in
this subcategory to control emissions from electrodeposition,
impregnation, and cadmium powder production processes. Because
contaminants in the scrubber discharges are dilute, the water can be
recirculated through the scrubber. This may require the addition of
an alkali to the scrubber stream to neutralize collected acid fumes.
Wastewater discharge may be reduced by a factor of 1000 or more by
this technique.
Cleaning of_ Impregnated Electrodes - Both wet and dry cleaning
processes are used by plants in this subcategory to remove excess
material deposited in the process of impregnating cadmium anodes and
nickel cathodes. Dry cleaning can be used to eliminate the wastewater
discharge normally associated with wet cleaning. An alternative means
of restricting wastewater discharge volume from plants using wet
cleaning is to recirculate the water after settling or filtering to
remove suspended solids.
Reduction of Water Use iji Cell Washing - Three plants in this
subcategory presently wash assembled batteries. Water use in this
process is presently highly variable. Discharge from zinc subcategory
plants employing a similar cell wash process is significantly lower
than the cell wash discharge from cadmium plants. Two of the zinc
plants currently recycle and reuse this water, and cell wash water use
is generally more conservative and more carefully controlled than in
cadmium subcategory cell wash operations. BAT-1 limitations for the
cadmium subcategory cell wash operations are based on the achievement
of discharge flow rates equal to the median flow rate currently
discharged from zinc subcategory cell wash operations. This can be
accomplished by stringent control of water use, by recirculation of
rinse and wash waters, or by the use of multi-stage/countercurrent
rinsing techniques.
Countercurrent Rinsing of_ Silver Powder - Multi-stage countercurrent
rinses can be used to reduce wastewater discharge from the production
of silver powder. This technique is a proven method of providing high
rinsing efficiency while substantially reducing rinse discharge
volumes from those from other rinsing techniques.
748
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BAT Option Two
The end-of-pipe treatment system selected as BAT option 2 for cadmium
subcategory wastes is presented in Figure X-2 (Page 757). This system
is identical to the system used in BAT-1. pH adjustment and sulfide
precipitation are followed by a clarifier for solids removal. Sludge
is processed through a vacuum filter. The concentrations of
pollutants found in the effluent discharged from end-of-pipe treatment
should therefore be similar to that derived from BAT option 1 end-of-
pipe treatment. In-process control techniques implemented in BAT-2
significantly reduce wastewater volumes discharged to end-of-pipe
treatment, however. As a result, reduced effluent pollutant loadings
are attained by application of the complete BAT option 2 treatment and
control system.
The in-process control techniques used to effect raw wastewater
discharge reductions for BAT option 2 require use of multi-stage
countercurrent rinsing. This technique is applied to several
different processes in the cadmium subcategory to reduce the amounts
of wastewater discharged from product rinsing. BAT option 2 includes
the installation of countercurrent rinses in the production of
sintered and impregnated anodes, in electrodeposited nickel cathode
production, and in cadmium powder production. This requires
implementing specific rinse tank modifications for each type of rinse.
Several plants in the cadmium subcategory currently utilize continuous
multi-stage rinses which can be converted to countercurrent operation
with only minor piping changes. Two facilities in this subcategory
and a number of plants in other subcategories presently practice
countercurrent rinsing.
In-process controls provided in this BAT alternative also include all
in-process control techniques applied in BAT option 1 and BPT
treatment and control systems.
BAT Option Three
The system designed to treat wastewater discharges in the third BAT
alternative for the cadmium subcategory is presented in Figure X-3
(Page 753 ). This system consists of pH adjustment with lime, caustic
or sulfuric acid, followed by filtration to remove suspended solids
present in the waste stream. Then the filtrate is treated in a
reverse osmosis unit. The reverse osmosis, permeate is reused in the
process, and the concentrate is treated further by pH adjustment with
lime or caustic to raise the pH to approximately 10.0. This is
followed by sulfide precipitation and settling in a clarifier or
settling tank. The clarifier effluent is then discharged, while the
sludge is dewatered in a vacuum filter. The vacuum filter sludge cake
is removed for metal recovery or disposal, and the filtrate is
returned to the chemical precipitation tank. The concentrate stream
749
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discharged from reverse osmosis can be effectively treated by sulfide
precipitation and sedimentation, ensuring that very low concentrations
of toxic metals will be present in the clarified effluent. Other
solids removal devices, such as settling ponds, lagoons, granular bed
filters or membrane filters could be used in place of a clarifier.
The volume of effluent discharged to surface waters from the chemical
precipitation system will be greatly reduced in BAT Option 3 compared
to the preceeding options because of the process reuse of the RO
permeate. Since the concentrations achieved by sulfide precipitation
and sedimentation treatment will be the same as in other options, the
mass of pollutants discharged is also greatly reduced.
Additional in-process control techniques beyond those provided in BAT
options 1 and 2 are also included in BAT option 3 to reduce the
wastewater volume and pollutant loads discharged to end-of-pipe
treatment. These techniques include:
Formation of electrodes following battery assembly to
eliminate rinses presently associated with electrode
formation.
Effective process control to reduce or eliminate rework
cadmium powder production.
in
Formation of Electrodes After Cell Assembly - In case formation of
sintered and impregnated nickel cathodes was observed in two plants
and has the advantage of eliminating discharges from spent formation
solutions and post-formation rinses, while not affecting product
quality. Since formation is accomplished in the case using the
battery electrolyte, it is not necessary to dump the formation
electrolyte, and rinsing becomes unnecessary. Electrodeposited
cathodes and anodes are formed by operations identical to those used
in forming sintered placks and it is concluded that formation of
electrodeposited cathodes and anodes after battery assembly is also
feasible and this practice is included in BAT option 3.
Improved Process Control ijn Cadmium Powder Production - BAT option 3
also includes improved control in producing chemically precipitated
cadmium powder to ensure complete reaction and efficient rinsing.
Improved process and rinse flow control can achieve approximately a 40
percent reduction in wastewater discharge from this process element.
BAT Option 4
The fourth option presented for consideration as BAT for this sub-
category is modelled after a system implemented at one plant in the
subcategory subsequent to the completion of the data collection phase
of this study. This system achieves zero discharge of process
wastewater pollutants through a combination of in-process controls,
750
-------
wastewater treatment, and material recovery techniques as illustrated
in Figure X-4 (Page 759 ).
This option includes:
The use of countercurrent rinsing and sale of the con-
centrated rinse discharge to eliminate wastewater from
electrode rinsing operations.
Treatment of segregated wastewater streams from electrode
cleaning by sedimentation and recycle of the clarified water.
Treatment of all remaining wastewater and recycle of the
treated water to process use.
Distillation of the ion exchange regeneration wastewater and
recycle of the condensate to the manufacturing process.
This technology option has been shown to be feasible and economically
achievable by its implementation at a cadmium subcategory plant which
previously discharged large volumes of process wastewater. However,
information about this system became available too late for inclusion
in the cost estimates presented in Section of VIII of this draft.
Cost information for this option will be included in the proposal
development document.
CALCIUM SUBCATEGORY
Two different technology options are presented for consideration as
BAT for the calcium subcategory. The first provides improved endof-
pipe treatment technology by the addition of polishing filtration to
BPT. The second includes segregation, treatment and recycle of the
major process waste stream (from the heat paper production) produced
in the subcategory and total reuse or recycle of wastewater treated
using the same end-of-pipe system specified for BAT option 1. No
significant in-process control technologies were identified for
inclusion in these BAT options.
BAT Option One
The BAT option 1 treatment system for the calcium subcategory in
Figure X-5 (Page 770) is equivalent to BPT with the addition of a
polishing filter following chemical precipitation and sedimentation
treatment. Two distinct process wastewater streams are treated prior
to combination in the chemical precipitation system.
The wastewater stream from heat paper production is passed through a
clarifier or settling tank where the suspended material is allowed to
settle. The settled sludge is removed periodically and contractor
751
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hauled. Effluent from the settler is treated chemically to reduce
hexavalent chromium to the trivalent state prior to chemical
precipitation and clarification. Once the heat paper wastewater
stream has undergone chemical chromium reduction, it may be combined
with the wastes associated with the second wastewater stream.
Wastewater from cell leak testing may contain dissolved metals such as
cadmium, nickel, and iron in addition to various trace metal
contaminants. The stream may also contain oil and grease and
miscellaneous suspended solids which have accumulated on the cell
during the various assembly operations. The option 1 treatment system
removes the various dissolved metals using chemical precipitation
(with lime) followed by clarification of the wastewater stream in a
clarifier or settling tank. The settler may also incorporate an oil
skimming unit for removal of oil and grease present in the wastewater
stream.
The settled solids are removed periodically from the clarifier; and
dewatered in a vacuum filtration unit. The sludge filter cake is
disposed on a contract haul basis, along with any oil and grease
removed by the skimming mechanism on the settler. The liquid filtrate
from the vacuum filter is returned to the treatment system to undergo
further treatment.
To further reduce the concentrations of metal and suspended solids in
the effluent, the waste stream is passed through a multimedia filter
prior to discharge. This filter is intended to act as a polishing
unit on the treated wastewater stream. Periodic backwashes from the
filter are returned to the treatment system.
BAT Level 2
For the calcium subcategory, BAT option 2 treatment includes
segregation of heat paper and cell testing wastewater. The cell test
wastewater is identical to BAT option 1 treatment, except that
following treatment the wastewater is recycled or reused with makeup
water added as required. For the heat paper wastewater stream BAT
option 2 treatment consists of settling to remove particulate
contaminants. The clarified effluent from the settling unit is
discharged to a holding tank, from which it is recycled back to the
process operation as required. It is intended that all of this
wastewater stream be recycled with makeup water added to the system as
required. Recycle of this wastewater stream eliminates asbestos and
chromium from the effluent discharged from plants in this subcategory.
This waste treatment system is illustrated in Figure X-6 (Page 771 ).
752
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LEAD SUBCATEGORY
Four distinct technology options are presented for consideration as
BAT for this subcategory. These options build incrementally upon BPT
and achieve either reduced process wastewater volume or reduced efflu-
ent pollutant concentrations in comparison to the previous option.
In-process controls included in these options are observed in present
practice within the lead subcategory. End-of-pipe technologies trans-
ferred from other industrial categories are employed as well as those
which are presently practiced at lead subcategory plants.
BAT option 1 combines end-of-pipe treatment identical to BPT with
additional in-process control technologies which greatly reduce the
volume of process wastewater which is treated and discharged. Option
2 includes the in-process controls provided in option 1 and also
provides reduced effluent pollutant concentrations as a result of a
change from hydroxides (and carbonates) to sulfides in chemical
precipitation. Further reductions in pollutant concentrations are
achieved in option 3 by the addition of a polishing filter to the
chemical precipitation and sedimentation treatment system of option 2.
Finally, option 4 applies reverse osmosis technology to allow the re-
cycle of additional process wastewater, further reducing the volume
which is treated in the option 3 end-of-pipe system and discharged.
BAT Option One
The first option for BAT for the lead subcategory combines end-of-pipe
treatment identical to that provided at BPT and is shown in Figure X-7
(Page 772 ) with improved in-process control techniques which
significantly reduce the volume of wastewater treated and discharged.
In-process controls are included in this alternative to significantly
reduce or eliminate process wastewater discharges resulting from the
formation of wet or damp batteries, the formation and dehydration of
plates for dehydrated batteries, and battery washing. In addition,
all in-process control techniques included in BPT are also considered
part of this treatment and control alternative. These in-process
controls included in BPT eliminate wastewater discharge from plate
curing, paste preparation and application, leady oxide production,
electrolyte preparation and handling, and general plant clean-up.
Closed Case Formation Discharge Elimination - Wastewater discharges
from closed case formation processes are eliminated by application of
a variety of in-process control techniques included in this BAT
alternative. All are presently observed within the subcategory. At
any individual facility, it is unlikely that the implemenation of all
of these control techniques will be required, but some subset of these
techniques can be combined to eliminate wastewater discharge from
these operations at each plant. Specific in-process controls included
are:
753
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Low rate charging or recycle of contact cooling water
Recirculation of wet scrubber water
Control of spillage in electrolyte filling and dumping to
reduce case contamination and eliminate battery rinsing, or
recirculation of rinse water
Slow charging rates are used in formation to eliminate the use of con-
tact cooling water and the resultant process wastewater discharge. As
an alternative to this BAT option 1 control, contact cooling water
used in higher rate formation processes may be recycled through a
cooling tower and neutralized as required (to prevent corrosion) thus
permitting continued use of the water. Widespread practice of these
techniques is indicated by the fact that many plants report no process
wastewater discharge from contact cooling on formation processes.
Where wet scrubbers are used to control acid fumes and mist resulting
from formation processes, recycle of the scrubber water is also re-
quired for this level of control. Neutralization of the scrubber
water may be required to maintain efficient scrubbing and to limit
equipment corrosion.
The use of appropriate technology and reasonable care in filling bat-
teries with acid electrolyte prior to formation limits the extent of
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 of acid from the battery
is also required. Production by single-fill techniques simplifies the
controls which must be employed since only the single filling
operation, and 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. Effective
control of spills and overflows during filling is widespread. These
practices limit or eliminate the requirement for battery rinsing or
washing prior to further handling or shipment, significantly reducing
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 combining a lesser degree of
control during filling with recycle of the battery rinse water. In
some cases, the attainment of a sufficient degree of recycle may
require neutralization of the rinse stream.
In all of the instances discussed above where recycle is used to re-
duce or eliminate wastewater discharges associated with closed case
formation processes, the build-up of dissolved salts, and sulfuric
754
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acid may eventually preclude continued recycle and necessitate a bleed
from the system. In this BAT option these bleed streams are directed
to either the acid cutting or paste preparation processes. Both of
these operations have negative water balances and require continual
influxes of makeup water. Together, these streams total approximately
0.4 I/kg at a typical lead subcategory plant. This volume of water is
consumed in production either as a result of being shipped with the
battery as electrolyte or evaporation from the plates during curing
and drying. These reuse practices have been observed at existing
facilities.
Damp batteries may be a small wet generator of wastewater even with
major water use technologies. The normal plant production mix of wet
and damp batteries allows ample opportunity to use the wastewater
excess from damp batteries.
Plate Formation and Dehydration Discharge Reduction - Significant
reductions in process wastewater- discharges from the formation and de-
hydration of plates for dehydrated batteries are achieved by several
in-process control techniques provided in BAT. These include:
Use of countercurrent rinsing and rinse flow control or
recycle of wastewater from post-formation plate rinses
Elimination or recycle of process water used in plate
dehydration
Recycle of wet scrubber water.
Multi-stage, countercurrent rinses and rinse flow control can provide
significant reductions in wastewater discharge from rinsing electrodes
after open case formation. The extent of reduction achievable is dis-
cussed in Section VII. Although countercurrent and multi-stage rinses
after open case formation are reported by a number of plants in this
subcategory, these are not coupled with effective rinse flow control
and consequently generally achieve comparable wastewater discharge
volumes to those from single stage rinses. At plants which presently
employ rinse flow control, however, the implementation of
countercurrent rinses will generally require minimal equipment
modifications. As an alternative to countercurrent rinsing and strict
rinse flow control, rinse wastewater may be recycled for reuse in
product rinsing either before or after treatment. Because this
technique affords lower rinsing efficiency than countercurrent
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 electrodes. This
755
-------
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. These results
are achieved by many plants producing dehydrated batteries although
most plants did not specifically identify the techniques employed.
Battery Wash Discharge Reduction - In-process control techniques for
the reduction of wastewater discharges from battery washing include
use of efficient acid addition and removal techniques as discussed
previously; use of a rinse to remove most lead and acid prior to
washing with detergent formulations. Water use for battery rinsing is
minimized by use of countercurrent rinsing; or eliminated by reuse of
rinse water for paste formulation. A viable alternative for many
facilities is the elimination of battery washing, which eliminates all
associated wastewater discharges.
Many plants in the lead subcategory demonstrate the feasibility of the
discharge reductions projected by these in-process control techniques
and presently discharge little or no process wastewater from battery
washing, although specific washing techniques were not generally iden-
tified in dcp's. The use of a water rinse prior to detergent washing
was observed at a sampled battery manufacturing plant, as was the man-
ufacture of batteries without any battery wash operation.
BAT Option 2
The second option for BAT treatment and control combines in-process
control techniques identical to those included in BAT option 1 with
improved end-of-pipe treatment providing lower effluent pollutant
concentrations. For BAT option 2 the lead subcategory end-of-pipe
treatment shown in Figure X-8 (Page 773 ) consists of pH adjustment
with lime or sodium hydroxide and chemical precipitation with sodium
sulfide or ferrous sulfide followed by sedimentation in a clarifier or
settling tank for solids removal. The treated effluent is discharged
and settled solids are removed and dewatered in a vacuum filter.
Solids from the vacuum filter are removed for recovery or disposal,
and the filtrate is returned for further treatment.
This treatment system differs from that provided in BPT and BAT option
1 by the addition of sulfide precipitation in addition to lime
precipitation. Since lead sulfide is much less soluble than lead
hydroxide or lead carbonate, improved removal of this pollutant can be
achieved. However, the use of sodium carbonate may be advantageous in
some instances because the treated effluent from a carbonate pre-
cipitation system is compatible with reuse in lead subcategory manu-
facturing processes whereas the effluent from sulfide precipitation
cannot generally be reused in the process. With careful operation,
the removal of lead as the basic carbonate can match the effluent per-
756
-------
formance cited for removal as the sulfide because after precipitation
occurs effuent concentrations are primarily governed by solids removal
rather than residual solubility.
BAT Option 3
This BAT option includes both in-process controls and end-of-pipe
treatment identical to those provided at BAT option 2, but augments
the effectiveness of end-of-pipe treatment by incorporationg a
polishing filter. The BAT option 3 treatment schematic is shown in
Figure X-9 (Page 774 )• A membrane filter is provided to reduce
suspended solids to less than 10 mg/1. Because the sulfides of lead
and of other metals are relatively insoluble in alkaline solutions,
these metals are present in the effluent from settling primarily as
residual precipitate particles. These precipitated particulates will
be removed by the membrane filter together with other suspended
solids. Consequently, effluent concentrations of these pollutants are
also significantly reduced by addition of the membrane filter. 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.
An alternate BAT Option 3 has been shown as part of BAT Option 3 in
Figure X-9 (Page 774). This technology train consists of pH
adjustment using lime augmented by carbonate precipitation, settling,
and mixed media filtration. The performance of this system should be
almost as effective in lead removal as Option 3. This technology
train has not been included in cost calculations in Section VIII, but
should be substantially less costly than Option 3 because of the lower
filter cost.
BAT Option 4
In the fourth alternative for BAT for the lead subcategory, in-process
control techniques identical to those included in other BAT alterna-
tives are combined with an end-of-pipe treatment system, shown in
Figure X-10 (Page 775 )• The system provides for neutralization and
filtration of the process wastewater after which it is treated by
reverse osmosis. The permeate from the reverse osmosis unit is
returned to the manufacturing process for use as make-up water, and
the concentrate, containing essentially all of the process wastewater
pollutants, is treated in a system identical to the end-of-pipe system
provided in BAT option 3.
This system allows a significant reduction in the volume of process
wastewater released to the environment. Because pollutants are
presented to the chemical precipitation process in substantially
higher concentrations, treatment effectiveness is significantly
increased. While this treatment system is not presently employed
757
-------
within the lead subcategory, similar systems are in use in other
industries producing process wastewater streams which contain
significant concentrations of toxic metals. These systems are
reported not only to reduce pollutant discharges but also to reduce
the volume of sludge requiring disposal because increased precipitate
density is achieved.
LECLANCHE SUBCATEGORY
No BAT options are presented for the Leclanche subcategory because BAT
is identical to BPT as described in Section IX.
LITHIUM SUBCATEGORY
Three alternative levels of treatment and control technology are pre-
sented for consideration as BAT for this subcategory. Each of these
options builds upon BPT, and like BPT, provides somewhat different
treatment for each of three distinct wastewater streams generated in
this subcategory. All three options incorporate improvements in end-
ofpipe treatment or recycle of treated wastewater. In-process
controls providing substantial reductions in process wastewater
volumes or pollutant loads have not been identified.
BAT Option 1 achieves reduced effluent pollutant concentrations by the
addition of a polishing filter to the chemical precipitation and
sedimentation system included in BPT. Option 2 reduces the volume of
wastewater discharged by providing for the separate treatment and
recycle of heat paper production wastewater. Further effluent volume
reduction is achieved by Option 3 through total recycle of wastewater
from sulfur dioxide and thionyl chloride handling.
BAT Option One
The BAT option 1 treatment system for the lithium subcategory, shown
in Figure X-ll (Page 775 ), consists of three distinct treatment
systems, each of which is directly associated with one of the three
major wastewater streams generated by this subcategory.
The first wastewater stream, from heat paper production, is passed
through a clarifier or settling tank where the suspended material is
allowed to settle. The settled sludge is removed periodically, and
disposed of on a contract basis. The effluent from the initial
clarifier is treated by chemical reduction to reduce hexavalent
chromium to the trivalent state. Once the heat paper wastewater
stream has undergone chemical reduction of chromium, it is combined
with the wastewater associated with the second major wastewater stream
prior to further treatment.
758
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The combined wastewaters are treated to remove dissolved metals using
chemical precipitation (with lime) followed by settling of the
wastewater stream by settling in a clarifier. The clarifier may also
incorporate an oil skimming unit for the removal of oil and grease.
The settled solids are removed from the clarifier, and dewatered in a
vacuum filtration unit. The sludge filter cake is disposed of on a
contract haul basis, along with any oil and grease removed by the
skimming mechanism on the clarifier. The liquid filtrate from the
vacuum filter is recycled back to the treatment system to undergo
further treatment.
In order to provide improved removal of metals and suspended solids,
the clarified wastewater stream is passed through a multi-media filter
prior to discharge. This filter is intended to act as a polishing
unit on the treated wastewater stream. Periodic backwashes from the
filter are recycled back to the treatment system.
The third major wastewater stream is initially aerated to decrease the
oxygen demand. In the process, sulfuric acid is formed from the sul-
furous acid originally present. Subsequently, the low pH wastewater
is neutralized prior to discharge. Lime used to neutralize the waste
stream may precipitate calcium sulfate and calcium chloride. Because
of the possibility of the formation of precipitates, the neutralized
wastewater stream is passed through a clarifier or settling tank prior
to discharge. The clarifier also removes miscellaneous suspended
solids contained in the wastewater streams. It is expected that
solids removed in settling will be disposed on a contract haul basis.
BAT Option 2
For the lithium subcategory, BAT option 2 treatment, shown in Figure
X-12 (Page 777 ), is very similar to BAT option 1 treatment. For the
heat paper wastewater stream, however, BAT option 2 treatment consists
of settling after which the clarified effluent is discharged to a
holding tank, from which 100 percent of this wastewater stream is
recycled with makeup water added to the system as required. The BAT
option 2 treatment applied to the second major wastewater stream is
identical to the system described for this wastewater stream in BAT
option 1. Because of the recycle of the treated heat paper wastewater
back to the process operation, the BAT option 2 treatment equipment
will not be required to remove trivalent chromium from solution.
The BAT option 2 treatment system for the third major wastewater
stream is also identical to the system described in BAT option 1.
BAT Option 3
The BAT option 3 treatment system for the lithium subcategory, shown
in Figure X-13 (Page 778 )/ is very similar to the system previously
759
-------
described for BAT 2 treatment. It differs only in that the treated
wastewater from thionyl chloride or sulfur dioxide handling is
recycled for further process use.
MAGNESIUM SUBCATEGORY
Three different options are presented for consideration as BAT for
this subcategory. Each builds upon BPT and provides improved end-of-
pipe treatment or recycle of treated wastewater. All of the options
presented provide somewhat different treatment for each of four chemi-
cally distinct wastewater streams described in Section IX. No
significant in-process controls beyond water use controls presently
applied in the subcategory are included in any BAT option.
The first BAT option provides end-of-pipe treatment identical to BPT
for all wastewater streams, but adds a polishing filter to reduce
effluent pollutant concentrations. The second achieves reduced
effluent volume by separate treatment and recycle of heat paper
production wastewater. The third option achieves reduced pollutant
concentrations by providing carbon adsorption treatment for process
wastewater streams containing significant organic contaminants.
BAT Option One
The BAT option 1 treatment system for the magnesium subcategory is
identical to BPT for this subcategory except that a polishing filter
is added prior to discharge of the final treated effluent. It
provides four distinct treatment trains as shown in Figure X-14 (Page
779)• Three are directly associated with individual wastewater
streams generated by this subcategory. The fourth receives wastewater
from' other process sources.
The first treatment train removes ammonium fluoride and silica parti-
culates in multiple treatment steps. In the first treatment
operation, fluoride is removed from the wastewater by chemical
precipitation and sedimentation. Lime is added to the wastewater
stream to raise the pH of the stream to 12, and the fluoride is
precipitated as calcium fluoride. The wastewater is then passed to a
clarifier where the calcium fluoride precipitate and silica
particulates settle out.
The third wastewater stream, from heat paper production, is passed
through a clarifier where suspended material is allowed to settle.
The settled sludge is removed periodically from the clarifier and dis-
posed of on a contract hauling basis. The effluent from the clarifier
undergoes chemical reduction in order to reduce any hexavalent
chromium to the trivalent state prior to chemical precipitation and
clarification.
760
-------
Each of the above wastewater streams, after the treatment described,
and the fourth wastewater stream is individually treated by chemical
precipitation, sedimentation, and filtration in order to remove
trivalent chromium, silver, and any other metals which may be present
in the wastewater. Initially, the pH of the wastewater is raised to
9.0 using lime. The wastewater is then discharged to a clarifier
where the precipitates are allowed to settle out of solution. In
addition, the clarifier also removes any miscellaneous suspended
solids. The clarifier also incorporates an oil skimming unit for re-
moval of any oil and grease which may be present.
The settled solids are removed periodically from the clarifier, with
the sludge being dewatered by a vacuum filtration unit. The sludge
filter cake is disposed of on a contract haul basis, along with any
oil and grease removed by the skimming mechanism on the clarifier.
The liquid filtrate from the vacuum filter is recycled back to the
treatment system where it undergoes further treatment.
In order to ensure effective removal of metals and suspended solids,
the clarified wastewater stream is passed through a multi-media filter
prior to discharge. This filter is intended to act as a polishing
unit on the treated stream. Periodic backwashes from the filter are
recycled back to the treatment system.
BAT Option Two
For the magnesium subcategory, BAT option 2 treatment (shown in Figure
X-15 (Page 780 )) is identical to BAT option 1 treatment with one
exception. For heat paper wastes the clarified (settled) effluent
does not undergo chemical reduction. Instead, the treated heat paper
waste stream is discharged to a holding tank, from which all of this
stream is recycled. Make-up water is added to the system as required.
Because of the recycle of the treated heat paper wastewaters back to
the process operation, BAT option 2 treatment equipment will not be
required to precipitate and remove chromium from solution.
BAT Option Three
As shown in Figure X-16 (Page 781) the BAT option 3 treatment system
for the magnesium subcategory is very similar to the system previously
described for BAT option 2 treatment. However, the waste treatment
applied to the first and second waste streams is somewhat different
from that employed in the BAT options 1 and 2 treatment systems.
As discussed previously, the second major wastewater stream contains a
combination of silver, silver chloride, and organic photo developers.
In BAT options 1 and 2, the oxygen demand exerted by this waste stream
is alleviated by aerating the wastewater. In BAT option 3, this waste
761
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stream is passed through an activated carbon adsorption column. This
provides removal of the organics rather than simple reduction of oxy-
gen demand. Once removal of the organics has taken place, the parti-
ally treated second wastewater stream is treated in the same way as
effluent from the first wastewater stream and the untreated fourth
major wastewater stream - treatment for removal of dissolved metals,
oil and grease and miscellaneous suspended solids as provided in
options 1 and 2.
ZINC SUBCATEGORY
Three technology options are presented for BAT for the zinc
subcategory. All three options build upon BPT and provide reduced
pollutant discharge by reducing wastewater volumes through the
application of in-process control techniques. In addition, two of the
options provide augmented end-of-pipe treatment technology.
The first technology option presented for consideration adds in-
process control technology to the end-of-pipe treatment provided at
BPT, yielding considerably reduced effluent discharge volumes. The
second involves additional in-process controls, but also provides
improved solids removal in end-of-pipe treatment and reduces both
wastewater discharge volumes and pollutant concentrations. The third
option retains chemical precipitation and solids removal technologies
identical to those provided at BPT but minimizes wastewater discharge
volumes by the application of in-process control beyond those provided
in option two and by inclusion of reverse osmosis and treated
wastewater recycle in the end-of-pipe system.
BAT Option One
This alternative combines end-of-pipe treatment technology identical
to that provided for BPT with improved in-process control practices to
reduce the volume of wastewater which is treated and discharged. End-
of-pipe treatment provided at this level, as shown in Figure X-17
(Page 782 )/ includes pH adjustment, sulfide precipitation, settling
for suspended solids removal, and polishing treatment in a multi-media
granular bed or equivalent filter. Water use control techniques
included in BPT as discussed in Section IX are also included in this
treatment and control alternative.
In addition to BPT treatment and control practices, this alternative
includes a number of in-process control techniques to reduce the
volume of wastewater and mass of pollutants presented to the end-of-
pipe treatment system. These include:
Countercurrent rinsing of wet amalgamated zinc powder to
reduce the volume of this mercury contaminated waste stream.
762
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Treatment and recirculation of water used to wash
amalgamation area floors.
Use of a multistage countercurrent rinse after formation of
zinc anodes.
Countercurrent rinsing of silver powder produced by
electrolytic deposition.
Use of countercurrent rinses after formation of silver oxide
cathodes.
Control of rinse flow rates and countercurrent rinsing of
silver peroxide produced by chemical oxidation.
Control of water use in equipment and product rinsing in
silver peroxide cathode production. Use of countercurrent
rinsing or wastewater recirculation to effectively limit
wastewater discharges.
Control of impregnated nickel cathode wastewater discharges
as specified in BAT option 1 for the cadmium subcategory.
Use of countercurrent rinses or rinse water recycle in cell
washing.
Countercurrent rinsing after silver etching operations to
prepare electrode support grids.
Use of dry cleanup techniques for general plant floor areas,
or complete recycle of floor wash water.
Countercurrent Rinsing and Water Flow Control - Rinsing electrodes and
active materials for use in electrodes accounts for most of the
process wastewater discharged from this subcategory. As discussed in
Section VII, a variety of techniques including water use control,
multi-stage rinsing, countercurrent rinsing, and wastewater recycle
and reuse are applicable to the reduction of the volume of wastewater
discharged from this source. Countercurrent rinsing, when combined
with effective control of rinse water flow rates, provides the lowest
discharge volumes attainable without an adverse effect on rinsing
effectiveness. Multistage rinsing is frequently practiced at present
although it is rarely combined with effective control of rinse flow
rates. Equipment presently in place for multi-stage rinses will
frequently allow the implementation of countercurrent rinses with
little additional investment and little or no requirement for
additional floor space.
763
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Amalgamation Clean-Up Discharge Elimination - Water used in washing
amalgamation area floors becomes contaminated with mercury as well as
zinc and suspended solids. Recycle of this water for continued use in
floor washing is possible if the mercury is removed by treatment prior
to recycle. This may be accomplished using sulfide to precipitate
mercury sulfide prior to removal of suspended solids. When the
sulfide is added in the form of ferrous sulfide, effective
precipitation is achieved and mimimum levels of residual sulfide ion
result. An alternative in-process control technique which eliminates
process wastewater discharge from this source is the substitution of a
totally dry amalgamation process. In these
BAT Option Two
Erid-of-pipe treatment technology and in-process control techniques are
augmented in this alternative to provide lower pollutant discharges
than are attained by BAT option 1. Consequently, the effluent flow
rate and pollutant concentrations are reduced as a result of implemen-
ting this level of treatment and control.
End-of-pipe treatment provided in this alternative is similar to that
provided for BPT and BAT option 1 except that a membrane filter is
used for polishing filtration in place of the multi-media filter
included in the two previous levels of treatment. This end-of-pipe
treatment system is shown in Figure X-18 (Page 783 ). Because metals
are present primarily as solids after sulfide precipitation, improved
TSS removal provides lower effluent concentrations of many metals.
In-process control techniques included in this alternative for BAT in-
clude all of the controls cited for BAT option 1, plus four additional
measures.
In wet amalgamation processes, separate treatment of product
rinse wastewater using ferrous sulfide and settling, and use
of the resultant treated stream for floor washing in place of
makeup water.
Elimination of all wastewater discharge from gelled amalgam
processes, by process modification to eliminate water use.
Treatment of segregated wastewater from silver peroxide pro-
duction by reverse osmosis (RO) and reuse of the RO permeate;
or process modification to allow direct reuse of process
solutions.
Elimination of the use of chromates in cell washing.
764
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BAT Option Three
This alternative for BAT combines in-process control techniques simi-
lar to those included in BAT option 2 with an end-of-pipe treatment
system which permits the recycle of a substantial part of the waste-
water discharged to treatment. Recycle is made feasible by use of a
reverse osmosis unit..
End-of-pipe treatment included in the BAT alternative as shown in
Figure X-19 (Page 734) includes pH adjustment, filtration, and reverse
osmosis. The permeate from the RO unit is returned to the process
where it may be used in place of fresh makeup water. The RO
concentrate stream is treated by pH adjustment, sulfide precipitation,
settling and multimedia filtration, and subsequently discharged.
Treated wastewater is used to backwash the multi-media filter, and
the filter backwash is returned to the clarifier or settling tank.
Solids settled from the wastewater are dewatered in a vacuum filter or
equivalent device and the filtrate is returned to the treatment
system.
The implementation of this end-of-pipe system results in the presen-
tation of a low flow of concentrated wastewater stream to the chemical
precipitation process since most of the wastewater permeates the RO
membrane and is returned to the process. As a result, the mass of
pollutants discharged is reduced. The feasibility and effectiveness
of reverse osmosis in this application is demonstrated by its
successful use under similar circumstances in other industries.
In-process control techniques in this option include process modi-
fication to perform all amalgamation by dry processes producing no
process wastewater discharges, formation of nickel cathodes after cell
assembly as discussed for the cadmium subcategory, and all the in-
process control techniques included in BAT option 2. These techniques
combine to significantly reduce the volume of process wastewater
flowing to end-of-pipe treatment, to increase the treatability of the
wastewater, and to eliminate cyanide and hexavalent chromium from
process wastewater discharges in this subcategory.
Process modification to replace wet amalgamation with dry amalgamation
has been demonstrated at one plant where this process substitution had
been partially accomplished at the time of on-site data collection and
sampling. The amalgam produced by the two processes was reported to
be interchangeable.
765
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Ml Wastewater
pH Adjustment
Filtrate
Sulfide
Precipitation
And
Sedimentation
Discharge
Sludge
Vacuum
Filter
Sludge Hauled
Additional In-Process Technology: Control rinse flow rates
Recirculate wastewater from air scubber
Dry clean impregnated electrodes
Reduce eel I wash water use
Countercurrent rinse silver powder
FIGURE X-l
CADMIUM SURCATF.GORY
DAT OPTION 1 TREATMENT
-------
All Wastewater
After In-Process
Water Reduction
pH Adjustment
0\
Filtrate
Sulfide
Precipitation
And
Sedimentation
Discharge
Sludge
Vacuum
Filter
Sludge Hauled
Additional In-Process Technology:
Countercurrent rinse for
sintered and impregnated
anodes, electrodeposited nickel
cathodes, cadmium powder
FIGURE X-2
CADMIUM SUBCATEGORY
BAT OPTION 2 TREATMENT
-------
Ml Wastewater After
In-Process Hater
Reduct ion
pH Adjustment
Filtration
Sludge Disposal
01
CD
Filtrate
Additional In-Process Technology: Form electrodes in cells
Reduce cadmium powder reworK
Reverse Osmosis
Concentrate
pH Adjust
SuTfide
Precipitation
And
Sedimentation
Sludge
Vacuum
Filter
Discharge
Sludge Hauled or
Reclaimed
FIGURE X-3
CADMIUM SUBCATF.GORY
HAT OPTION 3 TREATMENT
-------
Fresh Hater
Cdustlc SoluHon bold
Special Treatwnt
vo
To Process
And Oetonuer*
Kegeneraled
Uater
Vapor
Hec impression
Evaporatur (VRl)
To Deionizer
Brine
Liquor
T
Dry Solids To
Landfill
Figure X-*
tAONlUM
BAT OPIIOH 4 IRtAIMlNI
-------
Heat Paper
Production Wastewater
Cell Testing
Wastewater
±
Settle
. Sludge
^^ Hauled
Hexavalent
Chromium
Reduction
Filtrate
-•j
o
Chemical
Precipitation
(Line)
Vacuum
Filter
Sedimentation
Sludge Hauled
Polishing
Filter
(Multimedia)
In-Proc«s$ Technology: None specified
Discharge
FIGURE X-5
CALCIUM SURCATRGORY
RAT OPTION 1 TRRATMKNT
-------
Cell Testing
Wastewater
Heat Paper
Production Wastewater
i
Filtrate
Chemical
Precipitation
(Lime)
-«-
t
Vacuum
Filter
| f
Uudqe Hauled
Polishing
Filter
(Multimedia)
M*J
1
Settle
Return To
k Process
Holding
Tank
1
lackwash
Return To Process
In-Progress Technology: None specified
FIGURE X-6
CALCIUM SUBCATEGORY
BAT OPTION 2 TREATMENT
-------
Paste Formulation
And Ajvl»cation
Area Washdown Mater
Multistage
Settling
Reuse or Recycle
Solids To Paste Formulation
Other Wastewater
After In-Process
Water Reduction
pM Adjustment
Filtrate
Settling
Vacuum
Filter
Discharge
Sludge Hauled
ln-Pr««s Technology:
water
FIGURE X-7
LEAD SUUCATECOKY
DAT OPTION 1 TREATMENT
-------
Paste Fonulation and
Application Area
Hashdown Mater
Multistage
Settling
Reuse or Recycle
Solids to Paste Formulation
CO
Battery Wash and
Dehydrated Plate
Rinse Wastewater
pH Adjustment
Addition*,! In-Process Technology: None
Filtrate
Sludge Handling
SulClde
Precipitation
and Sedimentation
Vacuum
Filter
Discharge
Sludge Hauled
FIGURE X-8
LEAD SUBCATEGORY
BAT OPTION 2 TREATMENT
-------
Paste Formation
And Application—
MashdOMn Hater
Battery Utsti
And Dehydrated
Mate Rinse
MsstoMater
Multistage
Settlin9
Heuse
-a»- Solids To Paste Formation
pH Adjustment
Filtrate
Sultide
Precipitation
and
Sed Mentation
Siudije Mauled
HMfcrane
Filtration
Discharge
Option 3 Alternate
Battery Mash
And Dehydrated _
Plate Rinse
Wastewater
pH Adjustment
(1ime)
Carbonate
Precipitation
And
Sedimentation
filtrate
sludge
•^Discharge
Sludge Hauled
Addition*) In-Process Technology: None
FIGURE X-9
I.KAO SUBCATIXIOIIY
HAT OPTION 3 THKATMKNT
-------
Paste Formulation
and Application
Area Washdown
Wastewater
Recycle
Multistage
Settling
n
Lead Oxide*
Return To Process
Recycle To Process
Peraeate
Battery wash
dehydrated Plate
Rinse
pH Adjust
en
I
Filter
Reverse
Osmosis
Back Wash
FiItrate
Brine
-»•
Duiiiue
Precipitation
fc Settling
i
Vacu
Fill
'
lum
.er
^
Membrane
Filter
To
••••i
i
i
t
Use In
Filters
Discharge
Additional In-Process Technology: None
Sludge Hauled
FIGURE X-10
LEAD SUBCATEGORY
BAT OPTION 4 TREATMENT
-------
Heat Paper Production
Mastewater
Sludge*-
Hauled
Settle
Other Wastewater
Streams
Sulfur Dioxide
Thionyl Chloride
Wastewater
Alternate
Hexavalent
Chromium
Reduction
r
i
Aerate
Filtrate
Chemical
Precipitation
(Lime)
I
Vacoun
Pilter
Settling
(With Ski
Sludge Hauled
Polishing
Pilter
(Multimedia)
Pill
rate
Vacua*
Filter
f
•*•
iludge Hauled
Chemical
Preciol tat Irwi
(Lime)
»
Settling
(With
Skimmer)
i
Polishing
Filter
(Multimedia)
1
Discharge
Backwash
!
Discharge
I
Neutralise
And Settle
T
Sludge
Hauled
Discharge
Backwash
FIGURE X-ll
LITHIUM SUBCATEGORY
BAT OPTION 1 TREATMENT
-------
Heat Paper Production
Mastewater
Sludqe
Hauled "^
Settle
Other Wastewater
Streams
t
Heturn To
Process
Filtrate
Holdinq
Tank
Chemical
Precipitation
(Line)
Vacuun
Filter
Settling
(With Skimmer)
Sludge Hauled
Polishing
Filter
(Multimedia)
t
Discharge
Sulfur Dioxide
Thionyl Chloride
Wastewater
Aerate
Neutralize
And
Settle
Sludge
' Hauled
Discharge
Backwash
FIGURE: x-12
LITHIUM SUDCATEGOHY
UAT OPTION 2 TKEATMKNT
-------
—I
00
Paper Production
Mastewater
t
C^fr &• 1 A
•JC^k *^
Dot
t
Holding
Tank
1
Fil
urn To
ooess
Vac
_ Fil
C
trate
uum
ter "*"
Sludge Hauled
)ther Wastwater
Streams
t
Chemical
Precipitation
(Lime)
)
Settling
(With
Sk inner)
t
Polishing
Filter
(Multimedia)
Ba<
Sulfur Dioxide
Thionyl Chloride
Wastewater
Aerate
Return To
Process
Neutralize
And Settle
I
Sludge
Hauled
Discharge
Discharge
FIGURE X-13
LITHIUM SUBCATLGOKY
DAT OPTION 3 THEATMENT
-------
IM !• tH Hi
r*
I »IUtf
, , Slue* *
10
tottlt
•eritt
y t«tut«i i
4
i
•oliMiint
Filter
Silver Chloride Cathode
Surface TreatBents
MeateMtcr
Oiacharq*
•ec»<*e«k
Oiecharee
Slit*
nitrite
|l
^
r
Vecw«B
filter
Sin
FIGURE X-14
MAGNESIUM SUBCATEGORY
BAT OPTION 1 TREATMENT
Oiecharqe
-------
Several*r Precttt
(MtlMler
Si I vn t'h loridv C a
Sui (*»•«• Tt««t*«ntl
Sludge
Maultd
FIGURE X-15
MAGNESIUM SUBCATEGORY
BAT OPTION 2 TREATMENT
-------
faptrdcr Prwttu
MMMtw
Sllvei Chlm life l«|huil«
Return To
Process
1
I* Mjotl
(Milk
Six***
dlltr
f •••••!
Iillr«l*
•(•chart*
FIGURE X-16
MAGNESIUM SUBCATEGORY
BAT OPTION 3 TREATMENT
-------
Backwash
All Nastewater After
Ii» Process water
Reduction
00
ro
Additional In-Process Technology:
pH Adjustment
Filtrate
I
Suicide
Precipitation
And
Sedimentation
Filtration
Discharge
Sludge
VacuiM
Filter
Sludge Hauled
Countercurrent rinse amalgamated zinc powder
Reclrculate amalgamation area floor wash water
Countercurrent rinse after zinc anode formation
Countercurrent rinse of electrodeposited silver powder
Countercurrent rinse after silver oxide electrode formation
Reduce flow and Countercurrent rinse silver peroxide
Rinse flow controls for impregnated nickel cathode rinsing
Countercurrent rinse or rinse recycle for cell washing
Countercurrent rinse after etching silver grids
Dry cleanup of plant floor; or wash water reuse
FIGURE X-17
ZINC SUBCATEGORY
BAT OPTION 1 TREANENT
-------
Backwash
Ml Wastewater After
In-Procestt Mater
i
Reduction
pH Adjustment
Filtrate
f
Sul£ide
Precipitation
And
Sedimentation
00
CO
Filtration
Discharge
Sludge
Vacuum
Filter
Sludge Hauled
FIGURE X-18
ZINC SUBCATEGORY
BAT OPTION 2 TREATMENT
-------
Recycle To Process
All Wastewater
After In-Process
Water Reduction
PH
Adjustment
Filtration
Sludge
Hauled
—i
00
Filtrate
Reverse
Osmosis
Permeate
Brine
Adjustment
Backwash
Sulfide
Precipitation
And
Sedimentation
Sludge
Vacuum
Filter
Filtration
*• Discharge
Sludge Hauled
Additional In-Process Technology: Amalgamation by dry processes
Form nickel cathodes in cells
FIGURE X-19
ZINC SUBCATEGORY
BAT OPTION 3 TREATMENT
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
INTRODUCTION
This section describes the best available demonstrated technology
(BDT), processes, operating methods or other alternatives applicable
to the control of wastewater pollutant discharges from new sources in
the battery manufacturing category. Several options are presented for
consideration as BDT for each subcategory, and costs for each are
addressed in Section VIII of this document. Section VIII provides
information concerning environmental benefits for each of the
component technologies considered in these options. In general,
options presented for consideration as BDT are identical to those
presented for BAT in section X.
TECHNICAL APPROACH TO BDT
As a general approach for the category three options were developed
for consideration as BDT for each subcategory. Each option generally
includes both in-process and end-of-pipe technologies. For one
subcategory, BDT is zero discharge because BPT is zero discharge of
process wastewater pollutants and for another subcategory, one BDT
option is zero discharge because one BAT option achieves zero
discharge. Two BDT options are presented which achieve zero discharge
of process wastewater pollutants from all process elements. Other
options provide reduced pollutant discharge by reducing both the
volume of process wastewater and the concentrations of pollutants and
may include the elimination of wastewater discharge from specific
process elements.
In-process technologies included in BDT options are observed in
present practice within the battery manufacturing category. The
emphasis in most options is on control of water use and discharge and
on in-process control contributing to the efficient use of process
water. These include: wastewater segregation, counter-current rinse,
wastewater recycle and reuse, and flow rate controls in addition to
process modifications specific to each subcategory. These control
techniques have been described in Section VII, and in their specific
application to each subcategory, in Section X.
End-of-pipe treatment is provided to remove toxic metals by chemical
precipitation and suspended solids (including metal precipitates) by
sedimentation and filtration. Different BDT options for each
subcategory include different chemical precipitation or solids removal
techniques. For several subcategories one BDT option provides for the
use of reverse osmosis technology to significantly reduce the volume
785
-------
of process wastewater which is treated for metals and TSS removal and
discharged.
IDENTIFICATION OF BDT
End-of-pipe treatment included in each option considered for BDT is
identical to that presented for BAT as discussed in Section X.
Cadmium Subcateqory
Four options are presented for the cadmium subcategory. BDT Options
1, 2, and 3 include the same in-process and end-of-pipe technology as
BAT Options 1, 2, and 3 plus the addition of multi-stage counter-
current rinse tanks for the production of electrodeposited cadmium
anodes. BDT Option 4 is the same as BAT Option 4. Figure X-l, 2, 3,
and 4 (Pages 766 - 769) illustrate the end-of-pipe treatment for BDT
Options 1, 2, 3, and 4, respectively.
Calcium Subcateqory
Two options are presented for the calcium subcategory. BDT Options 1
and 2 are the same as BAT Options 1 and 2 and are illustrated in
Figure X-5 and 6 (Pages 770 and 771 )/ respectively.
Lead Subcategory
Four options are presented for the lead subcategory. BDT Options 1,
2, and 3 correspond to BAT Options 2, 3, and 4, respectively, and are
illustrated by Figures X-8, 9, and 10 (Pages 773-775), respectively.
BDT Option 4 achieves zero discharge of process wastewater pollutants
by adding a second reverse osmosis unit on the effluent from BDT
Option 3 and recycling permeate to the process and the brine to
treatment. BDT Option 4 is illustrated in Figure XI-1 (Page 788).
Leclanche Subcategory
BDT for the Leclanche subcategory is the same as the BAT, which, in
turn, is the same as BPT - zero discharge.
Lithium Subcategory
Three options are presented for the lithium subcategory. BDT Options
1, 2, and 3 are the same as BAT Options 1, 2, and 3, respectively, and
are illustrated in Figures X-ll, 12, and 13 (Pages 775 - 778)/
respectively.
786
-------
Magnesium Subcateqorv
Three options are presented for the magnesium subcategory. BDT
Options 1, 2, and 3 are the same as BAT Options 1, 2, and 3,
respectively, and are illustrated in Figures X-14, 15, and 16 (Pages
779 -781 ), respectively.
Zinc Subcateqorv
Four options are presented for the zinc subcategory. BDT Options 1,
2, and 3 are the same as BAT Options 1, 2, and 3, respectively, and
are illustrated by Figures X-17, 18, and 19 (Pages 782- 734 ),
respectively. BDT Option 4 achieves zero discharge of process
wastewater pollutants by adding a second reverse osmosis unit on the
effluent from BDT Option 3 and recycling permeate to the process and
the brine to treatment. BDT Option 4 is illustrated in Figure XI-2
(Page 789 ).
787
-------
Pasting
Wastewater
Recycle
Multi-stage
Settling
Lead Oxides
Return To Process
Battery Nash
Dehydrated Plate
Rinse
Recycle To Process
Permeate
—i
00
00
pH Adjust
4
-»»-
Filter
k
Back Mash
Filtrate
Reverse
Osmosis
Brine
Suitide
Precipitation
t Settling
Membrane
Filter
Vacuum
Filter
Reverse
Osmosis
To Use In Backwashing
Filters
Sludge To Contract
Removal Or Disposal
FIGURE XI-l
LEAD SUBCATEGORY
NSPS TREATMENT
-------
Permeate
Recycle To Process
All Waste Water
After In-Process
Water Reduction
PH
Adjustment
Filtration
Sludge
Hauled
00
Reverse
Osmosis
Brine
pH
Adjustment
Backwash
Sulfide
Precipitation
And
Sedimentation
Filtration
Reverse
Osmosis
Sludge
Vacuum
Filtration
Sludge
Hauled
FIGURE XI-2
ZINC SUBCATEGORY
NSPS TREATMENT
-------
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 POTW's.
The Clean Water Act of 1977 adds a new dimension by requiring
pretreatment for pollutants, such as heavy 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,
analagous to the best available technology for removal of toxic
pollutants.
Section 307(c) of the Act requires EPA to promulgate pretreatment
standards for new sources (PSNS) at the same time that it promulgates
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 tech-
nology, are indicted by the data presented in Sections V and VII.
Most POTW 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 interfere with the normal operations of
these systesm. 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 utilizability.
TECHNICAL APPROACH TO PRETREATMENT
As a general approach for the category, three options were developed
for consideration as the basis for PSES and three for PSNS. These
options generally provide for the removal of metals by chemical
precipitation and of suspended solids by sedimentation or filtration.
In addition, they generally provide for the reduction or control of
791
-------
wastewater discharge volume through the application of water use
controls and a variety of in-process control techniques. 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 manufacturing wastewater streams
characteristically contain toxic heavy metals which are incompatible
with 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 generally combine both in-plant
technology and wastewater treatment to reduce the mass of pollutants
(especially heavy 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.
IDENTIFICATION OF PRETREATMENT OPTIONS
Option one for pretreatment standards for existing sources (PSES) is
identical to BPT for all subcategories as described in Section IX.
Options two and three for each subcategory are identical to BAT
options one and two respectively. End-of-pipe treatment systems for
each of these options are depicted in Sections IX or X as appropriate.
Pretreatment options for new sources are identical to BDT options for
each subcategory as described in Section XI.
Effluent performance achieved by these pretreatment options will the
same as that provided by the respective BPT, BAT and BDT options and
is indicated by the flow rate information provided in Section V and
the technology performance data shown in Section VII.
792
-------
SECTION XIII
DiiST CONVENTIONAL POLLUTANT CCNTRCL TECHNOLOGY
Tne 1977 amendments added section 301 (b) (<4) (E) to the Act,
establishing "oest conventional pollutant control technology"
(bCT) tor discharges of conventional pollutants from existing
industrial point sources. Conventional pollutants are those
defined in section 304 (b) (1) - BOO, TSS, fecal coliform and
ph - and any additional pollutants defined by the Administrator
as "conventional." On July 30, 1979, EPA designated oil and
grease as a conventional pollutant (UU Fed. Reg. U4501).
BCT is itot an aJditional limitation, but. replaces dAT tor
tne control of conventional pollutants. ECT requires that
limitations for conventional pollutants be assessed in light
of a new "cost-reasonableness" test, which involves a compari-
son of the cost and level of reduction of conventional pollu-
tants from the discharge of POTfc*s to the cost and level of
reduction 01 such pollutants from a class or category of indus-
trial sources. As part of its review of BAT for certain indus-
tries, EPA proposed methodology tor this cost test. (See UU
Fed. Reg. 50732, August 29, 1979). This method is now used
for the primary industries covered ty the Consent Agreement.
EPA is proposing that the conventional "indicator" pollutants,
which are used as "indicators" of control for toxic pollutants,
be treated as toxic pollutants. In this way, effluent limita-
tions will be established for the conventional indicator pollu-
tants at BAT levels, and the limitations will not have to pass
the BCT cost test. When a permittee, in a specific case, can
snow tnat the waste stream does not contain any of the toxic
tollutants that a conventional toxic "indicator" was designed
to remove, then the BAT limitation on that conventional pollu-
tant will no longer be treated as a limitation on a toxic pol-
lutant. The technology identified as BAT control of toxic pol-
lutants also affords removal of conventional pollutants to BAT
levels.
793
-------
SECTION XIV
ACKNOWLEDGEMENTS
The Environmental Protection Agency was aided in the preparation of
this Development Document by Hamilton Standard, Division of United
Technologies Corporation. Hamilton Standard's effort was managed by
Daniel J. Lizdas and Robert W. Blaser. Edward Hodgson directed the
engineering activities and field operations were under the direction
of Richard Kearns. Major contributions to the report were made by
Dana Pumphrey, Remy Halm, and other technical and support staff at
Hamilton Standard.
Acknowledgement is given to Robert W. Hardy of the Environmental
Protection Agency for his technical contributions to the report.
Acknowledgement and appreciation is also given to Mrs. Kaye Storey,
Ms. Nancy Zrubek, and Ms. Carol Swann of the word processing staff
for their tireless and dedicated effort in this manuscript.
Finally, appreciation is also extended to all battery manufacturing
plants and individuals who participated in and contributed data for
the formulation of this document.
795
-------
SECTION XV
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U.S. Environmental Protection Agency, Presented at Division
of Environmental Chemistry 179th National Meeting, American
Chemical Society, Houston, TX, March 23-28, 1980.
"Sources of metals in municipal sludge and industrial pretreat-
ment as a control option." ORD Task Force on Assessment of
Sources of Metals in Sludges and Pretreatment as a Control
Option, U.S. EPA, 1977.
Stone, G. "Your best buy in small batteries." Popular Science,
p. 76, 79-81, 116 (August 1979).
800
-------
Strier, M. P. "Heavy metals in wastewater." U.S. Environmental
Protection Agency, Presented at National Association of
Corrosion Engineers Regional Meeting, Newport, RI, October
2-4, 1978.
Strier, M. P. "Treatability of organic priority pollutants -
Part E - the relationship of estimated theoretical treata-
bility with water solubility, partition coefficient, bio-
concentration and aquatic life toxicity." U.S. Environmental
Protection Agency, EPA 440/1-79/100, May 22, 1979.
"Sulfex TM heavy metals waste treatment process." Permutit Co.,
Inc., Technical Bulletin 13(6), October 1976.
Tappett, T. "Some facts about your car's battery." Mechanix
Illustrated, p. 100, 102-103 (March 1978).
"Treatability of 65 chemicals - Part A - biochemical oxidation of
organic compounds." Memorandum from M. P. Strier to R. B.
Schaffer, June 24, 1977.
"Treatability of chemicals - Part B - adsorption of organic com-
pounds on activated carbon." Memorandum from M. P. Strier to
R. B. Schaffer, December 8, 1977.
"Treatability of the organic priority pollutants - Part C - their
estimated (30 day avg) treated effluents concentration - a
molecular engineering approach." Memorandum from M. P. Strier
to R. B. Schaffer, June 1978.
Unit Operations for Treatment of Hazardous Industrial Wastewater.
D. J. Denyo (editor), 1978.
Vaccari, J. A. Product Engineering, p. 48-49 (January 1979).
Verschueren, K. Handbook of Environmental Data on Organic
Chemicals. Van Nostrand Reinhold Co., 1977.
Vinal, G. W. Primary Batteries. John Wiley & Sons, Inc., 1950.
Vinal, G. W. Storage Batteries. John Wiley & Sons, Fourth
Edition, 1955.
Water Quality Criteria. The Resources Agency of California,
State Water Quality Control Board, Publication No. 3-A,
Second Edition, 1963.
"1977 census of manufacturers - primary batteries, dry and wet
801
-------
(SIC 3692)." U.S. Department of Commerce, MC-77-I-36F-2(p),
April 1979.
"1977 census of manufacturers - storage batteries (SIC 3691)."
U.S. Department of Commerce, MC-77-I-36F-l(p),
April 1979.
802
-------
Additional References
Scott, Murray C., " Sulfex™ - A New Process Technology for Removal of
Heavy Metals from Waste Streams," presented at 1977 Purdue Industrial
Waste Conference, May 10, 11, and 12, 1977.
11 Sulfex™ Heavy Metals Waste Treatment Process," Technical Bulletin,
Vol. XII, code 4413.2002 (Permutit®) July, 1977.
Scott, Murray C., " Treatment of Plating Effluent by Sulfide Process,"
Products Finishing, August, 1978.
Lonouette, Kenneth H., " Heavy Metals Removal," Chemical Engineering,
October 17, pp. 73-80.
Curry, Nolan A., " Philogophy and Methodology of Metallic Waste Treatment,"
27l!l Industrial Waste Conference.
Patterson, James W., Allen, Herbert E. and Scala, John J., "Carbonate
Precipitation for Heavy Metals Pollutants," Journal of Water Pollution
Control Federation, December, 1977 pp. 2397-2410.
BeHack, Ervin, " Arsenic Removal from Potable Water," Journal American
Water Works Association, July, 1971.
Robinson, A. K. " Sulfide -vs- Hydroxide Precipitation of Heavy Metals
from Industrial Wastewater," Presented at EPA/AES First Annual conference
on Advanced Pollution Control for the Metal Finishing Industry, January
17-19, 1978.
Sorg, Thomas J., " Treatment Technology to meet the Interim Primary
Drinking Water Regulations for Inorganics," Journal American Water Works
Association, February, 1978, pp. 105-112.
Strier, Murray P., " Suggestions for Setting Pretreatment Limits for
Heavy Metals and Further Studies of POTW's," memorandum to Carl J.
Schafer, Office of Quality Review, U.S. E.P.A., April 21, 1977.
Rohrer, Kenneth L., " Chemical Precipitants for Lead Bearing Wastewaters,"
Industrial Water Engineering, June/July, 1975.
Jenkins, S. H., Keight, D.G. and Humphreys, R.E., " The Solubilities of
Heavy Metal Hydroxides in Water, Sewage and Sewage Sludge-I. The
Solubilities of Some Metal Hydroxides," International Journal of Air and
Water Pollution, Vol. 8, 1964, pp. 537-53FI
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.
Patterson, James W., " Carbonate Precipitation Treatment for Cadmium and
Lead," presented at WWEMA Industrial Pollutant conference, April 13,
1978.
803
-------
" An Investigation of Techniques for Removal of Cyanide from Electro-
plating Wastes," Battelle Columbus Laboratories, Industrial Pollution
Control Section, November, 1971.
Patterson, James W. and Minear, Roger A., "Wastewater Treatment Tech-
nology," 2nd edition (State of Illinois, Institute for Environmental
Quality) January, 1973.
Chamberlin. N.S. and Snyder, Jr., H.B., " Technology of Treating Plating
Waste," 10HI Industrial Waste Conference.
Hayes, Thomas D. and Theis, Thomas L., " The Distribution of Heavy
Metals in Anaerobic Digestion," Journal of Water Pollution Control
Federation, January, 1978, pp. 61-72.
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.
Neufeld, Ronald D., Gutierrez, Jorge and Novak, Richard A., A Kinetic
Model and Equilibrium Relationship for Metal Accumulation," Journal of
Water Pollution Control Federation, March, 1977, pp. 489-498.
Stover, R.C., Sommers, I.E. and Silviera, D.J., " Evaluation of Metals
in Wastewater Sludge," Journal of Water Pollution Control Federation,
Vol. 48, No. 9, September, 1976, pp. 2165-2175.
Neufeld, Howard D. and Hermann, Edward R., " Heavy Metal Removal by
Activated Sludge," Journal of Water Pollution Control Federation, Vol.
47, No. 2, February, 1975, pp. 310-329.
Schroder, Henry A. and Mitchener, Marian, " Toxic Effects of Trace
Elements on the Reproduction of Mice and Rats," Archieves of Environmental
Health, Vol. 23, August, 1971, pp. 102-106.
Venugopal, B. and Luckey, T.D., "Metal Toxicity in Mannals .2," (Plenum
Press, New York, N.Y), 1978.
Poison, C.J. and Tattergall, R.N., "Clinical Toxicology," (J.B. Lipincott
Company), 1976.
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.
Mytelka, Alan I., Czachor, Joseph S., Guggino, William B. and Golub,
Howard, "Heavy Metals in Wastewater and Treatment Plant Effluents,"
Journal of Water Pollution Control Federation, Vol. 45, No. 9, September,
1973, pp. 1859-1884.
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.
804
-------
Klein, Larry A., Lang, Martin, Nash, Norman and Kirschner, Seymour E.,
"Sources of Metals in New York City Wastewater, "Journal of Water
Pollution Control Federation, Vol. 46, No. 12, December, 1974, pp. 2653-
~
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.
Ghosh, Mriganka M. and Zugger, Paul D., "Toxic Effects of Mercury on the
Activated Sludge Process, "Journal of Water Pollution Control Federation,
Vol. 45, No. 3, March, 1973, pp. 424-433.
Mowat, Anne, " Measurement of Metal Toxicity by Biochemical Oxygen De-
mand," Journal of Water Pollution Control Federation, Vol. 48, No 5,
May, 1976, pp. 853-866.
Oliver, Barry G. and Cosgrove, Ernest G., " The Efficiency of Heavy
Metal Removal by a Conventional Activated Sludge Treatment Plant," Water
Research, Vol. 8, 1074, pp. 869-874.
"Chlorinated Ethanes" Proposed Water Quality Criteria, PB297920, Criteria
and Standards (44 FR 56628-56657, October 1, 1979).
"Chloroform" Proposed Water Quality Criteria, PB292427, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Dichloroethylenes" Proposed Water Quality Criteria, PB292430, Criteria
and Standards Division, Office of Water Regulations and Standards (44 FR
15925-15981, March 15, 1979).
"Ethylbenzene" Proposed Water Quality Criteria, PB296784, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Halomethanes" Proposed Water Quality Criteria, PB296797, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Naphthalene" Proposed Water Quality Criteria, PB296786, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
43660-43697, July 25, 1979).
"Pentachlorophenol" Proposed Water Quality Criteria PB292439, Criteria
and Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Phenol" Proposed Water Quality Criteria, PB296787, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
43660-43697, July 25, 1979).
805
-------
"Phthalate Esters" Proposed Water Quality Criteria, PB296804, Criteria
and Standards Division, Office of Water Regulations and Standards (44 FR
43660-43696, July 25, 1979).
"Polynuclear Aromatic Hydrocarbons" Proposed Water Quality Criteria,
PB297926, Criteria and Standards Division, Office of Water Regulations
and Standards (44 FR 56628-56657, October 1, 1979).
"Tetrachloroethylene" Proposed Water Quality Criteria, PB292445, Criteria
and Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Toluene" Proposed Water Quality Criteria, PB296805, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
3660-3697, July 25, 1979).
"Trichloroethylene" Proposed Water Quality Criteria, PB292443, Criteria
and Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Antimony" Proposed Water Quality Criteria, PB296789, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
43660-43696, July 25, 1979).
"Arsenic" Proposed Water Quality Criteria, PB292420, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
15926-15981, March 15, 1979).
"Cadmium" Proposed Water Quality Criteria, PB292423, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Chromium" Proposed Water Quality Criteria, PB297922, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Copper" Proposed Water Quality Criteria, PB296791, Criteria and
Standards Division Office of Water Regulations and Standards (44 FR
43660-43697, July 25, 1979).
"Cyanide" Proposed Water Quality Criteria, PB296792, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
56628-56657, October 1, 1979).
"Lead" Proposed Water Quality Criteria, PB292437, Criteria and Standards
Division, Office of Water Regulations and Standards (44 FR 15926-15981,
March 15, 1979).
"Mercury" Proposed Water Quality Criteria, PB297925, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
43660-43697, July 25, 1979).
806
-------
"Nickel" Proposed Water Quality Criteria, PB296800, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
43660-43697, July 25, 1979).
"Selenium" Proposed Water Quality Criteria, PB292440, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
15926-15981, March 15, 1979).
"Silver" Proposed Water Quality Criteria, PB292441, Criteria and
Standards Division, Office of Water Regulations and Standards (44 FR
15926-15981, March 15, 1979).
"Zinc" Proposed Water Quality Criteria, PB296807, Criteria and Standards
Division, Office of Water Regulations and Standards (44 FR 43660-4369/,
July 25, 1979).
807
-------
SECTION XV
GLOSSARY
Active Material - Electrode material that reacts chemically to
produce ele trical energy when a cell discharges. Also, such
material ir: its original composition, as applied to make an
electrode.
Air Scrub! ing - A method of removing air impurities such as dust or
fume by contact with sprayed water or an aqueous chemical soljtion.
Alkalinity - (1) The extent to which an aqueous solution contains
more hydroxyl ions than hydrogen ions. (2) The capacity of
water to nejtralize acids, a property imparted by the water's
content of carbonates, bicarbonates, hydroxides, and occasiorally
borates, silicates and phosphates.
Amalgamation - (1) Alloying of a zinc anode with mercury to prever c
internal corrosion and resultant gassing in a cell. (2) Treat-
ment of waste water by passing it through a bed of metal particles
to alloy an3 thereby remove mercury from the water.
Anode - The electrode by which electrons leave a cell. The negative
electrode in a cell during discharge.
Attrition Hill - A ball mill in which pig lead is ground to a powc er
and oxidized to make the active material in lead acid batteries.
Backwashing - The process of cleaning a filter or ion exchange co) .v.r>
by a reverse flow of water.
Baffles - Deflector vanes, guides, grids, gratings, or similar de\ ic« ::
constructed or placed in flowing water or sewage to (1) effect
a more uni'orm distribution of velocities; (2) divert, guide.
or agitate the liquids.
Bag House - The large chamber for holding bag filters used to fil'er
gas streams from a furnace such as in manufacture of lead c::^ac.
Ball Mill - A reactor in which pig lead is ground to a powder nn.c.
oxidized to wake the active material for lead acid batteries .
Barton Pot - Another device for making leady oxide.
Batch Treatment - A waste treatment method where waste water is
collected f-vc?r a period of time «n3 then treated prior to
discharge, often in the same vessel in which it is coll?oU-«. .
Datifry - A device that trnnr.f orws chomic.il r»norgy into elponicvi
enorgy. THr, term *:)>.-> ; :p •] i.-r to l-:o c: MO- •-• ci-llr c-- v.-.1.
in series, parallel or a combination ot holh .
809
-------
Bobbin - An assembly of the positive current collector and cathode
material, usually molded into a cylinder.
Buffer - Any of certain combinations of eiemicals used to stabilize
the pH values or alkalinities of solutions.
Button Cell - A tiny, circular battery, any of several types, made
for a watch or other microelectroni ' application.
Burn - Connection of terminals or connectors to a lead acid battery
by welding.
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 shaping molten lead in molds.
Cathode - The electrode by which electrons enter a cell. The
positive electrode in a cell during discharge.
Calhodic Polarize tion - Electrical connection of a nickel electro: e
plaque to promote deposition of active nickel material.
Caustic - (1) An alkaline battery electrolyte, sodium or potassi1..1;'
hydroxide. (2) Sodium hydroxide, used to precipitate heavy
metals from waste water.
Cell - The basic building block of a battery. It is an electroch', rrdcal
device consisting of an anode and a cathode in a common c2:c-rolyte
kept apart vith a separator. This assembly may be in itr, o;::
container or be an individual compartment of a battery.
Central Treatment Facility - Treatment plant which co-treats pror-. cs
waste waters from more than one manufacturing operation or c*--
treats process waste waters with norcontact cooling water, or'
with nonprocess waste waters (e.g., utility blowdown, misccl. an-
eous runoff, etc).
Centrifugation - Use of a centrifuge to i^move water in the rcnrml\ CM.UV
of active nuiterial or in the treatment of waste water Siludc»-.
Charne - The conversion of electrical energy into chemical enor
-------
Chemical Oxygen temand (COD) - (1) A test based on the fact that
all organic compounds, with few exceptions, can be oxidized
to carbon dioxide and water by the action of strong oxidizing
•gents under acid conditions. Organic matter is converted to
carbon dioxide and water regardless of the biological assimi-
lability of the substances. One of the chief limitations is
its ability to differentiate between biologically oxidizable
and biologically inert organic matter. The major advantage
of this te*>t is the short time required for evaluation (2 hr).
(2) The amojnt of oxygen required for the chemical oxidization
of organics in a liquid.
Chemical Precipitation - The use of an alkaline chemical to remove
dissolved hsavy metals from waste water.
Chemical Treatment - Treating contaminated water by chemical means.
Clarifier - A unit which provides settling and removal of solids
from waste water.
CMC - Sodium carboxymethyl cellulose; an organic liquid used as a
binder in electrode formulations.
Colloids - A finely divided dispersion o; one material called the
"dispersed phase" (solid) in anothe:: material which is called
the "dispersion medium" (liquid).
Compatible. Pollutant - An industrial pollutant that is successfully
treated by a secondary municipal treatment system.
Composite Waste Water Sample - A combination of individual sanples
of water or waste water taken at selected intervals and mixoc
in proportion to flow or time to minimize the effect of the
variability of an individual grab sample.
Concentration, Kydrogen Ion - The weight of hydrogen ions in gram:
per liter of solution. Commonly expressed as the pH value that
represents the logarithm of the reciprocal of the hydrogen icn
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 Rpnoval - The disposal of oils, spent colutionr., waste
waters, or sludge by means of an approved scavenger service.
Cool ing Tower - A device used to cool noncontact water used in tlu
manufacturing processes before returning the water for rouse.
C ur rent Collectcr - The grid portion of the electrode which
the current to the tormina!.
811
-------
Cyclone Separator - A funnel-shaped device for removing particles
from air or other fluids by centrifugal means. »
Decantation - A method for mechanical dewetering of a wet solid by
pouring off the liquid without disturbing the underlying
sediment or precipitate.
Demineralization - The removal from water of mineral contaminants
usually present in ionized form. Tho 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 fron a battery.
Discharge of Po3Iutant(s) - The addition of any pollutant to
navigable waters 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 waste v/atcr
treatment, the Standard Methods testa are used.
Dry Charge Process - A process for the manufacture of lead acid
storage batteries in which the plates are charged by electro--
lysis in silfuric acid, rinsed, and dried prior to shipment t,f
the batterj. Charging of the plates usually occurs in separ-
ate contairers before assembly of the battery but may be acc^r--
plished in the battery case. Batteries produced by the dry-
charge process are shipped without acid electrolyte.
Drying Beds - Aieas for dewatering of sludge by evaporation and
seepage.
Effluent - Industrial waste water 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.
Electrodoposition - Deposition of an active material from solution
onto on electrode grid or plaque by electrochemical noons.
Electroforminri - See (1) electrodeposilion, and (2) formation.
Electroimpregnation - See cathodic polarization.
Electrolvto - Tiio liquid or r.mi.oirial thnt pormits conduction of
ioru bet we- n cell elect rodcr,.
812
-------
Electrolytic Precipitation - Generally re fers 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 cathode 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-icid storage battery.
End-of-Pipe Treatment - The reduction and/or removal of pollutants
by treatment just prior to actual discharge to a point outside
an industrial plant.
Equalization - The process whereby waste streams from different
sources varying in pH, chemical constituents, and flow rates
are collected in a common container. The effluent stream
from this equalization tank will havs a fairly constant flow
and pH level, and will contain a homogeneous chemical mixtur? .
This tank will help to prevent an unnecessary shock to the
waste treatment system.
Evaporation Pondf - A pond, usually lined, for disposal of waste
water by evaporation; effective only in areas of low rainfall.
Filter, Rapid Sard - 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 cons, sting
of a layer of sand or prepared anthracite coal or other suitable
material, usually from 24 to 30 inch-es thick and resting on ;
supporting bed of gravel or a porous medium such as carborunou;.:.
The filtrate is removed by a drain system. The filter is cl« anca
periodically by reversing the flow of the water upward throuch the
filtering medium. Sometimes supplemented by mechanical or a: r
agitation during backwashing to remove impurities that are 1< d^e-i
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 waste water ic distributed anci applied
in drops, films, or spray, from troughs, drippers, moviny dis-
tributors or fixed nozzles and throuqh which it trickier to 'H
under-drain, oxidizing organic materials by means of microor<
attached to the filter media.
Filter, Vacuum - A filter consisting of a cylindrical drum mount-,
on a horizontal axis, covered with a filler cloth revolving
with a partial cubmorgonce in liijuid. A vacuum is maintain.
under the cloth lor UK- larqor jx-rt of i vil inn to c-xti
813
-------
Filtrate - Liqui-i after passing through a filter.
Filtration - Renoval of solid particles from liquid or particles
from air or gas stream through a permeable membrane or deep
bed.
Types: Gravity, Pressure, microstrrining, ultrafiltration,
Reverse Os.r.osis (hyperf iltration).
Float Gauge - A device for measuring the elevation of the surface
of.a liquid, the actuating element of which is a buoyant float
that rests on the surface of the liquid 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 b" the aggregation of fine
suspended particles.
Flocculator - Ar apparatus designed for :he formation of floe in
water or sewage.
Flocculation - In water and waste water treatment, the agglomeration
of colloidal and finely divided suspended matter after coagula-
tion 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.
Flov.* Proportioned Sample - See "Composite Waste Water Sample".
Formation - An electrochemical process w'lich converts the battery
electrode material into the desired chemical condition. For
example, in a silver-zinc battery tne silver applied to the
cathode is converted to silver oxide and the zinc oxide applr.ed
to the anode is converted to elemental zinc. "Formation" is
generally used interchangably with "charging", although it may
involve a repeated charge-discharge cycle.
Gelled Electrolyte - Electrolyte which may or may not be mixeJ wi;h
electrode material, that has been gelled with a chemical mjcr.t
to immobilize it.
GPP - Gallons pc-r day.
Grab Sample - A single sample of waste water taken at. neither
set time nor flow.
Grease - In waste water, a group of substances including fats,
waxes, free fatty acids, calcium and mannesium soaps,
oil, and certain other nonfatty mat'-rialr..
814
-------
Grease Skimmer - A device for removing grease or sc,um from the
surface of waste water in a tank.
Grid - The support for the active materials and a means to conduc.
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 calciu i,
magnesium, and iron such as bicarbonates, carbonates, sulfat;s,
chlorides, and nitrates that cause curdling of soap, deposit '.on
of scale in boilers, damage in some industrial processes, an 3
sometimes objectionable taste. It nay be determined by a stan-
dard 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 tfe ions of metallic elements
such as cooper, zinc, chromium, and nickel. They are normally
removed from waste water by forming an insoluble precipitate
(usually a metallic hydroxide).
Holding Tank - \ tank for accumulating Wcste water prior to treat rent.
Hydrazine Treat.nent - Application of a rt'ducing agent to form a
conductive metal film on a silver o> ide cathode.
Hydroquinone - \ developing agent used to form a conductive metal
film on a silver oxide cathode.
Impregnation - Methode of making an elec.rode by precipitating active
material on a sintered nickel plaquo.
In-Proccos Control Technology - The regulation and conservation
of chemicals and rinse water throughout the operations as
opposed tc end-of-pipe treatment.
Industrial Wastgs - The liquid wastes from industrial processes
as distinct from domestic or sanitary wastes.
Influent - Water or other liquid, cither raw or partly treated,
flowing into a treatment step or plant.
Ion Exchange - Waste water treotmpnt by contact with a rosin that
exchanges harmless ions (e.g. sodiuir,) for toxic inorganic i-';-i:.
(e.g. mercury), which the resin adsorbs.
Jacket - The outer cover of a dry cc»ll battery, usually a paper-
plaotic laminate.
Kjeldahl Nitron on - A mot hod of riot'-rmining th<» aimnnnii iincl PV ';po 1V
" bound ni t MVjon in the -3 v;;l-%iK-o rt.ite but ck>i" noi r.•! . •• .
nitrite, aside.';, nilro, nitro.-x), ox-me:; or nili.ilo nitro., ...
815
-------
Lagoon - A man-made pond or lake for holding waste water for the
removal of suspended solids. Lagoons are also'used as reten-
tion ponds after chemical clarificat on to polish the effluent
and to safegjard against upsets in the clarifier; for stabili-
zation of organic matter by biological oxidation; for storage
or sludge; and for cooling of water.
Landfill - The disposal of inert, insoluble waste solids by dumping
at an approved site and covering wicvi earth.
Leaching - Dissolving out by the action oi: a percolating liquid,
such as water, seeping through a landfill, which potentially
contaminates ground water.
Lime - Any of a family of chemicals consisting essentially of calciuTi
hydroxide made from limestone (calcite) which is composed almost
wholly of calcium carbonates or a mixture of calcium and magre-
sium carbonates.
Limiting Orifice - A device that limits flow by constriction to a
relatively small area. A constant flow can be obtained over
a v/ide range of upstream pressures.
Hake-Up Kater - Ket amount of water used oy any process/process
step, not including recycled water.
Mass - The active material used in a pockat plate cell, for
example "nickel mass."
Milligrams Per Liter (reg/1) - This is a weight per volume concentration
designation used in water and waste '.;ater analysis.
Mixed Media Filtration - A depth filter which uses tvro or more fi ter
materials of differing specific gravities selected so as to
produce a filter uniformly graded from coarse to fine.
National Pollutant Discharge Elimination System (NPDES) - The £c3-. ral
mechanism for regulating point source discharge by means of
permits.
Neutralization - Chemical addition of either acid or base to a
solution such that the pH is adjusted to approximately 7.
Non-Contnct Cooling Wntor - Writer used for cooling which door. not
come into direct contact with any rav; matoric-.l, interiucJ i>:t o-
product, waute product or finichcJ product.
Outfall - The point or location where wasio watc-r discharges
from a scwor, drain, or conduit.
Oxiclotion - 1. Chemical addition of oxygen e>t.0!i(r,) to a chemical
corpound; 2. In general, any chemical, rr'/'io*. ion in which ..MI
elf-'iionl or ion J5-, raiso-:! to a ir.or-- ror.j t i-.-< vM.•.••-,-.> ;•;• .;.-;
3. Uliu proec-Gr. at n U:ltcry i
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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 - Powdered1 active material mixed with a liquid to form a paste
for ease of application to a grid to make an electrode.
Pasting Machine - An automatic machine for applying lead oxide pas te
in the manufacture of lead-acid batteries.
pH - The reciprocal of the logarithm of the hydrogen ion concentretion.
The concentration is the weight of lydrogen ions, 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 high* r
than 7, a nolution is alkaline.
pF Adjustment - A means of treating waste water by chemical addit.on;
usually thu addition of lime to precipitate heavy metal pollutants
Plaque - A porous body of sintered metal on a metal grid used as ;;
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 out not limited to any pipe, ditch, channel, tunnc.i,
conduit, well, discrete fissure, container, rolling stock,
concentrated animal feeding operation, or vessel or other
floating craft, from which pollutants are or may be discharg d.
Pollutant Parameters - Those constitutents of waste water determined
to be detrimental and, therefore, requiring control.
Polyeloctrolytos - Materials used an a coagulant or a coagulant aid
in water and waste water treatment. They are synthetic or natural
polymers containing ionic constituents. They may be cationi.. ,
anionic, or nonionic.
Post - A battery terminal, especially on a lead-acid battery.
tat.ion - Process of separation of r dirjsiO vyd cuhstanco I r . i
a "aoi'uiiorj or tu.sponsion !>y cnnuic..! or physical ch
as an insoluble solid.
817
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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.
Pretreatment - Aay waste water treatment process used to reduce
pollution load partially before the waste water is introducec'
into a main sewer system or delivered to a municipal treatmert
plant.
Primary Battery - A battery which must usjally be replaced after one
discharge; i.e., the battery cannot :>e recharged.
Primary Settling - The first settling uni; for the removal of
settleable solids through which wast* water is passed in a
treatment works.
Primary Treatmert - A process to remove substantially all floating
and settleeble solids in waste water and partially reduce
the concentration of suspended solids.
Priority Pollutant - The 129 specific pollutants established by the
EPA from the 65 pollutants and classes of pollutants as outl ned
in the concent decree of June 8, 1976.
Process Waste Wc.ter - Any water which, during manufacturing or
processing, comes into direct contact with or results from
the produciion or use of any raw materials, intermediate
product, finished product, by-product, or waste product.
Process Water - Water prior to its direct contact use in a proces3
or operation. This water may be any combination of raw watec,
service water, or either process waste water or treatment
facility erfluent to be recycled or reused.
Raw Water - Plant intake water prior to any treatment or use.
Recycled Water - Process waste water or treatment facility effluent
which is recirculated to the same process.
Reduction - 1. A chemical process in which the positive valence of
a species is decreased.
2. Waste water treatment to (a) convert hexavalent chromium to
the trivalent form, or (b) reduce and precipitate mercury io:ir..
Reserve Cell - A class of cells which are designated as "reserve",
because thoy are supplied to the user in a non-activated stat.o.
Typical of this class of cell is the carbon-zinc air reserve coll,
which is produced with all the components in a dry or non-
activated state, and is activated with water when it is r«v..ly
to bo used.
818
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Retention Time - the time allowed for sol:.ds to collect in a settling
tank. Theoretically retention time ..s equal to the volume
of the tank divided by the flow rate The actual retention time
is determined by the purpose of the :ank. Also the design
residence time in a tan.k or reaction vessel which allows a
chemical reaction to go to completion, such as the reduction
of hexavalent chromium or the destruction of cyanide.
Reused Water - Process waste water or treatment facility effluent
which is further used in a different manufacturing process.
Reverse Osmosis (dyperfiltration) - 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 conc3ntrate.
Reversible Reaction - A chemical reaction capable of proceeding ir
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 sur-
face. In the battery industry, "rinse" may be used inter-
changeably with "wash."
Ruben - Developer of the Hg-Zn battery; also refers to the Hg-Zn
battery.
Sand Filtration - A process of filtering waste water through sand.
The waste water is trickled over the bed of sand, which retains
suspended solids. The clean water flows out through drains :n
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 - Waste water 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 Cell - An electrochemical cell or battery system thnt cvn
. be recharged; a storage battery.
Secondary Waste Knter Treatment-. - The treatment of waste water by
biological methods after primary treatment by sedimentation.
Sedimentation - The process of subsidence and deposition of sur.poi..lctl
matter carrJed by water, waste water/ or other liquids, by
gravity. It is us;uolly ncco.-ipl.i'r.hrd by ro'lui'inrj t'K volix ' % < '"
the licjujfl below th(; point at. which i I can trannpoit v!>c> tu::.-
pended material. Also called settling.
819
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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 or operation; i.e., make-up water.
Settling Ponds - A large shallow body of water into which industrial
waste waters are discharged. Suspended solids settle from t! e
waste waters due to the large retention time of water in the
pond.
Settleable Solic's - (1) That matter in waste water which will not
stay in suspension during a preselected settling period, suet
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 is om; 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 prepar< it
as a support for active material.
Sinter - Heatinj a metal powder such as nickel to a temperature
below its .nelting point whch causes it to agglomerate and ad'iere
to the supporting grid.
Sintered-plate Electrode - The electrode formed by sintering metallic
powders to form a porous structure, which serves as a curren;
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 wi ste water until removed, \?hile
the liquid discharges continuously under certain walls or scum
boards.
Sludge - A suspension, slurry, or solid matter produced in a waste
treatment process.
Sludge Conditioning - A process employed by prepare sludge for fiu-tl
disposal. Can be thickening, digesting, heat treatment etc.
Sludge Disposal - The final disposal of solid wastes.
Sludge Thickening - The increase in solids concentration of sludg.:
in a sedimentation or digestion tank or thickener.
ent - A ]i«.j'..id cfM>nb]c of rlist:nlvinf%; or di;-p?ising one or :;u->;--»
o t; h i: r s u b j U a n c <- s.
820
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chemical or material spill is an unintentional discharge
of more than 10 percent of the 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 closest equivalent
pollutant.
Sponge - A high..y porous metal powder.
Stabilization Lagoon - A shallow pond for storage of waste water
be.fo-re discharge. Such lagoons may serve only to detain and
equalize waste water composition belore regulated discharge
to a stream, but often they are used for bioligical oxidatioj.
Stabilization Pond - A type of oxidation pond in which biological
oxidation of organic matter is effected by natural or artif i -
cially accelerated transfer of oxygen to the water from air.
Storage Battery - A battery that can store chemical energy with tie
potential :o change to electricity. This conversion of chemical
energy to «Uectricity can be reversed thus allowing the batt.-ry
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 waste w*ter at the lowest point of a circulating or drainage
system.
Suspended Solids - (1) Solids that are in suspension in water, waste
water, or Dther liquids, and which nre largely removable by
laboratory filtering. (2) The quantity of material removed from
waste water in a laboratory test, as prescribed in "Standard
Methods for the Examination of Water and Waste Water" and referred
to as non-filterable residue.
Surface Waters - Any visible stream or body of water.
Terminal - The oart of a battery to which an external circuit is
connected.
Thickener - A device wherein the solids contents of slurries or
suspensions are increased by gravity settling and mechanical
separation of the phases, or by flotation and mechanical sep.M~;it ion
of the phases.
Total Cyanide - The total content of cyanide including simple ami /or
complex ions. In analytical terminology, total cyanide is t'u*
sum of cyanide amenable to chlorination and that which is not
according to standard analytical methods.
821
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Total Solids - The total amount of solids in a waste water in both
solution and suspension.
Toxicity - Referring to the ability of a uubstance to cause injury
to an organism through chemical acitlvty.
Treatment Efficiency - Usually refers to the percentage reduction
of a specific pollutant -or group of pollutants by a specific
waste water treatment step or treatment plant.
Treatment Facility Effluent - Treated process waste water.
Turbidity - (1) A condition in water or waste water 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 arLitrary 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 sclvent
to a battery part to remove contaminiting 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 naterial, 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 to measure flov; of liquid. The liquid surface is exposed
to the atmosphere. Flow is related to upstream height of water
above the crest, to position of crest with respect to downstiearn
water surface, and to geometry of the weir opening.
Wet Charge Process - Fabrication technique for lend-acid storcigo
batteries whoVeby elements are formed inside the assembled
battery case by elec'trical activation in sulfuric acid. Tho
battery is shipped with sulfuric aei 1 electrolyte inside* thu*
battery casing.
Wet Shelf Life - The period of time that a secondary battery can ;;tand
in the charged condition bofore total degradation.
Wot Scrubber - A unit in which dust and fumos arc removed from on
air or gas rt:rucim to a liouid. Gar.-j i'j'ii 1 v-)nt.,'ict fs prurui *
by jets, upiciyu, buI^Mc chMiiiSi.'!'.'.;, etc.
822
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METRIC TABLE
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by T0 OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
•ere 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 1n
degree Fahrenheit »F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
Inches 1n
Inches of mercury 1n Hg
pounds Ib
•1l11on gallons/day mgd
•rtle ml
pound/sguare
Inch (gauge) pslg
square feet sq ft
square Inches sq 1n
ton (short) ton
yard yd
0.405
1233.5
0.252
ha
cu m
kg cal
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
3,785
1.609
kg cal /kg
cu m/m1n
cu m/m1n
cu m
1
cu cm
•C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
(0.06805 pslg +1)* atn
0.0929 sq m
6.452 sq cm
0.907 kkg
0.9144 m
* Actual conversion, not a multiplier
hectares
cubic meters
kilogram - calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
11ters/second
klllowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilograms)
meter
•V.S. GOVERNMENT PRINTING OFFICE : 1980 0-311-726/5918
823
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